TW201900659A - Preparation of si-h containing iodosilanes via halide exchange reaction - Google Patents

Abstract

Methods of synthesizing Si-H containing iodosilanes, such as diiodosilane or pentaiododisilane, using a halide exchange reaction are disclosed.

Description

 Preparation of Si-H-containing iodine decane by halide exchange reaction   [Cross-reference to related applications]

The present application claims the benefit of PCT Patent Application No. PCT/US2017/033620, filed on Jan.

A process for synthesizing Si-H-containing iododecane, such as diiododecane or pentaiododicdioxane, using a halide exchange reaction is disclosed.

Halogenated decane chemistries are widely used in the industry. In particular, iodonyl decane precursors, such as diiododecane (SiH ₂ I ₂ ), are used to deposit a variety of ruthenium containing films for use in semiconductor fabrication processes.

Emeléus et al. disclose the synthesis of diiododecane (SiH ₂ I ₂ ) by the reaction of decane (SiH ₄ ), hydrogen iodide (HI) and aluminum iodide (AlI ₃ ). (Derivatives of monosilane. Part II. The Iodo compounds: Emeleus, HJ; Maddock, AG; Reid, C., J. Chem. Soc. 1941, 353-358). The reaction produces the desired SiH ₂ I ₂ reaction product as well as iododecane (SiH ₃ I), triiododecane (SiHI ₃ ) and tetraiododecane (SiI ₄ ). Ibid., at page 354.

Keinan et al. disclose the reaction of iodine with phenyl decane at a 1:1 molar ratio in the presence of traces of ethyl acetate at -20 ° C to yield 1 mole of SiH ₂ I ₂ and 1 molar. J. Org. Chem., Vol. 52, No. 22, 1987, pp. 4846 to 4851. Although the selectivity to SiH ₂ I ₂ is superior to other possible iododecanes (i.e., SiH ₃ I, SiHI _{3 ,} and SiI ₄ ), this method produces known human carcinogen benzene, making it difficult to commercialize. Despite this drawback, it is still a preferred synthetic method for the manufacture of diiododecane.

Impurities from such synthetic processes, such as hydrogen iodide and/or iodine, may decompose the resulting iododecane product. Current industrial practice is to stabilize these products using bismuth, silver or copper powder/pellet additives, as taught below: Eaborn, Organosilicon Compounds. Part II. " A Conversion Series for Organosilicon Halides, Pseudohalides, and Sulphides ", 1950, J. Chem. Soc., 3077-3089 and Beilstein 4, IV, 4009. Although the addition of copper stabilizes the product, impurities (Cu) may also be introduced, which may adversely affect the electrical properties of the deposited film.

The so-called Finkelstein reaction is a reaction involving a halogen atom exchanged with another halogen atom, S _N 2 (binucleophilic nucleophilic substitution reaction). Halide exchange is an equilibrium reaction, but the reaction can be advanced by using different soluble halide salts or by using a large excess of halide salt. Smith et al. (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th Edition), New York: Wiley-Interscience.

For example, trimethylsilyl iodide (TMS-I) has been reported to be prepared by reacting trimethyl decane chloride with lithium iodide in chloroform or with sodium iodide in acetonitrile (Reaction 4) ). Handbook of Reagents for Organic Synthesis, Reagents for Silicon-Mediated Organic Synthesis, Iodotrimethylsilane, Wiley 2011, page 325

Although Si-Cl is reactive toward iodine exchange by this route, the R group such as an alkyl group or an aryl group is not. On the other hand, it has been found that Si-H bonds are generally more reactive than Si-Cl bonds. Chemistry and Technology of Silicones, Academic Press, 1968, p. 50. Thus, those skilled in the art will be expected to exchange both H and Cl atoms of any Si-H containing halodecane in the Finkelstein reaction.

There is still a need for a commercially viable synthesis and supply of stable Si-H containing iododecane, such as diiododecane, for the semiconductor industry.

A method of synthesizing Si-H-containing iododecane is disclosed. The Si-H-containing iododecane 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 )

Where 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 to 3, each c is independently 0 to 3, a+b+c=3, with the constraint that at least one a and at least one c is 1, each m being independently 0 to 3, each n is independently 0 to 3, each o is independently 0 to 3, m+n+o=3, with the proviso that at least one m and at least one o is 1, and each R is independently a C1 to C12 hydrocarbon group, a Cl, Br or ER' ₃ group, wherein each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbyl group. The halodecane reactant reacts with an alkali metal halide reactant to produce 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 and MX a mixture, the halodecane reactant having the formula Si _w H _x R _y X _z , N(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 As defined above, the alkali metal halide reactant has the formula MI wherein M = Li, Na, K, Rb or Cs. The Si-H-containing iodine decane 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 is separated from the mixture. Alternatively, contacting the halodecane reactant with an alkali metal halide reactant to produce MX with Si _w H _x I _z , N(SiH _a R _b I _c ) ₃ or (SiH _m R _n I _o ) ₂ -CH ₂ The combination. The Si-H-containing iodine decane 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 is separated from the mixture. Any of the disclosed methods can have one or more of the following: • R is not Cl or Br; • R is a C1 to C12 hydrocarbyl group; • R is a C1 to C4 hydrocarbyl group; • R is an ER' ₃ groups; ●M=Li; ●y=0; ●z=2 to 2w+1; ●Add solvent to the reaction step; ●The solvent is Si-H-containing iododecane; ●The solvent is an alkane; ●Solvent And it is propane, butane, pentane, hexane, heptane, methyl chloride, dichloromethane, chloroform, carbon tetrachloride, methylene chloride, acetonitrile and combinations thereof; The separation step comprises filtering the mixture to separate MX from Si-H-containing iodine decane having the formula Si _w H _x R _y I _z ; • the halodecane reactant is SiH ₂ Cl ₂ ; the halo decane reactant is Si ₂ HCl ₅ ; ● halodecane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl); ● alkali metal halide reactant is LiI; ● Si-H containing iododecane has the formula Si _w H _x R _y I _z (1); ● Si-H-containing iododecane has the formula SiH _x I _4-x , wherein x=1 to 3; ● Si-H-containing iododecane is SiHI ₃ ; ● contains Si-H Silane is the iodo SiH ₂ I _2; ● SiH-containing silane-iodo of the SiH ₃ I; The SiH group-containing silane-iodide having the formula _{SiH x R y I 4-xy} , where x = 1 to 2, y = 1 to 2, x + y is less than or equal to 3, and each R is independently a C1 to C12 alkyl a Cl, Br or ER'3 group, wherein each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbon group; ● Si-H-containing iodonyl decane is MeSiHI ₂ ; -H iodonyl decane is MeSiH ₂ I; ● Si-H-containing iodine decane is Me ₂ SiHI; ● Si-H-containing iodine decane is EtSiHI ₂ ; ● Si-H-containing iodine decane is EtSiH ₂ I; ● Si-H-containing iodine decane is Et ₂ SiHI; ● Si-H-containing iodine decane is ClSiHI ₂ ; ● Si-H-containing iodine decane is ClSiH ₂ I; ● Si-H-containing iodine The decyl alkane is Cl ₂ SiHI; the Si-H-containing iodine decane is BrSiHI ₂ ; the Si-H-containing iodine decane is BrSiH ₂ I; the Si-H-containing iodine decane is Brl ₂ SiHI; The iodonyl decane of Si-H is H ₃ SiSiHI ₂ ; the iodonyl decane containing Si-H is H ₃ SiSiH ₂ I; the iodonyl decane containing Si-H is (H ₃ Si) ₂ SiHI; -H iodonyl decane is H ₃ GeSiHI ₂ ; ● Si-H containing iodine decane is H ₃ GeSiH ₂ I; ● Si-H containing iodine decane is (H ₃ Ge) ₂ SiHI; ● containing Si- Iodo group Alkoxy of Me ₃ SiSiHI _2; ● containing Si-H of iodo Silane is Me ₃ SiSiH ₂ I; ● containing Si-H of iodo Silane is _{(Me 3 Si) 2 SiHI;} ● containing Si-H of iodo Silane Is Me ₃ GeSiHI ₂ ; ● Si-H-containing iodine decane is Me ₃ GeSiH ₂ I; ● Si-H-containing iodine decane is (Me ₃ Ge) ₂ SiHI; ● Si-H-containing iodine decane is Me ₂ HSiSiHI ₂ ; ● Si-H-containing iodonyl decane is Me ₂ HSiSiH ₂ I; ● Si-H-containing iodine decane is (Me ₂ HSi) ₂ SiHI; ● Si-H-containing iodine decane is Me ₂ HGeSiHI ₂ ; ● Si-H-containing iodine decane is Me ₂ HGeSiH ₂ I; ● Si-H-containing iodine decane is (Me ₂ HGe) ₂ SiHI; ● Si-H-containing iodine decane has the formula Si ₂ H _x I _6-x , wherein x = 1-5; ● Si-H-containing iodonyl decane is Si ₂ HI ₅ ; ● Si-H-containing iodine decane is Si ₂ H ₂ I ₄ ; -H iodonyl decane is Si ₂ H ₃ I ₃ ; ● Si-H-containing iodine decane is Si ₂ H ₄ I ₂ ; ● Si-H-containing iodine decane is Si ₂ H ₅ I; ● Si-containing -H-iododecane has the formula Si ₂ H _x R _y I _6-xy , wherein x=1 to 4, y=1 to 4, x+y is less than or equal to 5, and each R is independently a C1 to C12 hydrocarbon group , Cl, Br or ER'3 groups, wherein each E independently Si or Ge, and each R 'is independently H or C1 to C12 alkyl; ● containing Si-H of iodo Silane is MeSi ₂ HI _4; ● containing Si-H of iodo Silane is MeSi ₂ H ₂ I _3; ● The Si-H-containing iodonyl decane is MeSi ₂ H ₃ I ₂ ; the Si-H-containing iodine decane is MeSi ₂ H ₄ I; the Si-H-containing iodine decane is Me ₂ Si ₂ HI ₃ ; The Si-H-containing iodine decane is Me ₂ Si ₂ H ₂ I ₂ ; the Si-H-containing iodine decane is Me ₂ Si ₂ H ₃ I; ● The Si-H-containing iodine decane is Me ₃ Si ₂ HI ₂ ; ● Si-H-containing iodine decane is Me ₃ Si ₂ H ₂ I; ● Si-H-containing iodine decane is Me ₄ Si ₂ HI, ● Si-H-containing iodine decane is EtSi ₂ HI ₄ ; ● Si-H-containing iododecane is EtSi ₂ H ₂ I ₃ ; ● Si-H-containing iododecane is EtSi ₂ H ₃ I ₂ ; ● Si-H-containing iododecane is EtSi ₂ H ₄ I; ● Si-H-containing iododecane is Et ₂ Si ₂ HI ₃ ; ● Si-H-containing iododecane is Et ₂ Si ₂ H ₂ I ₂ ; ● Si-H-containing iododecane is Et ₂ Si ₂ H ₃ I; ● Si-H-containing iodine decane is Et ₃ Si ₂ HI ₂ ; ● Si-H-containing iodine decane is Et ₃ Si ₂ H ₂ I; ● Si-H-containing iodine decane of Et ₄ Si ₂ HI, ● the Si-H-containing silane-iodo of ClSi ₂ HI ₄ ● Si-H containing the iodo Silane is ClSi ₂ H ₂ I _3; ● containing Si-H of iodo Silane is ClSi ₂ H ₃ I _2; ● containing Si-H of iodo Silane is ClSi ₂ H ₄ I; ● Si-H-containing iodine decane is Cl ₂ Si ₂ HI ₃ ; ● Si-H-containing iodine decane is Cl ₂ Si ₂ H ₂ I ₂ ; ● Si-H-containing iodine decane is Cl ₂ Si ₂ H ₃ I; ● Si-H-containing iodonyl decane is Cl ₃ Si ₂ HI ₂ ; ● Si-H-containing iodine decane is Cl ₃ Si ₂ H ₂ I; ● Si-H-containing iodine decane is Cl ₄ Si ₂ HI, ● Si-H-containing iodonyl decane is BrSi ₂ HI ₄ ; ● Si-H-containing iodine decane is BrSi ₂ H ₂ I ₃ ; ● Si-H-containing iodine decane is BrSi ₂ H ₃ I ₂ ; ● Si-H-containing iodonyl decane is BrSi ₂ H ₄ I; ● Si-H-containing iodine decane is Br ₂ Si ₂ HI ₃ ; ● Si-H-containing iodine decane is Br ₂ Si ₂ H ₂ I ₂ ; ● Si-H-containing iodonyl decane is Br ₂ Si ₂ H ₃ I; ● Si-H-containing iodine decane is Br ₃ Si ₂ HI ₂ ; ● Si-H-containing iodine decane Is Br ₃ Si ₂ H ₂ I; ● Si-H-containing iodine decane is Br ₄ Si ₂ HI, ● Si-H-containing iodine decane is H ₃ SiSi ₂ HI ₄ ; ● Si-H-containing iodine group The decane is H ₃ SiSi ₂ H ₂ I ₃ ; ● The Si-H-containing iodine decane is H ₃ SiSi ₂ H ₃ I ₂ ; ● Si-H-containing iodonyl decane is H ₃ SiSi ₂ H ₄ I; ● Si-H-containing iodine decane is (H ₃ Si) ₂ Si ₂ HI ₃ ; ● Si-H-containing The iododecane is (H ₃ Si) ₂ Si ₂ H ₂ I ₂ ; the Si-H-containing iodine decane is (H ₃ Si) ₂ Si ₂ H ₃ I; ● the Si-H-containing iodine decane is (H ₃ Si) ₃ Si ₂ HI ₂ ; ● Si-H-containing iodine decane is (H ₃ Si) ₃ Si ₂ H ₂ I; ● Si-H-containing iodine decane is (H ₃ Si) ₄ Si ₂ HI, ● Si-H-containing iodonyl decane is H ₃ GeSi ₂ HI ₄ ; ● Si-H-containing iodine decane is H ₃ GeSi ₂ H ₂ I ₃ ; ● Si-H-containing iodine decane is H ₃ GeSi ₂ H ₃ I ₂ ; ● Si-H-containing iodonyl decane is H ₃ GeSi ₂ H ₄ I; ● Si-H-containing iodine decane is (H ₃ Ge) ₂ Si ₂ HI ₃ ; ● Si-containing -H iodonyl decane is (H ₃ Ge) ₂ Si ₂ H ₂ I ₂ ; ● Si-H-containing iodine decane is (H ₃ Ge) ₂ Si ₂ H ₃ I; ● Si-H-containing iodine group The decane is (H ₃ Ge) ₃ Si ₂ HI ₂ ; the Si-H-containing iodine decane is (H ₃ Ge) ₃ Si ₂ H ₂ I; the Si-H-containing iodine decane is (H ₃ Ge) ₄ Si ₂ HI, ● Si-H containing the iodo Silane is Me ₃ SiSi ₂ HI _4; ● containing Si-H of iodo Silane is _{Me 3 SiSi 2 H 2 I 3} ; ● iodine-containing group Si-H of Alkoxy of _{Me 3 SiSi 2 H 3 I 2} ; ● containing Si-H of iodo Silane is _{Me 3 SiSi 2 H 4 I;} ● containing Si-H of iodo Silane is _{(Me 3 Si) 2 Si 2} HI 3; ● Si-H-containing iodine decane is (Me ₃ Si) ₂ Si ₂ H ₂ I ₂ ; ● Si-H-containing iodine decane is (Me ₃ Si) ₂ Si ₂ H ₃ I; ● Si-H-containing The iodonyl decane is (Me ₃ Si) ₃ Si ₂ HI ₂ ; the Si-H-containing iodine decane is (Me ₃ Si) ₃ Si ₂ H ₂ I; ● the Si-H-containing iodine decane is (Me ₃ Si) ₄ Si ₂ HI, ● Si-H-containing iodine decane is Me ₃ GeSi ₂ HI ₄ ; ● Si-H-containing iodine decane is Me ₃ GeSi ₂ H ₂ I ₃ ; ● Si-H-containing Iododecane is Me ₃ GeSi ₂ H ₃ I ₂ ; ● Si-H-containing iododecane is Me ₃ GeSi ₂ H ₄ I; ● Si-H-containing iododecane is (Me ₃ Ge) ₂ Si ₂ HI ₃ ; ● Si-H-containing iododecane is (Me ₃ Ge) ₂ Si ₂ H ₂ I ₂ ; ● Si-H-containing iododecane is (Me ₃ Ge) ₂ Si ₂ H ₃ I; ● Si-containing -H iodonyl decane is (Me ₃ Ge) ₃ Si ₂ HI ₂ ; ● Si-H-containing iodine decane is (Me ₃ Ge) ₃ Si ₂ H ₂ I; ● Si-H-containing iodine decane is (Me ₃ Ge) ₄ Si ₂ HI, ● Si-H-containing iodonyl decane is Me ₂ HSiSi ₂ HI ₄ ; ● Si-H-containing iodine decane is Me ₂ HSiSi ₂ H ₂ I ₃ ; ● Si-H-containing iodonyl decane is Me ₂ HSiSi ₂ H ₃ I ₂ ; ● Si-H-containing iodine decane is Me ₂ HSiSi ₂ H ₄ I; ● Si-H-containing iodine The decane is (Me ₂ HSi) ₂ Si ₂ HI ₃ ; the Si-H-containing iodine decane is (Me ₂ HSi) ₂ Si ₂ H ₂ I ₂ ; the Si-H-containing iodine decane is (Me ₂ HSi) ₂ Si ₂ H ₃ I; ● Si-H-containing iododecane is (Me ₂ HSi) ₃ Si ₂ HI ₂ ; ● Si-H-containing iododecane is (Me ₂ HSi) ₃ Si ₂ H ₂ I; ● Si-H-containing iododecane is (Me ₂ HSi) ₄ Si ₂ HI, ● Si-H-containing iododecane is Me ₂ HGeSi ₂ HI ₄ ; ● Si-H-containing iododecane is Me ₂ HGeSi ₂ H ₂ I ₃ ; ● Si-H-containing iodonyl decane is Me ₂ HGeSi ₂ H ₃ I ₂ ; ● Si-H-containing iodine decane is Me ₂ HGeSi ₂ H ₄ I; ● Si-H-containing The iodonyl decane is (Me ₂ HGe) ₂ Si ₂ HI ₃ ; the Si-H-containing iodine decane is (Me ₂ HGe) ₂ Si ₂ H ₂ I ₂ ; the Si-H-containing iodine decane is ( Me ₂ HGe) ₂ Si ₂ H ₃ I; ● Si-H-containing iodine decane is (Me ₂ HGe) ₃ Si ₂ HI ₂ ; ● Si-H-containing iodine decane is (Me ₂ HGe) ₃ Si ₂ H ₂ I; ● Si-H-containing iodine decane is (Me ₂ HGe) ₄ Si ₂ HI, ● Si-H-containing iodine decane has the formula Si ₃ H _x I _8-x , wherein x=1 to 8; ● Si-H-containing iodonyl decane is Si ₃ H ₇ I; ● Si-H-containing iodine decane is Si ₃ H ₆ I ₂ ; The Si-H-containing iodine decane is Si ₃ H ₅ I ₃ ; the Si-H-containing iodine decane is Si ₃ H ₄ I ₄ ; the Si-H-containing iodine decane is Si ₃ H ₃ I ₅ ; ● Si-H-containing iododecane is Si ₃ H ₂ I ₆ ; ● Si-H-containing iododecane is Si ₃ HI ₇ ; ● Si-H-containing iododecane has the formula N (SiH _a I _c ) ₃ , wherein each a is independently 0 to 3 and each c is independently 0 to 3, with the constraint that at least one a and at least one c is 1; ● Si-H-containing iododecane is N(SiH ₃ ) ₂ (SiH ₂ I); ● Si-H-containing iododecane is N(SiH ₃ ) ₂ (SiHI ₂ ); ● Si-H-containing iododecane is N(SiH ₃ )(SiH ₂ I) ₂ ; ● Si-H-containing iodine decane is N(SiH ₃ )(SiHI ₂ ) ₂ ; ● Si-H-containing iodine decane is N(SiHI ₂ ) ₂ (SiH ₂ I); ● Si-H-containing iodine The decane is N(SiHI ₂ )(SiH ₂ I) ₂ ; the Si-H-containing iodine decane is N(SiH ₂ I) ₃ ; The Si-H-containing iodine decane is N(SiHI ₂ ) ₃ ; ● the SiH-containing silane-iodo group having the formula _{N (SiH a R b I c} ) 3, wherein each a is independently 0 to 3, each b is independently 0 to 3, each c is independently 0 to 3, a+b+c=3, and each R is independently a C1 to C12 hydrocarbyl group, a Cl, Br or an ER'3 group, wherein each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbon group, the constraint being (a) at least one x, at least one y and at least one z being 1, and (b) at least one Si bonded to H and I ● Si-H-containing iododecane is N(SiH ₃ ) ₂ (SiMeHI); ● Si-H-containing iododecane is N(SiH ₂ Me) ₂ (SiMeHI); ● Si-H-containing iodine The decane is N(SiHMe ₂ ) ₂ (SiMeHI); ● the Si-H-containing iodine decane is N(SiMe ₂ H) ₂ (SiH ₂ I); ● The Si-H-containing iodine decane is N (SiMe _{3) 2} (SiH ₂ I); ● Si-H-containing iododecane is N(SiMe ₂ H) ₂ (SiHI ₂ ); ● Si-H-containing iododecane is N(SiMe ₃ ) ₂ (SiHI ₂ ) ● Si-H-containing iododecane has the formula (SiH _m R _n I _o ) ₂ -CH ₂ (3); ● Si-H-containing iododecane has the formula (SiH _x I _y ) ₂ CH ₂ , wherein Each x is independently 0 to 3, and each y is independently 0 to 3, with the constraint that at least one x and at least one y are 1; ● Si-H-containing iododecane is (SiH ₂ I) ₂ -CH _2; ● containing Si-H of the silane-iodo _{(SiHI 2) 2 -CH 2;} ● containing Si-H Is iodo Silane _{(SiH 2 I) -CH 2 -} (SiH 3); ● SiH-containing silane-iodo sum of _{(SiHI 2) -CH 2 - (} SiH 3); ● or the SiH group-containing iodine The decane is (SiH ₂ I)-CH ₂ -(SiHI ₂ ).

