KR102038215B1 - Preparation of Si-H-Containing Iodosilanes via a Halide Exchange Reaction - Google Patents

Abstract

A method for synthesizing Si-H containing iodosilanes such as diiodosilane or pentaiododisilane using a halide exchange reaction is described.

Description

Preparation of Si-H-Containing Iodosilanes via a Halide Exchange Reaction

Cross Reference to Related Application

This application claims the benefit of US patent application Ser. No. 62 / 338,882, filed May 19, 2016, which is incorporated herein by reference in its entirety for all purposes.

Field of technology

A method for synthesizing Si-H containing iodosilanes such as diiodosilane or pentaiododisilane using a halide exchange reaction is described.

Halosilane chemicals find many uses in the industry. In particular, iodosilane precursors such as diiodosilane (SiH ₂ I ₂ ) are used to deposit various silicon containing films for use in semiconductor fabrication processes.

) 등은 실란(SiH₄), 요오드화수소(HI), 및 알루미늄 요오다이드(AlI₃)의 반응에 의한 디요오도실란(SiH₂I₂)의 합성을 밝혀내었다[Derivatives of monosilane. Part II. The Iodo compounds: Emeleus, H. J.; Maddock, A. G.; Reid, C., J. Chem . Soc . 1941, 353-358]. 이러한 반응은 요오도실란(SiH₃I), 트리요오도실란(SiHI₃), 및 테트라요오도실란(SiI₄)과 함께 요망되는 SiH₂I₂ 반응 생성물을 형성시킨다[Id. at p. 354].Emelus (

) Et al. Revealed the synthesis of diiodosilanes (SiH ₂ I ₂ ) by the reaction of silane (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. This reaction forms the desired SiH ₂ I ₂ reaction product with iodosilane (SiH ₃ I), triiodosilane (SiHI ₃ ), and tetraiodosilane (SiI ₄ ) [ Id. at p. 354].

Keinan et al. Found that the reaction of 1: 1 molar ratio of iodine and phenylsilane in the presence of traces of ethyl acetate at -20 ° C produced 1 mol of SiH ₂ I ₂ and 1 mol of benzene [J . Org. Chem., Vol. 52, no. 22, 1987, pp. 4846-4851. Although selective for SiH ₂ I ₂ over other possible iodosilanes (ie SiH ₃ I, SiHI ₃ , and SiI ₄ ), this method produces benzene, a known human carcinogen, which makes commercial practice difficult. . Despite these drawbacks, they exist as a preferred synthetic method for producing diiodosilanes.

Impurities from this synthesis process, such as hydrogen iodide and / or iodine, can decompose the obtained iodosilane product. Current industry practice is described in 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, use antimony, silver, or copper powder / pellet additives to stabilize these products. Although the addition of copper can stabilize the product, it can also introduce impurities (Cu) that can adversely affect the electrical properties of the deposited film.

The so-called Finkelstein reaction is an S _N 2 reaction (substituted nucleophilic dimolecular reaction) involving the exchange of one halogen atom with another. Halide exchange is an equilibrium reaction, but this reaction can be completed by using the differential solubility of the halide salt, or by using a large excess of halide salt [Smith et al., (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience.

For example, the preparation of trimethylsilyl iodide (TMS-I) through the reaction of trimethylsilyl chloride with lithium iodide in chloroform or sodium iodide in acetonitrile has been reported (Scheme 4). for Organic Synthesis, Reagents for Silicon-Mediated Organic Synthesis, Iodotrimethylsilane, Wiley 2011, p. 325].

Scheme 4

Although Si-Cl is reactive to iodine exchange by this route, R groups such as alkyl groups or aryl groups are not. On the other hand, Si—H bonds have generally been found to be more reactive than Si—Cl bonds [Chemistry and Technology of Silicones, Academic Press, 1968, p. 50]. As a result, one skilled in the art would expect the exchange of both H and Cl atoms of any Si—H containing halosilane in the Finkelstein reaction.

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

A method for synthesizing Si-H containing iodosilanes is described. Si-H containing iodosilanes have the formula:

[Formula 1]

Si _w H _x R _y I _z

[Formula 2]

N (SiH _a R _b I _c ) ₃ or

[Formula 3]

(SiH _m R _n I _o ) ₂ -CH ₂

Wherein w is 1 to 3, x + y + z is 2w + 2, x is 1 to 2w + 1, y is 0 to 2w + 1, z is 1 to 2w + 1, and each a Are independently 0 to 3, each b is independently 0 to 3, each c is independently 0 to 3, a + b + c is 3, provided that 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 is 3, provided at least One m and at least one o is 1 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, Each R 'is independently H or a C1 to C12 hydrocarbyl group. 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, halosilane reactants having z, a, b, c, m, n, and o as defined above are Si _w H _x R _y I _z , N (SiH _a R _b I _c ) ₃ or ( SiH _m R _n I _o ) _2- reacts with an alkali metal halide reactant having the formula MI, wherein M is Li, Na, K, Rb, or Cs, to produce a mixture of ₂ -CH ₂ and MX. Si-H containing iodosilanes 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 are separated from the mixture. Alternatively, the halosilane reactant is an alkali metal halide reactant to produce a mixture of Si _w H _x I _z , N (SiH _a R _b I _c ) ₃ or (SiH _m R _n I _o ) ₂ -CH ₂ and MX. Mixed with The mixture is filtered to produce Si-H containing iodosilanes having the formula Si _w H _x I _z , N (SiH _a R _b I _c ) ₃ or (SiH _m R _n I _o ) ₂ -CH ₂ . Any of the methods described may have one or more of the following aspects:

R is not Cl or Br;

R is a C1 to C12 hydrocarbyl group;

R is an ER ' ₃ group;

M is Li;

Y is 0;

Z is 2 to 2w + 1;

Add solvent to reaction step;

The solvent is a Si-H containing iodosilane;

The solvent is an alkane;

The solvent is propane, butane, pentane, hexane, heptane, chloromethane, dichloromethane, chloroform, carbon tetrachloride, methylene chloride, acetonitrile, and combinations thereof;

The solvent is pentane;

The separation step comprises filtering the mixture to separate MX from Si-H containing iodosilanes having the formula Si _w H _x R _y I _z ;

The halosilane reactant is SiH ₂ Cl ₂ ;

The halosilane reactant is Si ₂ HCl ₅ ;

The halosilane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl);

Alkali metal halide reactant is LiI;

Si-H containing iodosilanes have the formula Si _w H _x R _y I _z (1);

Si-H containing iodosilanes have the formula SiH _x I _{4 -x} where x is 1 to 3;

Si-H containing iodosilanes are SiHI ₃ ;

Si-H containing iodosilanes are SiH ₂ I ₂ ;

Si-H containing iodosilanes are SiH ₃ I;

Si-H-containing iodosilanes have the formula SiH _x R _y I _{4 -xy} where x is 1 to 2, y is 1 to 2, x + y is 3 or less, 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 C1 to C12 hydrocarbyl Qi;

Si-H containing iodosilanes are MeSiHI ₂ ;

Si-H containing iodosilanes are MeSiH ₂ I;

Si-H containing iodosilanes are Me ₂ SiHI;

Si-H containing iodosilanes are EtSiHI ₂ ;

Si-H containing iodosilanes are EtSiH ₂ I;

Si-H containing iodosilanes are Et ₂ SiHI;

Si-H containing iodosilanes are ClSiHI ₂ ;

Si-H containing iodosilanes are ClSiH ₂ I;

Si-H containing iodosilanes are Cl ₂ SiHI;

Si-H containing iodosilanes are BrSiHI ₂ ;

Si-H containing iodosilanes are BrSiH ₂ I;

Si-H containing iodosilanes are Brl ₂ SiHI;

Si-H containing iodosilanes are H ₃ SiSiHI ₂ ;

Si-H containing iodosilanes are H ₃ SiSiH ₂ I;

Si-H containing iodosilanes are (H ₃ Si) ₂ SiHI;

Si-H containing iodosilanes are H ₃ GeSiHI ₂ ;

Si-H containing iodosilanes are H ₃ GeSiH ₂ I;

Si-H containing iodosilanes are (H ₃ Ge) ₂ SiHI;

Si-H containing iodosilanes are Me ₃ SiSiHI ₂ ;

Si-H containing iodosilanes are Me ₃ SiSiH ₂ I;

Si-H containing iodosilanes are (Me ₃ Si) ₂ SiHI;

Si-H containing iodosilanes are Me ₃ GeSiHI ₂ ;

Si-H containing iodosilanes are Me ₃ GeSiH ₂ I;

Si-H containing iodosilanes are (Me ₃ Ge) ₂ SiHI;

Si-H containing iodosilanes are Me ₂ HSiSiHI ₂ ;

Si-H containing iodosilanes are Me ₂ HSiSiH ₂ I;

Si-H containing iodosilanes are (Me ₂ HSi) ₂ SiHI;

Si-H containing iodosilanes are Me ₂ HGeSiHI ₂ ;

Si-H containing iodosilanes are Me ₂ HGeSiH ₂ I;

Si-H containing iodosilanes are (Me ₂ HGe) ₂ SiHI;

Si-H containing iodosilanes have the formula Si ₂ H _x I _{6 -x} , where x is 1 to 5;

Si-H containing iodosilanes are Si ₂ HI ₅ ;

Si-H containing iodosilanes are Si ₂ H ₂ I ₄ ;

Si-H containing iodosilanes are Si ₂ H ₃ I ₃ ;

Si-H containing iodosilanes are Si ₂ H ₄ I ₂ ;

Si-H containing iodosilanes are Si ₂ H ₅ I;

Si-H containing iodosilanes have the formula Si ₂ H _x R _y I _{6 -xy} where x is 1 to 4, y is 1 to 4, and x + y is 5 or less, 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 C1 to C12 hydro Carbyl group;

Si-H containing iodosilanes are MeSi ₂ HI ₄ ;

Si-H containing iodosilanes are MeSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are MeSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are MeSi ₂ H ₄ I;

Si-H containing iodosilanes are Me ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are Me ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are Me ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are Me ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are Me ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are Me ₄ Si ₂ HI;

Si-H containing iodosilanes are EtSi ₂ HI ₄ ;

Si-H containing iodosilanes are EtSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are EtSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are EtSi ₂ H ₄ I;

Si-H containing iodosilanes are Et ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are Et ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are Et ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are Et ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are Et ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are Et ₄ Si ₂ HI;

Si-H containing iodosilanes are ClSi ₂ HI ₄ ;

Si-H containing iodosilanes are ClSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are ClSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are ClSi ₂ H ₄ I;

Si-H containing iodosilanes are Cl ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are Cl ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are Cl ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are Cl ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are Cl ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are Cl ₄ Si ₂ HI;

Si-H containing iodosilanes are BrSi ₂ HI ₄ ;

Si-H containing iodosilanes are BrSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are BrSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are BrSi ₂ H ₄ I;

Si-H containing iodosilanes are Br ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are Br ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are Br ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes is Br ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are Br ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes is Br ₄ Si ₂ HI;

Si-H containing iodosilanes are H ₃ SiSi ₂ HI ₄ ;

Si-H containing iodosilanes are H ₃ SiSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are H ₃ SiSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are H ₃ SiSi ₂ H ₄ I;

Si-H containing iodosilanes are (H ₃ Si) ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are (H ₃ Si) ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are (H ₃ Si) ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are (H ₃ Si) ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are (H ₃ Si) ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are (H ₃ Si) ₄ Si ₂ HI;

Si-H containing iodosilanes are H ₃ GeSi ₂ HI ₄ ;

Si-H containing iodosilanes are H ₃ GeSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are H ₃ GeSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are H ₃ GeSi ₂ H ₄ I;

