SILICON-BASED SELF-ASSEMBLING MONOLAYER COMPOSITIONS AND SURFACE PREPARATION USING THE SAME

Abstract

Disclosed is a SAM forming composition comprising a SAM monomer or precursor having a backbone with a surface reactive group, wherein the backbone contains no Si—C bonds and is selected from the group consisting of a Si—C bond-free polysilane and a trisilylamine. The surface reactive groups are disclosed for the surface to be covered being a dielectric surface and a metal surface, respectively. A process of forming a SAM on a surface and a process of forming a film on the SAM are also disclosed.

Claims

1.-20. (canceled)

21. A film-forming process, the process comprising the steps of: preparing a surface on a substrate for exposure of the surface to a self-assembling monolayer (SAM) forming composition, the composition comprising a SAM precursor having a backbone with a surface reactive group X, wherein the backbone contains no Si—C bonds and is selected from the group consisting of a Si—C-free polysilane and a trisilylamine, wherein the surface reactive group X is selected from: a halide selected from Cl, Br, I; a cyanate, an isocyanate or a thiocyanate group; an amino group —NR.sup.1R.sup.2, wherein R.sup.1 is selected from H, a linear, branched or cyclic C.sub.1-C.sub.10 alkyl or alkenyl group or an alkyl silyl group; R.sup.2 is selected from a linear, branched or cyclic C.sub.2-C.sub.10 alkyl or alkenyl group, provided that R.sup.1═R.sup.2≠Et; or an alkyl silyl group; or R.sup.1 and R.sup.2 are bridged so that NR.sup.1R.sup.2 forms a cyclic ligand, provided that the cyclic ligand includes heteroatoms S, N or O; an amidinate group —R.sup.3—N—C(R.sup.4)═N—R.sup.5, wherein R.sup.3 and R.sup.5 are each independently selected from a C.sub.1 to C.sub.10 linear or branched alkyl or a trialkylsilyl; and R.sup.4 is selected from H, a C.sub.1 to C.sub.10 linear or branched alkyl; or a thiol —SH, a phosphonic acid or a carboxylic acid; exposing of the surface to the SAM forming composition; forming the SAM on the surface through a liquid or gas phase exposure; and growing a film on top of the SAM through a wet or dry deposition process using a film-forming precursor selected from a main group element, or a transition metal element selected from Ti, Ta, W, Mo, Nb, or V, a fluoride, a chloride, a bromide, an iodide, an oxychloride, an oxybromide, an oxyfluoride and combinations thereof.

22. The process of claim 1, wherein the film-forming precursor is selected from WF.sub.6, WOF.sub.4, WOCl.sub.4, WCl.sub.6, WCl.sub.5, MoCl.sub.5, MoOCl.sub.4, MoO.sub.2Cl.sub.2, TiCl.sub.4, TiBr.sub.4, TiI.sub.4, TaCl.sub.5, AlCl.sub.3, VCl.sub.4, NbCl.sub.5, BCl.sub.3, BBr.sub.3, GeCl.sub.4, GeBr.sub.4 or GeCl.sub.2, GeBr.sub.2 and combinations thereof.

23. The process of claim 1, wherein the dry deposition process is an ALD or CVD process.

24. The process of claim 1, wherein X is a dialkylamino group —NR.sup.1R.sup.2, wherein R.sup.1 is H, a C.sub.2 to C.sub.5 alkyl, and R.sup.2 is a C.sub.1 to C.sub.5 alkyl, provided that if R.sup.1═H, R.sup.2 is a C.sub.3 to C.sub.5 alkyl, and if R.sup.1 not H, R.sup.1 and R.sup.2 are identical.

25. The process of claim 1, wherein X is an amidinate group —NR.sup.3—C(R.sup.4)═N—R.sup.5 wherein R.sup.3 and R.sup.5 are each independently selected from Et, nPr, iPr, nBu, tBu, sBu, iBu; and R.sup.4 is H or Me.

26. The process of claim 1, wherein the Si—C-free polysilane backbone of the SAM precursor is selected from —SiH.sub.2—SiH.sub.3 or —SiH.sub.2—SiH.sub.2—SiH.sub.3.

27. The process of claim 1, wherein the SAM precursor having the Si—C-free polysilane backbone is selected from
X—(SiH.sub.2).sub.n—SiH.sub.3, wherein n=1 to 3,
X—(Si.sub.nH.sub.2n-1), wherein Si.sub.nH.sub.2n-1 refers to a cyclic hydridosilane backbone with n=5,6,7,
X—(SiH(SiH.sub.3).sub.2), or
X—SiH.sub.2—Si(SiH.sub.3).sub.3.

28. The process of claim 1, wherein the SAM precursor having the Si—C-free polysilane backbone is selected from NiPr.sub.2—(SiH.sub.2)—SiH.sub.3, NnBu.sub.2-(SiH.sub.2)—SiH.sub.3, NtBu.sub.2-(SiH.sub.2)—SiH.sub.3, NsBu.sub.2-(SiH.sub.2)—SiH.sub.3, NiBu.sub.2-(SiH.sub.2)—SiH.sub.3, NPen.sub.2-(SiH.sub.2)—SiH.sub.3, NnPr.sub.2—(SiH.sub.2).sub.2—SiH.sub.3, NiPr.sub.2—(SiH.sub.2).sub.2—SiH.sub.3, NnBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NtBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NsBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NiBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NsPen.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NHtBu-(SiH.sub.2).sub.2—SiH.sub.3, NHPen-(SiH.sub.2).sub.2—SiH.sub.3, NHsBu-(SiH.sub.2).sub.2—SiH.sub.3, NHiBu-(SiH.sub.2).sub.2—SiH.sub.3, NnPr.sub.2—(SiH.sub.2).sub.3—SiH.sub.3, NiPr.sub.2—(SiH.sub.2).sub.3—SiH.sub.3, NnBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NtBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NsBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NiBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NsPen.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NEt.sub.2-(SiH(SiH.sub.3).sub.2), NiPr.sub.2—(SiH(SiH.sub.3).sub.2), NnPr.sub.2—(SiH(SiH.sub.3).sub.2), NiBu.sub.2-(SiH(SiH.sub.3).sub.2), NtBu.sub.2-(SiH(SiH.sub.3).sub.2), NnBu.sub.2-(SiH(SiH.sub.3).sub.2), NsBu.sub.2-(SiH(SiH.sub.3).sub.2), NsPen.sub.2-(SiH(SiH.sub.3).sub.2), NHtBu-(SiH(SiH.sub.3).sub.2), NHnBu-(SiH(SiH.sub.3).sub.2), NHiBu-(SiH(SiH.sub.3).sub.2), or NHPen-(SiH(SiH.sub.3).sub.2).