A composition for forming a Si-containing film comprising any of Si-H-containing iododecanes listed above is also disclosed. The disclosed composition for forming a Si-containing film comprises one or more of the following: ̇ forming a Si-containing film-containing composition comprising a Si-containing layer between about 99% v/v and about 100% v/v -H iodonyl decane; ̇ forming a Si-containing film composition comprising a Si-H-containing iodine decane between about 99.5% v/v and about 100% v/v; ̇ forming a Si-containing film composition The composition comprises a Si-H-containing iodonyl decane between about 99.97% v/v and about 100% v/v; and the composition forming the Si-containing film contains Cu between about 0 ppbw and about 100 ppbw; The composition forming the Si-containing film contains Ag between about 0 ppbw and about 100 ppbw; the composition forming the Si-containing film contains Sb between about 0 ppbw and about 100 ppbw; and the composition forming the Si-containing film contains about Cu between 0 ppbw and about 50 ppbw; ̇ forming a composition containing a Si film containing Ag between about 0 ppbw and about 50 ppbw; ̇ forming a composition containing a Si film containing Sb between about 0 ppbw and about 50 ppbw; The composition forming the Si-containing film contains Cu between about 0 ppbw and about 10 ppbw; the composition forming the Si-containing film contains about 0 ppbw and large Ag between about 10 ppbw; ̇ forming a composition containing a Si film containing Sb between about 0 ppbw and about 10 ppbw; or ̇ forming a composition containing a Si film containing C between about 0 ppmw and about 100 ppmw.

Also disclosed is a composition delivery device for forming a Si-containing film comprising a can having an inlet conduit and an outlet conduit and containing any of the above-described compositions for forming a Si-containing film. The disclosed apparatus may include one or more of the following: one end of the inlet conduit is above the surface forming the composition containing the Si film and one end of the outlet conduit is below the surface forming the composition containing the Si film; One end of the inlet conduit is located below the surface forming the composition containing the Si film and one end of the outlet conduit is above the surface forming the composition containing the Si film; the crucible further includes a diaphragm valve at the inlet and the outlet; the inner surface of the crucible is Glass; the inner surface of the crucible is a passivated stainless steel; the crucible is a light-resistant glass having a light-resistant coating on the outer surface of the can; the inner surface of the crucible is alumina; and the crucible further comprises one or more in the can a barrier layer on the surface; the crucible further comprising one to four barrier layers on the inner surface of the can; the crucible further comprising one or two barrier layers on the inner surface of the can; the barrier layers comprising a hafnium oxide layer, nitriding a tantalum layer, a niobium oxynitride layer, tantalum carbonitride, niobium oxycarbonitride or a combination thereof; wherein each of the barrier layers has a thickness of from 1 to 100 nm; or wherein each of the barrier layers has a thickness of from 2 to 10 nm.

Notation and nomenclature

Certain abbreviations, legends, and terms are used throughout the following description and claims, and include the indefinite article "a" or "an".

As used herein, the term "approximately" or "about" means ±10% of the value.

As used herein, the term "independently" when used in the context of describing an R group, is understood to mean that the target R group is not only relative to other R groups bearing the same or different subscripts or superscripts. Independently selected, it is also independently selected relative to any other 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 may, but need not be identical to each other or to R ² Or R ^{3 is the} same. In addition, it is to be understood that the values of the R groups are independent of one another when used in a different formula, unless specifically stated otherwise.

As used herein, the term "hydrocarbyl group" refers to a functional group containing carbon and hydrogen; the term "alkyl group" refers to a saturated functional group containing only carbon and a hydrogen atom. The hydrocarbyl group can be saturated or unsaturated. Any term refers to a straight chain, a branched chain or a cyclic group. Examples of linear alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, and the like. Examples of branched alkyl groups include, but are not limited to, isopropyl, tert-butyl. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, and the like.

As used herein, the term "aryl" refers to an aromatic ring compound in which one hydrogen atom has been removed from the ring. As used herein, the term "heterocycle" refers to a cyclic compound having atoms of at least two different elements as members of its ring.

As used herein, the abbreviation "Me" means methyl; the abbreviation "Et" means ethyl; the abbreviation "Pr" means any propyl (ie, n-propyl or isopropyl); the abbreviation "iPr" means Propyl; the abbreviation "Bu" means any butyl (n-butyl, isobutyl, tert-butyl, second butyl); the abbreviation "tBu" means the third butyl; the abbreviation "sBu" means Dibutyl; the abbreviation "iBu" means isobutyl; the abbreviation "Ph" means phenyl; the abbreviation "Am" means any pentyl (isopentyl, second amyl, third pentyl); "Cy" means a cycloalkyl group (cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.).

As used herein, the initial expression "HCDS" means hexachlorodioxane; the initial "PCD" means pentachlorodioxane; the initial word "OCTS" means n-octyltrimethoxynonane; the initial "TSA" means Tridecylamine or N(SiH ₃ ) ₃ .

As used herein, the term "iodosilane" means a molecule containing at least one Si-I bond, independent of Si or other bonds of the molecular backbone. More generally, "halosilane" means a molecule containing at least one bond containing Si-X, wherein X is a halogen atom, independent of Si or other bonds of the molecular backbone.

As used herein, the term "Si-H containing" means a molecule containing at least one Si-H bond, independent of Si or other bonds of the molecular backbone.

As used herein, the term "coordinating solvent (coordinating solvent)" means any solvent of the electron supply, such as a solvent containing OH groups or NH ₃ of. Exemplary coordinating solvents include amines, phosphines, ethers, and ketones.

As used herein, the initial expression "LCD-TFT" means a liquid crystal display film transistor; the initial "MIM" means metal-insulator-metal; the initial word "DRAM" means dynamic random access memory; the initials " FeRAM" ferroelectric random access memory; the initial word "sccm" means standard cubic centimeters per minute; and the initial word "GCMS" means gas chromatography-mass spectrometry.