Si-H containing iodosilanes are (H ₃ Ge) ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are (H ₃ Ge) ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are (H ₃ Ge) ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are (H ₃ Ge) ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are (H ₃ Ge) ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are (H ₃ Ge) ₄ Si ₂ HI;

Si-H containing iodosilanes are Me ₃ SiSi ₂ HI ₄ ;

Si-H containing iodosilanes are Me ₃ SiSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are Me ₃ SiSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are Me ₃ SiSi ₂ H ₄ I;

Si-H containing iodosilanes are (Me ₃ Si) ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are (Me ₃ Si) ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are (Me ₃ Si) ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are (Me ₃ Si) ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are (Me ₃ Si) ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are (Me ₃ Si) ₄ Si ₂ HI;

Si-H containing iodosilanes are Me ₃ GeSi ₂ HI ₄ ;

Si-H containing iodosilanes are Me ₃ GeSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are Me ₃ GeSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are Me ₃ GeSi ₂ H ₄ I;

Si-H containing iodosilanes are (Me ₃ Ge) ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are (Me ₃ Ge) ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are (Me ₃ Ge) ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are (Me ₃ Ge) ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are (Me ₃ Ge) ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are (Me ₃ Ge) ₄ Si ₂ HI;

Si-H containing iodosilanes are Me ₂ HSiSi ₂ HI ₄ ;

Si-H containing iodosilanes are Me ₂ HSiSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are Me ₂ HSiSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are Me ₂ HSiSi ₂ H ₄ I;

Si-H containing iodosilanes are (Me ₂ HSi) ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are (Me ₂ HSi) ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are (Me ₂ HSi) ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are (Me ₂ HSi) ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are (Me ₂ HSi) ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are (Me ₂ HSi) ₄ Si ₂ HI;

Si-H containing iodosilanes are Me ₂ HGeSi ₂ HI ₄ ;

Si-H containing iodosilanes are Me ₂ HGeSi ₂ H ₂ I ₃ ;

Si-H containing iodosilanes are Me ₂ HGeSi ₂ H ₃ I ₂ ;

Si-H containing iodosilanes are Me ₂ HGeSi ₂ H ₄ I;

Si-H containing iodosilanes are (Me ₂ HGe) ₂ Si ₂ HI ₃ ;

Si-H containing iodosilanes are (Me ₂ HGe) ₂ Si ₂ H ₂ I ₂ ;

Si-H containing iodosilanes are (Me ₂ HGe) ₂ Si ₂ H ₃ I;

Si-H containing iodosilanes are (Me ₂ HGe) ₃ Si ₂ HI ₂ ;

Si-H containing iodosilanes are (Me ₂ HGe) ₃ Si ₂ H ₂ I;

Si-H containing iodosilanes are (Me ₂ HGe) ₄ Si ₂ HI;

Si-H containing iodosilanes have the formula Si ₃ H _x I _{8 -x} where x is from 1 to 8;

Si-H containing iodosilanes are Si ₃ H ₇ I;

Si-H containing iodosilanes are Si ₃ H ₆ I ₂ ;

Si-H containing iodosilanes are Si ₃ H ₅ I ₃ ;

Si-H containing iodosilanes are Si ₃ H ₄ I ₄ ;

Si-H containing iodosilanes are Si ₃ H ₃ I ₅ ;

Si-H containing iodosilanes are Si ₃ H ₂ I ₆ ;

Si-H containing iodosilanes are Si ₃ HI ₇ ;

Si-H containing iodosilanes have the formula N (SiH _a I _c ) ₃ , where each a is independently 0-3, each c is independently 0-3, provided that at least one a and at least one c is 1;

Si-H containing iodosilanes are N (SiH ₃ ) ₂ (SiH ₂ I);

Si-H containing iodosilanes are N (SiH ₃ ) ₂ (SiHI ₂ );

Si-H containing iodosilanes are N (SiH ₃ ) (SiH ₂ I) ₂ ;

Si-H containing iodosilanes are N (SiH ₃ ) (SiHI ₂ ) ₂ ;

Si-H containing iodosilanes are N (SiHI ₂ ) ₂ (SiH ₂ I);

Si-H containing iodosilanes are N (SiHI ₂ ) (SiH ₂ I) ₂ ;

Si-H containing iodosilanes are N (SiH ₂ I) ₃ ;

Si-H containing iodosilanes are N (SiHI ₂ ) ₃ ;

Si-H containing iodosilanes have the formula N (SiH _a R _b I _c ) ₃ , where each a is independently 0-3, each b is independently 0-3, and each c is Independently, 0 to 3, a + b + c is 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, each R 'is independently H or a C1 to C12 hydrocarbyl group, provided that (a) at least one x, at least one y, and at least one z is 1, (b) At least one Si is bonded to both H and I;

Si-H containing iodosilanes are N (SiH ₃ ) ₂ (SiMeHI);

Si-H containing iodosilanes are N (SiH ₂ Me) ₂ (SiMeHI);

Si-H containing iodosilanes are N (SiHMe ₂ ) ₂ (SiMeHI);

Si-H containing iodosilanes are N (SiMe ₂ H) ₂ (SiH ₂ I);

Si-H containing iodosilanes are N (SiMe ₃ ) ₂ (SiH ₂ I);

Si-H containing iodosilanes are N (SiMe ₂ H) ₂ (SiHI ₂ );

Si-H containing iodosilanes are N (SiMe ₃ ) ₂ (SiHI ₂ );

Si-H containing iodosilanes have the formula (SiH _m R _n I _o ) ₂ -CH ₂ (3);

Si-H containing iodosilanes have the formula (SiH _x I _y ) ₂ CH ₂ , where each x is independently 0 to 3, and each y is independently 0 to 3, provided that at least one X and at least one y is 1;

Si-H containing iodosilanes are (SiH ₂ I) ₂ —CH ₂ ;

Si-H containing iodosilanes are (SiHI ₂ ) ₂ —CH ₂ ;

Si-H containing iodosilanes are (SiH ₂ I) —CH ₂ — (SiH ₃ );

Si-H containing iodosilanes are (SiHI ₂ ) —CH ₂ — (SiH ₃ ); or

Si-H containing iodosilanes are (SiH ₂ I) —CH ₂ — (SiHI ₂ ).

Also described are Si-containing film forming compositions comprising any of the Si-H containing iodosilanes listed above. The Si-containing film forming compositions described include one or more of the following aspects:

The Si-containing film forming composition comprises from about 99% v / v to about 100% v / v of one Si—H containing iodosilane;

The Si-containing film forming composition comprises from about 99.5% v / v to about 100% v / v of one Si—H containing iodosilane;

The Si-containing film forming composition comprises from about 99.97% v / v to about 100% v / v of one Si—H containing iodosilane;

The Si-containing film forming composition contains from about 0 ppbw to about 100 ppbw Cu;

The Si-containing film forming composition contains Ag from about 0 ppbw to about 100 ppbw;

The Si-containing film forming composition contains from about 0 ppbw to about 100 ppbw Sb;

The Si-containing film forming composition contains from about 0 ppbw to about 50 ppbw Cu;

The Si-containing film forming composition contains Ag from about 0 ppbw to about 50 ppbw;

The Si-containing film forming composition contains about 0 ppbw to about 50 ppbw Sb;

The Si-containing film forming composition contains from about 0 ppbw to about 10 ppbw Cu;

The Si-containing film forming composition contains Ag from about 0 ppbw to about 10 ppbw; or

The Si-containing film forming composition contains from about 0 ppbw to about 10 ppbw of Sb.

Also described is a Si-containing film forming composition delivery device comprising a canister having an inlet conduit and an outlet conduit and containing any of the Si-containing film forming compositions described above. The described device can include one or more of the following aspects:

The end of the inlet conduit is located above the surface of the Si-containing film forming composition and the end of the outlet conduit is located below the surface of the Si-containing film forming composition;

The end of the inlet conduit is located below the surface of the Si-containing film forming composition and the end of the outlet conduit is located above the surface of the Si-containing film forming composition;

Further comprises a diaphragm valve on the inlet and outlet;

The inner surface of the canister is glass;

The inner surface of the canister is passivated stainless steel;

The canister is a light resistant glass having a light resistant coating on the outer surface of the canister;

The inner surface of the canister is aluminum oxide;

Further comprising one or more barrier layers on the inner surface of the canister;

Further comprising one to four barrier layers on the inner surface of the canister;

Further comprising one or two barrier layers on the inner surface of the canister;

Each barrier layer comprises a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a silicon carbonitride, a silicon oxycarbonitride layer, or a combination thereof;

Where the thickness of each barrier layer is between 1 and 100 nm; or

Where the thickness of each barrier layer is from 2 to 10 nm.

Notation and nomenclature

Certain abbreviations, symbols, and terms are used throughout the following description and claims, and include:

As used herein, the singular form “a” or “an” means one or more than one.

As used herein, the term “approximately” or “about” means ± 10% of the stated values.

As used herein, the term “independently”, when used in the context of describing an R group, is independently selected for other groups having the same or different subscripts or superscripts as well as any additional of those same R groups. It should be understood to mean being chosen independently for the species. 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 can be the same as each other or as R ² or R ³ But not necessarily the same. Also, unless stated otherwise detailed, it is to be understood that the values of the R groups are independent of each other when used in different formulas.

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 atoms and hydrogen atoms. Hydrocarbyl groups can be saturated or unsaturated. Either term refers to a linear, branched, or cyclic group. Examples of linear alkyl groups include, but are not limited to, methyl groups, ethyl groups, n-propyl groups, n-butyl groups, and the like. Examples of branched alkyl groups include, but are not limited to, iso-propyl, t-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, and the like.

As used herein, the term “aryl” refers to an aromatic ring compound with one hydrogen atom removed from the ring. The term "heterocycle" as used herein refers to a cyclic compound having atoms of at least two different components as members of its ring.

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

As used herein, the acronym “HCDS” refers to hexachlorodisilane; The acronym "PCDS" stands for pentachlorodisilane; The acronym "OCTS" refers to n-octyltrimethoxysilane; The acronym "TSA" stands for trisilylamine or N (SiH ₃ ) ₃ .

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

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

As used herein, the term "coordination solvent" means any solvent that donates a pair of electrons, such as a solvent containing OH or NH ₃ groups. Exemplary coordinating solvents include amines, phosphines, ethers, and ketones.

The acronym "LCD-TFT" as used herein refers to a liquid-crystal display-thin-film transistor; The acronym "MIM" stands for Metal-insulator-metal; The acronym "DRAM" stands for dynamic random-access memory; The acronym "FeRAM" stands for Ferroelectric random-access memory; The acronym "sccm" stands for standard cubic centimeters per minute; The acronym "GCMS" stands for Gas Chromatography-Mass Spectrometry.

Standard abbreviations of the elements from the periodic table of elements are used herein. It is to be understood that the elements may be referred to by these abbreviations (eg, Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, etc.).

Any and all ranges described herein include their endpoints, regardless of whether the term “inclusively” is used (ie, x equals 1 to 4 such that x = 1, x = 4, And x = any number between them).

For further understanding of the nature and objects of the invention, reference should be made to the following detailed description in conjunction with the accompanying drawings.
1 is a schematic diagram of an apparatus in which the described synthesis method may be performed.
2 is a schematic diagram of an alternative apparatus in which the described synthesis method may be performed.
3 is a cross-sectional side view of one embodiment of a Si-containing film forming composition delivery device 1.
4 is a cross-sectional side view of a second embodiment of a Si-containing film forming composition delivery device 1.
5 is a cross-sectional side view of an exemplary embodiment of a solid precursor sublimator 100 for sublimating a solid Si-containing film forming composition.
6 is a Gas Chromatographic / Mass Spectrometric (GC / MS) graph of the SiH ₂ I ₂ reaction product of Example 5. FIG.
7 is a GC / MS graph of the reaction mixture of Example 7 after 90 minutes of stirring.

desirable Implementation  Explanation

A method for synthesizing Si-H containing iodosilanes having the formula:

[Formula 1]

Si _w H _x R _y I _z

[Formula 2]

N (SiH _a R _b I _c ) ₃ or

[Formula 3]

(SiH _m R _n I _o ) ₂ -CH ₂

Wherein w is 1 to 3, x + y + z is 2w + 2, x is 1 to 2w + 1, y is 0 to 2w + 1, z is 1 to 2w + 1, and each a Are independently 0 to 3, each b is independently 0 to 3, each c is independently 0 to 3, a + b + c is 3, provided that 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 is 3, provided at least One m and at least one o is 1 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, Each R 'is independently H or a C1 to C12 hydrocarbyl group.

