Silicon-based self-assembled monolayer composition and surface preparation using the same

Abstract

A composition for forming a SAM is disclosed, comprising a SAM monomer or precursor having a backbone having surface-reactive groups, wherein the backbone does not contain Si-C bonds and is selected from the group consisting of Si-C bond-free polysilanes and trisilylamine. The surface-reactive groups are disclosed for use on surfaces to be coated, including dielectric surfaces and metallic surfaces. Also disclosed are a method for forming a SAM on a surface and a method for forming a film on the SAM.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority under 35 U.S.C. §119(a) and (b) to U.S. Provisional Patent Application No. 63 / 040,833, filed on June 18, 2020, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to self-assembled monolayer (SAM) monomers or precursors having a Si-based tail or backbone that does not contain Si-C bonds (SiT-SAM), their synthesis and their use in surface preparation in film-forming processes, and in particular to SiT-SAM monomers selected from the group consisting of tail SiT-SAM monomers based on Si-C-free polysilanes and tail SiT-SAM monomers based on trimethylsilylamine. Background Art

[0004] Self-assembled monolayer (SAM) is because they control the ability of surface characteristics (such as wettability, corrosion resistance) and their application in electronic equipment manufacturing and has been widely studied and used.SAM refers to that surface is covered by molecular array, and this molecular array is called SAM monomer or precursor hereinafter.The molecule that can form SAM comprises surface active head group, tail functional group or main chain, this surface reactive head group has reactive side group and is combined with the surface of substrate, this tail functional group or main chain are inert for this surface and are usually exposed to SAM surface and can be used for adjusting the chemical and physical properties of this surface.In view of the density of the site of reacting with SAM monomer head and for making the appropriate conditions of this monomer head and this site reaction, then this surface is exposed to the formation of SAM monomer and causes SAM monolayer.When SAM monomer has long tail, their final self-alignment becomes like grass-like structure. An overview of SAM chemistry and applications can be found in the following review document: Frank Schreiber, "Structure and growth of self-assembling monolayers"; Progress in Surface Science 65 (2000) 151-256.

[0005] The SAM monomer head contains chemical functionalities designed to selectively react and attach to specific surfaces and substrates. The most common SAM heads / chemical functionalities and the corresponding surfaces that react with the SAM heads / chemical functionalities are summarized in Table 1 below:

[0006] Table 1. Most common SAM monomer head groups

[0007]

[0008] *X is a -OH reactive group, such as halogen (Cl, Br, I), isocyanate, alkylamino-NR 1 R 2 , where R 1 and R 2 Each independently selected from H, C1 to C 10 A linear or branched or cyclic alkyl or alkenyl group, a trialkylsilyl group, provided that if R 1 =H, then R 2 Greater than C1.

[0009] The SAM monomer tail is usually composed of -(CH2) n -CH3 alkyl chain, where n ranges from 0 to about 20. However, the tail may contain additional functional groups / chemical groups and may be represented as: -(CH2) n -X, where n = 1 to 20, and X is a specific chemical group on the surface that will provide the secondary reactivity of the SAM. For example, X can be an amino group, an alkoxy group, an epoxy group, and an unsaturated group such as -CH=CH2, -C≡CH or a phenyl group. The SAM tail group can also contain a perfluoroalkyl group and have the general formula: -(CH2) n -(CF2) m -CF3, wherein n = 0 to 5, and m = 0 to 16. The addition of the perfluorinated chain contributes to increasing the hygrophobic forces of the SAM-coated surface.

[0010] Very few SAMs with tails containing Si have been described, and are limited to the following references: K. Ebata et al. ("Synthesis and Characterization of End-Grafted Polysilane on a Substrate Surface", J. Am. Chem. Soc. 1998, 120, 7367-7368) disclose that the Si moiety is grafted onto the classic SAM tail, and the "Si2" moiety is fully alkylated.

[0011]

[0012] K. Furukawa et al. (“Polysilane Bearing “Sulfide Tripod” Terminus: Preparation and Selective Chemisorption on Gold Surface”, Macromolecules, 2003, 36, 9-11) disclose that SAMs are designed to attach to metal surfaces with a trithiol head group and the tail is functionalized with an alkylated Si2 moiety.

[0013] Figure 1 Synthesis route of polysilanes with sulfide tripod-shaped ends

[0014]

[0015] SAMs have applications and industrial uses in surface treatments to increase the adhesion of one surface to another (i.e., as coupling agents) or to modify the affinity for certain fluids, such as water. SAMs with alkyl chains are designed and used to reduce affinity for polar molecules (typically water) and increase affinity for non-polar molecules and fluids. Various surface treatments to increase the hydrophobicity of, for example, glass are based on the use of SAMs with trifunctional silyl head groups and alkyl tails. A monograph on the subject can be found here: https: / / www.gelest.com / wp-content / uploads / Hydrophobicity-Hdrophilicity_and_Silane_Surface_Modifcation.pdf.

[0016] SAMs can be constructed on surfaces in essentially two ways:

[0017] i) Wet routes, in which the surface to be treated is exposed to a SAM monomer or a solution of SAM monomer in a solvent. This method includes dip coating, slot coating, spin coating, spray coating, and the like. The substrate is then typically rinsed with a solvent that removes excess SAM monomer from the surface that has not yet chemically reacted with the surface active sites. Exposure to the SAM monomer in the liquid phase can last from a few seconds to several days, depending on the type of SAM monomer.

[0018] ii) A vapor phase route, in which the surface to be treated is exposed to and reacts with the vapor of the SAM monomer. In this case, the substrate is typically heated above room temperature but below the decomposition temperature of the SAM monomer on the surface to promote and accelerate the reaction and attachment of the SAM monomer to the surface. This reaction can be achieved under atmospheric pressure or in a vacuum. The use of a vapor phase route requires that the SAM monomer be volatile enough to be evaporated and reach a sufficient vapor pressure to react with the surface within a reasonable time.