The standard abbreviations for the elements of the Periodic Table of the Elements are used herein. It should be understood that the elements may be referred to by such abbreviations (for example, Si refers to yttrium, N refers to nitrogen, O refers to oxygen, and C refers to carbon, etc.).

Any and all ranges recited herein are inclusive of their endpoints (i.e., x = 1 to 4 includes x = 1, x = 4, and x = any number therebetween), and whether the term "inclusively" is used. Nothing.

Figures 1 and 2

1 ‧‧‧reactor

2 ‧‧‧sheath

3 ‧‧‧Filter

4 ‧‧‧distillation vessel

6 ‧ ‧ Boiler

7 ‧‧‧ collection trough

8 ‧ ‧ container

9 ‧‧‧Inert gas

11 ‧‧‧ solvent container

13 ‧‧‧alkali metal halide container

14 ‧‧‧ solvent pipeline

16 ‧‧‧alkaline metal halide pipeline

17a ‧‧‧Iron

17b ‧‧‧Motor

19 ‧‧‧Draining tube

21 ‧‧‧ entrance

22 ‧‧‧Export

23 ‧‧‧Heat exchanger/cooler

24 ‧‧‧ Halogenated decane container

25 ‧‧‧ Halogenated decane pipeline

26 ‧‧‧Mixture

27 ‧‧‧distillation column

28 ‧‧‧heater

29 ‧‧‧heater

43 ‧‧‧Export

53 ‧‧‧Distillation tower

54 ‧‧‧Return distributor

57 ‧‧‧Condenser

60 ‧‧‧Export

Figures 3 and 4

101 ‧‧‧Forming a composition delivery device containing a Si film

110 ‧‧‧Forming a composition containing a Si film

140 ‧‧‧Heating element

200 ‧ ‧ container

300 ‧‧‧inlet catheter

400 ‧‧‧Export conduit

600 ‧‧‧ valve

700 ‧‧‧ valve

800 ‧‧‧End of inlet duct 300

900 ‧‧‧End of outlet duct 400

Figure 5

5 ‧‧‧Accessories

10 ‧‧‧Control valve

12 ‧‧‧Export tube

15 ‧‧‧ Sealable top

18 ‧‧‧Sealing parts

20 ‧‧‧shims

30 ‧‧‧Internal platters

31 ‧‧‧Open/outside gas passage

33 ‧‧‧ Container

34 ‧‧‧Internal platters

35 ‧‧‧External gas channel

36 ‧‧‧Internal platters

37 ‧‧‧External gas channel

40 ‧‧‧Concentric wall

41 ‧‧‧Concentric wall

42 ‧‧‧Concentric wall

44 ‧‧‧Internal platters

45 ‧‧‧External gas channel

47 ‧‧‧Concentric trough

48 ‧‧‧Concentric trough

49 ‧‧‧Concentric trough

50 ‧‧‧ feet

51 ‧‧‧Internal passage

52 ‧‧‧ louvers

55 ‧‧‧Selecting the end of the tube

56 ‧‧‧Internal gas channel

58 ‧‧‧Bottom of the container

59 ‧‧‧ gas passage

61 ‧‧‧ outer wall

62 ‧‧‧External platters

64 ‧‧‧ring groove

65 ‧‧‧ring groove

66 ‧‧‧ring groove

68 ‧‧‧ wall

69 ‧‧‧ wall

70 ‧‧‧ wall

78 ‧‧‧External discs

79 ‧‧‧Internal gas channel

82 ‧‧‧External platters

83 ‧‧‧Internal gas channel

86 ‧‧‧External platters

87 ‧‧‧Open/internal gas passage

90 ‧‧‧Control valve

92 ‧‧‧汲管

95 ‧‧‧Accessories

100 ‧‧‧Sublimator

In order to further understand the nature and objects of the present invention, reference should be made to the following [embodiments] with reference to the accompanying drawings, wherein: FIG. 1 is a schematic diagram of a device in which the disclosed synthetic method can be performed; FIG. 2 is a schematic diagram of an alternative device. The disclosed synthesis method can be carried out in the apparatus; Fig. 3 is a side cross-sectional view showing a specific example of the composition delivery apparatus 1 for forming a Si-containing film.

4 is a side cross-sectional view showing a second specific example of the composition delivery device 1 for forming a Si-containing film.

5 is a side cross-sectional view showing an exemplary specific example of a solid precursor sublimator 100 for sublimation forming a solid composition of a Si-containing film; and FIG. 6 is a gas chromatography of the SiH ₂ I ₂ reaction product of Example 5. A Gas Chromatographic/Mass Spectrometric (GC/MS) chart; and Figure 7 is a GC/MS chart of the reaction mixture of Example 7 after stirring for 90 minutes.

A method for synthesizing Si-H-containing iodine decane having 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)

Where 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 to 3, each c is independently 0 to 3, a+b+c=3, with the constraint that at least one a and at least one c is 1, each m being independently 0 to 3, each n is independently 0 to 3, each o is independently 0 to 3, m+n+o=3, with the proviso that at least one m and at least one o is 1, and each R is independently a C1 to C12 hydrocarbon group, a Cl, Br or ER' ₃ group, wherein each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbyl group.

Such compounds, such as diiododecane (SiH ₂ I ₂ ) or pentaiododicdioxane (Si ₂ HI ₅ ), contain highly reactive Si-H groups, and in the case of y or b or n=0, Does not have any organic protecting groups. Therefore, such ruthenium hydrides are prone to nucleophilic attack by ruthenium hydride due to the coordination solvent. See, for example, Keinan et al., J. Org. Chem. 1987 , 52 , 4846-4851 (Describes catalytic deoxygenation of alcohols and ethers, carbonyl conjugate addition reactions, and alpha-alkanes of ketones by trimethyldecyl iodide) Oxymethylation). In other words, when a solvent is used, special care must be taken in selecting an appropriate solvent because the final product may react with the solvent. This may result in product degradation and side reactions. This also limits the choice of solvents suitable for synthesis.

The Finkelstein-type S _N 2 reaction typically relies on the solubility and insolubility of the reagents and salt by-products, respectively, to act as a propulsive force for the reaction. For example, trimethyl decane iodide (TMS-I) can be prepared by reacting trimethyl decane chloride with an alkali metal iodide salt (see Reaction Scheme 4 above) in a suitable solvent such as chloroform or acetonitrile. . In this particular example, trimethyl decane chloride (TMS-Cl) and sodium iodide salts have some solubility in such solvents, while the by-product sodium chloride does not. The precipitation of by-product sodium chloride contributes to the propulsive force of the reaction.

Si _w H _x R _y I _z (for example SiH ₂ I ₂ or Si ₂ HI ₅ ), N(SiH _a R _b I _c ) ₃ (for example N(SiH ₃ ) ₂ (SiH ₂ I)) or (SiH _m R Preparation of _n I _o ) ₂ -CH ₂ (for example, (SiH ₂ I)-CH ₂ -(SiH ₃ )) may be susceptible to halogen scrambling and side reactions attributed to the reactivity of Si-H bonds influences. Coordination solvents may exacerbate such halogen disturbances and side reactions. The reaction between dichlorosilane (DCS) and lithium iodide produces diiododecane in the absence of solvent at ambient temperature (see Example 3 below). Non-coordinating solvents such as n-pentane and chloroform are helpful during filtration of the lithium chloride salt by-product. The non-coordinating solvent can also promote the reaction by improved mixing (i.e., dilution of the reaction mass) and side reaction inhibition (heat exchange medium). Suitable non-coordinating solvents include hydrocarbons (such as pentane, hexane, cyclohexane, heptane, octane, benzene, toluene) and chlorinated aliphatic hydrocarbons (such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride). , acetonitrile, etc.). However, the use of chlorinated solvents is a less attractive option because such solvents are often strictly controlled (as required) and may be carcinogenic. The solvent should be selected to have a sufficient difference in boiling point from the target product, such boiling point difference being typically > 20 ° C, and preferably > 40 ° C.

Exemplary Si-H containing iododecane reaction products include, but are not limited to: • SiH _x I _4-x , where x=1 to 3, such as SiHI ₃ , SiH ₂ I ₂ or SiH ₃ I; • SiH _x R _y I _4-xy , wherein x=1 to 2, y=1 to 2, x+y is less than or equal to 3, and each R is independently a C1 to C12 hydrocarbyl group, a Cl, Br or ER'3 group, wherein Each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbon group such as 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 HGeSiHI ₂ , Me ₂ HGeSiH ₂ I, (Me ₂ HGe) ₂ SiHI, etc.; ● Si ₂ H _x-6 I _x , where x=1-5, 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, wherein x is preferably equal to 5 (i.e., _{Si 2 HI 5); ● Si} 2 H _x R _y I _6-xy , where x=1 To 4, y = 1 to 4, x + y is less than or equal to 5, and each R is independently a C1 to C12 hydrocarbyl, Cl, Br or ER'3 group, wherein each E is independently Si or Ge and each R 'Independently H or a C1 to C12 hydrocarbon group such as 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 Si 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 ₄ 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 HS i) 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 , Me 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 HI, etc.; ● Si ₃ H _x-8 I _x , where x=1 to 7, such as 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 ; ● N(SiH _x I _y ) ₃ , wherein each x is independent The ground is 0 to 3 and each y is independently 0 to 3, with the constraint that at least one x and at least one y are 1, such as 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 ) ₂ (SiH ₂ I), N(SiHI ₂ )(SiH ₂ I) ₂ , N(SiH ₂ I) ₃ or N(SiHI ₂ ) ₃ ; ●N(SiH _x R _y I _z ) ₃ , wherein each x is independently 0 to 3, and each y is independently 0 to 3, each z independently 0 to 3, x+y+z=3, and each R is independently a C1 to C12 hydrocarbyl, Cl, Br or ER'3 group, wherein each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbyl group, System conditions (a) at least one of x, y, and at least one of the at least one z is 1, and (b) at least one Si-bonded to both the H and I, such as _{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.; or ●(SiH _x I _y ) ₂ CH ₂ , wherein each x is independently 0 to 3, and each y is independently 0 to 3, which is limited The condition is that at least one x and at least one y are 1, such as (SiH ₂ I) ₂ -CH ₂ , (SiHI ₂ ) ₂ -CH ₂ , (SiH ₂ I)-CH ₂ -(SiH ₃ ), (SiHI ₂ ) -CH ₂ -(SiH ₃ ) or (SiH ₂ I)-CH ₂ -(SiHI ₂ ).

The Si-H-containing iododecane is synthesized by reacting or contacting the corresponding halodecane with an alkali metal halide as follows: Si _w H _x R _y X _z + n MI → Si _w H _x R _y I _z + n MX (6) N(SiH _a R _b X _c ) ₃ + n MI→N(SiH _a R _b I _c ) ₃ + n MX (7) (SiH _m R _p X _o ) ₂ -CH ₂ + n MI→(SiH _m R _p I _o ) ₂ -CH ₂ + n MX (8) where w=1 to 3; x=1 to 2w+1; y=0 to 2w+1; z=1 to 2w+ 1; x + y + z = 2w + 2; each a is independently 0 to 3; each b is independently 0 to 3; each c is independently 0 to 3; a + b + c = 3, the constraints Is at least one a and at least one c is 1; each m is independently 0 to 3; each p is independently 0 to 3; each o is independently 0 to 3; m+p+o=3, with the constraint being At least one m and at least one o is 1; n = 1 to 4; X = Br or Cl; M = Li, Na, K, Rb or Cs, preferably Li; and each R is independently a C1 to C12 hydrocarbon group, Cl a Br or ER' ₃ group wherein each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbyl group. As shown in Example 3, the contact between the two reactants can automatically initiate a chemical reaction. Alternatively, depending on the particular reactants, heating and/or mixing may be required to initiate the reaction.

The alkali metal salt (i.e., MI) can be used in excess or in absorptive amounts depending on the degree of halogen exchange desired. However, an excess of MI promotes complete replacement of the halide ion on the halodecane with iodide ions, reducing the amount of chlorine or bromine impurities contained in the reaction product. Those skilled in the art will adjust the stoichiometry to produce 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 and the like.

As discussed above, the salt-promoted reaction determines which reagent to use. However, unlike prior art Finkelstein reactions, lithium iodide and lithium chloride exhibit little or no solubility in hydrocarbons or fluorocarbons. For example, the reaction of SiCl ₂ H ₂ with two moles of lithium iodide in an aliphatic, aromatic or chlorinated hydrocarbon will form SiI ₂ H ₂ and lithium chloride as the main product and salt by-product, respectively. . LiI and LiCl remained solid during this reaction. Li forms a hard acid/base pair with Cl. Li and I have a hard/soft acid/base mismatch. Therefore, the applicant believes that the formation of insoluble LiCl can provide propulsion for the reaction. However, the formation of SiH ₂ I ₂ itself can partially dissolve LiI and help advance the reaction. Therefore, it may be beneficial to add the desired Si-H containing iododecane product to the initial reaction mixture.

SiH ₂ Cl ₂ (g or l)+2LiI(s)→SiH ₂ I ₂ (l)+2LiCl(s) (9)

Where g = gas, l = liquid and s = solid. In some cases, other alkali metal salts, such as sodium iodide (NaI), are suitable for the preparation of halogen exchange products. However, the reactivity of NaI in a similar solvent is lower than that of LiI and for any reaction, a coordinating solvent will typically be required to be carried out at an industry-relevant reaction rate, with the proviso that the coordinating solvent is selected to make the product The adverse effects of synthesis and/or production are minimized.

In another example, the reaction of Si ₂ Cl ₅ H with sodium pentoxide iodide in a chlorinated hydrocarbon such as chloroform will form a chlorination of Si ₂ I ₅ H and a five molar as a major product and a by-product of the salt, respectively. sodium. The formation of NaCl is the propulsive force of the reaction.

Si ₂ HCl ₅ (l)+5NaI(s)→Si ₂ HI ₅ (l)+5NaCl(s) (10)

Those skilled in the art will recognize that competition between Si-Si bond cleavage and halogen exchange may require the use of less reactive NaI or alternative alkali metal halides and/or alternative solvents. Product yield can be maximized by optimizing reaction parameters, such as removal of any salt by-products with the reaction to further prevent halogenation and side reactions from occurring.