Such compounds, for example diiodosilane (SiH ₂ I ₂ ) or pentaiododisilane (Si ₂ HI ₅ ) contain highly reactive Si—H groups, and when y or b or n is zero It does not have any organic protection. As a result, such silicon hydrides may be susceptible to nucleophilic attack of silicon hydrides from coordinating solvents [see, eg, Keinan et al., J. Org. Chem. 1987 , 52, 4846-4851 (catalytic deoxygenation of alcohols and ethers, carbonyl conjugate addition reaction and α-alkoxymethylation of ketones with trimethylsilyl iodine)]. In other words, since the final product can react with the solvent, special care must be taken in the selection of the appropriate solvent when the solvent is used. This can lead to product degradation and side reactions. It also limits the choice of a suitable solvent for the synthesis.

Finkelstein-type S _N 2 reactions are typically dependent on the solubility and insolubility of the reagents and salt byproducts, respectively, in order to act as a driving force in the reaction. For example, trimethylsilyl iodide (TMS-I) can be prepared by reacting trimethylsilyl chloride and alkali metal iodide salt in a suitable solvent such as chloroform or acetonitrile (see Scheme 4 above). . In this particular example, trimethylsilyl chloride (TMS-Cl) and sodium iodide salts have some solubility in these solvents, and by-product sodium chloride has no solubility. Precipitation of the by-product sodium chloride contributes to the driving force of the reaction.

Si _w H _x R _y I _z (eg SiH ₂ I ₂ or Si ₂ HI ₅ ), N (SiH _a R _b I _c ) ₃ (eg N (SiH ₃ ) ₂ (SiH ₂ I) ), Or (SiH _m R _n I _o ) ₂ -CH ₂ (e.g., (SiH ₂ I) -CH _2- (SiH ₃ )), is known as halogen scrambling due to the reactivity of Si-H bonds. And side reactions. Coordinating solvents can exacerbate such halogen scrambling and side reactions. The reaction between dichlorosilane (DCS) and lithium iodide forms diiodosilane in the absence of solvent at ambient temperature (see Example 3 below). Non-coordinating solvents (eg n-pentane and chloroform) assist during the filtration of lithium chloride salt byproducts. Non-coordinating solvents may also enhance the inhibition of reactions and side reactions (heat exchange media) by improved mixing (ie, dilution of reactants). Suitable non-coordinating solvents are hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, benzene, toluene, and chlorinated aliphatic hydrocarbons such as chloromethane, dichloromethane, chloroform, carbon tetrachloride, acetonitrile and the like. It includes. However, the use of chlorinated solvents is a less attractive option, since such solvents are usually heavily regulated (requires permission) and can be carcinogenic. The solvent should be selected to have a sufficient difference in boiling point with the target product, and this boiling point difference is typically above 20 ° C, and preferably above 40 ° C.

Exemplary Si-H containing iodosilane reaction products include, but are not limited to:

SiH _x I _{4 -x} where x is 1 to 3, for example SiHI ₃ , SiH ₂ I ₂ , or SiH ₃ I;

SiH _x R _y I _{4 -xy} wherein x is 1 to 2, y is 1 to 2, x + y is 3 or less, and each R is independently a C1 to C12 hydrocarbyl group, Cl, Br, or ER'3 groups, wherein each E is independently Si or Ge, and each R 'is independently H or a C1 to C12 hydrocarbyl group), eg, 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 and the like;

Si ₂ H _{x - 6} I _x (where x is 1 to 5), for example 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, preferably x is 5 (ie Si ₂ HI ₅ );

Si ₂ H _x R _y I _{6 -xy} where x is 1 to 4, y is 1 to 4, x + y is 5 or less, and each R is independently C1 to C12 hydrocarbyl Group, Cl, Br, or ER'3 group, wherein each E is independently Si or Ge and each R 'is independently H or a C1 to C12 hydrocarbyl group), for example 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 HSi) ₃ Si ₂ H ₂ I, (Me ₂ HSi) ₄ Si ₂ HI, Me ₂ HGeSi ₂ HI ₄ , Me ₂ HGeSi ₂ H ₂ I ₃ , Me ₂ HGeSi ₂ H ₃ I ₂ , 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, and the like;

Si ₃ H _{x - 8} I _x (where x is 1 to 7), for example 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 , where each x is independently from 0 to 3, each y is independently from 0 to 3, provided that at least one x and at least one y is 1, For example, 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 , where each x is independently from 0 to 3, each y is independently from 0 to 3, and each z is independently from 0 to 3, x + y + z is 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 hydrocarbyl group, provided that (a) at least one x, at least one y, and at least one z is 1 and (b) at least one Si is in both H and I Bound), for example 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 ), and the like; or

(SiH _x I _y ) ₂ CH ₂ , wherein each x is independently 0 to 3, each y is independently 0 to 3, provided that at least one x and at least one y is 1 For example, (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 ).

As shown below, Si-H containing iodosilanes are synthesized by reacting the corresponding halosilanes with alkali metal halides:

Scheme 6

Scheme 7

Scheme 8

Wherein w is 1 to 3; x is 1 to 2w + 1; y is 0 to 2w + 1; z is 1 to 2w + 1; x + y + z is 2w + 2; Each a is independently 0 to 3; Each b is independently 0-3; Each c is independently 0-3; a + b + c is 3 provided that at least one a and at least one c are 1; Each m is independently 0-3; Each p is independently 0-3; Each o is independently 0 to 3; m + p + o is 3 provided that at least one m and at least one o are 1; n is 1 to 4; X is Br or Cl; M is Li, Na, K, Rb, or Cs, preferably Li; 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 C1 to C12 Hydrocarbyl groups. Alkali metal salts (ie, MI) may be used in excess or in insufficient amounts depending on the degree of halogen exchange desired. However, excess MI will promote complete substitution of the halides on the halosilane by iodide, thus reducing the amount of chlorine or bromine impurities contained in the reaction product. Those skilled in the art will adjust the reaction stoichiometry to produce some 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 driven reaction indicates which reagent is used. However, unlike the Finkelstein reaction of the prior art, lithium iodide and lithium chloride show little or no solubility in hydrocarbons or fluorocarbons. For example, the reaction of SiCl ₂ H ₂ with 2 mol of lithium iodide in an aliphatic, aromatic, or chlorinated hydrocarbon will form SiI ₂ H ₂ and 2 mol of lithium chloride, respectively, as the main product and salt byproduct. Both LiI and LiCl are present as solids during this reaction. Li and Cl form a hard acid / base pair, and LiI has a hard / soft acid / base mismatch. As a result, Applicants believe that the formation of insoluble LiCl can provide the driving force for the reaction. However, the formation of SiH ₂ I ₂ itself may dissolve some of the LiI and may help induce the reaction. As a result, it may be beneficial to add the desired Si—H containing iodosilane product to the original reaction mixture.

Scheme 9

Wherein g is a gas, l is a liquid and s is a solid. Other alkali metal salts, such as sodium iodide (NaI), are in some cases useful for the preparation of halogen exchange products. However, NaI will typically require coordinating solvents to advance any reaction at a reaction rate that is less reactive than lithium iodide in similar solvents and at an industrially relevant reaction rate, provided that the coordinating solvents are product synthesis and / or It is chosen to minimize adverse effects on yield.

In another example, the reaction of Si ₂ Cl ₅ H with 5 mol of sodium iodide in chlorinated hydrocarbons, such as chloroform, forms Si ₂ I ₅ H and 5 mol of sodium chloride, respectively, as main products and salt byproducts. something to do. The formation of NaCl is the driving force for the reaction.

Scheme 10

Those skilled in the art will appreciate that competition between Si-Si bond cleavage and halogen exchange will require the use of less reactive NaI or alternative alkali metal halides, and / or alternative solvents. Product yield can be further maximized by optimizing the reaction parameters, such as removing any salt byproducts as the reaction proceeds to further prevent halogen scrambling and side reactions.

Although the examples below illustrate the described synthetic processes using inorganic halosilane reactants, those skilled in the art will recognize that organic Si—R groups are less reactive than Si—X and Si—H and thus will remain undisturbed during the described synthetic processes. You will recognize the possibility.

Halosilanes and alkali metal halide reactants may be commercially available. Alternatively, the halosilane reactant may have a corresponding fully halogenated silane (ie, Si _x R _y X _{2x + 2-y} , N (SiR _b X _{3 -b} ) ₃ , or (SiR _n X _{3 -n} ) _2- CH ₂ ) can be synthesized by reducing with a standard reducing agent such as lithium aluminum hydride (eg LiAlH ₄ ), NaBH ₄ , and the like. As another alternative, halosilane reactants are described in Morrison et al., J. Organomet. Chem., 92, 2, 1975, 163-168, corresponding to silanes [ie, Si _x R _y H _{2x + 2-y} , N for 1 to 12 hours in toluene, at temperatures ranging from 0 ° C to reflux. (SiH _a R _{3 -a} ) ₃ , or (SiH _m R _{3 -m} ) ₂ -CH ₂ ] with a halogenating agent such as N-chloro, -bromo, or -iodo-succinimide Can be synthesized. Although the form of the reactants is not critical (ie, solid, liquid, or gas), one of ordinary skill in the art will recognize that reactants with larger surface areas provide more reaction sites and thus provide more efficient reactions. For example, finer grain powders typically provide more reaction sites than solid beads or chunks.

The water content of the reactants and any solvents should be minimized to prevent the formation of siloxane byproducts (ie Si-O-Si). Preferably, the water content ranges from approximately 0% w / w to approximately 0.001% w / w (10 ppmw). If necessary, the reactants can be subjected to standard techniques such as refluxing on P ₂ O ₅ , treatment with molecular sieves, or heating under vacuum (eg, anhydrous LiI is 8+ at 325 ° C. under vacuum). Can be formed by baking for a period of time).

The reaction vessel is made of, lined with, or treated with a material miscible with the reactants and products. Exemplary materials include passivated stainless steel, glass, perfluoroalkoxy alkanes (PFA), and polytetrafluoroethylene (PTFE). The vessel may be jacketed or placed in a heating or cooling bath. The reaction vessel may comprise a stirring mechanism made of miscible material, for example a glass stirring shaft, a PTFE paddle stirrer, and / or a PTFE coated stainless steel impeller. The reaction vessel may also be equipped with a number of “injection ports,” pressure gauges, diaphragm valves. The reaction vessel is designed to carry out the synthesis under an inert atmosphere, for example N ₂ or rare gas. Precautions to minimize exposure of reactants and reaction mixtures to light, for example covering any transparent glassware in tin foil may also be performed. For the synthesis of SiH ₂ I ₂ , amber glassware is not suitable because the iron oxide coating can contaminate the product. Additionally, reaction vessels, agitation mechanisms, and any other related equipment, such as Schlenk lines or gloveboxes, may be standard drying techniques such as vacuum, inert gas flow, oven drying, and the like. It shall be air- and moisture-free using

As discussed above with respect to the reactants and shown in the examples below, the reaction vessel and any and all parts in contact with the reactants and products should have high purity. High purity reaction vessels are typically vessels that are miscible with Si-H containing iodosilanes and are free of impurities that can react with or contaminate Si-H containing iodosilanes. A typical example of such a high purity container is a stainless steel canister, which has a low surface roughness and a mirror finish. Low surface roughness and mirror finish are typically obtained by mechanical polishing and optionally by additional electropolishing. High purity is typically achieved by (a) washing with dilute acid (HF, HNO ₃ ), then (b) rinsing with high purity deionized water to ensure complete removal of traces of acid, and then (c) drying the vessel. It is obtained by the process containing. Deionized water (DIW) rinsing is typically performed until the resistivity of the rinsing water reaches 100 μS / cm, and preferably less than 25 μS / cm. The drying step may be a purge step using an inert gas such as He, N ₂ , Ar (preferably N ₂ or Ar), during which the pressure in the container during the vacuum step outgassing from the surface, heating of the container, or It may include a vacuum step that is reduced to accelerate any combination of these.