[0019] In the semiconductor industry, SAM surface treatment is used to prepare silicon substrates for deposition of organic photoresist layers by pre-treatment in a silylating agent such as HMDS (Me3Si-NH-SiMe3), which is a short chain monofunctional SAM monomer that, upon reaction with an -OH terminated surface, leaves a MeSi-O-terminated surface. HMDS was first described as a photoresist adhesion promoter for semiconductor applications by RH Collins and FT Devers in U.S. Pat. No. 3,549,368 to IBM (1970). Trialkyl silylation of the surface promotes increased wettability of the surface to the photoresist formulation, thereby increasing film adhesion, uniformity, and limiting defects such as voids or microbubbles.

[0020] Similarly, the use of surface alkyl silylation is often prior to deposition by various coating methods of film-forming formulations such as spin-on-dielectric (SOD).

[0021] SAMs have recently gained attention for the selective deposition of thin films using atomic layer deposition (ALD) techniques, known as selective area atomic layer deposition (AS-ALD). The ability to selectively deposit thin films in a controlled manner on certain areas of a substrate but not others holds promise for reducing the complexity and cost of chip production. The use of SAMs is now proliferating as a viable solution for enabling AS-ALD by preventing selected surfaces from reacting with precursors during the ALD cycle, thereby allowing films to grow selectively on areas not covered by the SAM.

[0022] Therefore, the use of SAMs is becoming more common in film formation processes, either as wettability enhancers for liquid-based film formation or as surface blocking agents for vapor deposition processes, and potentially also in the liquid phase.

[0023] However, in all of the above cases, the tail of the SAM monomer is based on a carbon backbone. Given that carbon can be a detrimental impurity in certain thin film applications and that the tail is chemically attached to the surface, having a non-carbon backbone-based SAM monomer can be beneficial. Furthermore, non-carbon backbone-based SAM monomers can also be used for additional applications such as seed layers to enhance nucleation in CVD and ALD processes due to their increased reactivity towards specific chemical families, such as metal halides.

[0024] Therefore, there is still a need to find new SAM monomers with non-carbon backbones that can enhance nucleation for CVD and ALD processes. Summary of the Invention

[0025] A self-assembled monolayer (SAM)-forming composition is disclosed to form a SAM, the composition comprising:

[0026] A SAM precursor having a main chain with surface reactive groups X,

[0027] wherein the main chain does not contain Si—C bonds and is selected from the group consisting of polysilanes without Si—C bonds and trisilylamine (TSA),

[0028] Wherein the surface reactive group X is selected from:

[0029] a. Halogen (Cl, Br, I);

[0030] b. cyanate, isocyanate or thiocyanate groups;

[0031] c. Amino-NR 1 R 2 , where R 1 Selected from H, linear, branched or cyclic C1-C 10 Alkyl or alkenyl or alkylsilyl; R 2 Selected from linear, branched or cyclic C2-C 10 Alkyl or alkenyl or alkylsilyl; or R 1 and R 2 Bridge, thus NR 1 R 2 Formation of a cyclic ligand, provided that the cyclic ligand contains a heteroatom S, N or O;

[0032] d. amidino-R 3 -NC(R 4 )=NR 5 , where R 3 and R 5 Each independently selected from C1 to C 10 a linear or branched alkyl or trialkylsilyl group; and R 4 Selected from H, C1 to C10 a straight-chain or branched alkyl group; or

[0033] e. thiol -SH, phosphonic acid or carboxylic acid. The disclosed method may include one or more of the following aspects:

[0034] X is a halogen, such as Cl, Br or I;

[0035] X is a cyanate group;

[0036] X is isocyanate;

[0037] X is a thiocyanate group;

[0038] ·X is dialkylamino-NR 1 R 2 , where R 1 is H, C2 to C5 alkyl, and R 2 is C1 to C5 alkyl, provided that if R 1 =H, then R 2 is a C3 to C5 alkyl group, if R 1 If not H, then R 1 and R 2 preferably identical;

[0039] ·X is amidino-NR 3 -C(R 4 )=NR 5 , where R 3 and R 5 Each is independently selected from Et, nPr, iPr, nBu, tBu, sBu, iBu; and R 4 It is H or Me;

[0040] the backbone does not contain Si-C bonds and is selected from the group consisting of polysilanes without Si-C bonds and trisilylamine,

[0041] X is a thiol group -SH;

[0042] X is phosphonic acid;

[0043] X is a carboxylic acid;

[0044] The surface to be covered is a dielectric surface;

[0045] The surface to be covered is metal;

[0046] The main chain does not contain Si-C bonds;

[0047] The main chain is a polysilane without Si-C bonds;

[0048] The backbone is trimethylsilylamine;

[0049] The SAM precursor having a Si-C-free polysilane backbone is selected from

[0050] X-(SiH2) n -SiH3, wherein n=1 to 3,

[0051] X-(Si n H 2n-1 ), where Si n H 2n-1 Represents a cyclic hydrosilane main chain, where n=5, 6, or 7,

[0052] X-(SiH(SiH3)2), or

[0053] X-SiH2-Si(SiH3)3;

[0054] The SAM precursor having a Si-C-free polysilane backbone is selected from

[0055] X-(SiH2) n -SiH3, wherein n=1 to 3;

[0056] The SAM precursor having a Si-C-free polysilane backbone is selected from

[0057] X-(Si n H 2n-1 ), where Si n H 2n-1 represents a cyclic hydrosilane backbone, where n = 5, 6, or 7;

[0058] The SAM precursor having a Si-C-free polysilane backbone is selected from

[0059] X-(SiH(SiH3)2);

[0060] The SAM precursor having a Si-C-free polysilane backbone is selected from

[0061] X-SiH2-Si(SiH3)3;