While the following examples illustrate the disclosed synthetic processes using inorganic halodecane reactants, those skilled in the art will recognize that organic Si-R groups are less reactive than Si-X and Si-H, And thus may remain undisturbed during the disclosed synthetic process.

Halodecane and alkali metal halide reactants are commercially available. Alternatively, the halodecane reactant can be reduced by replacing the corresponding fully halogenated decane with a standard reducing agent such as lithium aluminum hydride (e.g., LiAlH ₄ ), NaBH ₄ or the like (i.e., Si _x R _y X _2x+2-y , N (SiR _b X _3-b ) ₃ or (SiR _n X _3-n ) ₂ -CH ₂ ) was synthesized. In another alternative, according to Morrison et al, J. Organomet. Chem., 92, 2, 1975, 163-168, the halodecane reactant can be obtained by reacting the corresponding decane [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 ] and a halogenating agent such as N-chloro-butanediamine, N-bromo-butane The imine or N-iodo-butanediimine is synthesized by reacting in toluene at a temperature ranging from 0 ° C to reflux for 1 to 12 hours. Although the form of the reactants (i.e., solid, liquid, or gas) is not critical, those skilled in the art will recognize that reactants having larger surface areas provide more reactive sites and therefore are more efficient. reaction. For example, finer particulate powders typically provide more reactive sites than solid beads or chunks.

The water content of the reactants and any solvent should be minimized to prevent the formation of oxane by-products (i.e., Si-O-Si). Preferably, the water content is in the range of from about 0% w/w to about 0.001% w/w (10 ppmw). If desired, the reactants can be dried prior to synthesis using standard techniques, such as refluxing over P ₂ O ₅ , passing through molecular sieves or heating under vacuum (eg, anhydrous LiI can be baked under vacuum at 325 ° C 8 + hours to produce).

The reaction vessel is made of a material compatible with the reactants and products, lined with materials compatible with the reactants and products, or treated to be compatible with the reactants and products. Exemplary materials include passivated stainless steel, glass, perfluoroalkoxy alkane (PFA), and polytetrafluoroethylene (PTFE). The container can be jacketed 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 agitator shaft, a PTFE paddle agitator, and/or a PTFE coated stainless steel impeller. The reaction vessel can also be equipped with a plurality of "injection ports", pressure gauges, and diaphragm valves. The reaction vessel is designed to be synthesized under an inert atmosphere such as N ₂ or an inert gas. Protective measures such as covering any transparent glassware in the tin foil may also be employed to minimize exposure of the light to the reactants and reaction mixture. Amber glassware is not suitable for the synthesis of SiH ₂ I ₂ because the iron oxide coating may contaminate the product. In addition, the reaction vessel, agitation mechanism, and any other associated equipment, such as a Schlenk line or glove box, should be airless and moisture free using standard drying techniques such as vacuum, inert gas flow, drying, and the like. of.

As discussed above with respect to the reactants and as illustrated in the examples below, the reaction vessel in contact with the reactants and products should be of high purity with any and all components. The high purity reaction vessel is typically a vessel compatible with Si-H containing iododecane. The high purity reaction vessel contains no impurities which may react with the Si-H containing iododecane or contaminate the Si-H containing iododecane. A typical example of such a high purity container is a stainless steel can having a low surface roughness and a mirror finish. Low surface roughness and mirror finish are typically obtained by mechanical polishing and, as the case may be, additional electropolishing. High purity is typically obtained by treatment including: (a) a cleaning step using dilute acid (HF, HNO ₃ ) followed by (b) rinsing with high purity deionized water to ensure complete removal of traces of acid Then (c) the container is dried. Deionized water (DIW) rinsing is typically carried out until the resistivity of the rinse water reaches 100 μS/cm, and preferably less than 25 μS/cm. The drying step may comprise a purge step using an inert gas such as HE, N ₂ , Ar (preferably N ₂ or Ar); a vacuum step during which the pressure in the vessel is lowered to promote degassing from the surface, heating the vessel , or any combination thereof.

The gas used for purging should be of a semiconductor grade, i.e., free of contaminants such as traces of moisture and oxygen (<1 ppm, preferably <10 ppb) and particles (<5 particles per liter at 0.5 μm). The drying step can include an alternate purge process during which a particular gas stream flows through the vessel and the vacuum step. Alternatively, the drying step can be carried out by continuously flowing the purge gas while maintaining a low pressure in the vessel. The efficiency and end point of tank drying can be assessed by measuring the amount of H ₂ O in the gas released from the vessel. The inlet gas having less than 10ppb H ₂ O under the circumstances, the moisture content of the outlet gas should be in the range of from about 10ppm to about 0ppm, preferably in the range from about 1ppm to about 0ppm, and more preferably in the range of from about to about 200ppb 0ppb Inside. It is known that the heating vessel accelerates the drying time during the purging step and the vacuum step. Typically, the vessel is maintained at a temperature in the range of from about 40 °C to about 150 °C during drying.

After cleaning and drying, the total leak rate of such high purity containers must be less than 1E-6 std cm ³ /s, preferably <1E-8 std cm ³ /s.

Optionally, the container may have an inner coating or coating to further reduce the risk of corrosion or improve the stability of the product in the container. Exemplary coatings include those disclosed by Silcotek (https://www.silcotek.com) or as disclosed in U.S. Patent Application Publication No. 2016/046408. The vessel may also be passivated by exposure to a decylating agent such as decane, dioxane, monochlorodecane, hexamethyldioxane prior to reaction and/or filling with Si-H containing iododecane.

Those skilled in the art will recognize the source of the device components of the system for practicing the disclosed methods. Some custom levels of components can be required based on the desired temperature range, pressure range, local adjustment, and the like. Exemplary equipment suppliers include Buchi Glass Uster, Shandong ChemSta Machinery Manufacturing Co., Ltd., Jiangsu Shajiabang Chemical Equipment Co., and the like. As discussed above, the assembly is preferably made of a corrosion resistant material such as glass, steel with a glass liner or steel with a corrosion resistant liner.

The air-free and moisture-free high purity reactor is packed with an alkali metal halide. The solvent selected as the heat exchange medium and/or the mixing and/or product extraction may be added before or after the alkali metal halide is added to the reactor. Exemplary solvents include C3-C20 alkanes (such as propane, butane, pentane, etc.) or chlorinated hydrocarbons (such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride, and the like), and mixtures thereof. As discussed above, the desired Si-H containing iododecane can also be used as a solvent. The alkali metal halide salt is soluble in the solvent. However, depending on the reactants, salt solubility may not be a critical factor. For example, as shown in Example 5 below, solid lithium iodide will react with liquid dichloromethane in a solid-liquid reaction in pentane. The reaction mixture can be stirred to further promote contact between the reactants. Alternatively, the reaction can be carried out without using a solvent, as shown in Example 3 below.

The halodecane can be added to the reactor via the headspace or via subsurface addition in the form of a gas, liquid (condensation) or solution. The halodecane can be in gaseous form and added to the headspace above the lithium iodide/solvent mixture. Alternatively, a condenser can be used to condense the gaseous form of halodecane and added directly to the lithium iodide/solvent mixture. In another alternative, the liquid form of halodecane can be added from the top of the reactor using a conduit that is delivered to the reactor. In another alternative, a gas or liquid form can be added below the surface of the iodine/solvent mixture using a reactor equipped with a draw tube inserted into the salt/solvent mixture. In the following examples, condensation of dichloromethane was performed to facilitate faster reagent transfer.

The halodecane may be added in an excess, stoichiometric or substoichiometric amount depending on which product distribution is desired. Excessive halodecane relative to the metal iodide salt will cause the halide to be partially substituted with iodine on the halodecane and result in the formation of a Si _w H _x R _y I _z compound wherein at least one R is Cl or Br. Excess iodide metal salts will promote the complete replacement of the iodide ions on the halodecane (i.e., without R = Cl or Br).

Alternatively, halodecane can be added to the reactor prior to the addition of the alkali metal halide. The addition mechanism of the halodecane and the alkali metal halide described above remains the same whether or not the reactants are added first or second to the reactor.

The halodecane/alkali metal halide combination can be agitated to further promote contact between the reactants. The reaction can be exothermic. In the following examples, the reaction mixture is stirred for a time sufficient to permit the reaction to continue at ambient temperature (i.e., from about 20 ° C to about 26 ° C). Heating is not required in the following examples, but it may be an option to promote the reaction. Those skilled in the art will be able to determine the most suitable temperature range, depending on the individual kinetics of each halodecane. For example, a halodecane having a partial hydrocarbyl group may require a reaction temperature higher than that of a halodecane having no hydrocarbyl substituent due to steric hindrance caused by a hydrocarbon group.

The progress of the reaction can be monitored using, for example, gas chromatography or commercially available in situ probes such as FTIR or RAMAN probes. For a stoichiometric excess of metal iodide salt, the main reaction product is Si _w H _x R _y I _z + n MX, and a small amount of Si _w H _x R _y X _z , MI, solvent and Si _w H _x R _y (IX) _z intermediate reaction product containing both the amounts I and X of z. For example, the SiH ₂ I ₂ reaction mixture can include a SiH ₂ I ₂ reaction product, a LiCl reaction by-product, some residual SiCl ₂ H ₂ and/or LiI reactants, a solvent, and a ClSiH ₂ I intermediate reaction product.

The Si-H-containing iodine decane can be separated from the reaction mixture by filtration and distillation. Any solid impurities and salt by-products can be filtered from the reaction mixture. Typical filters include glass or polymer sintered filters.

Alternatively, when the salt by-product is dissolved in the solvent, the mixture can be filtered to remove solid by-products prior to the further separation process. A filter such as anhydrous diatomaceous earth can be used to improve the process. Typical filters include glass or polymer sintered filters.

Alternatively, further processing may be required to separate the Si-H containing iododecane. For example, when the filtrate produces a heterogeneous suspension of solid material, the Si-H-containing iodine decane can be subsequently separated by flash distillation via a short-run column distillation, which removes the undesired reaction Some or all of the product or impurities. Alternatively, the Si-H containing iododecane reaction product can be separated from the filtrate via a distillation column or by heating the filtrate to near the boiling point of the non-organohydrazine hydride reaction product. In another alternative, both a flash process and a distillation column may be required. It will be appreciated by those skilled in the art that when the Si-H containing iododecane reaction product is separated from the elevated temperature mixture, the boiling point of the elevated temperature mixture will vary and thus the recovery temperature will be adjusted. Any unreacted halodecane can be withdrawn through the distillation column because, because of the higher mass of iodine compared to Br or Cl, it tends to be more volatile than the product obtained. Those of ordinary skill in the art will recognize that the halogenated decane can be recovered for subsequent use or disposal.

The disclosed process converts from about 40% mol/mol to about 99% mol/mol of the halodecane reactant to a Si-H containing iododecane reaction product. The purity of the isolated Si-H containing iododecane reaction product is typically in the range of from about 50% mol/mol to about 99% mol/mol.

The Si-H containing iododecane reaction product can be further purified by distillation, sublimation or recrystallization. Suitable distillation methods include atmospheric fractionation, batch fractionation or vacuum fractionation. Batch fractionation can be carried out at low temperature and low pressure. Alternatively, the Si-H containing iododecane reaction product can be purified by continuous distillation via two distillation columns to separate the Si-H containing iododecane reaction product from the low and high boiling impurities in a continuous step. The purified Si-H-containing iodonyl decane reaction product can be used as a composition for forming a Si-containing film.

The composition forming the Si-containing film has a purity of from about 97% mol/mol to about 100% mol/mol, preferably from about 99% mol/mol to about 100% mol/mol, more preferably from about 99.5% mol/mol to about. It is in the range of 100% mol/mol and even more preferably from about 99.97% mol/mol to about 100% mol/mol.

The composition for forming the Si-containing film preferably comprises various possible metal contaminants (for example, at least Ag, Al, Au, Ca, Cr, Cu, Fe, Mg, Mo, Ni, K) between a detection limit and 100 ppbw. , Na, Sb, Ti, Zn, etc.). More specifically, as shown in Example 11, the composition for forming a Si-containing film synthesized according to the disclosed method does not require the use of any Sb, Ag or Cu powder/pellet stabilizer. Accordingly, the composition forming the Si-containing film contains Cu between about 0 ppbw and about 100 ppbw, preferably between about 0 ppbw and 50 ppbw, and more preferably between about 0 ppbw and 10 ppb. The ability to synthesize a composition comprising a Si film without the need for Cu stabilizers is beneficial because any CU contaminants can adversely affect the electrical properties of the resulting Si-containing film. The composition forming the Si-containing film also contains Sb between about 0 ppbw and about 100 ppbw, preferably between about 0 ppbw and 50 ppbw, and more preferably between about 0 ppbw and 10 ppb. The composition forming the Si-containing film contains Ag between about 0 ppbw and about 100 ppbw, preferably between about 0 ppbw and 50 ppbw, and more preferably between about 0 ppbw and 10 ppb.

The concentration of X (where X = Cl, Br or I) in the composition forming the Si film may range from about 0 ppmw to about 100 ppmw, and more preferably from about 0 ppmw to about 10 ppmw.

When y or b or n = 0 (i.e., the composition forming the Si-containing film does not have any organic protecting group), the composition forming the Si-containing film contains C between about 0 ppmw and about 100 ppmw. Depending on the type of Si-containing film deposited, incorporation of carbon may be extremely undesirable because a small amount of C in the film can cause large changes in film properties. Film properties that can be largely affected by a small amount of C incorporation include wet etch rate, leakage current, film stress, and/or Young's modulus. Therefore, it is desirable to control the amount of C in the Si-containing film. The synthesis of a composition comprising a Si-containing film that does not contain C provides more flexibility in the composition of the Si-containing film required for engineering. Alternative synthetic methods utilizing organic ligands have a significantly higher probability of containing C impurities in the final product, independent of the purification steps performed after the synthesis reaction. When y or b or n = 0, the methods disclosed herein do not use any organic ligands, and thus avoid the source of contamination that may be present, providing high reliability and similarity of the product with the run.