29. The process of claim 1, wherein the SAM precursor having the trisilylamine backbone has a general formula
XR.sub.2Si—N(SiR.sub.3).sub.n(SiX′R.sub.2).sub.2-n, wherein n=1 or 2; R is selected from H or a C.sub.1 to C.sub.6 branched or linear alkyl; X′ has the same definition as X and is independent from X.

30. The process of claim 1, wherein the SAM precursor having the trisilylamine backbone is XH.sub.2Si—N(SiH.sub.3).sub.n(SiX′H.sub.2).sub.2-n or XR.sub.2Si—N(SiR.sub.3).sub.2.

31. The process of claim 1, wherein the SAM precursor having the trisilylamine backbone contains more than one N(—Si).sub.3 units and has backbones of (Si).sub.2N—Si—N(Si)(Si—X) or X—Si—N(Si)—Si—N(Si)(Si—X).

32. The process of claim 1, wherein the SAM precursor is (Diisopropylamine)trisilylamine ((CMe.sub.2).sub.2-N—SiH.sub.2—N—(SiH.sub.3).sub.2, TSA-N(CMe.sub.2).sub.2).

33. The process of claim 1, wherein the SAM precursor is Chlorotrisilylamine (SiH.sub.3).sub.2—N—SiH.sub.2Cl, TSA-Cl).

34. The process of claim 1, wherein the SAM precursor is amidinate (AMD, —R.sup.1HN(CR.sup.3)═NR.sup.2, ##STR00005##

35. The process of claim 1, wherein the SAM precursor is bi-disilylaminohalogensilane (BDSASi—X), wherein X═F, Cl, Br or I.

36. The process of claim 1, wherein the SAM precursor is Diisobutylamine)trisilane (DIBATS, (iBu).sub.2-N—SiH.sub.2—SiH.sub.2—SiH.sub.3).

37. The process of claim 1, wherein the SAM precursor is Amidinateneopentylsilane (NPS-AMD, C.sub.5H.sub.11—SiH.sub.2—R.sup.1HN(CR.sup.3)═NR.sup.2).

38. The process of claim 1, wherein the SAM precursor is Dialkylaminoneopentylsilane (NPS-NR.sup.4R.sup.5).

39. The process of claim 1, wherein the SAM precursor is Amidinatecyclohexylsilane (CHS-AMD).

40. The process of claim 1, wherein the SAM precursor is Dialkylaminocyclohexylsilane (CHS-NR.sup.4R.sup.5).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0134] For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements are given the same or analogous reference numbers and wherein:

[0135] FIG. 1 is spin-on deposited thin film residues aggregated in cluster when using HMDS as adhesion agent;

[0136] FIG. 2 is WCA results for the mono-amino trisilane (Si.sub.3H.sub.7—NR.sub.2, wherein R.sup.1 is a C.sub.2 to C.sub.5 alkyl) derivative;

[0137] FIG. 3 is WCA results for the monoamino-trisilylamine derivative (Si.sub.3H.sub.8N—NR.sub.2, wherein R.sup.1 is a C.sub.2 to C.sub.5 alkyl):

[0138] FIG. 4 is a spin-on deposition of thin film using (Diisobutylamine)trisilane (DIBATS) as adhesion agent;

[0139] FIG. 5 is a spin-on deposition of thin film using (Diisopropylamine) trisilylamine as adhesion agent; and

[0140] FIG. 6 is water contact angle (WCA) of vapor SiT SAM (DIBATS) treated SiO surface.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0141] Self-assembling monolayer (SAM) monomers having a Si-based tail or backbone (SiT-SAM) that contains no Si—C bonds, their syntheses, and their applications in surface preparations in film forming processes are disclosed.

[0142] The disclosed SiT-SAM monomers are described as a backbone with a surface reactive group (or head) (denoted as “X”).

[0143] When a surface to be covered is a dielectric surface, the surface reactive group “X” is reactive to a surface hydroxyl (—OH) group. In this case, X is selected from: [0144] a. a halide (Cl, Br, I); [0145] b. a cyanate, an isocyanate or a thiocyanate group; [0146] c. an amino group —NR.sup.1R.sup.2, wherein R.sup.1 is selected from H, a linear, branched or cyclic C.sub.1-C.sub.10 alkyl or alkenyl group or an alkyl silyl group; R.sup.2 is selected from a linear, branched or cyclic C.sub.2-C.sub.10 alkyl or alkenyl group, or an alkyl silyl group; or R.sup.1 and R.sup.2 are bridged so that NR.sup.1R.sup.2 forms a cyclic ligand, provided that the cyclic ligand includes heteroatoms S, N or O; or [0147] d. an amidinate group —R.sup.3—N—C(R.sup.4)═N—R.sup.5, wherein R.sup.3 and R.sup.5 are each independently selected from a C.sub.1 to C.sub.10 linear or branched alkyl or a trialkylsilyl; and R.sup.4 is selected from H, a C.sub.1 to C.sub.10 linear or branched alkyl.

[0148] Preferably, X is a dialkylamino group —NR.sup.1R.sup.2 wherein R.sup.1 is selected from H or a C.sub.2 to C.sub.5 alkyl; and R.sup.2 is a C.sub.1 to C.sub.5 alkyl. If R.sup.1═H, R.sup.2 is C.sub.3 or more, and if R.sup.1 not H, R.sup.1 and R.sup.2 are preferably identical. Preferably, X is an amidinate group —NR.sup.3—C(R.sup.4)═N—R.sup.5 wherein R.sup.3 and R.sup.5 are each independently selected from Et, nPr, iPr, nBu, tBu, sBu, iBu, and R.sup.4 is H, Me.

[0149] When a surface to be covered is a metal, the surface reactive head “X” is a thiol —SH group, phosphonic acid or carboxylic acid. For example, the thiol group reacts to the metal surface forming a sulfur-metal interface.