[0062] The SAM precursor having a Si-C-free polysilane backbone is selected from the group consisting of: NiPr2-(SiH2)-SiH3, NnBu2-(SiH2)-SiH3, NtBu2-(SiH2)-SiH3, NsBu2-(SiH2)-SiH3, NiBu2-(SiH2)-SiH3, NPen2-(SiH2)-SiH3, NnPr2-(SiH2)2-SiH3, NiPr2-(SiH2)2-SiH3, NnBu2- (SiH2)2-SiH3, NtBu2-(SiH2)2-SiH3, NsBu2-(SiH2)2-SiH3, NiBu2-(SiH2)2-SiH3, NsPen2-(SiH2)2-SiH 3. NHtBu-(SiH2)2-SiH3, NHPen-(SiH2)2-SiH3, NHsBu-(SiH2)2-SiH3, NHiBu-(SiH2)2-SiH3, NnPr2-(SiH2 )3-SiH3, NiPr2-(SiH2)3-SiH3, NnBu2-(SiH2)3-SiH3, NtBu2-(SiH2)3-SiH3, NsBu2-(SiH2)3-SiH3, NiBu 2-(SiH2)3-SiH3, NsPen2-(SiH2)3-SiH3, NEt2-(SiH(SiH3)2), NiPr2-(SiH(SiH3)2), NnPr2-(SiH(SiH3) 2), NiBu2-(SiH(SiH3)2), NtBu2-(SiH(SiH3)2), NnBu2-(SiH(SiH3)2), NsBu2-(SiH(SiH3)2), NsPen2-(S iH(SiH3)2), NHtBu-(SiH(SiH3)2), NHnBu-(SiH(SiH3)2), NHiBu-(SiH(SiH3)2), or NHPen-(SiH(SiH3)2);

[0063] The Si-C-free polysilane backbone of the SAM precursor is selected from -SiH2-SiH3 or -SiH2-SiH2-SiH3;

[0064] The SAM precursor with a trisilylamine backbone has the general formula

[0065] XR2Si-N(SiR3) n (SiX'R2) 2-n ,

[0066] wherein n=1 or 2; R is selected from H or C1 to C6 branched or straight chain alkyl; X' has the same definition as X and is independent of X;

[0067] The SAM precursor with trisilylamine backbone is XH2Si-N(SiH3) n (SiX'H2) 2-n or XR2Si-N(SiR3)2;

[0068] The SAM precursor having a trisilylamine backbone contains more than one N(-Si)3 unit and has a backbone of (Si)2N-Si-N(Si)(Si-X) or X-Si-N(Si)-Si-N(Si)(Si-X);

[0069] The SAM precursor is TSA-N(CHMe2)2;

[0070] The SAM precursor is TSA-Cl;

[0071] The SAM precursor is (R 1 R 2 N) n1 (R 3 R 4 N) n2 Si m H (2(m+1)-n1-n2) , wherein n=1 to (2(m+1); m=2 to 6; R 1 and R 2 Each is independently selected from the group consisting of a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl ether, silyl, trimethylsilyl, or linear or branched C1 to C6 alkyl substituted silyl;

[0072] The SAM precursor is (R 1 HN(CR 3 )=NR 2 ) n -Si m H (2(m+1)-n) ), wherein n=1 to 2(m+1); m=2 to 6; R 1 and R 2 Each is independently selected from the group consisting of a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl ether, silyl, trimethylsilyl, or linear or branched C1 to C6 alkyl substituted silyl;

[0073] The SAM precursor is BDSASi-X, where BDSASi-=(SiH3)2N-SiH2-N(SiH3)(SiH2-), X=F, Cl, Br, I;

[0074] The SAM precursor is DIBATS (diisobutylaminotrisilane);

[0075] The SAM precursor is NPS-AMD (NPS is neopentasilane);

[0076] The SAM precursor is NPS-NR 4 R 5 , where R 4 and R 5 Each is independently H, a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl;

[0077] The SAM precursor is CHS-AMD (CHS is cyclohexasilane);

[0078] The SAM precursor is CHS-NR 4 R 5 , where R 4 and R 5 Each is independently H, a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl;

[0079] The SAM precursor is Si3H7-NR2, where R 1 is a linear or branched C2 to C5 alkyl group;

[0080] The SAM precursor is Si3H8N-NR2, where R 1 is a linear or branched C2 to C5 alkyl group;

[0081] The SAM precursor contains less than 5% v / v of any of the following: undesirable congeners, reactants, or other reaction products thereof;

[0082] The SAM precursor contains less than 1% v / v, more preferably less than 0.1% v / v, of its undesirable congeners, reactants or other reaction products;

[0083] The SAM precursor contains less than 0.1% v / v of any of the following: undesirable congeners, reactants, or other reaction products thereof;

[0084] The SAM precursor contains less than 0.01% v / v of any of the following: undesirable congeners, reactants, or other reaction products thereof;

[0085] The SAM precursor contains between 5% v / v and 50% v / v of one or more of the same monomers or other reaction products, particularly when the mixture offers improved processing parameters or isolating the target compound is too difficult or expensive;

[0086] The SAM precursor contains between about 0 ppbw and about 500 ppbw of metal impurities;

[0087] The concentrations of trace metals and metalloids in the SAM precursor each range from about 0 ppb to about 100 ppb; and

[0088] • The concentrations of trace metals and metalloids in the SAM precursor each range from about 0 ppb to about 10 ppb.

[0089] Also disclosed is a method of forming a self-assembled monolayer (SAM) on a surface, the method comprising the steps of:

[0090] The surface is prepared so as to be exposed to a SAM-forming composition comprising a SAM precursor having a backbone having surface-reactive groups X,

[0091] wherein the backbone does not contain Si—C bonds and is selected from the group consisting of Si—C-free polysilanes and trisilylamine,

[0092] Wherein the surface reactive group X is selected from:

[0093] - halogen (Cl, Br, I);

[0094] - cyanate, isocyanate or thiocyanate groups;

[0095] -Amino-NR 1 R 2 , where R 1 Selected from H, linear, branched or cyclic C1-C 10 Alkyl or alkenyl or alkylsilyl; R 2 Selected from linear, branched or cyclic C2-C 10 Alkyl or alkenyl or alkylsilyl; or R 1 and R 2 Bridge, thus NR 1 R 2 Formation of a cyclic ligand, provided that the cyclic ligand contains a heteroatom S, N or O;

[0096] -amidino-R 3 -NC(R 4)=NR 5 , where R 3 and R 5 Each independently selected from C1 to C 10 a linear or branched alkyl or trialkylsilyl group; and R 4 Selected from H, C1 to C 10 a straight-chain or branched alkyl group; or

[0097] - mercapto -SH, phosphonic acid or carboxylic acid;

[0098] exposing the surface to the SAM-forming composition; and

[0099] A SAM is formed on the surface. The disclosed method may include one or more of the following aspects:

[0100] The SAM-forming composition is a solution;

[0101] exposing the surface to the SAM-forming composition is liquid phase exposure;

[0102] The SAM-forming composition is a vapor; and

[0103] • Exposing the surface to the SAM-forming composition is a vapor phase exposure.