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

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

FIG. 1 is an illustrative system suitable for performing the disclosed methods. Air may be removed from multiple components of the system (e.g., reactor 1 , vessel 8 , boiler 6 ) by inert gas 9 (e.g., nitrogen, argon, etc.). The inert gas 9 can also be used to pressurize the solvent container 11 as the case may be selected to permit solvent delivery to the reactor 1 . A plurality of components of the system (e.g., reactor 1 , distillation column 27 , condenser 57 ) may be cooled using nitrogen, refrigerated ethanol, an acetone/dry ice mixture, or a heat transfer agent such as monoethylene glycol (MEG).

Reactor 1 can be maintained at the desired temperature by jacket 2 . The sheath 2 has an inlet 21 and an outlet 22 . Inlet 21 and outlet 22 may be coupled to heat exchanger/cooler 23 and/or a pump (not shown) to provide recirculation of cooling fluid. Alternatively, if the batch size is sufficiently small and the mixing time is sufficiently short, the sheath 2 may not require the inlet 21 and the outlet 22 because the thermal fluid may be sufficiently cold for the duration of the reaction. In another alternative and as discussed above, the jacketed temperature controller may not be required and the four components (i.e., 2 , 21 , 22, and 23 ) are removed from the system.

The reactants (optionally selected as a solvent (such as pentane) stored in the solvent container 11 and the halodecane stored in the halodecane container 24 are respectively taken through a solvent line 14 and a halodecane line 25 , which are optionally used. Addition to reactor 1 such as ethyl dichloromethane. A solvent and a halodecane, optionally selected, may be added to the reactor 1 via a liquid metering pump (not shown) such as a diaphragm pump, a peristaltic pump or a syringe pump. An alkali metal halide (such as LiI) stored in the alkali metal halide container 13 may be added to the reactor 1 via a gravity flow or suspended in a solvent compatible with the Si-H-containing iodonyl decane reaction product, and It is introduced into the reactor in a manner similar to the introduction of a solvent and a halodecane (i.e., via an alkali metal halide line 16 ). The contact between the reactants can be further promoted by mixing with the impeller 17a rotated by the motor 17b to form the mixture 26 . Preferably, the mixing is carried out under an inert atmosphere at near atmospheric pressure. A temperature sensor (not shown) can be used to monitor the temperature of the contents of the reactor 1 .

After the addition is complete, the progress of the reaction can be monitored using, for example, gas chromatography. After the reaction is completed, the mixture 26 can be removed from the reactor 1 through the filter 3 via the drain pipe 19 to the still vessel 4 . The main reaction products are ethyl diiododecane (EtSiHI ₂ , liquid at standard temperature and pressure) and LiCl (solid at standard temperature and pressure) and a small amount of LiI and EtSiIClH impurities. Therefore, the filtration will separate the liquid product of ethyldiiododecane from the LiCl reaction by-product. In this particular example, reactor 1 will most likely be located above filter 3 to best utilize the benefits of gravity. When the MX reaction by-product (X = Cl, Br), such as LiCl (not shown), is suspended in the mixture 26 , the plugging of the reactor 1 is not a problem.

The filtered stirred mixture (filtrate) (not shown) can be collected in a container (not shown) and transferred to a new location, after which the next processing step is carried out. Alternatively, the filtrate can be immediately directed to the still vessel 4 to further separate the reaction product from any solvent or other impurities using the heater 28 . The filtrate was warmed by a heater 28 . The heat forces any volatile solvent through the distillation column 27 and the discharge port 43 . Thereafter, the separated reaction product is collected in the vessel 8 .

Likewise, the container 8 can be transported to a new location, after which the next processing step is performed. If desired, the separated reaction product can be transferred from vessel 8 to boiler 6 for further purification. The boiler 6 is heated by a heater 29 . The separated reaction product is purified by fractional distillation using a distillation column 53 , a condenser 57, and a reflux distributor 54 . The purified reaction product is collected in a collection tank 7 . The collection tank 7 includes a discharge port 60 .

2 is an alternative exemplary system suitable for performing the disclosed methods. In this alternative embodiment, the reactor also acts as a distillation kettle FIG. 4 of the container 1. This specific example can be applied to the synthesis of large batches of Si-H containing iododecane. After thorough mixing, the cooling medium (not shown) in the jacket 2 is replaced by a heating medium (not shown). Those of ordinary skill in the art will recognize that if the cooling medium is capable of acting as both a heating and cooling medium (e.g., MEG), then a "replacement" of the cooling medium would not be required. Alternatively, the temperature of the medium can be varied via, for example, heat exchanger 23 .

The volatile solvent can be separated from the mixture 26 via the distillation column 27 and the discharge port 43 . Thereafter, Si-H-containing iodine decane was separated into the vessel 8 . The remaining solvent/salt mixture can be removed from the reactor 1 via a drain 19 where the salt is collected on the filter 3 . Likewise, the container 8 can be transported to a new location, after which the next processing step is performed. If desired, Si-H containing iododecane can be transferred from vessel 8 to boiler 6 for further purification. The boiler 6 is heated by a heater 29 . The Si-H-containing iodine decane was purified by fractional distillation using a distillation column 53 , a condenser 57, and a reflux distributor 54 . The purified Si-H-containing iodine decane was collected in a collection tank 7 . The collection tank 7 includes a discharge port 60 .

In another alternative, the halodecane reactant (either in gaseous or liquid form or diluted in a solvent) and the alkali metal iodide reactant can be used in a continuous reactor by controlled residence time and temperature (possibly Suspended in a solvent) passed through a flow reactor to carry out the reaction. The flow of each reagent can be controlled by a metering pump, such as a peristaltic pump. Alternatively, the halodecane reactant (either in gaseous or liquid form or diluted in a solvent) can be passed through the fixed alkali metal iodide reactant. The reaction mixture can be collected in a receiving vessel and the Si-H containing iododecane can be isolated, as in the above batch synthesis examples. Alternatively, the solid fraction can be removed directly using, for example, a centrifugal pump (commercially available). In another alternative, the Si-H containing iododecane product can be separated from any solvent by continuously feeding the filtered fraction to a continuous distillation unit.

The advantages of the disclosed synthetic methods are as follows: • a catalyst-free process that helps reduce cost, contaminant and product separation problems; • substantially eliminates most of the side reactions associated with prior art reactions using iodine reactants, the reaction Forming lower iso- and higher iso-iododecane in the form of impurities; • does not produce an HX intermediate reaction product which can contribute to side reactions and increased impurity distribution, and thus, the resulting product does not require prior art Ag, Cu or Sb stabilizer; ● When y or b or n = 0, no carbon-containing impurities are generated, which may adversely affect the properties of the resulting Si-containing film; ● The majority of the starting materials are inexpensive and It can be easily obtained; ● one-step one-pot reaction; ● the process can be solvent-free; ● simple purification; ● low reaction exotherm; ● can be carried out at ambient temperature (ie about 20 ° C to about 26 ° C); Waste is produced sparingly and environmentally friendly.

All of the above are advantageous from the perspective of developing an expandable industrial process. Furthermore, the resulting product is relatively stable compared to products made using X ₂ or HX reactants. Thus, the reaction product maintains purity suitable for the semiconductor industry without the use of stabilizers, such as Cu, which may adversely affect the electrical properties of the deposited film.

A method of forming a composition containing a Si film for use in a vapor deposition method is also disclosed. The disclosed method provides the use of a composition for forming a Si-containing film for the deposition of a ruthenium-containing film. The disclosed method can be applied to the fabrication of semiconductor, photovoltaic, LCD-TFT or flat panel devices. The method comprises: introducing a vapor phase of the disclosed composition for forming a Si-containing film into a reactor having a substrate disposed therein, and depositing at least a portion of the disclosed Si-H-containing iodine decane via a deposition process Deposited on the substrate to form a Si-containing layer.

The disclosed method also provides for forming a bimetallic-containing layer on a substrate using a vapor deposition process, and more particularly, for depositing a SiMO _x or SiMN _x film, where x can be 0-4 and M is Ta , Nb, V, Hf, Zr, Ti, Al, B, C, P, As, Ge lanthanide (such as Er) or a combination thereof.

The disclosed method of forming a germanium-containing layer on a substrate can be applied to the fabrication of semiconductor, photovoltaic, LCD-TFT or flat panel devices. The disclosed Si-H containing iododecane can be deposited 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). Exemplary CVD methods include thermal CVD, plasma enhanced CVD (PECVD), pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD). Or atmospheric pressure CVD (APCVD), flow CVD (f-CVD), metal organic chemical vapor deposition (MOCVD), hot-wire CVD (HWCVD) Called cat-CVD, where the line acts as a source of energy for the deposition process, free radical incorporation CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatially isolated ALD, hot-wire ALD (HWALD), free radical incorporation ALD, and combinations thereof. Supercritical fluid deposition can also be used. In order to provide suitable step coverage and film thickness control, the deposition method is preferably ALD, space ALD or PE-ALD.

The gas phase forming the composition containing the Si film is introduced into the reaction chamber containing the substrate. The temperature and pressure in the reaction chamber and the temperature of the substrate are maintained under conditions suitable for vapor deposition of at least a portion of the Si-H containing iododecane on the substrate. In other words, after introducing the vaporized composition into the chamber, the conditions in the chamber cause at least a portion of the vaporized precursor to deposit on the substrate to form a hafnium-containing film. Co-reactants can also be used to help form Si-containing layers.

The reaction chamber can be any housing or chamber of the apparatus performing the deposition method, such as, but not limited to, a parallel plate type reactor, a cold wall type reactor, a hot wall type reactor, a single wafer reactor, polycrystalline Round reactors or other such types of deposition systems. All such exemplary reaction chambers can function as ALD reaction chambers. The reaction chamber can be maintained at a pressure in the range of from about 0.5 mTorr to about 760 Torr. Additionally, the temperature in the reaction chamber can range from about 20 °C to about 700 °C. Those of ordinary skill in the art will recognize that temperature can be optimized by experimentation only to achieve desired results.

The reactor temperature can be controlled by controlling the temperature of the substrate holder and/or controlling the temperature of the reactor wall. Devices for heating substrates are known in the art. The reactor wall can be heated to a temperature sufficient to obtain the desired membrane at a sufficient growth rate and having the desired physical state and composition. A non-limiting exemplary temperature range to which the reactor wall can be heated includes from about 20 °C to about 700 °C. When utilizing a plasma deposition process, the deposition temperature can range from about 20 °C to about 550 °C. Alternatively, the deposition temperature may range from about 300 ° C to about 700 ° C when subjected to a thermal process.

Alternatively, the substrate can be heated to a temperature sufficient to obtain the desired ruthenium containing film at a sufficient growth rate and having the desired physical state and composition. A non-limiting exemplary temperature range to which the substrate can be heated includes from 150 °C to 700 °C. Preferably, the substrate temperature is maintained below or equal to 500 °C.

The type of substrate on which the ruthenium containing film will be deposited will vary depending on the intended end use. A substrate is generally defined as the material on which the method is performed. Substrates include, but are not limited to, any suitable substrate used in the fabrication of semiconductor, photovoltaic, flat panel or LCD-TFT devices. Examples of suitable substrates include wafers such as germanium, germanium dioxide, glass, Ge or GaAs wafers. The wafer may have one or more different layers of material deposited according to previous manufacturing steps. For example, the wafer may include a tantalum layer (crystalline, amorphous, porous, etc.), a tantalum oxide layer, a tantalum nitride layer, a hafnium oxynitride layer, a carbon doped yttrium oxide (SiCOH) layer, or a combination thereof. Additionally, the wafer can 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 such as manganese, manganese oxide, tantalum, tantalum nitride, or the like. The layers can be planar or patterned. In some embodiments, the substrate can be coated with a patterned photoresist film. In some embodiments, the substrate can include an oxide layer that functions as a MIM, DRAM, or FeRam technology (eg, ZrO ₂ -based materials, HfO ₂ -based materials, TiO ₂ -based materials, rare earth oxide-based materials, ternary oxides) a dielectric material in a material or the like; or a nitride-based film (for example, TaN) used as an electromigration barrier layer and an adhesion layer between copper and a low-k layer. The disclosed process can deposit a germanium containing layer directly onto a wafer or directly onto one or more of the top of the wafer (when the patterned layer is formed into a substrate) layer. In addition, those skilled in the art will recognize that the term "film" or "layer" as used herein refers to the thickness of some material that is laid or spread on a surface and that may be a groove. Or lines. Throughout the specification and patent application, the wafer and any associated layers thereon are referred to as substrates. The actual substrate utilized may also depend on the particular precursor embodiment utilized. In many cases, however, the preferred substrate used will be selected from the group consisting of hydrogenated carbon, TiN, SRO, Ru, and Si-type substrates, such as polycrystalline germanium or crystalline germanium substrates.

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

The composition forming the Si-containing film can be supplied in a pure form. Alternatively, the composition forming the Si-containing film may further comprise a solvent suitable for vapor deposition. The solvent may especially be selected from C ₁ -C ₁₆ saturated or unsaturated hydrocarbons.

For vapor deposition, the composition forming the Si-containing film is introduced into the reactor in the form of a gas phase by a conventional means such as a tube and/or a flow meter. The vapor can be vaporized in the carrier gas by conventional vaporization steps, such as direct liquid injection, direct pumping in the absence of carrier gas, bubbling carrier gas through the liquid, or in the absence of bubbling through the liquid. Vaporization forms a composition of the Si-containing film to produce a gas phase form. When the current body is solid at room temperature, a sublimator can be used, such as the sublimator disclosed in PCT Publication No. WO 2009/087609 to Xu et al. The composition forming the Si-containing film can be fed to the vaporizer (direct liquid injection) in a liquid state, which is vaporized and mixed with the carrier gas before being introduced into the reactor. Alternatively, the composition forming the Si-containing film may be vaporized by transferring a carrier gas into a container containing the composition or by bubbling a carrier gas in the composition. The carrier gas can include, but is not limited to, Ar, He or N ₂ and mixtures thereof. The carrier gas and composition are then introduced into the reactor in gaseous form.

The composition for forming the Si-containing film can be delivered to the reactor or vapor deposition chamber by the composition-forming apparatus for forming a Si-containing film of FIGS. 3 to 5 . 3 to 5 show three illustrative specific examples of forming a composition delivery device containing a Si film. As discussed in detail above and as shown in the examples below, the delivery device must be clean and dry and made of a material that does not react with the composition that forms the Si-containing film.