[0150] The disclosed SiT-SAM monomers are molecules suitable to form SAMs on a surface of a substrate in the film forming processes. The monomer backbones of the disclosed SiT-SAM monomers may be selected from the group consisting of (i) a Si—C-free polysilane, containing at least one Si—Si bond and no direct Si—C bond and (ii) a trisilylamine (TSA).

[0151] More specifically, the disclosed SiT-SAM monomers are Si—C-free polysilane-based SiT-SAM monomers comprising (i) the Si—C-free polysilane backbone and an “X” surface reactive group.

[0152] The disclosed Si—C-free polysilane-based SiT-SAM monomers are selected from

X—(SiH.sub.2).sub.n—SiH.sub.3 wherein n=1 to 3,

X—(Si.sub.nH.sub.2n) wherein Si.sub.nH.sub.2n refers to a cyclic hydridosilane backbone with n=5,6,7,

X—(SiH(SiH.sub.3).sub.2), or

X—SiH.sub.2—Si(SiH.sub.3).sub.3.

Preferably the polysilane backbone is —SiH.sub.2—SiH.sub.3 or —SiH.sub.2—SiH.sub.2—SiH.sub.3.

[0153] Exemplary Si—C-free polysilane-based SiT-SAM monomers include NiPr.sub.2—(SiH.sub.2)—SiH.sub.3, NnBu.sub.2-(SiH.sub.2)—SiH.sub.3, NtBu.sub.2-(SiH.sub.2)—SiH.sub.3, NsBu.sub.2-(SiH.sub.2)—SiH.sub.3, NiBu.sub.2-(SiH.sub.2)—SiH.sub.3, NPen.sub.2-(SiH.sub.2)—SiH.sub.3, NnPr.sub.2—(SiH.sub.2).sub.2—SiH.sub.3, NiPr.sub.2—(SiH.sub.2).sub.2—SiH.sub.3, NnBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NtBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NsBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NiBu.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NsPen.sub.2-(SiH.sub.2).sub.2—SiH.sub.3, NHtBu-(SiH.sub.2).sub.2—SiH.sub.3, NHPen-(SiH.sub.2).sub.2—SiH.sub.3, NHsBu-(SiH.sub.2).sub.2—SiH.sub.3, NHiBu-(SiH.sub.2).sub.2—SiH.sub.3, NnPr.sub.2—(SiH.sub.2).sub.3—SiH.sub.3, NiPr.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NnBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NtBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NsBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NiBu.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NsPen.sub.2-(SiH.sub.2).sub.3—SiH.sub.3, NEt.sub.2-(SiH(SiH.sub.3).sub.2), NiPr.sub.2—(SiH(SiH.sub.3).sub.2), NnPr.sub.2—(SiH(SiH.sub.3).sub.2), NiBu.sub.2-(SiH(SiH.sub.3).sub.2), NtBu.sub.2-(SiH(SiH.sub.3).sub.2), NnBu.sub.2-(SiH(SiH.sub.3).sub.2), NsBu.sub.2-(SiH(SiH.sub.3).sub.2), NsPen.sub.2-(SiH(SiH.sub.3).sub.2), NHtBu-(SiH(SiH.sub.3).sub.2), NHnBu-(SiH(SiH.sub.3).sub.2), NHiBu-(SiH(SiH.sub.3).sub.2), and NHPen-(SiH(SiH.sub.3).sub.2).

[0154] Furthermore, the disclosed SiT-SAM monomers are TSA-based SiT-SAM monomers comprising (ii) the TSA backbone and an “X” head. The TSA-based SiT-SAM monomers contain at least one N(—Si).sub.3 unit in their backbone and one or two “X” surface reactive groups. For simplicity, H and non-hydrolysable groups are not represented throughout the entire description and claims.

[0155] The disclosed TSA-based SiT-SAM monomers have a general formula

XR.sub.2Si—N(SiR.sub.3).sub.n(SiX′R.sub.3).sub.2-n,

wherein X′ has the same definition as X as described above and is independent from X; n=1 or 2; R is selected from H, a C.sub.1 to C.sub.6 branched or linear alkyl chain. Preferably, each R═H, in which case the formula becomes XH.sub.2Si—N(SiH.sub.3).sub.n(SiX′H.sub.3).sub.2-n. Preferably, n=2, in which case the formula becomes XR.sub.2Si—N(SiR.sub.3).sub.2. The TSA-based SiT-SAM monomers may contain more than one N(—Si).sub.3 units and have backbones such as (Si).sub.2N—Si—N(Si)Si—X or X—Si—N(Si)—Si—N(Si)Si—X.

[0156] The disclosed SiT-SAM monomers may be used for exposure to a surface or substrate in a liquid phase, either pure or preferably diluted in a solvent, which is inert to the disclosed SiT-SAM monomer and to the surface reactive groups. The solvents are typically non-protic solvents such as hydrocarbons, toluene, ethers, trialkylamines, etc. The surface or substrate exposure may be achieved by any coating method such as dip coating, spin coating, spray coating. The exposure may last between 1 seconds and 24 hours. After exposure, the surface or substrate is preferably rinsed with the solvent and dried. The existence and characteristics of a suitable SAM layer may be assessed by techniques such as water contact angle (WCA), attenuated total reflection FTIR (ATR-FTIR), or high angle XPS.

[0157] Alternatively, the disclosed SiT-SAM monomers may be used for exposure to a surface or substrate in a gas phase. Again, the method used for forming SiT-SAM does not differ from methods used for forming classical SAMs, such as the one described by F. Schreiber (“Structure and growth of self-assembling monolayers”, Frank Schreiber, Progress in Surface Science, Vol. 65, issues 5-8, 2000, 151-257). The surface or substrate is preferably heated to promote the reaction of surface sites with the disclosed SiT-SAM monomers, typically at a temperature ranging from room temperature to approximately 45° ° C., which is the temperature at which the disclosed SiT-SAM monomers typically self-decompose. The exposure time may range from 1 second to 24 hours, preferably no more than 10 minutes.

[0158] Whether the exposure to the disclosed SiT-SAM monomer is done in the gas phase or liquid phase, the surface/substrate may be pre-treated to improve the reaction of the disclosed SiT-SAM monomer with the surface. Such treatment may increase the reactive site density (e.g., —OH on an oxide surface), decrease the film adventitious contamination (e.g, carbon on a metal surface), or remove a passivating oxide on a metal, Such dry or wet surface preparations and cleaning techniques are well known in the arts and may be applied to the usage with the disclosed SiT-SAM monomers.