The gas used for purging must be semiconductor grade, ie contaminants such as trace amounts of water and oxygen (less than 1 ppm, preferably less than 10 ppb), and particles (less than 5 particles per liter @ 0.5) Μm) should not be present. The drying step may include an alternating purge sequence during which a particular flow of gas flows through the vessel, and a vacuuming step. Alternatively, the drying step can be performed by constantly flowing the purge gas while maintaining a low pressure in the vessel. The efficiency and end point of canister drying can be assessed by measuring trace amounts of H ₂ O in the gas exiting the vessel. If the inlet gas has less than 10 ppb H ₂ O, the outlet gas ranges from about 0 ppm to about 10 ppm, preferably from about 0 ppm to about 1 ppm, and more preferably from about 0 ppb to about It should have a moisture content in the range of 200 ppb. During the purge step and the vacuum step, heating the vessel is known to accelerate drying, and the vessel is typically maintained at a temperature in the range of about 40 ° C to about 150 ° C.

Immediately after being cleaned and dried, this high purity container should have a total leak rate of less than 1E-6 std cm ^{3 /} s, preferably less than 1E-8 std cm ³ / s.

Optionally, the vessel may have an internal coating or plating to further reduce the risk of corrosion of the product in the vessel or to improve its stability. Exemplary coatings include those provided by Silcotek (https://www.silcotek.com) or described in US Patent Application Publication No. 2016/046408. The vessel is also subjected to exposure to silylating agents such as silanes, disilanes, monochlorosilanes, hexamethyldisilazane prior to reaction and / or filling with Si-H containing iodosilanes. It may be passivated.

Those skilled in the art will recognize the source for the equipment components of the system used to carry out the described method. Some level of customization of components may be required based on desired temperature ranges, pressure ranges, local regulations, and so on. Exemplary equipment suppliers include Buchi Glass Uster AG, Shandong ChemSta Machinery Manufacturing Co. Ltd., Jiangsu Shajiabang Chemical Equipment Co. Ltd and the like. As discussed above, the part is preferably made of a corrosion resistant material, such as glass, glass-lined steel, steel with a corrosion resistant liner, or the like.

Air- and moisture-free high purity reactors are filled with alkali metal halides. Optional solvents which do not decompose or react with the final product may be added before or after the addition of the alkali metal halide, as a supplement in the heat exchange medium and / or in the mixing and / or product extraction. Exemplary solvents include C3-C20 alkanes such as propane, butane, pentane and the like, or chlorinated hydrocarbons such as chloromethane, dichloromethane, chloroform, carbon tetrachloride, and the like, and mixtures thereof. As discussed above, the desired Si—H containing iodosilanes may also be used as the solvent. Alkali metal halide salts may be soluble in the solvent. However, depending on the reactants, salt solubility may not be an important factor. For example, as shown in Example 5 below, lithium iodide in pentane reacts with dichlorosilane in a solid-liquid reaction. The reaction mixture can be stirred to enhance contact between the reactants. Alternatively, the reaction can proceed without the use of a solvent, as illustrated in Example 3 below.

Halosilanes can be added to the reactor via headspace, or through subsurface addition, as a gas, liquid (condensation), or in solution. Halosilanes may be in gaseous form and added to the headspace above the lithium iodide / solvent mixture. Alternatively, halosilanes in gas form can be condensed using a condenser and added directly to the lithium iodide / solvent mixture. In another alternative, halosilanes in liquid form can be added from the top of the reactor using conduits piped to the reactor. In another alternative, the gaseous or liquid form may be added below the surface of the iodine / solvent mixture using a reactor equipped with a dip tube plunged inside the salt / solvent mixture. In the examples below, condensation of dichlorosilane was performed to promote faster reagent delivery.

Halosilanes may be added in amounts below excess, stoichiometric, or stoichiometric amounts, as desired for product distribution. Excess halosilanes to the metal iodide salt will result in partial substitution of the halides by iodine on the halosilanes and formation of Si _w H _x R _y I _z compounds, wherein at least one R is Cl or Br To make it possible. Excess iodide metal salts will promote full substitution of the iodide on the halosilanes (ie R is not Cl or Br).

Alternatively, halosilanes can be added to the reactor prior to the addition of alkali metal halides. The addition mechanism for the halosilanes and alkali metal halides described above remains the same, whether the reactants are added first or second to the reactor.

The halosilane / alkali metal halide mixture can be agitated to enhance contact between the reactants. The reaction can be exothermic. In the examples below, the reaction mixture is stirred for a time sufficient to complete the reaction at ambient temperature (ie, approximately 20 ° C. to approximately 26 ° C.). Although heating is not essential in the examples below, it may be an option to accelerate the reaction. One skilled in the art can determine the most suitable temperature range according to the individual kinetics of each halosilane. For example, halosilanes with partial hydrocarbyl substitutions may require higher reaction temperatures than halosilanes without hydrocarbyl substituents, due to steric hindrance formed by hydrocarbyl groups.

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

The stirred mixture can be filtered to remove any solid impurities and salt byproducts. Typical filters include glass or polymer fritted filters.

Alternatively, when the salt byproduct is dissolved in the solvent, the stirred mixture can be filtered to remove solid byproducts before further processing. Filters such as anhydrous diatomaceous earth can be used to improve the process. Typical filters include glass or polymer frit filters.

Occasionally, the filtrate may require further processing. For example, when the filtrate produces a heterogeneous suspension of solid material, the filtrate then produces a Si-H containing iodosilane through a flash distillation process that removes some or all of the undesirable reaction byproducts or impurities. Distillation over a short path column. Alternatively, the Si—H containing iodosilane reaction product may be separated from the filtrate through a distillation column or by heating the filtrate to approximately the boiling point of the non-organic silicon hydride reaction product. In other alternatives, both the flash process and the distillation column may be necessary. Those skilled in the art will appreciate that the boiling point of the warmed stirred mixture will change as the Si—H containing iodosilane reaction product is separated from the warmed stirred mixture and the recovery temperature is adjusted accordingly. Any unreacted halosilane can be evacuated through the distillation column because of its higher mass of iodine compared to Br or Cl because it tends to be more volatile than the product obtained. Those skilled in the art will appreciate that the evacuated halosilane may be recovered for subsequent use or disposal.

The described process can convert approximately 40% mol / mol to approximately 99% mol / mol of halosilanes into Si—H containing iodosilane reaction products. The separated Si-H containing iodosilane reaction product typically has a purity ranging from approximately 50% mol / mol to approximately 99% mol / mol.

Si-H containing iodosilane reaction products may be further purified by distillation, sublimation, or recrystallization. Suitable distillation methods include atmospheric fractional distillation or batch fractional distillation or vacuum fractional distillation. Batch fractional distillation may be carried out at low temperatures and pressures. Alternatively, the Si-H containing iodosilane reaction product may be subjected to continuous distillation over two distillation columns to separate the Si-H containing iodosilane reaction product from both low and high boiling impurities in sequential steps. Can be purified. The purified Si-H containing iodosilane reaction product can be used as the Si-containing film forming composition.

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

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

As discussed in detail above and illustrated in the examples below, Si-containing film forming compositions must be stored in a clean, dry storage container that does not react with such compositions to maintain their purity.

1 is an exemplary system suitable for carrying out the described method. Air can be removed from various parts of the system (eg, reactor 1, vessel 8, boiler 6) by inert gas 9, for example nitrogen, argon, or the like. The inert gas 9 can also serve to pressurize the solvent 11 to enable its delivery to the reactor 1. Nitrogen, refrigerated ethanol, acetone / dry ice mixtures, or heat transfer agents such as monoethylene glycol (MEG) may be used in various parts of the system (eg reactor 1, distillation column 27, condenser (57). Can be used to cool)).

The reactor 1 can be maintained at the desired temperature by the jacket 2. The jacket 2 has an inlet 21 and an outlet 22. Inlet 21 and outlet 22 may be connected to a heat exchanger / freezer 23 and / or a pump (not shown) to provide recirculation of cooling fluid. Alternatively, if the batch size is small enough and the mixing time is short enough, the jacket 2 will not require the inlet 21 and outlet 22 because the thermal fluid can be sufficiently cooled during the reaction period. Can be. In another alternative, and as discussed above, a jacketed temperature controller may not be necessary and these four components (ie, 2, 21, 22 and 23) may be removed from the system.

The reactants (solvent, eg, pentane, stored in vessel 11, and halosilane, eg, ethyldichlorosilane, stored in vessel 24) are respectively reacted via line 14 and line 25 to the reactor ( Is added to 1). Solvent and halosilane may be added to reactor 1 via a liquid metering pump (not shown), for example a diaphragm pump, peristaltic pump, or syringe pump. Alkali metal halides, for example LiI, stored in the vessel 13 can be added to the reactor 1 via gravity flow, or suspended in solvents and halo miscible with Si-H containing iodosilane reaction products. It can be introduced into the reactor in a similar manner as silane (ie, via line 16). The reactants may be mixed in the reactor by the impeller 17a which is turned by the motor 17b to produce the mixture 26. Preferably, the mixing is performed under inert atmosphere at approximately atmospheric pressure. A temperature sensor (not shown) can be used to monitor the temperature of the contents of the reactor 1.

Upon completion of the addition, the progress of the reaction can be monitored using gas chromatography, for example. Upon completion of the reaction, the mixture 26 can be removed from the reactor 1 through the drain 19 through the filter 3 into the container 4. The dominant reaction product is ethyldiiodosilane (EtSiHI ₂ ), which is liquid at standard temperature and pressure, and LiCl, which is solid at standard temperature and pressure, with minor amounts of LiI and EtSiIClH impurities. In this embodiment, the reactor 1 will most likely be located above the filter 3 to make the best use of the benefits of gravity. As the MX reaction byproduct (X is Cl, Br), for example LiCl (not shown), is suspended in the mixture 26, clogging of the reactor 1 is not a problem.

The filtered stirred mixture (filtrate) (not shown) may be collected in a container (not shown) and transferred to a new location prior to performing the next process step. Alternatively, the filtrate may be directed directly to a still pot 4 to separate the reaction product from the filtrate using the heater 28. The filtrate is warmed by the heater 28. Heat is applied to the volatile solvent through the distillation column 27 and the exhaust port 43. Subsequently, the separated reaction product is collected in vessel 8.

Once again, the container 8 can be transferred to a new position before the next process step is carried out. The separated reaction product can be transferred from the vessel 8 to the boiler 6 for further purification if necessary. The boiler 6 is heated by the heater 29. The separated reaction product is purified by fractional distillation using distillation tower 53, condenser 57, and reflux divider 54. The purified reaction product is collected in the collection tank 7. The collection tank 7 includes an exhaust port 60.