[0104] Also disclosed is a method of forming a film, the method comprising the steps of:

[0105] preparing a surface on a substrate so as to expose the surface to a self-assembled monolayer (SAM)-forming composition comprising a SAM precursor having a backbone having surface-reactive groups X,

[0106] wherein the backbone does not contain Si—C bonds and is selected from the group consisting of Si—C-free polysilanes and trisilylamine,

[0107] Wherein, when the surface to be covered is a dielectric surface, the surface reactive group X is selected from:

[0108] - halogen (Cl, Br, I);

[0109] - cyanate, isocyanate or thiocyanate groups;

[0110] -Amino-NR 1 R 2 , where R 1 Selected from H, linear, branched or cyclic C1-C 10 Alkyl or alkenyl or alkylsilyl; R 2 Selected from linear, branched or cyclic C2-C 10 Alkyl or alkenyl or alkylsilyl; or R 1 and R2 Bridge, thus NR 1 R 2 Formation of a cyclic ligand, provided that the cyclic ligand contains a heteroatom S, N or O;

[0111] -amidino-R 3 -NC(R 4 )=NR 5 , where R 3 and R 5 Each independently selected from C1 to C 10 a linear or branched alkyl or trialkylsilyl group; and R 4 Selected from H, C1 to C 10 a straight-chain or branched alkyl group; or

[0112] - mercapto -SH, phosphonic acid or carboxylic acid;

[0113] exposing the surface to the SAM-forming composition;

[0114] forming a SAM on the surface by liquid or vapor phase exposure; and

[0115] The film is grown on the SAM using a film-forming precursor by a wet deposition process or a dry deposition process. The disclosed method may include one or more of the following aspects:

[0116] The film-forming precursor is a metal or metalloid precursor, wherein the backbone of the SAM precursor acts as a reducing agent for the metal or metalloid precursor;

[0117] The metal precursor is 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, or a combination thereof;

[0118] The metal precursor is selected from WF6, WOF4, WOCl4, WCl6, WCl5, MoCl5, MoOCl4, MoO2Cl2, TiCl4, TiBr4, TiI4, TaCl5, AlCl3, VCl4, NbCl5, BCl3, BBr3, GeCl4, GeBr4 or GeCl2, GeBr2, or a combination thereof;

[0119] The film is a polycarbosilazane film;

[0120] The Si film is porous silicon deposited by PECVD;

[0121] The wet deposition process is a spin coating deposition process;

[0122] The dry deposition process is ALD or CVD process;

[0123] The substrate is any solid having functional groups on its surface that tend to react with the reactive head X of the SAM;

[0124] The substrates are silicon wafers, glass wafers and glass panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc.

[0125] The substrate is a powder used in rechargeable battery technology;

[0126] The substrate is NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials;

[0127] The substrate is a powder; and

[0128] The substrate is nano powder.

[0129] Annotation and naming

[0130] The following detailed description and claims make use of a number of abbreviations, symbols, and terms that are commonly known in the art.

[0131] As used herein, the indefinite article "a" or "an" means one or more than one.

[0132] As used herein, "about" or "around" or "approximately" in the text or claims means ±10% of the stated value.

[0133] As used herein, "room temperature" in the text or claims means from about 20°C to about 25°C.

[0134] The term "ambient temperature" refers to an ambient temperature of about 20°C to about 25°C.

[0135] As used in the disclosed embodiments, the term "independently" when used in the context of describing R groups should be understood to mean that the subject R group is independently selected not only with respect to other R groups with the same or different subscripts or superscripts, but also with respect to any additional species of the same R group. For example, in the formula MR 1 x (NR 2 R 3 ) (4-x) Where x is 2 or 3, two or three R 1 The groups may (but need not) be identical to each other or to R 2 or R 3 Furthermore, it should be understood that unless specifically stated otherwise, the values of the R groups when used in different formulae are independent of one another.

[0136] The term "substrate" refers to one or more materials on which a process is performed. A substrate may refer to a wafer having one or more materials on which a process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductor, photovoltaic, flat panel or LCD-TFT devices. The substrate may also have one or more layers of different materials deposited thereon from a previous manufacturing step. For example, the wafer may include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.) or a combination thereof. In addition, the substrate may be planar or patterned. The substrate may be an organic patterned photoresist film. The substrate may include an oxide layer used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (e.g., a ZrO2-based material, an HfO2-based material, a TiO2-based material, a rare earth oxide-based material, a ternary oxide-based material, etc.), or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. One of ordinary skill in the art will recognize that the terms "film" or "layer" used herein refer to a certain thickness of a material laid or spread on a surface and that the surface may be a groove or line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as the substrate. The substrate may be any solid having functional groups on its surface that tend to react with the reactive heads of the SAM, and may include, but are not limited to, a 3D object or powder.

[0137] It should be noted that the terms "film" and "layer" are used interchangeably herein. It should be understood that a film may correspond to or be associated with a layer, and that the layer may refer to the film. Furthermore, one of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a thickness of a material placed or spread over a surface, and that the surface may range from as large as an entire wafer to as small as a trench or line.

[0138] The terms "via," "aperture," and "hole" are sometimes used interchangeably and generally refer to an opening in an interlayer insulator.

[0139] As used herein, the abbreviation “NAND” refers to a “Negated AND” or “Not AND” gate; the abbreviation “2D” refers to a 2-dimensional gate structure on a planar substrate; and the abbreviation “3D” refers to a 3-dimensional or vertical gate structure in which gate structures are stacked in a vertical direction.

[0140] Standard abbreviations for the elements from the Periodic Table of the Elements are used herein. It should be understood that elements can be referred to by these abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).