[0159] The substrate final application is not limited to the present invention, but this technology may find particular benefits for the following types of substrates: silicon wafers, glass wafers and panels, beads, powders and nano-powders, monolithic porous media, printed circuit board, plastic sheets, etc. Exemplary powder substrates include a powder used in rechargeable battery technology. A non-limiting number of powder materials include NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.

[0160] It is understood that substrate designates physical elements and their composition may differ from the composition of the layer(s) onto which the disclosed SiT-SAM monomers are deposited. For instance, a silicon wafer may be coated with various dielectric (SiO.sub.2, SiN, SiC, SiCOH, SiCN, SiON, SiOCN, a-C, etc), semiconductor (Ge, SiGe, GeSn, InGaAs, GaSb, InP, etc), or conductive films (Cu, Co, W, Al, Mo, MoN, Ti, TiN, TaN, Ru, Pt, Pd, WN, WC, Ni, etc.)

[0161] Like classical SAM and specifically silylating SAMs, the disclosed SiT-SAM monomers are useful to improve the wettability of substrate to certain solution-based film forming formulations such as spin on dielectrics, anti-reflective coatings, or photoresist materials.

[0162] Unlike classical SAMs, which only act as surface blocking agents, the disclosed SiT-SAM monomers may prove beneficial as their Si-tail exhibits interesting chemical reactivity that may be beneficial for further processing of the surface. As such, the disclosed SiT-SAM monomers act as a way to direct certain reactions on the surface that the disclosed SiT-SAM monomers specifically cover, as opposed to plainly blocking a surface, and may thus act as a positive mask for area selective deposition processes.

[0163] To ensure process reliability, the disclosed SiT-SAM monomers may be purified by continuous or fractional batch distillation or sublimation prior to use to a purity ranging from approximately 95% by weight or w/w to approximately 100% w/w, preferably ranging from approximately 99% w/w to approximately 99.999% w/w, more preferably, ranging from approximately 99% w/w to approximately 100% w/w.

[0164] The disclosed SiT-SAM monomers may contain any of the following impurities: undesired congeneric species; solvents; or other reaction products. In one alternative, the total quantity of these impurities is below 5.0% w/w, preferably, below 0.1% w/w.

[0165] Solvents, such as hexane, pentane, dimethyl ether, or anisole, may be used in the precursor's synthesis. The concentration of the solvent in the disclosed SiT-SAM monomers may range from approximately 0% w/w to approximately 5% w/w, preferably from approximately 0% w/w to approximately 0.1% w/w. Separation of the solvents from the precursor may be difficult if both have similar boiling points. Cooling the mixture may produce solid precursor in liquid solvent, which may be separated by filtration. Vacuum distillation may also be used, provided the precursor product is not heated above approximately its decomposition point.

[0166] In one alternative, the disclosed SiT-SAM monomers contain less than 5% v/v, preferably less than 1% v/v, more preferably less than 0.1% v/v, and even more preferably less than 0.01% v/v of any of its undesired congeneric species, reactants, or other reaction products. This alternative may provide better process repeatability. This alternative may be produced by distillation of the disclosed SiT-SAM monomers.

[0167] In another alternative, the disclosed SiT-SAM monomers may contain between 5% v/v and 50% v/v of one or more of congeneric monomers, or other reaction products, particularly when the mixture provides improved process parameters or isolation of the target compound is too difficult or expensive. For example, a mixture of two SiT-SAM monomers may produce a stable, liquid mixture suitable for SAM formation.

[0168] In another alternative, the disclosed SiT-SAM monomers may contain between approximately 0 ppbw and approximately 500 ppbw metal impurities. The concentration of trace metals and metalloids in the disclosed SiT-SAM monomers may each range from approximately 0 ppb to approximately 100 ppb, and more preferably from approximately 0 ppb to approximately 10 ppb.

[0169] This disclosure also includes processes of forming a SAM on a surface. The process comprises the steps of preparing the surface for exposure of the surface to the disclosed SAM forming composition; exposing of the surface to the SAM forming composition; and forming the SAM on the surface. When the SAM forming composition is a solution, the exposure of the surface to the SAM forming composition is a liquid phase exposure. When the SAM forming composition is a vapor, the exposure of the surface to the SAM forming composition is a gas phase exposure.

[0170] The disclosed also includes film forming processes using the disclosed SiT-SAM monomers. The process comprises the steps of preparing the surface for exposure of the surface to a SAM forming composition; exposing of the surface to the SAM forming composition; forming the SAM on the surface through a liquid or gas phase exposure; and growing a film on top of the SAM through a wet or dry deposition process using a film-forming precursor. When the SAM forming composition is a solution, the exposure of the surface to the SAM forming composition is a liquid phase exposure. The step of exposing of the surface to the SAM forming composition may be a liquid phase exposure or a gas phase exposure. When the SAM forming composition is a vapor, the exposure of the surface to the SAM forming composition is a gas phase exposure. The wet deposition process may be a spin-on-deposition process and the dry deposition process may be an ALD or CVD process.

[0171] In one exemplary embodiment, a precursor used for depositing a film over the SAM formed by the SiT-SAM monomer may be a metal or metalloid precursor, and the tail of the SiT-SAM monomer acts as a reducing agent to the metal or metalloid precursor. The metal precursor may be preferably selected from a main group element, or a transition metal element selected from Ti, Ta, W, Mo, Nb, or V. The metal precursor may be a fluoride, chloride, a bromide, an iodide, an oxychloride, an oxybromide, an oxyfluoride, or combinations thereof. More specifically, the metal or metalloid precursor may be selected from WF.sub.6, WOF.sub.4, WOCl.sub.4, WCl.sub.6, WCl.sub.5, MoCl.sub.5, MoOCl.sub.4, MoO.sub.2Cl.sub.2, TiCl.sub.4, TiBr.sub.4, TiI.sub.4, TaCl.sub.5, AlCl.sub.3, VCl.sub.4, NbCl.sub.5, BCl.sub.3, BBr.sub.3, GeCl.sub.4, GeBr.sub.4 or GeCl.sub.2, GeBr.sub.2, or combinations thereof. It is noted that several of these halides compounds may form stable and volatile adducts, and may be used in such a form of thin film deposition, for example, GeCl.sub.2:dioxane, TaCl.sub.5:SEt.sub.2, TiBr.sub.4:SiPr.sub.2.