2 is an alternative exemplary system suitable for carrying out the described method. In this alternative, the reactor 1 also serves as the steel pot 4 of FIG. 1. Such embodiments may be useful for the synthesis of large batches of Si—H containing iododisilanes. After sufficient mixing, the cooling medium (not shown) in the jacket 2 is replaced by the heating medium (not shown). Those skilled in the art will appreciate that if the cooling medium can also act as both a heating medium and a cooling medium (eg MEG), no "relocation" of the cooling medium will be necessary. Instead, the temperature of the medium can be changed, for example via heat exchanger 23.

Volatile solvents may be separated from the mixture 26 via distillation column 27 and vent 43. Subsequently, Si-H containing iodosilanes are collected in the vessel 8. Residual solvent / salt mixture may be removed from reactor 1 via drain 19, and salt is collected on filter 3. Once again, the vessel 8 can be moved to a new position prior to carrying out the next process step. Si-H containing iodosilanes can be transferred from the vessel 8 to the boiler 6 for further purification if necessary. The boiler 6 is heated by the heater 29. Si-H-containing iodosilane is purified by fractional distillation using a distillation tower 53, a condenser 57, and a reflux divider 54. Purified Si-H containing iodosilanes are collected in a collection tank 7. The collection tank 7 includes an exhaust port 60.

The reaction also feeds halosilanes, possibly diluted in solvents, with metal iodides, possibly suspended in a solvent, and passed through these at controlled residence times and temperatures in a flow through reactor. By a continuous reactor. The flow of each reagent can be controlled by metering a pump, eg, a peristaltic pump. The reaction mixture can then be collected in a receiving vessel and separated as in the batch synthesis example above. Alternatively, the solid fraction can be removed from the line, for example using a centrifugal pump (commercially available). The product may also be separated from the solvent (s) by continuously feeding the filtered fractions to a continuous distillation unit.

The advantages of the described synthetic method are as follows:

A catalyst free process, which helps to reduce costs, contamination, and product separation problems;

Use of iodine reactants essentially eliminates most of the side reactions associated with prior art reactions, which form low and high-order iodosilanes as impurities;

No production of HX intermediate reaction products, which may contribute to side reactions and increased impurity profiles, and as a result, the products obtained do not require prior art Ag, Cu or Sb stabilizers;

Many starting materials are inexpensive and readily available;

Phase 1-1 pot reaction;

The process can be solvent free;

Simple tablets;

Low reaction exothermicity;

• can be carried out at ambient temperature (ie from about 20 ° C. to about 26 ° C.); And

● Waste generation is minimized and environmentally friendly.

All of the above are advantageous from the standpoint of developing scalable industrial processes. In addition, the product obtained is more stable than the product prepared using X ₂ or HX reactants. As a result, the reaction product maintains a purity level suitable for the semiconductor industry without the use of stabilizers such as Cu, which can adversely affect the electrical properties of the deposited film.

Also described are methods of using the described Si-containing film forming compositions for vapor deposition methods. The described method provides for the use of Si-containing film forming compositions for the deposition of silicon-containing films. The described method may be useful in the fabrication of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices. The method introduces the vapor of the described Si-containing film forming composition into a reactor having a substrate disposed therein, and deposits at least a portion of the described Si-H containing iodosilane on the substrate via a deposition process to deposit a Si-containing layer. It includes generating.

The described method also provides for creating a dissimilar metal-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 to 4 and , M is Ta, Nb, V, Hf, Zr, Ti, Al, B, C, P, As, Ge, lanthanide (for example Er), or a combination thereof.

The described method of creating a silicon-containing layer on a substrate may be useful in the fabrication of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices. The described Si-H containing iodosilanes can deposit Si-containing films 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), atmospheric pressure CVD (SACVD) or atmospheric pressure CVD (APCVD), flowable CVD (f-CVD), metals Organic chemical vapor deposition (MOCVD), hot-wire CVD (HWCVD, also known as cat-CVD, hot wire serves as an energy source for the deposition process), radically introduced CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), space isolation ALD, hot-wire ALD (HWALD), radically introduced ALD, and combinations thereof. Supercritical fluid deposition can also be used. The deposition method is preferably ALD, spatial ALD, or PE-ALD to provide suitable step coverage and film thickness control.

Vapor of the Si-containing film forming composition is introduced into the reaction chamber including the substrate. The temperature and pressure in the reaction chamber and the temperature of the substrate are maintained at conditions suitable for vapor deposition of at least a portion of the Si-H containing iodosilane onto the substrate. In other words, after introduction of the vaporized composition into the chamber, the conditions in the chamber allow at least a portion of the vaporized precursor to be deposited on the substrate to produce a silicon-containing film. Co-reactants can also be used to assist in the formation of Si-containing layers.

The reaction chamber may be any enclosure or chamber of the device in which the deposition method takes place, for example, but not limited to, parallel plate type reactor, cooling wall type reactor, hot wall type reactor, single-wafer reactor, multi-wafer Reactor, or other such type of deposition system. All of these exemplary reaction chambers can serve as ALD reaction chambers. The reaction chamber may be maintained at a pressure in the range of about 0.5 mTorr to about 760 Torr. Additionally, the temperature in the reaction chamber may range from about 20 ° C to about 700 ° C. Those skilled in the art will appreciate that the temperature can be optimized through simple experiments to achieve the desired result.

The temperature of the reactor can be controlled by either adjusting the temperature of the substrate holder or adjusting the temperature of the reactor walls. Devices used to heat the substrate are known in the art. The reactor wall is heated at a sufficient growth rate and to a temperature sufficient to obtain the desired film with the desired physical state and composition. Non-limiting exemplary temperature ranges in which the reactor walls can be heated include from about 20 ° C to about 700 ° C. When a plasma deposition process is used, the deposition temperature may range from about 20 ° C to about 550 ° C. Alternatively, when the thermal process is performed, the deposition temperature may range from about 300 ° C to about 700 ° C.

Alternatively, the substrate can be heated to a sufficient temperature to obtain a desired silicon-containing film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges in which the substrate can be heated include 150 ° C to 700 ° C. Preferably, the temperature of the substrate is maintained at 500 ° C. or less.

The type of substrate on which the silicon-containing film is deposited will depend on the intended end use. The substrate is generally defined as the material on which the process is performed. The substrate may be any suitable substrate used in semiconductor, photovoltaic, flat panel, or LCD-TFT device fabrication. Examples of suitable substrates include wafers such as silicon, silica, glass, Ge, or GaAs wafers. The wafer may have one or more layers of different materials deposited on the layers from previous fabrication steps. For example, the wafer may include a silicon layer (crystalline, amorphous, porous, etc.), silicon oxide layer, silicon nitride layer, silicon oxynitride layer, carbon doped silicon oxide (SiCOH) layer, or a combination thereof. have. In addition, the wafer may include a copper layer, a tungsten layer or a metal layer (eg, platinum, palladium, nickel, rhodium, or gold). The wafer may include a barrier layer such as manganese, manganese oxide, tantalum, tantalum nitride, and the like. The layer can be flat or patterned. In some embodiments, the substrate can be coated with a patterned photoresist film. In some embodiments, the substrate is a dielectric material (eg, ZrO ₂ based material, HfO ₂ based material, TiO ₂ based material, rare earth oxide based material, tertiary oxide based material, etc.) in MIM, DRAM, or FeRam technology. Or a layer of oxide used from a nitride-based film (eg, TaN) used as an electromigration barrier and adhesive layer between the copper and low-k layers. The described process can deposit the silicon-containing layer directly on the wafer or directly on one or more layers (when the patterned layer forms a substrate) on top of the wafer. Those skilled in the art will also recognize that the term "film" or "layer" as used herein refers to the thickness of some material provided on or sprayed on a surface, and that the surface may be a trench or a line. Throughout the specification and claims, a wafer and any related layers thereon are referred to as a substrate. The actual substrate used may also depend on the specific precursor implementation used. In many cases, preferred substrates to be used will be selected from hydrogenated carbon, TiN, SRO, Ru, and Si type substrates, such as polysilicon or crystalline silicon substrates.

The substrate may be patterned to include vias or trenches having a high aspect ratio. For example, a conformal Si-containing film, such as SiO _2, may employ any ALD technique on a through silicon via (TSV) having an aspect ratio ranging from approximately 20: 1 to approximately 100: 1. Can be deposited using.

The Si-containing film forming composition may be supplied in neat state. Alternatively, the Si-containing film forming composition may further comprise a solvent suitable for use in vapor deposition. The solvent may be selected from among other C ₁ -C ₁₆ saturated or unsaturated hydrocarbons.

For vapor deposition, the Si-containing film forming composition is introduced into the reactor in vapor form by conventional means, such as tubing and / or flow meters. The vapor form is a conventional vaporization step, for example by direct liquid injection, direct vapor withdrawal in the absence of carrier gas, by bubbling the carrier gas through the liquid, thereby evaporating the vapor in the carrier gas without bubbling through the liquid, Or when the precursor is solid at room temperature, it may be formed by vaporizing the Si-containing film forming composition by using a sublimer such as that described in PCT Publication No. WO2009 / 087609 (Xu et al.). The Si-containing film forming composition can be supplied in the liquid state to the vaporizer (direct liquid injection), where it is vaporized and mixed with the carrier gas, which is then introduced into the reactor. Alternatively, the Si-containing film forming composition may be vaporized by passing the carrier gas into a container containing the composition, or by bubbling the carrier gas into the composition. The carrier gas may include, but is not limited to, Ar, He, or N ₂ , and mixtures thereof. The carrier gas and the composition are then introduced into the reactor as steam.

The Si-containing film forming composition may be delivered to the reactor or vapor deposition chamber by the Si-containing film forming composition delivery device of FIGS. 3 to 5, and FIGS. 3 to 5 illustrate three of the Si-containing film forming composition delivery devices. Four exemplary embodiments are shown. As discussed in detail above and illustrated in the examples below, the delivery device should be made of a material that is clean and dry and that does not react with the Si containing film forming composition.

3 is a side view of one embodiment of a Si-containing film forming composition reactant delivery device 101. In FIG. 3 , the described Si-containing film forming composition 110 is contained within a container 200 having two conduits, an inlet conduit 300 and an outlet conduit 400. One of ordinary skill in the art of reactants will know that the container 200, the inlet conduit 300, and the outlet conduit 400 may prevent the release of the Si-containing film forming composition 110 in gaseous form even at elevated temperatures and pressures. It will be recognized.

The outlet conduit 400 of the delivery device 101 is fluidly connected via a valve 700 to a reactor (not shown) or other component between the delivery device and the reactor, such as a gas cabinet. Preferably, container 200, inlet conduit 300, valve 600, outlet conduit 400, and valve 700 are made of passivated 316L EP or 304 passivated stainless steel. However, one skilled in the art will recognize that other non-reactive substances may also be used in the teachings herein.

In FIG. 3 , the end 800 of the inlet conduit 300 is positioned over the surface of the Si-containing film forming composition 110, and the end 900 of the outlet conduit 400 is the Si-containing film forming composition 110. Is located below the surface of the. In this embodiment, the Si-containing film forming composition 110 is preferably in liquid form. Inert gases, including but not limited to nitrogen, argon, helium, and mixtures thereof, may be introduced into inlet conduit 300. The inert gas compresses the delivery device 200 such that the liquid Si-containing film forming composition 110 is pressurized through the outlet conduit 400 and into the reactor (not shown). The reactor vaporizes the liquid Si-containing film forming composition 110 with or without a carrier gas such as helium, argon, nitrogen or a mixture thereof to deliver vapor to the substrate on which the film is formed. It may include a vaporizer to convert to. Alternatively, the liquid Si-containing film forming composition 110 may be delivered directly to the wafer surface as a jet or aerosol.