[0141] Unique CAS Registry Numbers (ie, "CAS") assigned by the Chemical Abstract Service are provided to identify specific molecules disclosed.

[0142] The term "wafer" or "patterned wafer" refers to a wafer having a stack of silicon-containing films on a substrate and a patterned hard mask layer on the formed stack of silicon-containing films for pattern etching. The term "wafer" or "patterned wafer" may also refer to a trench wafer having a certain aspect ratio.

[0143] It is noted herein that the terms “deposition temperature” and “substrate temperature” may be used interchangeably. It should be understood that substrate temperature may correspond to or be related to deposition temperature, and deposition temperature may refer to substrate temperature.

[0144] It is noted herein that the terms "precursor," "deposition compound," and "deposition gas" may be used interchangeably when the precursor is gaseous at room temperature and ambient pressure. It should be understood that a precursor may correspond to or be associated with a deposition compound or deposition gas, and that a deposition compound or deposition gas may refer to a precursor.

[0145] As used in the disclosed embodiments, the term "hydrocarbyl" refers to a functional group containing carbon and hydrogen; the term "alkyl" refers to a saturated functional group containing only carbon and hydrogen atoms. Hydrocarbyl groups can be saturated or unsaturated. Each term refers to a straight-chain, branched-chain, or cyclic group. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, and butyl. Examples of branched-chain alkyl groups include, but are not limited to, tert-butyl. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, and cyclohexyl.

[0146] As used in the disclosed examples, the abbreviation "Me" refers to methyl; the abbreviation "Et" refers to ethyl; and the abbreviation "Pr" refers to propyl.

[0147] In this article, ranges can be expressed as from about one specific value and / or to about another specific value. When expressing such a range, it should be understood that another embodiment is from the one specific value and / or to the other specific value, together with all combinations within the range. Any and all ranges listed herein include their endpoints (i.e., x=1 to 4, or x is in the range from 1 to 4, including x=1, x=4 and x=any number in between), regardless of whether the term "inclusive" is used.

[0148] Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the present invention. The phrase "in one embodiment" appearing in various places in the specification is not necessarily referring to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. This also applies to the term "implementation."

[0149] As used herein, the word "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as superior or advantageous over other aspects or designs. Instead, the use of the word exemplary is intended to describe concepts in a concrete manner.

[0150] Additionally, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless specified otherwise or clear from the context, "X employs A or B" is intended to mean any of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, then "X employs A or B" is satisfied in any of the foregoing instances. Furthermore, the articles "a" and "an" used in this application and the appended claims should generally be construed to mean "one or more," unless specified otherwise or clear from the context to direct to a singular form. BRIEF DESCRIPTION OF THE DRAWINGS

[0151] 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 similar reference numerals, and in which:

[0152] Figure 1 It is the residue of spin-coating deposited thin films that aggregate in clusters when HMDS is used as a binder;

[0153] Figure 2 It is monoaminotrisilane (Si3H7-NR2, where R 1 is the WCA result of C2 to C5 alkyl) derivatives;

[0154] Figure 3 It is a monoamino-trimethylsilylamine derivative (Si3H8N-NR2, where R 1 is the WCA result of C2 to C5 alkyl);

[0155] Figure 4 The thin film is deposited by spin coating using (diisobutylamine) trisilane (DIBATS) as a binder;

[0156] Figure 5The thin film is deposited by spin coating using (diisopropylamine)trimethylsilylamine as a binder; and

[0157] Figure 6 is the water contact angle (WCA) of the SiO surface treated with vapor SiT SAM (DIBATS). DETAILED DESCRIPTION

[0158] Disclosed are self-assembled monolayer (SAM) monomers having a Si-based tail or backbone that does not contain Si-C bonds (SiT-SAM), their synthesis, and their use in surface preparation in film-forming processes.

[0159] The disclosed SiT-SAM monomer is described as having a backbone with surface reactive groups (or heads) (denoted as "X").

[0160] When the surface to be coated is a dielectric surface, the surface reactive group "X" is reactive towards surface hydroxyl groups (-OH). In this case, X is selected from:

[0161] a. Halogen (Cl, Br, I);

[0162] b. cyanate, isocyanate or thiocyanate groups;

[0163] c. Amino-NR 1 R 2 , where R 1 Selected from H, linear, branched or cyclic C1-C 10 Alkyl or alkenyl or alkylsilyl; R 2 Selected from linear, branched or cyclic C2-C 10 Alkyl or alkenyl or alkylsilyl; or R 1 and R 2 Bridge, thus NR 1 R 2 to form a cyclic ligand, provided that the cyclic ligand contains a heteroatom S, N or O; or

[0164] d. amidino-R 3 -NC(R 4 )=NR 5 , where R 3 and R 5 Each independently selected from C1 to C 10 a linear or branched alkyl or trialkylsilyl group; and R 4 Selected from H, C1 to C 10 A straight-chain or branched alkyl group.

[0165] Preferably, X is a dialkylamino-NR 1 R 2 , where R1 is selected from H or C2 to C5 alkyl; and R 2 is a C1 to C5 alkyl group. 1 =H, then R 2 is C3 or greater, if R 1 If not H, then R 1 and R 2 Preferably, X is amidino-NR 3 -C(R 4 )=NR 5 , where R 3 and R 5 are each independently selected from Et, nPr, iPr, nBu, tBu, sBu, iBu, and R 4 It’s H and Me.

[0166] When the surface to be coated is a metal, the surface reactive head "X" is a mercapto group -SH, a phosphonic acid, or a carboxylic acid. For example, the mercapto group reacts with the metal surface to form a sulfur-metal interface.

[0167] The disclosed SiT-SAM monomer is a molecule suitable for forming a SAM on the surface of a substrate during a film formation process. The monomer backbone of the disclosed SiT-SAM monomer can 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 bonds, and (ii) trisilylamine (TSA).

[0168] More specifically, the disclosed SiT-SAM monomer is a Si-C-free polysilane-based SiT-SAM monomer comprising (i) a Si-C-free polysilane backbone and "X" surface reactive groups.