[0172] In addition to the precursor, a reactant or a co-reactant may also be introduced into the reactor. The co-reactant may be an oxygen-containing gas or a nitrogen-containing gas. The co-reactants include, but are not limited to, oxidizers such as, O.sub.3, O.sub.2, H.sub.2O, H.sub.2O.sub.2, D.sub.2O, ROH (R is a C.sub.1-C.sub.10 linear or branched hydrocarbon), etc. H.sub.2O and ROH (R is a C.sub.1-C.sub.10 linear or branched hydrocarbon) are preferred oxidation sources to avoid reacting with the SAM layer formed on the substrates. The nitrogen-containing gas includes, but is not limited to, NH.sub.3, NO, N.sub.2O, hydrazines, primary amines such as methylamine, ethylamine, tertbutylamine; secondary amines such as dimethylamine, diethylamine, diisopropylamine, ethylmethylamine, pyrrolidine; tertiary amines such as trimethylamine, triethylamine, trisilylamine, N.sub.2, N.sub.2/H.sub.2 mixture thereof, preferably NH.sub.3. The co-reactant may be selected from H.sub.2, NH.sub.3, NO, N.sub.2O, hydrazines, amines or combinations thereof. Preferably, plasma-treated co-reactants are avoided as they tend to damage the SAM layer, unless the SAM layer is re-formed at each ALD cycle.

EXAMPLES

[0173] 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 inventions described herein.

Comparative Example 1

Using Hexamethyldisilazane, Me.SUB.3.Si—NH—SiMe.SUB.3 .(HMDS), as an Adhesion Promoter Agent to Deposit a Polycarbosilazane Film

[0174] A silicon wafer with native oxide, cut into coupons 2×2 cm, was cleaned for 10 min under ultraviolet-ozone cleaning (hereinafter referred to as UV-O.sub.3 cleaning) to remove organic contaminants. After UV-O.sub.3 cleaning, the surface was completely hydrophilic, showing a distilled deionized water contact angle <5°. Afterwards, the coupon was brought into a N.sub.2 glovebox and 200 μl of HMDS solution was spun onto it for 60 s at 2000 rpm using Brewer Science Cee 200× spin coater. After spinning the HDMS adhesion promoter, the surface shows a hydrophobic character with an average contact angle of 95°. Afterwards, 200 μl polycarbosilazane solution was spun for 60 s at 2000 rpm. Spin-on process has been followed by prebake step in the N.sub.2 glovebox at 200° C. for 5 min to promote solvent and volatile evaporation.

[0175] FIG. 1 shows that spin-on deposited thin film residues aggregated in clusters when using HMDS as adhesion agent. After the prebake step, the polycarbosilazane thin film that was formed during the spin-on process was completely degraded and the material left aggregated into islands.

[0176] Thus, this example demonstrates that HMDS, which is a common adhesion promoter used in the industry, may not be compatible with the polycarbosilazane polymer used since it may not favor the adhesion between the polymer and the silicon coupon.

Example 1

Syntheses of (Diisopropylamine)trisilylamine ((CMe.SUB.2.).SUB.2.-N—SiH.SUB.2.—N—(SiH.SUB.3.).SUB.2., TSA-N(CMe.SUB.2.).SUB.2.)

[0177] TSA-N(CMe.sub.2).sub.2 SAM precursor is synthesized in a pressurized reactor by the reaction between trisilylarnine (TSA) and diisopropylamine (Me.sub.2-CH).sub.2—NH) catalyzed by commercially available Ruthenium on carbon catalyst: A 0.3 L autoclave equipped with a mechanical stirrer, a thermocouple, a pressure gauge and a pressure transducer and 3 metering valves was charged with 5.3 g (0.0025 mmol of ruthenium) of 5% weight ruthenium on carbon catalyst. The reactor was then heated under dynamic vacuum at about 125° C. for 3 hr. Dynamic vacuum as used herein describes a vacuum of about 1 Torr. After cooling to room temperature, 14.8 g (0.202 mol) of diisopropylamine was added to the reactor and then it was cooled to about −130° C. in a liquid nitrogen bath. 40 g (0.372 mol) of trisilylamine was transferred to the reactor. The reactor was then gradually heated to about 100° C. After stirring at about 400 rpm for 65 rpm, pressure increased about 300 psi. The pressure increase is proportional to the amount of hydrogen (and product) formed, so it will vary depending on the scale of the reaction. The reaction is complete when the pressure stops increasing. It may be desirable to stop the reaction before it is complete. The reactor was cooled to room temperature (“RT”). Volatiles were collected in a cryotrap at liquid nitrogen temperature in a SSLB. The reactor pressure went down to 50 Torr.

[0178] The resulting solution contained about 30% (11.3 g) of TSA-N(CMe.sub.2).sub.2. The non-isolated yield was 30%.

Example 2

Synthesis of Chlorotrisilylamine (SiH.SUB.2.).SUB.2.—N—SiH.SUB.2.Cl, TSA-Cl)

[0179] TSA-Cl SAM precursor is synthesized according to the reaction: SnCl.sub.4+N(SiH.sub.3).sub.3.fwdarw.N(SiH.sub.3).sub.2(SiH.sub.2Cl)+SnCl.sub.2⬇+HCl (see J. Chem. Soc. Dalton Trans. 1975, p. 1624). Alternatively, dichlorosilane [SiH.sub.2Cl.sub.2] and monochlorosilane [SiH—X] may be introduced continuously in the gas phase in a 1/20 to ¼ ratio and at room temperature with 400 sccm of NH.sub.3 in a flow-through tubular reactor as described by Miller in U.S. Pat. No. 8,669,387. The reaction of NH.sub.3 with 2 equivalents of monochlorosilane produces mostly disilylamine (DSA). DSA then reacts with the dichlorosilane to form (SiH.sub.3).sub.2—N—SiH.sub.2Cl and HCl. One of ordinary skill in the art would recognize that the reaction may take place in one or two steps (first forming DSA from the monochlorosilane and NH.sub.3 and second adding dichlorosilane) or in one step (combining the monochlorosilane, dichlorosilane, and NH.sub.3 in one step).