4 is a side view of a second embodiment of a Si-containing film forming composition delivery device 101. In FIG. 4 , the end 800 of the inlet conduit 300 is positioned below the surface of the Si-containing film forming composition 110, and the end 900 of the outlet conduit 400 is the Si-containing film forming composition 110. ) Is located on the surface. 4 also includes an optional heating element 140, which may increase the temperature of the Si-containing film forming composition 110. In such embodiments, the Si-containing film forming composition 110 may be in solid or liquid form. Inert gases, including but not limited to nitrogen, argon, helium, and mixtures thereof, are introduced into inlet conduit 300. The inert gas is bubbled through the Si-containing film forming composition 110 and conveys a mixture of the inert gas and vaporized Si-containing film forming composition 110 to the outlet conduit 400 and onto the reactor.

3 and 4 include a valve 600 and a valve 700. Those skilled in the art will appreciate that valve 600 and valve 700 may be disposed in an open position or a closed position to allow flow through conduit 300 and conduit 400, respectively. The simpler delivery device having a delivery device 101 in FIGS. 3 and 4 , or a single conduit terminating on the surface of any solid or liquid present, is when the Si-containing film forming composition 110 is in vapor form. Or when sufficient vapor pressure is present on the solid / liquid phase. In this case, the Si-containing film forming composition 110 is delivered in vapor form through conduit 300 or conduit 400 by simply opening valve 600 in FIG. 3 or valve 700 in FIG. 4 . . The delivery device 101 may be maintained at a temperature suitable to provide sufficient vapor pressure for delivering the Si-containing film forming composition 110 in vapor form, for example, by the use of the optional heating member 140.

Although FIGS. 3 and 4 describe two embodiments of the Si-containing film forming composition delivery device 101, those skilled in the art will recognize that both the inlet conduit 300 and the outlet conduit 400 are also outside the description herein. It will be appreciated that it may be located above or below the surface of the Si-containing film forming composition 110 without. Inlet conduit 300 may also be a charging port.

The vapor of the Si-containing film forming composition in solid form can be delivered to the reactor using a sublimer. 5 illustrates one implementation of an example sublimer 100. Sublimer 100 includes a container 33. The container 33 may be a cylindrical container or, alternatively, may be any shape, without limitation. Container 33 is comprised of materials such as, but not limited to, passivated stainless steel, aluminum oxide, glass, and other chemically compatible materials. In certain cases, the container 33 is composed of, but is not limited to, other metals or metal alloys. In certain cases, the container 33 has an inner diameter of about 8 centimeters to about 55 centimeters, and, alternatively, an inner diameter of about 8 centimeters to about 30 centimeters. As will be appreciated by those skilled in the art, alternative configurations may have different dimensions.

The container 33 includes a sealable top 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. In addition, the sealable top 15 is configured for passage of conduits to the container 33. Alternatively, the sealable top 15 is configured to enable fluid flow to the container 33. The sealable top 15 is configured to receive and pass through a conduit comprising a dip tube 92 to be in fluid in contact with the container 33. The dip tube 92 with the regulating valve 90 and the fitting 95 is configured to flow the carrier gas into the container 33. In certain cases, dip tube 92 extends below the central axis of container 33. In addition, the sealable top 15 is configured to receive and pass the conduit comprising the outlet tube 12. The vapor of the carrier gas and the Si-containing film forming composition is removed from the container 33 through the outlet tube 12. The outlet tube 12 includes a control valve 10 and a fitting 5. In certain cases, the outlet tube 12 is fluidly coupled to the gas delivery manifold to direct carrier gas from the sublimer 100 to the reactor.

The container 33 and the sealable top 15 are sealed by at least two sealing members 18, alternatively by at least about four sealing members. In certain cases, the sealable top 15 is sealed to the container 33 by at least about eight sealing members 18. As will be appreciated by those skilled in the art, the sealing member 18 releasably couples the sealable top 15 to the container 33 and includes a gas resistant seal with a gasket 20. To form. The sealing member 18 may comprise any suitable means known to those skilled in the art for sealing the container 33. In certain cases, the sealing member 18 comprises a thumbscrew.

As illustrated in FIG . 5 , the container 33 further comprises at least one disk disposed therein. The disk includes a shelf, or a horizontal support, for a solid material. In certain embodiments, the disk 30 includes an outer diameter or circumference that is less than the inner diameter or circumference of the container 33 such that the inner disk 30 is annularly disposed within the container 33 to form an opening 31. do. The outer disk 86 is arranged circumferentially within the container 33 such that the disk 86 includes an outer diameter or circumference that is the same, approximately the same, or generally coincides with the inner diameter of the container 33. The outer disk 86 forms an opening 87 disposed in the center of the disk. The plurality of disks is disposed in the container 33. The disks are stacked in an alternating manner, where the inner disks 30, 34, 36, 44 are stacked vertically in a container with alternating outer disks 62, 78, 82, 86. In an embodiment, the inner disks 30, 34, 36, 44 extend annularly outwardly and the outer disks 62, 78, 82, 86 extend annularly towards the center of the container 33. As illustrated in the embodiment of FIG. 5 , the inner disks 30, 34, 36, 44 are not in physical contact with the outer disks 62, 78, 82, 86.

Assembled sublimer 100 includes aligned and coupled support legs 50, inner passages 51, concentric walls 40, 41, 42, and concentric slots 47, 48, 49. It includes an internal disk (30, 34, 36, 44) comprising a. The inner disks 30, 34, 36, 44 are stacked vertically and oriented annularly around the dip tube 92. In addition, the sublimer includes external disks 62, 78, 82, 86. As illustrated in FIG. 5, the outer disks 62, 78, 82, 86 are connected to the container 33 for good contact for conducting heat from the container 33 to the disks 62, 78, 82, 86. It should fit snugly. Preferably, the outer disks 62, 78, 82, 86 are coupled to or in physical contact with the inner wall of the container 33.

As illustrated, the outer disks 62, 78, 82, 86 and the inner disks 30, 34, 36, 44 are stacked inside the container 33. When assembled to the container 33 to form the sublimer 100, the inner disks 30, 34, 36, 44 are external gas passages between the assembled outer disks 62, 78, 82, 86. (31, 35, 37, 45). In addition, the outer disks 62, 78, 82, 86 form inner gas passages 56, 79, 83, 87 with support legs of the inner disks 30, 34, 36, 44. The walls 40, 41, 42 of the inner disks 30, 34, 36, 44 form grooved slots for holding solid precursors. The outer disks 62, 78, 82, 86 include walls 68, 69, 70 for holding solid precursors. During assembly, the solid precursor is annular slots 47, 48, 49 of the inner disks 30, 34, 36, 44, and annular slots 64, 65, 66 of the outer disks 62, 78, 82, 86. Is loaded.

Solid powder and / or granular particles of size less than about 1 centimeter, alternatively less than about 0.5 centimeter, and alternatively less than about 0.1 centimeter, may be provided with annular slots 47, 48 of inner disks 30, 34, 36, 44. , 49, and annular slots 64, 65, 66 of the external disks 62, 78, 82, 86. The solid precursor is loaded into the annular slot of each disk by any method suitable for uniform distribution of solids in the annular slot. Suitable methods include, but are not limited to, direct pour, scoop use, funnel use, automated measured delivery, and pressurized delivery. Depending on the chemistry of the solid precursor material, loading may be performed in a sealed environment. In addition, an inert gas atmosphere and / or pressurization in the sealed box can be implemented for such toxic, volatile, oxidizable, and / or air sensitive solids. Each disc may be loaded after setting the disc in the container 33. A more preferred procedure is to load the solid before setting the disc in the container 33. The total weight of the solid precursor loaded into the sublimer can be recorded by metering the sublimator before and after the loading process. In addition, spent solid precursors can be calculated by metering the sublimer after the vaporization and deposition process.

The dip tube 92 with the regulating valve 90 and the fitting 95 is positioned in the central passage 51 of the aligned and joined support legs of the inner disks 30, 34, 36, 44. Accordingly, the dip tube 92 travels vertically toward the lower portion 58 of the container 33 through the inner passage 51. The dip tube end 55 is disposed proximal to the bottom 58 of the container at or above the gas window 52. The gas window 52 is disposed in the lower inner disk 44. Gas window 52 is configured to enable carrier gas flow out of dip tube 92. In the assembled sublimer 100, the gas passage 59 is formed by the lower surface 58 of the container 33 and the lower inner disk 44. In certain cases, the gas passage 59 is configured to heat the carrier gas.

In operation, the carrier gas is preheated prior to introduction into the container 33 via the dip tube 92. Alternatively, the carrier gas can be heated, during which it flows through the gas passage 59 by the lower surface 58. Bottom surface 58 is thermally coupled and / or heated by an external heater, consistent with the teachings herein. The carrier gas then passes into the gas passage 45 formed by the outer wall 42 of the inner disk 44 and the outer wall 61 of the outer disk 62. The gas passage 45 leads to the top of the inner disk 44. The carrier gas flows continuously over the top of the solid precursor loaded in the annular slots 47, 48, and 49. Sublimed solid vapor from annular slots 47, 48, 49 is mixed with the carrier gas and flows vertically upwards through container 33.

Although FIG. 5 describes one embodiment of a sublimer capable of delivering vapor of any solid Si-containing film forming composition to the reactor, those skilled in the art will appreciate that other sublimer designs may also be suitable without departing from the teachings herein. It will be recognized. Finally, those skilled in the art will appreciate that the described Si-containing film forming compositions may be transferred to a semiconductor processing tool using other delivery devices such as ampoules described in WO 2006/059187 (Jurcik et al.) Without departing from the teachings herein. It will be appreciated.

If desired, the Si-containing film forming composition delivery device of FIGS. 3-5 may be heated to a temperature such that the Si-containing film forming composition is present in its liquid phase and has sufficient vapor pressure. The delivery device may be maintained at a temperature in the range of 0 to 150 ° C., for example. 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 vaporized Si-containing film forming composition.

In addition to the compositions described, reactant gases may also be introduced into the reactor. The reaction gas may be an oxidizing agent such as O ₂ ; O ₃ ; H ₂ O; H ₂ O ₂ ; Oxygen containing radicals such as O. or OH .; NO; NO ₂ ; Carboxylic acids such as formic acid, acetic acid, propionic acid; Radical species of NO, NO ₂ , or carboxylic acid; Para-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, for example O · or OH ·, and mixtures thereof. Preferably, when the ALD process is performed, the co-reactant is plasma treated oxygen, ozone, or a combination thereof. When oxidizing gas is used, the resulting silicon containing film will also contain oxygen.

Alternatively, the reaction gas may be H ₂ , NH ₃ , (SiH ₃ ) ₃ N, hydridosilane (eg, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , Si ₅ H ₁₀ , Si ₆ H ₁₂ ), chlorosilanes and chloropolysilanes (eg, SiHCl ₃ , SiH ₂ Cl ₂ , SiH ₃ Cl, Si ₂ Cl ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ ), alkylsilanes (eg For example, Me ₂ SiH ₂ , Et ₂ SiH ₂ , MeSiH ₃ , EtSiH ₃ ), hydrazine (eg, N ₂ H ₄ , MeHNNH ₂ , MeHNNHMe), organic amines (eg, NMeH ₂ , NEtH ₂ , NMe ₂ H, NEt ₂ H, NMe ₃ , NEt ₃ , (SiMe ₃ ) ₂ NH), diamines such as ethylene diamine, dimethylethylene diamine, tetramethylethylene diamine, pyrazoline, pyridine, B-containing molecules ( For example, B ₂ H ₆ , trimethylboron, triethylboron, borazine, substituted borazine, dialkyl aminoborane), alkyl metals (eg, trimethylaluminum, triethylaluminum, methylzinc, diethylzinc ), Radical species thereof, or mixtures thereof. When H ₂ or inorganic Si containing gas is used, the silicon containing film obtained may be pure Si.

Alternatively, the reaction gas may be a fluorinated or unsaturated, linear, branched or cyclic hydrocarbon such as, but not limited to, ethylene, acetylene, propylene, isoprene, cyclohexane, cyclohexene, cyclohexadiene, pentene, pentine, Cyclopentane, butadiene, cyclobutane, terpinene, octane, or combinations thereof.