[0169] The disclosed SiT-SAM monomer based on Si-C-free polysilane is selected from:

[0170] X-(SiH2) n -SiH3 where n=1 to 3,

[0171] X-(Si n H 2n ) Among them, Si n H 2n Represents a cyclic hydrosilane main chain, where n=5, 6, or 7,

[0172] X-(SiH(SiH3)2), or

[0173] X-SiH2-Si(SiH3)3.

[0174] Preferably, the polysilane backbone is -SiH2-SiH3 or -SiH2-SiH2-SiH3.

[0175] Exemplary Si-C-free polysilane-based SiT-SAM monomers include: NiPr2-(SiH2)-SiH3, NnBu2-(SiH2)-SiH3, NtBu2-(SiH2)-SiH3, NsBu2-(SiH2)-SiH3, NiBu2-(SiH2)-SiH3, NPen2-(SiH2)-SiH3, NnPr2-(SiH2)2-SiH3, NiPr2-(SiH2)2-SiH3, NnBu2 -(SiH2)2-SiH3, NtBu2-(SiH2)2-SiH3, NsBu2-(SiH2)2-SiH3, NiBu2-(SiH2)2-SiH3, NsPen2-(SiH2)2-Si H3, NHtBu-(SiH2)2-SiH3, NHPen-(SiH2)2-SiH3, NHsBu-(SiH2)2-SiH3, NHiBu-(SiH2)2-SiH3, NnPr2-(SiH 2) 3-SiH3, NiPr2-(SiH2)3-SiH3, NnBu2-(SiH2)3-SiH3, NtBu2-(SiH2)3-SiH3, NsBu2-(SiH2)3-SiH3, NiB u2-(SiH2)3-SiH3, NsPen2-(SiH2)3-SiH3, NEt2-(SiH(SiH3)2), NiPr2-(SiH(SiH3)2), NnPr2-(SiH(SiH3) 2), NiBu2-(SiH(SiH3)2), NtBu2-(SiH(SiH3)2), NnBu2-(SiH(SiH3)2), NsBu2-(SiH(SiH3)2), NsPen2-(S iH(SiH3)2), NHtBu-(SiH(SiH3)2), NHnBu-(SiH(SiH3)2), NHiBu-(SiH(SiH3)2), and NHPen-(SiH(SiH3)2).

[0176] In addition, the disclosed SiT-SAM monomer is a TSA-based SiT-SAM monomer comprising (ii) a TSA backbone and an "X" head. The TSA-based SiT-SAM monomer comprises at least one N(-Si)3 unit in its backbone and one or two "X" surface reactive groups. For simplicity, H and non-hydrolyzable groups are not described throughout the specification and claims.

[0177] The disclosed TSA-based SiT-SAM monomer has the general formula

[0178] XR2Si-N(SiR3) n (SiX'R2)2-n ,

[0179] wherein X' has the same definition as X above and is independent of X; n = 1 or 2; R is selected from H, C1 to C6 branched or linear alkyl chain. Preferably, each R = H, in which case the formula becomes XH2Si-N(SiH3) n (SiX'H2) 2-n Preferably, n=2, in which case the formula becomes XR2Si-N(SiR3)2. TSA-based SiT-SAM monomers may contain more than one N(-Si)3 unit and have a backbone such as (Si)2N-Si-N(Si)(Si-X) or X-Si-N(Si)-Si-N(Si)(Si-X).

[0180] The disclosed SiT-SAM monomers can be used for exposure to a surface or substrate in a liquid phase (neat or preferably diluted in a solvent) that is inert to the disclosed SiT-SAM monomers and the surface reactive groups. The solvent is typically an aprotic solvent such as a hydrocarbon, toluene, ethers, trialkylamines, etc. The surface or substrate exposure can be achieved by any coating method such as dip coating, spin coating, or spray coating. The exposure can last between 1 second and 24 hours. After exposure, the surface or substrate is preferably rinsed with a solvent and dried. The presence and properties of a suitable SAM layer can be assessed by techniques such as water contact angle (WCA), attenuated total reflectance FTIR (ATR-FTIR), or high-angle XPS.

[0181] Alternatively, the disclosed SiT-SAM monomers can be used for exposure to a surface or substrate in the vapor phase. Furthermore, the method for forming the SiT-SAM is no different from the method for forming a classical SAM, such as the method described by F. Schreiber ("Structure and growth of self-assembling monolayers," Frank Schreiber, Progress in Surface Science, Vol. 65, Nos. 5-8, 2000, 151-257). The surface or substrate is preferably heated to promote reaction of the surface sites with the disclosed SiT-SAM monomers, typically at a temperature ranging from room temperature to about 450° C. (the temperature at which the disclosed SiT-SAM monomers typically self-decompose). The exposure time can range from 1 second to 24 hours, preferably not exceeding 10 minutes.

[0182] Regardless of whether exposure to the disclosed SiT-SAM monomers occurs in the gas phase or liquid phase, the surface / substrate can be pretreated to improve the reaction of the disclosed SiT-SAM monomers with the surface. Such treatment can increase the density of reactive sites (e.g., -OH groups on oxide surfaces), reduce incidental film contamination (e.g., carbon on metal surfaces), or remove passivating oxides on metals. Such dry or wet surface preparation and cleaning techniques are well known in the art and can be applied for use with the disclosed SiT-SAM monomers.

[0183] The substrate end application is not limited to the present invention, but this technology can be particularly beneficial for the following types of substrates: silicon wafers, glass wafers and glass panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders 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.

[0184] It should be understood that substrates represent physical elements and that their composition can be different from the composition of one or more layers on which the disclosed SiT-SAM monomers are deposited. For example, a silicon wafer can be coated with various dielectrics (SiO2, SiN, SiC, SiCOH, SiCN, SiON, SiOCN, aC, etc.), semiconductors (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.).

[0185] Similar to classical SAMs and particularly silylated SAMs, the disclosed SiT-SAM monomers are useful for improving the wettability of substrates to certain solution-based film-forming formulations, such as spin-on dielectrics, antireflective coatings, or photoresist materials.