Fig. 3 is a side view showing a specific example of the composition delivery device 101 for forming a Si-containing film. In FIG. 3 , the disclosed composition for forming a Si-containing film 110 is contained in a container 200 having two conduits, an inlet conduit 300 and an outlet conduit 400 . It will be appreciated by those skilled in the art that container 200 , inlet conduit 300, and outlet conduit 400 are fabricated to prevent the gaseous form of formation of Si-containing film 110 from escaping, even at elevated temperatures and pressures.

The outlet conduit 400 of the delivery device 101 is fluidly coupled via a valve 700 to a reactor (not shown) or other components between the delivery device and the reactor, such as a gas box. Preferably, vessel 200 , inlet conduit 300 , valve 600 , outlet conduit 400, and valve 700 are made of passivated 316L EP or 304 passivated stainless steel. However, those of ordinary skill in the art will recognize that other non-reactive materials can also be used in the teachings herein.

In FIG. 3 , the end portion 800 of the inlet conduit 300 is above the surface on which the Si-containing film-forming composition 110 is formed, and the end portion 900 of the outlet conduit 400 is located below the surface on which the Si-containing film-containing composition 110 is formed. In this embodiment, the composition 110 forming the Si-containing film is preferably in a liquid form. Inert gases, including but not limited to nitrogen, argon, helium, and mixtures thereof, can be introduced into the inlet conduit 300 . The inert gas gas pressurizes the vessel 200 to force the formation of the liquid composition 110 containing the Si film through the outlet conduit 400 and to the reactor (not shown). The reactor may include a vaporizer that converts the liquid composition 110 forming the Si-containing film into a gas phase with or without a carrier gas such as helium, argon, nitrogen, or a mixture thereof to deliver the gas phase to A substrate on which a film is formed. Alternatively, the liquid composition 110 forming the Si-containing film can be delivered directly to the wafer surface in the form of a jet or aerosol.

4 is a side view showing a second specific example of forming a composition delivery device 101 containing a Si film. In FIG. 4, the end portion 300 of the inlet duct 800 is located below the surface forming the composition of the Si-containing film 110, and the end portion 400 of outlet conduit 900 is positioned above the surface of the composition of the Si-containing film 110 is formed. Figure 4 also includes a heating element 140 , optionally selected, which increases the temperature at which the composition 110 comprising the Si film is formed. In this specific example, the composition 110 forming the Si-containing film may be in a solid or liquid form. Inert gases, including but not limited to nitrogen, argon, helium, and mixtures thereof, are introduced into the inlet conduit 300 . The inert gas is bubbled through the formation of the Si-containing film composition 110 and carries a mixture of inert gases and vaporizes the formation of the Si-containing film composition 110 to the outlet conduit 400 and to the reactor.

Figures 3 and 4 include valves 600 and 700 . Those of ordinary skill in the art will recognize that valves 600 and 700 can be placed in an open or closed position to allow flow through conduits 300 and 400, respectively . If the composition of the Si-containing film 110 is formed in the form of a gas phase or if there is sufficient vapor pressure above the solid phase/liquid phase, any of the delivery devices 101 of Figures 3 and 4 can be used, or have a termination in existence. A simpler delivery device for a single catheter on any solid or liquid surface. In this case, the formation of the Si-containing film-forming composition 110 through the conduit 300 or 400 is simply delivered in the vapor phase by opening the valve 600 in FIG. 3 or the valve 700 in FIG . The delivery device 101 can be maintained at a suitable temperature to provide sufficient vapor pressure to the Si-containing film-forming composition 110 to be delivered in a gaseous phase, such as by using optionally heating elements 140 .

Although FIGS. 3 and 4 disclose two specific examples of forming a composition film delivery device 101 containing a Si film, those skilled in the art will recognize that the inlet conduit 300 and the present invention do not deviate from the disclosure herein. The outlet conduits 400 may also be located above or below the surface of the composition 110 that forms the Si-containing film. Additionally, the inlet conduit 300 can be a fill port.

The vapor phase of the solid form forming the composition containing the Si film can be delivered to the reactor using a sublimator. FIG. 5 shows a specific example of an exemplary sublimator 100 . The sublimator 100 includes a container 33 . The container 33 can be a cylindrical container or can be of any shape without limitation. The container 33 is constructed of materials such as the following: passivated stainless steel, alumina, glass, and other chemically compatible materials. In some cases, the container 33 is constructed of another metal or metal alloy without limitation. In some cases, the inner diameter of the container 33 is from about 8 centimeters to about 55 centimeters, and alternatively, the inner diameter is from about 8 centimeters to about 30 centimeters. Alternate configurations can have different sizes as understood by those skilled in the art.

The container 33 includes a sealable top 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 for threading the catheter into the container 33 . Alternatively, the sealable top 15 is configured to permit fluid to flow into the container 33 . The sealable top 15 is configured to accept and pass a conduit containing the dip tube 92 to maintain fluid contact with the container 33 . The dip tube 92 has a control valve 90 and an accessory 95 configured to allow carrier gas flow into the container 33 . In some cases, the dip tube 92 extends downwardly along the central axis of the container 33 . In addition, the sealable top 15 is configured to accept and pass a conduit containing the outlet tube 12 . The gas phase of the carrier gas and the composition forming the Si-containing film are removed from the vessel 33 via the outlet pipe 12 . The outlet pipe 12 contains a control valve 10 and an accessory 5 . In some cases, the outlet tube 12 is fluidly coupled to the gas delivery manifold to conduct carrier gas from the sublimator 100 to the reactor.

The container 33 and the 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 seals the container 33 by at least about eight sealing members 18 . As understood by those skilled in the art, the sealing member 18 removably couples the sealable top 15 to the container 33 and forms a gas resistant seal with the gasket 20 . The sealing member 18 can comprise any suitable member known to those skilled in the art for sealing the container 33 . In some cases, the sealing member 18 includes a thumbscrew.

As shown in Figure 5, the container 33 further comprises at least one of which is disposed in the disc. For solid materials, the disc contains a shelf or a horizontal bracket. In some embodiments, the inner disc 30 is annularly disposed in the container 33 such that the disc 30 includes an outer diameter or circumference that is smaller than the inner diameter or circumference of the container 33 , forming an opening 31 . The outer disk 86 is circumferentially disposed in the container 33 such that the disk 86 includes an outer diameter or circumference that is the same, substantially the same, or generally uniform as the inner diameter of the container 33 . The outer disk 86 forms an opening 87 disposed at the center of the disk. A plurality of discs are placed in the container 33 . The discs are stacked in an alternating manner with inner discs 30 , 34 , 36 , 44 stacked vertically in the container while interlaced with outer discs 62 , 78 , 82 , 86 . In a particular example, the inner discs 30 , 34 , 36 , 44 extend outwardly annularly and the outer discs 62 , 78 , 82 , 86 extend annularly toward the center of the container 33 . As shown in the specific example of FIG. 5, the inner disk 30, 34, 36, 44 does not, 78, 82, 86 physical contact with the outer disk 62.

The assembled sublimator 100 includes internal discs 30 , 34 , 36 , 44 (which include aligned and coupled legs 50 ), internal passages 51 , concentric walls 40 , 41 , 42 and concentric grooves 47 , 48 , 49 . The inner discs 30 , 34 , 36 , 44 are stacked vertically and are oriented annularly around the dip tube 92 . In addition, the sublimator includes external discs 62 , 78 , 82 , 86 . As shown in Figure 5, the outer disk 62, 78, 82, 86 should fit tightly within the container 33 to provide a good contact so that heat conduction from the container 33 to the disk 62, 78, 82, 86. Preferably, the outer discs 62 , 78 , 82 , 86 are coupled to or in physical contact with the inner wall of the container 33 .

As shown, the outer discs 62 , 78 , 82 , 86 and the inner discs 30 , 34 , 36 , 44 are stacked inside the container 33 . When assembled in the container 33 to form the sublimator 100 , the inner discs 30 , 34 , 36 , 44 form external gas passages 31 , 35 , 37 , 45 between the assembled outer discs 62 , 78 , 82 , 86 . . In addition, the outer discs 62 , 78 , 82 , 86 and the legs of the inner discs 30 , 34 , 36 , 44 form internal gas passages 56 , 79 , 83 , 87 . The walls 40 , 41 , 42 of the inner discs 30 , 34 , 36 , 44 form grooves for receiving solid precursors. The outer discs 62 , 78 , 82 , 86 include walls 68 , 69 , 70 for receiving solid precursors. During assembly, the solid precursor is loaded into the concentric grooves 47 , 48 , 49 of the inner discs 30 , 34 , 36 , 44 and the annular grooves 64 , 65 , 66 of the outer discs 62 , 78 , 82 , 86 .

Solid powders and/or granules having a size of less than about 1 cm, or less than about 0.5 cm, and or less than about 0.1 cm, are placed in concentric grooves 47 , 48 , 49 and exterior of internal discs 30 , 34 , 36 , 44 In the annular grooves 64 , 65 , 66 of the discs 62 , 78 , 82 , 86 . The solid precursor is loaded into the annular groove of each disk by any method suitable for uniformly distributing the solids in the annular groove. Suitable methods include, but are not limited to, direct pouring, use of a spoon, use of a funnel, automated measurement delivery, and pressurized delivery. Depending on the chemical nature of the solid precursor material, it can be loaded in a sealed environment. In addition, inert gas atmospheres and/or pressurization can be achieved in the sealed box for their toxicity, volatility, oxidizability and/or air sensitive solids. Each of the discs can be loaded after the discs are set in the container 33 . A more preferred procedure is to load the solids prior to setting the disc in the container 33 . The total weight of the solid precursor loaded into the sublimator can be recorded by weighing the sublimator before and after the loading process. In addition, the solid precursor consumed can be calculated by weighing the sublimator after the vaporization and deposition process.

A dip tube 92 having a control valve 90 and fitting 95 is positioned in the internal passage 51 of the aligned and coupled legs of the inner discs 30 , 34 , 36 , 44 . Thus, the dip tube 92 is directed perpendicularly toward the bottom 58 of the container 33 through the internal passage 51 . The dip tube end 55 is disposed adjacent the bottom 58 of the container at the louver 52 or above the louver 52 . The louver 52 is disposed in the bottom inner disk 44 . The louver 52 is configured to allow the carrier gas to flow outside of the dip tube 92 . In the assembled sublimator 100 , the gas passage 59 is formed by the bottom 58 of the container 33 and the bottom inner disc 44 . In some cases, gas passage 59 is configured to heat the carrier gas.

In operation, the carrier gas is preheated prior to introduction into the vessel 33 via the dip tube 92 . Alternatively, the carrier gas can be heated while flowing through the gas passage 59 by the bottom 58 of the vessel 33 . The bottom 58 of the container 33 is thermally coupled and/or continuously heated by an external heater in accordance with the teachings herein. The carrier gas then passes through the outside air passage 45, the gas passage 45 formed by the inner wall 44 of the outer wall of a concentric disc 42 and 62 of the outer disk 61. The outer gas passage 45 leads to the top of the inner disc 44 . The carrier gas continues to flow over the solid precursors contained in the concentric grooves 47 , 48 and 49 . The solid sublimated gas phase from the concentric tanks 47 , 48 and 49 is mixed with the carrier gas and flows vertically upward through the vessel 33 .

Although FIG. 5 discloses a specific example of a sublimator capable of delivering any gas phase forming a solid composition containing a Si film to a reactor, it will be appreciated by those skilled in the art that, without departing from the teachings herein Other sublimator designs are also suitable. Finally, it will be appreciated by those skilled in the art that the disclosed Si-containing films can be formed using other delivery devices such as those disclosed in WO 2006/059187 to Jurcik et al., without departing from the teachings herein. The composition is delivered to a semiconductor processing tool.

If necessary, the composition-forming apparatus for forming a Si-containing film of FIGS. 3 to 5 can be heated to a temperature at which the composition for forming the Si-containing film is in its liquid phase and has a sufficient vapor pressure. The delivery device can be maintained at a temperature, for example, in the range of 0 °C to 150 °C. Those skilled in the art recognize that the temperature of the delivery device can be adjusted in a known manner to control the amount of composition that vaporizes to form a Si-containing film.

In addition to the disclosed compositions, a reactive gas can also be introduced into the reactor. The reaction gas may be an oxidant such as O ₂ ; O ₃ ; H ₂ O; H ₂ O ₂ ; an oxygen-containing radical such as O. Or OH. ; NO; NO ₂ ; carboxylic acid, such as formic acid, acetic acid, propionic acid; free radical species of NO, NO ₂ or carboxylic acid; formaldehyde; and mixtures thereof. Preferably, the oxidizing agent is selected from the group consisting of O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , oxygen-containing radicals thereof (such as O. or OH.), and mixtures thereof. Preferably, when performing the ALD process, the co-reactant is plasma treated oxygen, ozone or a combination thereof. When an oxidizing gas is used, the resulting ruthenium containing film will also contain oxygen.

Alternatively, the reaction gas may be H ₂ , NH ₃ , (SiH ₃ ) ₃ N, hydrogenated decane (such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , Si ₅ H ₁₀ , Si ₆ H ₁₂ ), chlorodecane and chloropolydecane (such as SiHCl ₃ , SiH ₂ Cl ₂ , SiH ₃ Cl, Si ₂ Cl ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ ), alkyl decane (such as Me ₂ SiH ₂ , Et _{2 )} SiH ₂ , MeSiH ₃ , EtSiH ₃ ), ruthenium (such as N ₂ H ₄ , MeHNNH ₂ , MeHNNHMe), organic amines (such as NMeH ₂ , NEtH ₂ , NMe ₂ H, NEt ₂ H, NMe ₃ , NEt ₃ , (SiMe) ₃ ) ₂ NH), diamines (such as ethylenediamine, dimethylethylidene diamine, tetramethylethylenediamine), pyrazoline, pyridine, B-containing molecules (such as B ₂ H ₆ , three Methyl boron, triethyl boron, boron azyne, substituted boron azynylene, dialkylamino borane), alkyl metal (such as trimethyl aluminum, triethyl aluminum, dimethyl zinc, two ethyl Zinc), its free radical species or mixtures thereof. When H ₂ or an inorganic gas containing Si is used, the resulting ruthenium-containing film may be pure Si.