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

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

The Si-containing film forming composition and one or more co-reactants may be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations. For example, the vapor of the Si-containing film forming composition may be introduced in one pulse and two additional metal sources may be introduced together in a separate pulse (modified atomic layer deposition). Alternatively, the reaction chamber may already contain a co-reactant prior to the introduction of the Si-containing film forming composition. The co-reactant can be passed into the plasma system remotely from the reaction chamber, or from the reaction chamber, and can be broken down into radicals. Alternatively, the Si-containing film forming composition can be introduced continuously into the reaction chamber and other precursors or reactants are introduced by pulses (pulsed chemical vapor deposition). In another alternative, the Si-containing film forming composition and one or more co-reactants can be sprayed simultaneously from the shower head, and susceptors are held (spatial ALD) to hold several wafers under the shower head.

In one non-limiting exemplary atomic layer deposition process, the vapor phase of the Si-containing film forming composition is introduced into the reaction chamber, where it is in contact with a suitable substrate. Excess composition may 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 Si-H containing iodosilane adsorbed in a self-limiting manner. Any excess oxygen source is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the desired film is a silicon oxide film, this two-step process may provide the desired film thickness or may be repeated until a film having the required thickness is obtained.

Alternatively, the desired film may be a silicon metal / metalloid oxide film (ie, SiMO _x , where x may be 0 to 4 and M is B, Zr, Hf, Ti, Nb, V, Ta, Al, Si , Ga, Ge, or a combination thereof, after the two-step process, vapor of the metal- or metalloid-containing precursor can be introduced into the reaction chamber. The metal- or metalloid-containing precursor will be selected based on the properties of the silicon metal / metalloid oxide film to be deposited. After introduction into the reaction chamber, the metal- or metalloid-containing precursor is in 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. Once again, an oxygen source can be introduced into the reaction chamber to react with the metal- or metalloid-containing precursor. Excess oxygen source is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the desired film thickness has been achieved, the process can be terminated. However, if thicker films are desired, the entire four-step process can be repeated. By alternating the provision of the Si-containing film forming composition, the metal- or metalloid-containing precursor, and the oxygen source, a film of the desired composition and thickness can be deposited.

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

Silicon-containing films obtained from the processes discussed above 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, depending on the course of the oxidation state of M. Those skilled in the art will recognize that the desired film composition can be obtained by judicial selection of suitable Si-containing film forming compositions and co-reactants.

In obtaining the desired film thickness, the film can be subjected to further processing such as thermal annealing, furnace annealing, high speed thermal annealing, UV or e-beam curing, and / or plasma gas exposure. Those skilled in the art recognize the systems and methods used to perform these additional processing steps. For example, the silicon-containing film is exposed to a temperature in the range of about 200 ° C. to about 1000 ° C. for a time ranging from about 0.1 seconds to about 7200 seconds under an inert atmosphere, H-containing atmosphere, N-containing atmosphere, or a combination thereof. Can be. Most preferably, the temperature is 600 ° C. for less than 3600 seconds. Even more preferably, the temperature is below 400 ° C. The annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate can be removed from the reaction chamber and the annealing / flash annealing process is performed in a separate apparatus. Any of these post-treatment methods, in particular UV-curing, have been found to be effective for improving the connectivity and crosslinking of the membrane and for reducing the H content of the membrane when the membrane is a SiN containing membrane. Typically, a combination of thermal annealing and UV curing below 400 ° C. (preferably between about 100 ° C. and 300 ° C.) is used to obtain the film with the highest density.

Example

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

Example 1: 9.56 g (33.7 mmol) dry lithium iodide powder (Sigma Aldrich, 99 +%) in a 250 mL, three-necked (24/40) European style flask with PTFE-coated magnetic stir bar and Filled with 80 mL of anhydrous chloroform. Dichlorosilane (8.4 g; 83.2 mmol, excess) ("DCS") was added to the reaction flask through the headspace, during which the mixture was stirred. Immediate color change was observed (bright violet color). The temperature increased from about 22 ° C. to 29 ° C. during the DSC exposure. The mixture was stirred at ambient temperature for an additional 18 hours. The appearance of the solid changed from a dense morphology with a beige color to white finely divided powder. The mass of solids decreased over this time. The solid was filtered off and dried under vacuum (2.75 g collected; 3.0 g calculated). The solvent was removed under static vacuum by condensation to a cold trap in liquid nitrogen. The remaining purple liquid was weighed (4.54 g; 10.0 g calculated; 45%) and analyzed by GCMS (80.5% SiH ₂ I ₂ ("DIS"), the remaining balance being higher boiling compound). Although the calculated product yield is unreliable due to the sample size and the means by which chloroform has been removed, this example shows a successful halide exchange to produce the DIS product.

Example 2: A similar reaction was performed using the same setup and reagent load as described in Example 1, except using toluene instead of chloroform. GC sample analysis of liquid (no additional workup) shows that DIS is the main product (no solvent) and some are DCS, and ClSiH ₂ I.

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

Example 4: Sodium iodide powder (10.61 g; granular, colorless, crystalline solid) was exposed to excess DCS under static vacuum in a 50 cc Schrank tube without visual signs of reaction. No pressure change was observed. Thereafter, DCS is condensed in the Schrank tube, thawed to ambient temperature several times, and shows no signs of reagent volume loss, color or pressure change (no reaction). The reaction with sodium iodide is likely to require solvents with some solubility (ie methylene chloride, chloroform, acetonitrile, etc.). Lithium iodide is clearly more reactive and preferred. This example shows that the NaI alkali metal halide reactant is not as reactive as LiI.

Example 5: 530 g product scale in pentane solvent: Fill a 2 L, three necked round bottom (RB) flask with PTFE coated stir bar with 500 g of dry LiI (3.74 mol; Acros Organics, 99%), Filled with anhydrous n -pentane to 1 L mark. Most of the headspace nitrogen was removed in vacuo (up to approximately 600 torr pressure) and excess DCS (492 g; 4.87 mol; 2.8 x mol excess) was added to the flask through the headspace. The flask was periodically cooled to 5-8 ° C. to enable full delivery. Since the solid is too heavy, stirring was not achieved using a stir plate / stirring rod. The mixture was stirred by frequently shaking / swirling the pot manually. The flask was allowed to stand overnight at room temperature, leaving on a magnetic stirrer. Agitation was not achieved. The solid was filtered off and dried under vacuum (169 g recovered; 158 g calculated). The light pink filtrate was distilled to remove pentane (bp = 36 ° C.). Together with the receiver cooled in dry ice pellets, the remaining colorless liquid was distilled under reduced pressure ( ca. 0 to 5 torr / 21 to 31 ° C.). This left little residual liquid in the distillation pot and resulted in a colorless frozen solid in the collector. The solid product was thawed and weighed (350 g; 530 g calculated; 65%). Gas chromatography / mass spectroscopy analysis showed 91% with small amounts of DCS (0.964%), pentane (0.326%), ClSiH ₂ I (4.953%), and perchlorinated / ioiodized disiloxane compounds with impurities found experimentally (Area Percentage) Pure DIS is shown (see FIG. 6 ).

The possible presence of siloxane-type impurities found in Example 5 indicates that these compounds are formed by moisture derived from one or more of the following:

Surface moisture (no possibility) from glass reactors / distillation systems.

● from air leaks into the system.

Moisture in the lithium iodide starting material (reasonable possibility). It may also include some level of lithium hydroxide.

• Moisture from fully optimized sample preparation and manipulation for GC analysis (completely possible).

This underscores the importance of careful measurement to remove any possible source of moisture throughout the process. Nevertheless, these siloxane impurities appear to be easily separable from the main product based on their GC elution time.

Example 6 530 g Product Scale in Pentane Solvent: A 2 L, 3-necked RB flask equipped with a mechanical stirrer, a cooling cup condenser and a 1/4 "PTFE sparging tube was charged with 500 g of dry LiI (3.74 mol; Acros Organics, 99). %) And anhydrous n-pentane up to the 1 L mark Dichlorosilane (183 g; 1.81 mol) was added below the surface over the course of 22 minutes with the temperature rising from 18.1 (cold pentane) to 31.0 ° C. The reaction mixture was stirred vigorously 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 Chromatography showed traces of DCS, pentane, ClSiH ₂ I partially substituted intermediates and DIS are shown The area percentages of ClSiH ₂ I and DIS are 6% and 13.5%, respectively The reaction mixture is stirred for an additional 18 hours The solid is then filtered and dried under vacuum (226 g collected, 158 g Calculated)) Solvent and lower boiling impurities were removed by distillation, crude DIS (by GC, 320 g, 89%) was obtained (about 62%). It is shown that altering the stoichiometric ratio of the reactants results in similar yields.

Example 7: 500 g of LiI (3.74 mole; 99.9% City Chemical, colorless powder) was charged to a 2 L, three necked RB flask equipped with a mechanical stirrer. A cold cup condenser and internal thermocouple were attached to the reactor. Approximately 800 mL of anhydrous chloroform was added to the LiI powder. The condenser was cooled to −78 ° C. and with stirring, 196 g of dichlorosilane (1.94 mol, 3.5 mol% excess) was added at 15 min under reduced pressure through a condenser (-78 ° C. dry ice, isopropyl alcohol shake bath). . The pressure was 680 torr at 23 ° C. Additional nitrogen gas was added to the reactor at a pressure of 780 torr. The mixture was stirred for 22 hours, at which time it had a pink-purple color. The solid was filtered off and dried under vacuum. The filtrate was collected in a 1 L flask. Chloroform was distilled at 61 ° C. and the remaining purple liquid was collected and metered (148 g, 28%, crude DIS product after solvent removal). Low yields suggest that pure LiI is limited to low solubility in chloroform. Some hydrogenation levels of LiI reactants may promote salt reactivity and, together with higher siloxane-based impurities, enhance the formation of the product.

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. To the obtained mixture, TSA-Cl ((SiH ₃ ) ₂ N (SiH ₂ Cl), 25 g, 0.18 mol) was added dropwise at room temperature over 15 minutes. No exothermicity was observed. After stirring at ambient temperature for about 90 minutes, the reaction mixture was analyzed by GC-MS, which revealed 57% unreacted TSA-Cl and 39% TSA-I ((SiH ₃ ) ₂ N (SiH ₂ I)). ( FIG. 4 ). At this time, the reaction mixture was stirred overnight at room temperature. After overnight stirring, GC analysis led to a major peak corresponding to SiH ₃ -I, with peaks corresponding to TSA-Cl and TSA-I disappeared. Optimization of the reaction time is underway.

Example 9: Comparison of LI Particle Size

0.5 to 1 mm LI

A 20 L jacketed filter reactor equipped with a mechanical stirrer, condenser (adjusted to −70 ° C.), a solid addition port, an inlet tube for addition under the dichlorosilane surface, and an inlet for liquid pentane addition 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. Thereafter, the reactor was stirred at about 200 RPM and then, while under nitrogen atmosphere, lithium iodide (12.25 kg, 91.52 mol) was charged to the reactor. Subsequent gravimetric addition of dichlorosilane (4.52 kg, 44.75 mol) was controlled at a rate of approximately 1 kg per hour. After completing the DCS addition, the reactor jacket was kept at + 35 ° C. and the condenser was kept at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were drained through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L) to yield 7.19 kg of solid residue. The combined filtrates and washes were subsequently distilled at 88 kPa to afford crude diiodosilane (9.04 kg, 83% purity). Remaining material, DCS, 1.3%, if indicated by GC analysis; Pentane, 0.6%; SiH ₂ ClI, 14.1% and SiHI ₃ , 0.1%. If this crude material was further distilled at 3.2 kPa and presented by GC analysis, DIS, 99.6%; SiH ₃ I, 0.1%; SiH ₂ ClI, 0.1%; Diiodosilane (7.39 kg, 58% yield) was obtained, comprising SiHI ₃ , 0.15%, other, 0.12%.