[0186] Unlike classical SAMs (which act only as surface blockers), the disclosed SiT-SAM monomers can prove beneficial because their Si-tails exhibit interesting chemical reactivity that can be beneficial for further processing of the surface. Thus, as opposed to simply blocking the surface, the disclosed SiT-SAM monomers act as a way to direct certain reactions on the surface specifically covered by the disclosed SiT-SAM monomers and can therefore be used as positive masks for area-selective deposition processes.

[0187] To ensure process reliability, the disclosed SiT-SAM monomers can be purified prior to use by continuous or fractionated batch distillation or sublimation to a purity ranging from about 95% by weight or w / w to about 100% w / w, preferably ranging from about 99% w / w to about 99.999% w / w, and more preferably ranging from about 99% w / w to about 100% w / w.

[0188] The disclosed SiT-SAM monomer may contain any of the following impurities: undesirable congeners; solvents; or other reaction products. In an alternative embodiment, the total amount of these impurities is less than 5.0% w / w, preferably less than 0.1% w / w.

[0189] A solvent such as hexane, pentane, dimethyl ether, or anisole can be used in the synthesis of the precursor. The concentration of the solvent in the disclosed SiT-SAM monomer can range from about 0% w / w to about 5% w / w, preferably from about 0% w / w to about 0.1% w / w. If both the solvent and the precursor have similar boiling points, separation of the solvent from the precursor can be difficult. Cooling the mixture can produce a solid precursor in the liquid solvent that can be separated by filtration. Vacuum distillation can also be used, provided that the precursor product is not heated above approximately its decomposition point.

[0190] In one alternative, the disclosed SiT-SAM monomer contains 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 undesirable congeners, reactants, or other reaction products. This alternative can provide better process reproducibility. This alternative can be produced by distillation of the disclosed SiT-SAM monomer.

[0191] In another alternative, the disclosed SiT-SAM monomers may contain between 5% v / v and 50% v / v of one or more of the same monomer or other reaction products, particularly when the mixture offers improved processing parameters or when isolating 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 forming a SAM.

[0192] In another alternative, the disclosed SiT-SAM monomers may contain between about 0 ppbw and about 500 ppbw of metal impurities. The concentrations of trace metals and metalloids in the disclosed SiT-SAM monomers may each range from about 0 ppb to about 100 ppb, and more preferably from about 0 ppb to about 10 ppb.

[0193] The present disclosure also includes a method for forming a SAM on a surface. The method comprises the steps of: preparing the surface so as to expose the surface to a disclosed SAM-forming composition; exposing 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 liquid-phase exposure. When the SAM-forming composition is a vapor, the exposure of the surface to the SAM-forming composition is vapor-phase exposure.

[0194] The disclosure also includes a method for forming a film using the disclosed SiT-SAM monomer. The method includes the steps of: preparing the surface so as to expose the surface to a SAM-forming composition; exposing the surface to the SAM-forming composition; forming a SAM on the surface by liquid or vapor phase exposure; and growing a film on the SAM using a film-forming precursor by a wet or dry deposition process. When the SAM-forming composition is a solution, exposing the surface to the SAM-forming composition is liquid phase exposure. Exposing the surface to the SAM-forming composition can be liquid phase exposure or vapor phase exposure. When the SAM-forming composition is a vapor, exposing the surface to the SAM-forming composition is vapor phase exposure. The wet deposition process can be a spin-on deposition process, and the dry deposition process can be an ALD or CVD process.

[0195] In an exemplary embodiment, the precursor for depositing a film on a SAM formed by a SiT-SAM monomer can be a metal or metalloid precursor, and the tail of the SiT-SAM monomer acts as a reducing agent for the metal or metalloid precursor. The metal precursor can preferably be selected from a main group element, or a transition metal element selected from Ti, Ta, W, Mo, Nb or V. The metal precursor can be a fluoride, a chloride, a bromide, an iodide, an oxychloride, an oxybromide, an oxyfluoride, or a combination thereof. More specifically, the metal or metalloid precursor can be selected from: WF6, WOF4, WOCl4, WCl6, WCl5, MoCl5, MoOCl4, MoO2Cl2, TiCl4, TiBr4, TiI4, TaCl5, AlCl3, VCl4, NbCl5, BCl3, BBr3, GeCl4, GeBr4 or GeCl2, GeBr2, or a combination thereof. It is noted that several of these halide compounds can form stable and volatile adducts and can be used in this form of thin film deposition, for example, GeCl2:dioxane, TaCl5:SEt2, TiBr4:SiPr2.

[0196] In addition to the precursor, reactants or co-reactants may be introduced into the reactor. The co-reactant may be an oxygen-containing gas or a nitrogen-containing gas. Co-reactants include, but are not limited to, oxidants such as O3, O2, H2O, H2O2, D2O, ROH (R is C1-C 10 Straight chain or branched hydrocarbons) etc. H2O and ROH (R is C1-C 10 Straight-chain or branched hydrocarbons) are preferred oxidizing sources to avoid reaction with the SAM layer formed on the substrate. Nitrogen-containing gases include, but are not limited to, NH3, NO, NO, hydrazine, primary amines such as methylamine, ethylamine, and tert-butylamine; secondary amines such as dimethylamine, diethylamine, diisopropylamine, ethylmethylamine, and pyrrolidine; tertiary amines such as trimethylamine, triethylamine, and trimethylsilylamine; N2, N2 / H2 mixtures thereof, and preferably NH3. The co-reactant can be selected from H2, NH3, NO, NO, hydrazine, amines, or combinations thereof. Preferably, plasma-treated co-reactants are avoided because they tend to damage the SAM layer unless the SAM layer is reformed in each ALD cycle.

[0197] Examples

[0198] The following non-limiting examples are provided to further illustrate embodiments of the present invention. However, these examples are not intended to be all-inclusive and are not intended to limit the scope of the invention described herein.