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

The reaction gas can be treated with a plasma to decompose the reaction gas into its free radical form. When treated by plasma, N ₂ can also be used as a reducing agent. For example, the plasma can be generated at a power ranging from about 50 W to about 500 W, preferably from about 100 W to about 200 W. The plasma can be produced or present within the reactor itself. Alternatively, the plasma can typically be removed from the reactor at a location (e.g., in a remotely located plasma system). Those skilled in the art will recognize methods and apparatus suitable for use in such plasma processing.

The desired ruthenium containing film also contains another element such as, but not limited to, B, P, As, Zr, Hf, Ti, Nb, V, Ta, Al, Si or Ge.

The composition forming the Si-containing film and the one or more co-reactants may be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations. For example, a composition that forms a Si-containing film can be introduced in one pulse and two other metal sources can be introduced together in a separate pulse (modified atomic layer deposition). Alternatively, the reaction chamber may already contain a co-reactant prior to introduction into the composition that forms the Si-containing film. The co-reactant can pass through the plasma system positioned or remote from the reaction chamber and decompose into free radicals. Alternatively, the composition forming the Si-containing film 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 formation of the Si-containing film composition and one or more co-reactants can be simultaneously sprayed from the shower head, which holds the wafer holder rotation (space ALD) of several wafers.

In a non-limiting exemplary atomic layer deposition process, a gas phase forming a composition comprising a Si film is introduced into a reaction chamber where it is in contact with 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 reacts with the absorbed Si-H containing iododecane in a self-limiting manner. Excess oxygen source is removed from the reaction chamber by flushing and/or evacuating the reaction chamber. If the desired film is a hafnium oxide film, this two-step process can provide the desired film thickness or can be repeated until a film having the necessary thickness has been obtained.

Alternatively, if the desired film is a base metal/metalloid oxide film (ie, SiMO _x , where x can be 0-4 and M is B, Zr, Hf, Ti, Nb, V, Ta, Al, Si, Ga, Ge or a combination thereof, the gas phase of the metal-containing or metalloid-containing precursor can be introduced into the reaction chamber after the above two-step process. The metal-containing or non-metallic precursor will be selected based on the nature of the deposited base metal/non-metal oxide film. After introduction into the reaction chamber, the metal-containing or metal-containing precursor is brought into contact with the substrate. Any excess metal or metalloid-containing precursor is removed from the reaction chamber by purging and/or evacuating the reaction chamber. Likewise, an oxygen source can be introduced into the reaction chamber to react with the metal-containing or metalloid-containing precursor. Excess oxygen source is removed from the reaction chamber by flushing and/or evacuating the reaction chamber. If the desired film thickness has been achieved, the process can be terminated. However, if a thicker film is desired, the entire four-step process can be repeated. A film having a desired composition and thickness can be deposited by alternately providing a composition for forming a Si-containing film, a metal-containing or metal-containing precursor, and an oxygen source.

Furthermore, by varying the number of pulses, a film having the desired stoichiometric amount of M:Si ratio can be obtained. For example, a SiMO ₂ film can be obtained by a pulse having a composition for forming a Si-containing film and a pulse of a metal-containing or metal-containing precursor (wherein each pulse is followed by an oxygen source pulse). However, those skilled in the art will recognize that the number of pulses required to obtain the desired film may not be equivalent to the stoichiometric ratio of the resulting film.

The ruthenium-containing film obtained by the above-discussed process may include SiO ₂ ; SiC; SiN; SiON; SiOC; SiONC; SiBN; SiBCN; SiCN; SiMO; SiMN, wherein M is selected from Zr, Hf, Ti, Nb, V , Ta, Al, Ge, of course, depending on the oxidation state of M. Those of ordinary skill in the art will recognize that the desired film composition can be obtained by fair selection of suitable compositions and co-reactants that form Si-containing films.

After obtaining the desired film thickness, the film can be subjected to further 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 will recognize the systems and methods used to perform these other processing steps. For example, the ruthenium containing film may be exposed to a temperature in the range of about 200 ° C and about 1000 ° C for a period of from about 0.1 second to about 7200 seconds in an inert atmosphere, an H-containing atmosphere, an N-containing atmosphere, or a combination thereof. . Most preferably, the temperature is 600 ° C and lasts less than 3600 seconds. Even more preferably, the temperature is less than 400 °C. The annealing step can be carried out in the same reaction chamber in which the deposition process is carried out. Alternatively, the substrate can be removed from the reaction chamber and an annealing/rapid annealing process performed in a separate device. Any of the above post-treatment methods have been found, but in particular UV curing will effectively enhance the film connectivity and cross-linking, and when the film is a SiN-containing film, the H content of the film will be lowered. Typically, a combination of thermal annealing to <400 ° C (preferably about 100 ° C to 300 ° C) and UV curing is used to obtain the film having the highest density.

Example

The following non-limiting examples are provided to further illustrate specific examples of the invention. However, the examples are not intended to be exhaustive or to limit the scope of the invention described herein.

Example 1: A 250 mL 3-neck (24/40) European style flask with a PTFE coated magnetic stir bar was charged with 9.56 g (33.7 mmol) of anhydrous lithium iodide powder (Sigma Aldrich, 99). +%) and 80 mL of anhydrous chloroform. Dichlorodecane (8.4 g; 83.2 mmol, excess) ("DCS") was added to the reaction flask via the headspace while stirring the mixture. A color change (lavender) was observed immediately. During DCS exposure, the temperature rose from about 22 °C to 29 °C. The mixture was stirred for an additional 18 hours at ambient temperature. The solid appearance changed from a beige coarse grain form to a white fine powdery powder. The solid mass decreases with this time. The solid was filtered and dried under vacuum (yield 2.75 g; The solvent is removed by condensation under a static vacuum in a well cooled in liquid nitrogen. Weighing the remaining purple liquid (4.54 g of; calcd 10.0g; 45%) and be analyzed by GCMS (80.5% SiH ₂ I ₂ ( "DIS"), the remainder being higher boiling compounds). Although the calculated product yield is not reliable due to sample size and means of removing chloroform, this example illustrates the successful halide exchange that produces the DIS product.

Example 2: A similar reaction was carried out using the same settings and the reagent loadings as explained in Example 1, except that toluene was used instead of chloroform. Analysis of the GC sample of the liquid (not further processed) showed that DIS was the main product (no solvent), and some DCS and ClSiH ₂ I.

Example 3: A 60 cc stainless steel ampoule having a diaphragm valve and a pressure gauge was charged with 4.25 g (31.7 mmol) of anhydrous lithium iodide in a nitrogen purge glove box. Nitrogen gas was removed under vacuum and DCS (1.60 g, 15.9 mmol) was added by condensation (-196 °C). The vessel was then closed and allowed to thaw to ambient temperature and allowed to stand for 30 minutes. Toluene extraction was carried out. Analysis of the toluene extract by GCMS revealed DCS, ClSiH ₂ I intermediate and DIS (major product). This example illustrates that the process can be completed without the use of a solvent.

Example 4: Sodium iodide powder (10.61 g; granulated colorless crystalline solid) was exposed to excess DCS gas in a 50 cc Schlenk tube under static vacuum with no visual indication of the reaction. No change in pressure was observed. The DCS was then condensed in a Schlenk tube and thawed to ambient temperature several times with no indication of reagent volume loss, color or pressure change (no reaction). The reaction with sodium iodide will likely require a solvent in which the solvent has some solubility (i.e., methylene chloride, chloroform, acetonitrile, etc.). Lithium iodide is significantly more reactive and preferred. This example demonstrates that the NaI alkali metal halide reactant is less reactive than LiI.

Example 5: 530 g of product in pentane solvent: A 2 L 3-neck round bottom (RB) flask with a PTFE coated stir bar was charged with 500 g of anhydrous LiI (solid) (3.74 mol; Acros Organics, 99%) and filled with anhydrous n-pentane (liquid) to the 1 L mark. Most of the headspace nitrogen was removed in vacuo (to approximately 600 Torr pressure) and excess DCS (liquid) (492 g; 4.87 mol; 2.8 x molar excess) was added to the flask via headspace. The flask was periodically cooled to 5 ° C to 8 ° C to allow complete transfer. Stirring was not achieved by using a stir plate/stirring bar because the LiI solids were too heavy. The mixture was stirred by frequent manual shaking/rotating the kettle. The flask was allowed to stand overnight at room temperature while the magnetic stirrer was turned on. Stirring was not achieved. The solid was filtered and dried under vacuum (yield 169 g; 158 g). The pale pink filtrate was distilled to remove pentane (boiling point = 36 ° C). The remaining colorless liquid was distilled under reduced pressure (about 0 to 5 Torr / 21 to 31 ° C) with a receiver cooled in dry ice pellets. This produces a colorless frozen solid in the collector with little residual liquid remaining in the still. The solid product was thawed and weighed (350 g; calculated 530 g; 65%). Gas chromatography/mass spectrometry showed 91% (area percent) of pure DIS and a small amount of DCS (0.964%), pentane (0.326%), ClSiH ₂ I (4.953%) and temporarily designated as perchlorinated/highly iodinated Impurities of the oxirane compound (see Figure 6 ).

The presence of a paraoxane-type impurity found in Example 5 indicates that these compounds are formed from moisture derived from one or more of the following:

• Moisture from the surface of the glass reactor/distillation system (impossible).

● From the leak in the system.

• Moisture in the lithium iodide starting material (with reasonable probability). This may also include a certain amount of lithium hydroxide.

• Moisture from the unoptimized sample preparation and GC analysis (completely possible).

This emphasizes the importance of careful measurement to eliminate any possible source of moisture throughout the process. However, based on the number of elution of such helium oxide impurities, the impurities appear to be easily separated from the main product.

Example 6: 530 g product scale in pentane solvent: A 2 L 3-neck RB flask with a mechanical stirrer, a cooling cup condenser and a 1/4" PTFE sparge tube was charged with 500 g of anhydrous LiI (3.74 mol; Acros Organics, 99%) and filled with anhydrous n-pentane to the 1 L mark. Dichloromethane (183 g; 1.81 mol) was added to the surface over a period of 22 minutes, wherein the temperature rose from 18.1 ° C (cold pentane) to 31.0 ° C. The reaction mixture was stirred and some reflux was observed during the addition of DCS. The reaction mixture was stirred at ambient temperature for 3 hours and the liquid was analyzed by GCMS. The chromatography showed traces of DCS, pentane, ClSiH ₂ I partially substituted intermediate and DIS. The area percentages of ClSiH ₂ I and DIS were 6% and 13.5%, respectively. The reaction mixture was stirred for a further 18 hours. The solid was then filtered and dried under vacuum (226 g, 158 g, calculated). Solvent and lower boiling impurities. Obtained crude (320 g, 89% (by GC)) (about 62%). Comparison of Example 5 and Example 6 shows that changing the stoichiometry of the reactants yields similar yields. .

Example 7: 500 g of LiI (3.74 mol; 99.9% City Chemical, colorless powder) was fed into a 2 L 3-neck RB flask with a mechanical stirrer. The cooling cup condenser is connected to the internal thermocouple to the reaction equipment. About 800 mL of anhydrous chloroform was added to the LiI powder. The condenser was cooled to -78 ° C and 196 g of dichloromethane (1.94 mol, 3.5 mol% excess) over 15 minutes with stirring under a reduced pressure (-78 ° C dry ice, isopropyl alcohol slurry). The pressure was 680 Torr at 23 °C. Additional nitrogen was added to the reactor to a pressure of 780 Torr. The mixture was stirred for 22 hours and thereafter appeared purple. The solid was filtered and dried under vacuum. The filtrate was collected in a 1 L flask. The chloroform was distilled at 61 ° C and the remaining purple liquid was collected and weighed (148 g, 28%, the crude DIS product after removal of the solvent). Low yields indicate that pure LiI is limited to low solubility in chloroform. A certain degree of hydrogenation of the LiI reactant promotes the reactivity of the salt and promotes the formation of products and such oxane-like impurities.

Example 8: A four-necked round bottom flask equipped with a mechanical stirrer, thermocouple and dry ice IPA condenser was charged with LiI (24.8 g, 0.19 mol) under a stream of nitrogen. Pentane (80 mL) was transferred via cannula. TSA-Cl ((SiH ₃ ) ₂ N (SiH ₂ Cl) 25 g, 0.18 mol) was added dropwise to the resulting mixture over a period of 15 minutes at room temperature. No exotherm was observed. After stirring at ambient temperature for about 90 minutes, by GC-MS analysis of the reaction mixture, which shows TSA-Cl and 39% TSA-I 57% of unreacted _{((SiH 3) 2 N (} SiH 2 I)) ( FIG. 7 ). At this time, the reaction mixture was stirred overnight at room temperature. GC analysis after overnight stirring produced a main peak corresponding to SiH ₃ -I and a peak corresponding to the disappeared TSA-Cl and TSA-I. The optimization of the reaction time is still ongoing.

Example 9: Comparison of LI particle size

0.5-1mm LiI

Reaction to a 20 L jacketed filter equipped with a mechanical stirrer, condenser (adjusted to -70 ° C), solid addition port, inlet tube for the surface addition of dichloromethane and inlet for the addition of liquid pentane The reactor was charged with 15 L of pentane. 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 while under a nitrogen atmosphere, then lithium iodide (12.25 kg, 91.52 mol) was charged to the reactor. The weight of dichloromethane (4.52 kg, 44.75 mol) was then adjusted at a rate of approximately 1 kg per hour. After completion of the DCS addition, the reactor jacket was still adjusted to +35 °C and the condenser was adjusted to -70 °C. After stirring for 16 hours, the agitation was stopped and the contents of the reactor were discharged via a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was subsequently washed with pentane (3 x 1 L) to obtain a solid residue of 7.19 kg. Thereafter, the combined filtrate and washing liquid were distilled at 88 kPa to obtain crude diiododecane (9.04 kg, purity: 83%). As indicated by GC analysis, the remainder of the material contained DCS, 1.3%; pentane, 0.6%; SiH ₂ ClI, 14.1% and SiHI ₃ , 0.1%. The crude material was further distilled at 3.2 kPa to obtain diiododecane (7.39 kg, yield 58%) which, as indicated by GC analysis, contained DIS, 99.6%; SiH ₃ I, 0.1%; SiH ₂ ClI, 0.1 %; SiHI ₃ , 0.15%; others, 0.12%. As discussed above, none of these impurities contain any carbon that can adversely affect the resulting Si-containing film.