Example 3

Synthesis of Amine Substituted Polysilane

[0180] The amine substituted polysilanes may be synthesized through the following steps. [0181] a) contacting the reactants R.sup.1R.sup.2NH and R.sup.3R.sup.4NH and Si.sub.mH.sub.2(m+1) in the presence of a transition metal catalyst forming a reaction mixture; [0182] b) optionally adding a solvent to the reaction mixture; [0183] c) maintaining the reaction mixture at a temperature between about 0° C. to about 300° C.; [0184] d) allowing the reactions to proceed to form (R.sup.1R.sup.2N).sub.n1(R.sup.3R.sup.4N).sub.n2Si.sub.mH.sub.2(m+1)−n1-n2); [0185] e) separating the (R.sup.1R.sup.2N).sub.n1(R.sup.3R.sup.4N).sub.n2Si.sub.mH.sub.(2(m+1)−n1-n2) from the reaction mixture;
wherein the reaction mixture temperature may vary during the synthesis and is maintained such that the temperature of the reaction mixture is not allowed to drop below about 0° C. and not exceed about 300° C.

[0186] For example, the structure formula for m=3; R.sup.1═R.sup.2=isopropyl; n1=1; n2=0 is as follows.

##STR00003##

wherein the reactants are Me.sub.2NH and Si.sub.3H.sub.3. See e.g. U.S. Pat. No. 10,494,387.

Example 4

Synthesis of Amidinate (AMD, —R.SUP.1.HN(CR.SUP.3.)═NR.SUP.2.,

[0187] ##STR00004##

 Substituted Polysilane

[0188] AMD substituted polysilanes refer to (R.sup.1HN(CR.sup.3)═NR.sup.2).sub.n—Si.sub.mH.sub.(2(m+1)−n)), where n=1 to (2(m+1); m=2 to 6; R.sup.1 and R.sup.2 are each independently selected from the group consisting of linear or branched C.sub.1 to C.sub.6 alkyl, linear or branched C.sub.1 to C.sub.8 alkenyl, linear or branched C.sub.1 to C.sub.8 alkynyl, C.sub.6 to C.sub.10 aryl, linear or branched C.sub.1 to C.sub.6 alkyl ether, silyl, trimethyl silyl, or linear or branched C.sub.1 to C.sub.6 alkyl-substituted silyl.

[0189] Replacing R.sup.1R.sup.2NH with R.sup.1HN(CR.sup.3)═NR.sup.2 in the above synthesis process of amine substituted polysilanes in Example 3, the AMD substituted polysilanes will be formed. See, e.g., U.S. Ser. No. 10/494,387.

Example 5

Synthesis of X Substituted Bi-Disilylaminohalogensilane (BDSASi—X), Wherein X═F, Cl, Br or I

[0190] SAM precursor BDSASi—X (F, Cl, Br, I) are preferentially synthesized from a direct reaction of (SiH.sub.3).sub.2N—SiH.sub.2—N(SiH.sub.3).sub.2 (BDSASi) with a halogen acid by dehydrogenative coupling, according to the same protocol as described in U.S. Pat. App. Pub. No. 2015/0094470.

[0191] (SiH.sub.3).sub.2N—SiH.sub.2—N(SiH.sub.3).sub.2+nHX.fwdarw.[N(SiH.sub.3-m(X).sub.m]—SiH.sub.2—[SiH.sub.3-n(X).sub.n]+(m+n)H.sub.2 with m=0 to 3, n=1 to 3. [0192] The reaction being carried neat or in an aprotic solvent such as, but not limited to a C.sub.3-C.sub.24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF. [0193] The reaction being carried at a temperature between room temperature and 150° C., preferably at 30-60° C. [0194] Optionally, the catalyst being filtered from the reaction mixture and the components of the remaining liquid composition being separated by distillation. [0195] Optionally, the reaction mixture being treated with an agent to de-activate the catalyst, selected but not limited to a tertiary amine or a coordinant compound such as XNR.sub.4 (X═F, Cl, Br, I; R═alkyl), R—CN, R.sub.2S, PR.sub.3. [0196] Optionally, the compound of BDSASi—X being purified by distillation to reach an assay of >98%, more preferably or >99%, and even more preferably >99.5%, which is typical of semiconductor grade precursors [0197] Optionally, the product may be filtered to reach specifications that are typical of products used in the semiconductor industry.

Example 6

Synthesis of Diisobutylaminetrisilane (DIBATS, (iBu).SUB.2.-N—SiH.SUB.2.—SiH.SUB.2.—SiH.SUB.3.)

[0198] SAM precursor DIBATS is synthesized in a pressurized reactor from trisilane (SiH.sub.3—SiH.sub.2—SiH.sub.3) and diisobutylamine ((iBu).sub.2-NH) catalyzed by commercially available Ruthenium on carbon comprises. A 0.3 L autoclave equipped with a mechanical stirrer, a thermocouple, a pressure gauge and a pressure transducer and 3 metering valves was charged with 6 g (0.003 mmol of ruthenium) of 5% weight ruthenium on carbon catalyst. The reactor was then heated under dynamic vacuum at 125° C. for 3 hr. After cooling down to room temperature, the reactor was filled with 1 atm of helium, sealed and disconnected from the manifold and placed in a glove box. Inside the glove box, 20.7 (0.205 mol) of diisobutylamine was added. Then, the reactor was taken out from the glove box and reconnected to the manifold and cooled down to −130° C. in a liquid nitrogen bath. 40 g of trisilane (0.433 mol) was transferred to the reactor through the manifold. The reactor was then heated up to 100° C. After stirring at 400 rpm for 23 hr, the reactor was cooled down to room temperature. Volatiles were cryotrapped in a stainless steel lecture bottle (SSLB). The reaction vessel pressure dropped to 20 Torr. The DIBATS was recovered from the reactor vessel. The reaction solution contained 11.49 g of DIBATS. The non-isolated yield was 29%, See e.g., U.S. Ser. No. 10/494,387.

Example 7

Synthesis of Amidinateneopentylsilane (NPS-AMD, C.SUB.5.H.SUB.11.—SiH.SUB.2.—R.SUP.1.HN(CR.SUP.3.)═NR.SUP.2.)