1 to 1.25 mm LI

15 L new pentane (Sigma Aldrich, 99%) equipped with a 20 L jacketed filter reactor equipped with a mechanical stirrer, condenser (adjusted to -70 ° C), solid addition port, inlet tube for subchlorosilane addition and inlet for liquid pentane addition Excess purity). The temperature in the reactor jacket was adjusted to +35 ° C and the reactor condenser was adjusted to -70 ° C. Thereafter, the reactor was stirred at about 200 RPM, after which while lithium iodide (9.99 kg, 74.64 mol) was charged to the reactor while under nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (3.88 kg, 38.42 mol) was controlled at a rate of approximately 1 kg per hour. After completing the DCS addition, the reactor jacket was kept at + 35 ° C. and the condenser was kept at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were drained through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L) to yield 4.96 kg of solid residue. The combined filtrates and washes were subsequently distilled at 88 kPa to afford crude diiodosilane (8.01 kg, 86% purity). The remaining material was DCS, 0.1%, pentane, 1.2% when presented by GC analysis; SiH ₃ I, 0.1%, SiH ₂ ClI, 4.5% and SiHI ₃ , 0.1%. This crude material was further distilled at 3.2 kPa to give DIS, 99.7%; SiH ₃ I, 0.01%; Diiodosilane (8.16 kg, 77% yield) was obtained comprising SiH ₂ ClI, 0.03% and SiHI ₃ , 0.1%.

As can be seen, the particle size of lithium iodide affects the isolated yield. Surprisingly, improved yields are observed when larger particle size lithium iodide is used compared to smaller particle size.

Example 10 Effect of Solvent Recycling

Solvent recycling

A 20 L jacketed filter reactor was charged with 15 L pentane, equipped with a mechanical stirrer, condenser (controlled at -70 ° C.), a solid addition port, an inlet tube for addition under the surface of dichlorosilane, and an inlet for liquid pentane addition. The temperature in the reactor jacket was adjusted to +35 ° C and the reactor condenser was adjusted to -70 ° C. Thereafter, the reactor was stirred at about 200 RPM, after which while lithium iodide (12.34 kg, 92.19 mol) was subsequently charged to the reactor. Subsequent gravimetric addition of dichlorosilane (4.25 kg, 42.08 mol) was controlled at a rate of approximately 1 kg per hour. After completing the DCS addition, the reactor jacket was kept at + 35 ° C. and the condenser was kept at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were drained through a reactor filter into a 22 L round bottom flask. Thereafter, the salt on the reactor filter was washed with pentane (3 × 1 L). The combined filtrates and washes were subsequently distilled at 88 kPa to afford crude diiodosilane (9.26 kg, 82% purity) in a distillation pot. Distillate (11 L, nearly pentane, 82%; DCS, 12%; containing SiH ₂ ClI, 4% and DIS, 1%) was recycled back to the reactor for continuous synthesis.

Thus, a 20 L jacketed filter reactor equipped with the above-described mechanical stirrer, condenser (adjusted to -70 ° C.), a solid addition port, an inlet tube for addition under the surface of dichlorosilane and an inlet for distillate / pentane addition was introduced. 4 L) with recycled distillate from the previous production process (11 L, almost pentane, 82%; DCS, 12%; SiH ₂ ClI, 4% and DIS, 1%). The temperature in the reactor jacket was adjusted to +35 ° C and the reactor condenser was adjusted to -70 ° C. Thereafter, the reactor was stirred at about 200 RPM and then lithium iodide (12.38 kg, 92.49 mol) was then charged to the reactor while under nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.17 kg, 41.28 mol) was controlled at a rate of approximately 1 kg per hour. After completing the DCS addition, the reactor jacket was kept at + 35 ° C. and the condenser was kept at -70 ° C. After stirring for 17 hours, stirring was stopped and the reactor contents were drained through a reactor filter into a 22 L round bottom flask. Thereafter, the salt on the reactor filter was washed with pentane (3 × 1 L). The combined filtrates and washes were subsequently distilled at 88 kPa to give crude diiodosilane (8.77 kg, 84% purity) as a distillation bottom in the distillation pot. This crude material was further distilled at 3.2 kPa to give DIS, 99.5%; SiH ₃ I, 0.14%; Diiodosilane (7.29 kg, 62% yield) was obtained comprising SiHI ₃ , 0.24%, other, 0.12%.

Fresh solvent

15 L new pentane (Sigma Aldrich, 99%) equipped with a 20 L jacketed filter reactor equipped with a mechanical stirrer, condenser (adjusted to -70 ° C), solid addition port, inlet tube for subchlorosilane addition and inlet for liquid pentane addition Excess purity). The temperature in the reactor jacket was adjusted to +35 ° C and the reactor condenser was adjusted to -70 ° C. Thereafter, the reactor was stirred at about 200 RPM, after which while lithium iodide (12.47 kg, 93.16 mol) was charged to the reactor while under nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.85 kg, 48.02 mol) was controlled at a rate of approximately 1 kg per hour. After completing the DCS addition, the reactor jacket was kept at + 35 ° C. and the condenser was kept at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were drained through a reactor filter into a 22 L round bottom flask. Thereafter, the salt on the reactor filter was washed with pentane (3 × 1 L). The combined filtrates and washes were subsequently distilled at 88 kPa to afford crude diiodosilane (8.01 kg, 86% purity). This crude material was further distilled at 3.2 kPa to give DIS, 99.9%; Diiodosilane (6.68 kg, 51% yield) was obtained comprising SiH ₃ I, 0.01% and SiHI ₃ , 0.02%.

As can be seen, recycling often offers advantages in terms of economic and environmental benefits, while often simplifying compliance, but impurities may accumulate. The removal of the recycle step and the use of fresh solvent charge for each synthesis process results in ultra high product purity levels that may not be achieved after solvent recycling.

Example 11: Material Compatibility

A small piece of material was immersed in SiH ₂ I ₂ (synthesized according to the method described in US Patent Application Publication No. 2016/0264426), sealed in a glass pressure tube, and described at the temperature described in the absence of light. Kept for hours. The initial control assay was 96.9% SiH ₂ I ₂ , with 1.3% SiH (Me) I ₂ and 1.6% SiHI ₃ , based on GCMS peak integration. The results are provided below and indicate that it is difficult to maintain the stability of SiH ₂ I ₂ . Applicants believe that the HX or X ₂ reactants used in such synthetic methods contribute to the instability of the SiH ₂ I ₂ reaction product shown in the control results below. As can be seen, some standard packaging materials further accelerate 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 ℃:

* 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 described herein were stored in a passivated stainless steel cylinder at room temperature. Before and after storage in the cylinders, the assay was performed using GCMS peak integration. The table below shows that this product maintains its purity without requiring any stabilizer.

Prophetic example: I ₃ Si -CH ₂ - SiI ₃ Synthesis of

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 was filled with lithium iodide and pentane or other suitable solvent, after which a solution of solventless liquid bis (trichlorosilyl) methane was added. The suspension was stirred vigorously until completion of the reaction was observed by the disappearance of bis (trichlorosilyl) methane in a GCMS trace of an aliquot of the reaction mixture. The resulting suspension was filtered over an intermediate glass frit loaded with a diatomaceous earth pad to obtain a pentane solution of the desired product. Bis (triiodosilyl) methane product was isolated in pure form by distillation under reduced pressure and / or sublimation.

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

While embodiments of the invention have been shown and described, variations thereof can be made by those skilled in the art without departing from the spirit or teaching of the invention. The embodiments described herein are merely illustrative and not restrictive. Many variations and modifications of the compositions and methods are possible and are within the scope of the present invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is limited by the following claims, which will include all equivalents of the subject matter of the claims.

Claims (16)

As a method of synthesizing Si-H-containing iodosilane having the formula:
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 , where X is Cl or Br and w, x, y, z a, b, c, m, n, and o is a halosilane reactant having the formula MI, wherein M is Li, Na, K, Rb, or Cs. Reacting with a halide reactant to produce a mixture of MX having formula (1), formula (2) or formula (3); And
Separating the Si-H containing iodosilane 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 from the mixture How to include:
[Formula 1]
Si _w H _x R _y I _z
[Formula 2]
N (SiH _a R _b I _c ) ₃ or
[Formula 3]
(SiH _m R _n I _o ) ₂ -CH ₂
Wherein w is 1 to 3, x + y + z is 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 is 3, provided that 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 is 3, At least one m and at least one o is 1 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 , Each R 'is independently H or a C1 to C12 hydrocarbyl group. The method of claim 1 wherein M is Li. The method of claim 1, further comprising adding a non-coordinating solvent to the reaction step. The method of claim 3, wherein the non-coordinating solvent is at least one selected from the group consisting of propane, butane, pentane, hexane, heptane, chloromethane, dichloromethane, chloroform, carbon tetrachloride, methylene chloride, and acetonitrile. The Si-H-containing iodosilane according to any one of claims 1 to 4, wherein the separation step filters the mixture to have a formula Si _w H _x R _y I _z or N (SiH _a R _b I _c ) ₃ . Separating the MX from the. 5. The method of claim 1, wherein the alkali metal halide reactant is LiI. 6. The method of claim 1, wherein the halosilane reactant is SiH ₂ Cl ₂ . The method of claim 1, wherein the halosilane reactant is Si ₂ HCl ₅ . The method of claim 1, wherein the halosilane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl). Formula Si _w H _x I _z or N (SiH _a I _c ) ₃ where w is 1 to 3, x + z is 2w + 2, x is 1 to 2w + 1 and z is 1 to 2w + 1, each a is independently 0 to 3, each c is independently 0 to 3, a + c is 3, provided that at least one a is 1 and at least one c is 1) As a method of synthesizing Si-H-containing iodosilane having
Halosilane reactants having the formula Si _w H _y X _z or N (SiH _a X _c ) ₃ , where X is Cl or Br and w, x, z, a, and c are as defined above; Mixing with an alkali metal halide reactant having the formula MI, where M is Li, Na, K, Rb, or Cs, to produce a mixture of Si _w H _x I _z or N (SiH _a I _c ) ₃ and nMX step; And
Filtering the mixture to produce a Si—H containing iodosilane having the formula Si _w H _x I _z or N (SiH _a I _c ) ₃ . The method of claim 10, wherein the halosilane reactant is SiH ₂ Cl ₂ . The method of claim 10, wherein the halosilane reactant is Si ₂ HCl ₅ . The method of claim 10, wherein the halosilane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl). The process of claim 10, wherein the alkali metal halide reactant is LiI. A Si-containing film forming composition delivery device comprising a canister having an inlet conduit and an outlet conduit and containing a Si-containing film forming composition,
The Si-containing film forming composition comprises Si-H containing iodosilane and 0 ppbw to 100 ppbw Ag, Au, or Sb;
Si-containing film forming composition delivery device, wherein the Si-H containing iodosilane has the formula:
[Formula 1]
SiHI ₃
[Formula 2]
N (SiH _a R _b I _c ) ₃ or
[Formula 3]
(SiH _m R _n I _o ) ₂ -CH ₂
Wherein each a is independently 0 to 3, each b is independently 0 to 3, each c is independently 0 to 3, and a + b + c is 3, provided that 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, and m + n + o is Wherein at least one m and at least one o is 1 and each R is independently a C1 to C12 hydrocarbyl group, Cl, Br, or ER ' ₃ group, wherein each E is independently , Si or Ge, each R 'is independently H or a C1 to C12 hydrocarbyl group). The Si-containing film forming composition delivery device according to claim 15, wherein the Si-H containing iodosilane is SiHI ₃ .

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