1-1.25mm LiI

Reaction to a 20 L jacketed filter equipped with a mechanical stirrer, condenser (adjusted to -70 ° C), solid addition port, inlet tube for the surface addition of dichloromethane and inlet for the addition of liquid pentane The reactor was charged with 15 L of fresh 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 while under a nitrogen atmosphere, and then lithium iodide (9.99 kg, 74.64 mol) was charged to the reactor. The weight of dichloromethane (3.88 kg, 38.42 mol) was then adjusted at a rate of approximately 1 kg per hour. After completion of the DCS addition, the reactor jacket was still adjusted to +35 °C and the condenser was adjusted to -70 °C. After stirring for 16 hours, the agitation was stopped and the contents of the reactor were discharged via a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was subsequently washed with pentane (3 x 1 L) to obtain 4.96 kg of a solid residue. Thereafter, the combined filtrate and washing liquid were distilled at 88 kPa to obtain crude diiododecane (8.01 kg, purity 86%). The analysis by GC showed the material comprising the remainder of the DCS, 0.1%; _{pentane, 1.2%; SiH 3 I,} 0.1%; SiH 2 ClI, 4.5% and SiHI _3, 0.1%. The crude material was further distilled at 3.2 kPa to obtain diiododecane (8.16 kg, yield 77%) containing DIS, 99.7%; SiH ₃ I, 0.01%; SiH ₂ ClI, 0.03% and SiHI ₃ , 0.1% . As discussed above, none of these impurities contain any carbon that can adversely affect the resulting Si-containing film.

These results also show that the particle size of lithium iodide affects the yield of the separation. Surprisingly, improved yields were observed when larger particle size lithium iodide was used relative to the smaller particle size.

Example 10: Effect of Solvent Recycling

Solvent recycling

Reaction to a 20 L jacketed filter equipped with a mechanical stirrer, condenser (adjusted to -70 ° C), solid addition port, inlet tube for the surface addition of dichloromethane and inlet for the addition of liquid pentane The reactor was charged with 15 L of pentane. 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 while under a nitrogen atmosphere, then lithium iodide (12.34 kg, 92.19 mol) was charged to the reactor. The weight of dichloromethane (4.25 kg, 42.08 mol) was then adjusted at a rate of approximately 1 kg per hour. After completion of the DCS addition, the reactor jacket was still adjusted to +35 °C and the condenser was adjusted to -70 °C. After stirring for 16 hours, the agitation was stopped and the contents of the reactor were discharged via a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was subsequently washed with pentane (3 x 1 L). Thereafter, the combined filtrate and washing liquid were distilled in a distillation pot at 88 kPa to obtain crude diiododecane (9.26 kg, purity 82%). The distillate (11 L, which mainly contained pentane, 82%; DCS, 12%; SiH2ClI, 4% and DIS, 1%) was recycled back to the reactor for continuous synthesis.

Therefore, the aforementioned 20L was equipped with a mechanical stirrer, a condenser (adjusted to -70 ° C), a solid addition port, an inlet pipe for the surface addition of dichloromethane, and an inlet for the addition of distillate/pentane. The jacketed reactor was charged with recirculated distillate from the previous production operation (11 L, which mainly contained pentane, 82%; DCS, 12%; SiH2ClI, 4% and DIS, 1%) and New pentane (4L). 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 while under a nitrogen atmosphere, then lithium iodide (12.38 kg, 92.49 mol) was charged to the reactor. The weight of dichloromethane (4.17 kg, 41.28 mol) was then adjusted at a rate of approximately 1 kg per hour. After completion of the DCS addition, the reactor jacket was still adjusted to +35 °C and the condenser was adjusted to -70 °C. After stirring for 17 hours, the agitation was stopped and the contents of the reactor were discharged via a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was subsequently washed with pentane (3 x 1 L). Thereafter, the combined filtrate and washing liquid were distilled in a distillation pot at 88 kPa to obtain crude diiododecane (8.77 kg, purity 84%) as a distillation bottom. This crude material was further distilled at 3.2 kPa to obtain diiododecane (7.29 kg, yield 62%) containing DIS, 99.5%; SiH ₃ I, 0.14%; SiHI ₃ , 0.24%, others, 0.12%.

New solvent

Reaction to a 20 L jacketed filter equipped with a mechanical stirrer, condenser (adjusted to -70 ° C), solid addition port, inlet tube for the surface addition of dichloromethane and inlet for the addition of liquid pentane The reactor was charged with 15 L of fresh 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 while under a nitrogen atmosphere, then lithium iodide (12.47 kg, 93.16 mol) was charged to the reactor. The weight of dichloromethane (4.85 kg, 48.02 mol) was then adjusted at a rate of approximately 1 kg per hour. After completion of the DCS addition, the reactor jacket was still adjusted to +35 °C and the condenser was adjusted to -70 °C. After stirring for 16 hours, the agitation was stopped and the contents of the reactor were discharged via a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was subsequently washed with pentane (3 x 1 L). Thereafter, the combined filtrate and washing liquid were distilled at 88 kPa to obtain crude diiododecane (8.01 kg, purity 86%). This crude material was further distilled at 3.2 kPa to obtain diiododecane (6.68 kg, yield 51%) containing DIS, 99.9%; SiH ₃ I, 0.01% and SiHI ₃ , 0.02%.

As can be seen, recycling provides advantages in terms of economic and environmental benefits, and generally simplifies regulatory compliance, however, impurities may accumulate. Each synthesis operation removes the recycle step and the use of a new solvent feed produces ultra-high product purity that cannot be achieved after solvent recycle.

Example 11: Material compatibility

The small piece of material is immersed in SiH ₂ I ₂ (synthesized according to the method disclosed in US Patent Application Publication No. 2016/0264426), sealed in a glass pressure tube and maintained at a prescribed temperature for a predetermined period of time in the absence of light. . Based on GCMS peak integration, the initial control analysis was 96.9% SiH ₂ I ₂ and 1.3% SiH(Me)I ₂ and 1.6% SiHI ₃ . The results are provided below and illustrate that the stability of SiH ₂ I ₂ is difficult to maintain. Applicants believe that he used in the process of synthesis HX or X ₂ the reaction was led to the instability of SiH ₂ I ₂ reaction products of the comparison results as shown. As can be seen, some standard packaging materials further promote the decomposition of the SiH ₂ I ₂ product.

Room temperature: *Different starting materials: 97.6% SiH ₂ I ₂ , 0.9% SiH(Me)I ₂ and 0.9% SiH ₃ .

40 ° C: *Different starting materials: 97.6% SiH ₂ I ₂ , 0.9% SiH(Me)I ₂ and 0.9% SiH ₃ .

Example 11: Stability

SiH ₂ I ₂ synthesized according to the methods disclosed herein was stored in a passivated stainless steel cylinder at room temperature. Analysis was performed using GCMS peak integration before and after storage in the cylinder. The table below illustrates that this product maintains its purity without any stabilizers.

Example 12 Dynamic Thermal Stability

Gas chromatography equipped with a thermal conductivity detector for 282 days under dynamic conditions that mimic the "vapor drawn mode" that can be used in some atomic layer deposition processes Liquid phase and gas phase DIS samples were analyzed with a thermal conductivity detector; GC-TCD) or GCMS. In a device similar to the composition for forming a Si-containing film of FIGS. 3 and 4 , a He gas is used to realize a "gas phase suction mode" in which the ends of both the inlet and the outlet are located to form a Si-containing film. Above the surface of the composition. The device initially contained 1 kg DIS and was maintained at 35 °C during the test. A liquid phase DIS sample was taken from the delivery device. A gas phase DIS sample is taken from the sampling port of the delivery line connected to the outlet of the delivery device. The results are summarized in the table below:

As indicated above, as shown by the 2/3 and >95% reduction in the DIS composition, the purity of the gas phase is still high and has a semiconductor regardless of some significant disproportionation in the liquid phase during the absence of the dispensing device. Level quality. Thus, a liquid DIS synthesized according to the methods disclosed herein will deliver a stable composition of the gas phase DIS to the vapor deposition tool without any stabilizer.

Predictive example: I ₃ Si-CH ₂ -SiI ₃ Synthesis

Cl ₃ Si-CH ₂ -SiCl ₃ +6 Li-I→I ₃ Si-CH ₂ -SiI ₃ +6 Li-Cl

Under inert and anhydrous conditions, the flask will contain lithium iodide and pentane or other suitable solvent, followed by slow addition of the solution or solvent-free liquid bis(trichlorodecanealkyl)methane. The suspension was stirred vigorously until completion of the reaction was observed by disappearance of bis(trichlorodecylalkyl)methane in the GCMS trace of the aliquot of the reaction mixture. The resulting suspension is filtered through a glass frit loaded with a diatomaceous earth pad to produce a pentane solution of the desired product. The bis(triiodoguanidino)methane product in pure form will be isolated by distillation under reduced pressure and/or sublimation.

The reactants are commercially available or can be synthesized according to J. Organomet. Chem. 92, 1975 163-168.

While the invention has been shown and described, it will be modified by those skilled in the art without departing from the scope of the invention. The specific examples described herein are illustrative only and not limiting. Many changes and modifications may be made to the compositions and methods, and such changes and modifications are within the scope of the invention. Therefore, the scope of protection is not limited to the specific examples described herein, but is only limited by the scope of the accompanying claims.

Claims (17)

A method for synthesizing Si-H-containing iodonyl decane having 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) where w is 1 to 3, x+y+z=2w+2, x is 1 to 2w+1, and y is 0 to 2w+1, z 1 to 2w+1, each a is independently 0 to 3, each b is independently 0 to 3, each c is independently 0 to 3, a+b+c=3, and the constraint is at least one a and At least one c is 1, each m is independently 0 to 3, each n is independently 0 to 3, each o is independently 0 to 3, m+n+o=3, and the constraint is at least one m and at least One o is 1, and each R is independently a C1 to C12 hydrocarbyl, Cl, Br or ER' ₃ group, wherein each E is independently Si or Ge and each R' is independently H or a C1 to C12 hydrocarbyl group, The method comprises reacting a halodecane reactant with an alkali metal halide reactant having the formula Si _w H _x R _y X _z or N(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, the alkali metal halide reactant has Formula MI, where M = Li, Na, K, Rb or Cs; produces MX with (1), (2 Or a mixture of (3); and a Si-H-containing compound 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 Iododecane is separated from the mixture.  For example, the method of claim 1 wherein M=Li.    The method of claim 1, further comprising adding a non-coordinating solvent to the reaction step.    The method of claim 3, wherein the coordinating solvent is propane, butane, pentane, hexane, heptane, methyl chloride, dichloromethane, chloroform, carbon tetrachloride, methylene chloride (methylene chloride), acetonitrile or a combination thereof.   The method of any one of clauses 1 to 4, wherein the separating step comprises filtering the mixture such that MX has the formula Si _w H _x R _y I _z or N (SiH _a R _b I _{c 3} ) The Si-H-containing iododecane is separated.  The method of any one of clauses 1 to 5 wherein the alkali metal halide reactant is LiI.   The method of any one of clauses 1 to 6, wherein the halodecane reactant is SiH ₂ Cl ₂ . The method of any one of clauses 1 to 6, wherein the halodecane reactant is Si ₂ HCl ₅ . The method of any one of clauses 1 to 6, wherein the halodecane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl). A method for synthesizing Si-H-containing iodonyl decane having the formula Si _w H _x I _z or N(SiH _a I _c ) ₃ , wherein w=1 to 3, x+z =2w+2, x=1 to 2w+1, z=1 to 2w+1, each a is independently 0 to 3, each c is independently 0 to 3, a+c=3, and the constraint is at least One a is 1 and at least one c is 1, the method comprising: contacting a halodecane reactant with an alkali metal halide reactant having 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, the alkali metal halide reactant having the formula MI, wherein M is Li, Na, K, Rb or Cs, Producing a combination of MX and Si _w H _x I _z or N(SiH _a I _c ) ₃ ; and isolating the mixture to produce the Si-containing species having the formula Si _w H _x I _z or N(SiH _a I _c ) ₃ H-iododecane. The method of claim 10, wherein the halodecane reactant is SiH ₂ Cl ₂ . The method of claim 10, wherein the halodecane reactant is Si ₂ HCl ₅ . The method of claim 10, wherein the halodecane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl).  The method of any one of clauses 10 to 13, wherein the alkali metal halide reactant is LiI.   A composition delivery device for forming a Si-containing film, comprising: a can having an inlet conduit and an outlet conduit and containing a composition for forming a Si-containing film, the composition for forming the Si-containing film comprising Si-H-containing iododecane and Ag, or Sb between about 0 ppbw and about 100 ppbw; the Si-H-containing iodine decane 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) where w is 1 to 3, x+y+z=2w+2, x is 1 to 2w+1, and y is 0 to 2w+1 z is 1 to 2w+1, each a is independently 0 to 3, each b is independently 0 to 3, each c is independently 0 to 3, a+b+c=3, and the constraint is at least one a and at least one c is 1, each m is independently 0 to 3, each n is independently 0 to 3, each o is independently 0 to 3, m+n+o=3, and the constraint is at least one m and at least one o is 1, and each R is independently a C1 to C12 alkyl, Cl, Br, or ER _'3 group, wherein each E is independently Si or Ge, and each R' is independently H or C1 to C12 alkyl .  A composition delivery device for forming a Si-containing film according to claim 15 wherein the composition for forming the Si-containing film comprises C between about 0 ppmw and about 100 ppmw when y or b or n = 0.   A composition delivery device for forming a Si-containing film according to claim 15 or 16, wherein the Si-H-containing iodine decane is SiH ₂ I ₂ .