[0199] The synthesis of SAM precursor NPS-AMD is as follows. [0200] a) contacting the reactants amidine (R.sup.1HN(CR.sup.3)═NR.sup.2) and neopentylsilane (C.sub.5H.sub.11—SiH.sub.3), in the presence of a transition metal catalyst forming a reaction mixture; wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of linear or branched C.sub.1 to C.sub.6 alkyl, linear or branched C.sub.1 to C.sub.8 alkenyl, linear or branched C.sub.1 to C.sub.8 alkynyl, C.sub.6 to C.sub.10 aryl, linear or branched C.sub.1 to C.sub.6 alkyl ether, silyl, trimethyl silyl, or linear or branched C.sub.1 to C.sub.6 alkyl-substituted silyl; where the molar ratio of neopentylsilane (C.sub.5H.sub.11—SiH.sub.3) to (R.sup.1HN(CR.sup.3)═NR.sup.2) is at least 1:1; [0201] b) optionally adding a solvent to the reaction mixture; [0202] c) maintaining the reaction mixture at a temperature between about 0° C. to about 300° C.; [0203] d) allowing the reaction to proceed to form NPS-AMD (C.sub.5H.sub.11—SiH.sub.2—(R.sup.1N(CR.sup.3)═NR.sup.2)) [0204] e) separating the product NPS-AMD from the reaction mixture; wherein the reaction temperature may vary during the synthesis and is maintained such that the temperature of the reaction mixture is not allowed to drop below about 0° C. and not exceed about 300° C. See e.g., U.S. Ser. No. 10/494,387.

Example 8

Synthesis of Dialkylaminoneopentylsilane (NPS-NR.SUP.4.R.SUP.5.)

[0205] In the above synthesis procedure of NPS-AMD in Example 7, replace the reactant amidine (R.sup.1HN(CR.sup.3)═NR.sup.2) with amine R.sup.4R.sup.5NH, the product SAM precursor NPS-NR.sup.4R.sup.5 will be formed, wherein R.sup.4 and R.sup.5 are each independently H, linear or branched C, to C.sub.6 alkyl, linear or branched C.sub.1 to C.sub.6 alkenyl, linear or branched C.sub.1 to Cr alkynyl, C.sub.6 to C.sub.10 aryl, linear or branched C.sub.1 to C.sub.6 alkyl. See e.g., U.S. Ser. No. 10/494,387.

Example 9

Synthesis of Amidinatecyclohexylsilane (CHS-AMD)

[0206] The synthesis of SAM precursor CHS-AMD is as follows. [0207] a) contacting the reactants amidine (R.sup.1HN(CR.sup.3)═NR.sup.2) and cyclohexylsilane (C.sub.6H.sub.11—SiH.sub.3), in the presence of a transition metal catalyst forming a reaction mixture; wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of linear or branched C.sub.1 to C.sub.6 alkyl, linear or branched C.sub.1 to C.sub.6 alkenyl, linear or branched C.sub.1 to C.sub.8 alkynyl, C.sub.6 to C.sub.10 aryl, linear or branched C.sub.1 to C.sub.6 alkyl ether, silyl, trimethyl silyl, or linear or branched C.sub.1 to C.sub.6 alkyl-substituted silyl; where the molar ratio of cyclohexylsilane (C.sub.6H.sub.11—SiH.sub.3) to (R.sup.1HN(CR.sup.3)═NR.sup.2) is at least 1:1; [0208] b) optionally adding a solvent to the reaction mixture; [0209] c) maintaining the reaction mixture at a temperature between about 0° C. to about 300° C.; [0210] d) allowing the reaction to proceed to form the SAM precursor CHS-AMD (C.sub.6H.sub.11—SiH.sub.2—(R.sup.1N(CR.sup.3)═NR.sup.2)); [0211] e) separating the product CHS-AMD from the reaction mixture; wherein the reaction temperature may vary during the synthesis and is maintained such that the temperature of the reaction mixture is not allowed to drop below about 0° C. and not exceed about 300° C. See e.g., U.S. Ser. No. 10/494,387.

Example 10

Synthesis of Dialkylaminocyclohexylsilane (CHS-NR.SUP.4.R.SUP.5.)

[0212] In the above synthesis procedure of CHS-AMD in Example 9, replace the reactant amidine (R.sup.1HN(CR.sup.3)═NR.sup.2) with amine R.sup.4R.sup.5NH, the product SAM precursor CHS-NR.sup.4R.sup.5 will be formed, wherein R.sup.4 and R.sup.5 are each independently H, linear or branched C.sub.1 to C.sub.6 alkyl, linear or branched C.sub.1 to C.sub.6 alkenyl, linear or branched C.sub.1 to C.sub.6 alkynyl, C.sub.6 to C.sub.10 aryl, linear or branched C.sub.1 to C.sub.6 alkyl. See e.g., U.S. Ser. No. 10/494,387.

Example 11

Wet Coating of SiT-SAMs

[0213] Neat SiT-SAM monomer (0.2 mL) were deposited on SiO.sub.2 (thermal oxide) wafers under N.sub.2 atmosphere and room temperature. The wafers were then spun at 2000 RPM for 60 sec (i.e. until apparent dryness of the wafer). The wafers were either as received or pretreated under O.sub.3 (5 min, room temperature) to clean and hydroxylate the surface. Water contact angle (WCA) measurement were immediately measured in air. The wafers were then baked under N.sub.2 at 300° C. for 10 min, and the WCA was re-measured after the anneal.

[0214] The results are listed in FIG. 2 and FIG. 3 that indicate a clear increase of the WCA for both the mono-amino trisilane (Si.sub.3H.sub.7—NR.sub.2, wherein R.sup.1 is a C.sub.2 to C.sub.5 alkyl) derivative and the monoamino-trisilylamine derivative (Si.sub.3H.sub.6N—NR.sub.2, wherein R.sup.1 is a C.sub.2 to C.sub.5 alkyl). The WCA remains high after annealing at 300° C., which indicates that these SiT-SAM monomers may withstand such a high temperature without decomposition and that wet exposure at room temperature is sufficient to chemically bind these SAMs to the surface.

Example 12

Application of SiT SAM as a SOD Coating Primer Using (Diisobutylamine)Trisilane (DIBATS) as an Adhesion Promoter to Deposit a Polycarbosilazane Film

[0215] Same process as described in comparative example 1 was performed using DIBATS as adhesion promoter instead of HDMS. A silicon wafer with native oxide, cut into coupons 2×2 cm, was cleaned for 10 min under UV-O.sub.3 cleaning. Afterwards, the coupon was brought into a N.sub.2 glovebox and 200 μl of DIBATS solution was spun onto it for 60 s at 2000 rpm using Brewer Science Cee 200× spin coater. After spinning the DIBATS adhesion promoter, the surface showed a hydrophobic character with an average contact angle of 88°. Afterwards, 200 μl polycarbosilazane solution was spun for 60 s at 2000 rpm. Spin-on process was followed by prebake step in the N.sub.2 glovebox at 200° C. for 5 min to promote solvent and volatile evaporation.

[0216] FIG. 4 shows a spin-on deposition thin film using DIBATS as adhesion agent. A film is retained and uniform across the coupons. After the prebake step, a polycarbosilizane thin film of 260 nm thick was retained. The film shows good uniformity across the film with few voids and defects. Thus, this example demonstrate that DIBATS is able to strongly bind with the polycarbosilazane and retain the bond after the prebake heating treatment. To test the adhesion of the polycarbosilazane to the silicon substrate a scotch tape test was performed. The thin film did not peel off or detach. No visual difference could be observed after multiple repetition (more than 5) of scotch tape test on the same coupon.

Example 13

Application of SiT SAM as a SOD Coating Primer Using (Diisopropylamine)Trisilylamine (TSA-N(CHMe.SUB.2.).SUB.2.) as an Adhesion Promoter to Deposit a Polycarbosilazane Film

[0217] Same process as described in Example 12 using DIBATS as adhesion promoter was performed using TSA-N(CHMe.sub.2).sub.2 as adhesion promoter instead of DIBATS. A silicon wafer with native oxide, cut into coupons 2×2 cm, was cleaned for 10 min under UV-O.sub.3 cleaning. Afterwards, the coupon was brought into a N.sub.2 glovebox and 200 μl of TSA-N(CHMe.sub.2).sub.2 solution was spun onto it for 60 s at 2000 rpm using Brewer Science Cee 200X spin coater. After spinning the TSA-N(CHMe.sub.2).sub.2 adhesion promoter, the surface showed a hydrophobic character with an average contact angle of 98°. Afterwards, 200 μl polycarbosilazane solution was spun for 60 s at 2000 rpm. Spin-on process was followed by prebake step in the N.sub.2 glovebox at 200° C. for 5 min to promote solvent and volatile evaporation.

[0218] FIG. 5 shows a spin-on deposition thin film using TSA-NH(CHMe.sub.2).sub.2 as adhesion agent. A film is retained and uniform across the coupons. After the prebake step, a polycarbosilazane thin film of 260 nm thick was retained. The film shows good uniformity across the film with few voids and defects. Thus, this example demonstrates that TSA-NH(CHMe.sub.2).sub.2 is able to strongly bind with the polycarbosilazane and retain the bond after the prebake heating treatment. To test the adhesion of the polycarbosilazane to the silicon substrate a scotch tape test was performed. The thin film did not peel off or detach. No visual difference could be observed after multiple repetition (more than 5) of scotch tape test on the same coupon.

Example 14

Vapor Coating of SiT-SAMs

[0219] SiO.sub.2 (thermal oxide) wafers were exposed to SiT-SAM monomer DIBATS (0.02 Torr partial pressure) vapor under vacuum (9.5T) at 100° C. The wafers were exposed to the SiT SAM vapor for 5 minutes. The wafers were either as received (native) or pretreated under O.sub.3 (10 min, room temperature) to clean and hydroxylate the surface. Water contact angle (WCA) measurements were immediately measured in air. The wafers were stored at ambient temperatures (23-24° C.) and humidity (41-56% RH), and the WCA was re-measured after 24 hours and 48 hours aging.

[0220] The results are listed in FIG. 6 that indicate a clear increase of the WCA for both the as native and pretreated SiO substrates exposed to the vapor SiT-SAM, DIBATS. The WCA remains high (>70 degrees) after aging at ambient conditions after 24 and 48 hours, which indicates that SiT-SAM monomers may be stable and withstand exposure at ambient conditions.

Prophetic Example 1

Dry Coating of SiT-SAMs

[0221] The disclosed SiT-SAM monomers used in a dry coating process are volatile enough to be evaporated and to reach a sufficient vapor pressure to react with the surface of a substrate/wafer within a reasonable time. The surface to be treated is exposed to and left to react with the vapors of the SiT-SAM monomers. CVD or ALD processes may be applied to dry coating of SiT-SAMs. The substrate/wafer is heated above room temperature but below the decomposition temperature of the SiT-SAM monomer on the surface to promote and accelerate the reaction and attachment of the SiT-SAM monomer to the surface. This reaction may be realized at atmospheric pressure (e.g., APCVD) or under vacuum.

Prophetic Example 2

Applications of SiT-SAMs as an Enhancement Layer for Thin Film Deposition

[0222] Example application for Si anodes in battery space may be done by comparisons of growing poly-Si on top of (Diisobutylamine)trisilane coated SiO vs non (Diisobutylamine)trisilane coated SiO (gas/liquid), and growing porous Si on top of (Diisobutylamine)trisilane coated Ni (with native oxide) O vs. non (Diisobutylamine)trisilane coated (gas/lid). The disclosed SiT-SAM monomers may be used as seed for metal barrier using metal halides (W, Mo, Ti, Ta . . . ) at temperatures below 600° C., preferably below 500° C.

Prophetic Example 3

Application of SiT-SAM for Powder Coating

[0223] Wet coating of powder/filtration/wet oxidation (H.sub.2O+IPA) to SiO.sub.2 on surface of powder could be done with the disclosed SIT-SAM monomers. Gas phase coating of powders for Carbon-free hydrophobic properties enhancement, such as Al.sub.2O.sub.3, SiO.sub.2 powders, Si powder with native oxide, any metallic powder with native or ALD oxide such as Al, W, Ti, Cu, could be done with the disclosed SiT-SAM monomers.

[0224] Although the subject matter described herein may be described in the context of illustrative implementations to process one or more computing application features/operations for a computing application having user-interactive components the subject matter is not limited to these particular embodiments. Rather, the techniques described herein may be applied to any suitable type of user-interactive component execution management methods, systems, platforms, and/or apparatus.

[0225] It will be understood that many additional changes in the details, materials, steps, and arrangement of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above and/or the attached drawings.

[0226] While embodiments of this invention have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and not limiting. Many variations and modifications of the composition and method are possible and within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is only limited by the claims which follow, the scope of which shall include all equivalents of the subject matter of the claims.