[0199] Comparative Example 1

[0200] Deposition of polycarbosilazane films using hexamethyldisilazane Me3Si-NH-SiMe3 (HMDS) as an adhesion promoter

[0201] Silicon wafers containing native oxide, cut into 2x2 cm samples, were subjected to UV-ozone cleaning (hereinafter referred to as UV-O3 cleaning) for 10 minutes to remove organic contaminants. After UV-O3 cleaning, the surface was completely hydrophilic, exhibiting a distilled deionized water contact angle of <5°. Subsequently, the sample was placed in an N2 glove box, and 200 μl of HMDS solution was spin-coated onto it using a Brewer Science Cee 200X spin coater at 2000 rpm for 60 seconds. After spin-coating the HDMS adhesion promoter, the surface exhibited hydrophobic properties, with an average contact angle of 95°. Subsequently, 200 μl of polycarbosilazane solution was spin-coated at 2000 rpm for 60 seconds. The spin-coating process was followed by a pre-bake step at 200°C for 5 minutes in an N2 glove box to promote evaporation of solvents and volatiles.

[0202] Figure 1Figure 3. Spin-coating deposited film residues showing clustered clusters when HMDS was used as a binder. After the prebake step, the polycarbosilazane film formed during the spin-coating process is completely degraded and the remaining material is clustered into islands.

[0203] Thus, this example demonstrates that HMDS, which is a common adhesion promoter in the industry, may be incompatible with the polycarbosilazane polymer used, as it may detrimentally affect the adhesion between the polymer and the silicon coupon.

[0204] Example 1

[0205] Synthesis of (diisopropylamine)trimethylsilylamine ((CHMe2)2-N-SiH2-N-(SiH3)2, TSA-N(CHMe2)2)

[0206] The TSA-N(CHMe2)2SAM precursor was synthesized in a pressurized reactor by the reaction of trisilylamine (TSA) and diisopropylamine (Me2-CH2-NH) catalyzed by a commercially available ruthenium / carbon catalyst: 5.3 g (0.0025 mmol of ruthenium) of a 5% by weight ruthenium / carbon catalyst was added to a 0.3 L autoclave equipped with a mechanical stirrer, a thermocouple, a pressure gauge and a pressure sensor, and three metering valves. The reactor was then heated at about 125°C for 3 hours under dynamic vacuum. As used herein, dynamic vacuum refers to a vacuum of about 1 Torr. After cooling to room temperature, 14.8 g (0.202 mol) of diisopropylamine was added to the reactor, which was then 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 seconds, the pressure increased to 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. The reaction can be terminated before completion if desired. The reactor is cooled to room temperature ("RT"). Volatile materials are collected in a cryogenic cold trap in an SSLB at liquid nitrogen temperature. The reactor pressure is dropped to 50 Torr.

[0207] The resulting solution contained approximately 30% (11.3 g) of TSA-N(CHMe2)2. The unisolated yield was 30%.

[0208] Example 2

[0209] Synthesis of Chlorotrisilylamine ((SiH3)2-N-SiH2Cl, TSA-Cl)

[0210] The TSA-Cl SAM precursor is synthesized according to the following reaction: SnCl4 + N(SiH3)3 → N(SiH3)2(SiH2Cl) + SnCl2↓ + HCl (see J. Chem. Soc. Dalton Trans. 1975, p. 1624). Alternatively, dichlorosilane [SiH2Cl2] and monochlorosilane [SiH3X] can be introduced continuously in the vapor phase at room temperature in a 1 / 20 to 1 / 4 ratio along with 400 sccm of NH3 into a flow-through tubular reactor such as that described by Miller in U.S. Patent No. 8,669,387. NH3 reacts with two equivalents of monochlorosilane to primarily produce disilylamine (DSA). DSA then reacts with dichlorosilane to form (SiH3)2-N-SiH2Cl and HCl. Those skilled in the art will recognize that the reaction can occur in one or two steps (first forming DSA from monochlorosilane and NH 3 , second adding dichlorosilane) or in one step (combining monochlorosilane, dichlorosilane, and NH 3 in one step).

[0211] Example 3

[0212] Synthesis of amine-substituted polysilanes

[0213] Amine-substituted polysilanes can be synthesized by the following steps.

[0214] a) Make the reactant R 1 R 2 NH and R 3 R 4 NH and Si m H 2(m+1) contacting in the presence of a transition metal catalyst to form a reaction mixture;

[0215] b) optionally adding a solvent to the reaction mixture;

[0216] c) maintaining the reaction mixture at a temperature between about 0° C. and about 300° C.;

[0217] d) allowing the reaction to proceed to form (R 1 R 2 N) n1 (R 3 R 4 N) n2 Si m H (2(m+1)-n1-n2) ;

[0218] e) will (R 1 R 2 N) n1 (R 3 R 4 N)n2 Si m H (2(m+1)-n1-n2) separating from the reaction mixture;

[0219] The temperature of the reaction mixture may be varied during the synthesis and maintained such that the temperature of the reaction mixture is not allowed to drop below about 0°C and does not exceed about 300°C.

[0220] For example, the structural formula is as follows, m=3; R 1 =R 2 =isopropyl; n1=1; n2=0.

[0221]

[0222] Wherein the reactants are Me2NH and Si3H8. See, for example, US 10494387.

[0223] Example 4

[0224] Synthetic amidine (AMD, -R 1 HN(CR 3 )=NR 2 , ) substituted polysilane

[0225] AMD substituted polysilane refers to (R 1 HN(CR 3 )=NR 2 ) n -Si m H (2(m+1)-n) ), wherein n=1 to 2(m+1); m=2 to 6; R 1 and R 2 Each is independently selected from the group consisting of a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl ether, silyl, trimethylsilyl, or linear or branched C1 to C6 alkyl substituted silyl.

[0226] In the above-mentioned synthesis method of the amine-substituted polysilane in Example 3, R 1 R 2 NH replaced by R 1 HN(CR 3 )=NR 2 , then AMD-substituted polysilanes will be formed. See, for example, US 10494387.

[0227] Example 5

[0228] Synthesis of X-substituted bis-disilylaminohalosilanes (BDSASi-X) where X = F, Cl, Br or I

[0229] According to the same scheme as described in U.S. Patent Application Publication No. 2015 / 0094470, the SAM precursor BDSASi-X(F, Cl, Br, I) is preferably synthesized by direct reaction of (SiH3)2N-SiH2-N(SiH3)2(BDSASi) with hydrohalic acid via dehydrogenative coupling.

[0230] (SiH3)2N-SiH2-N(SiH3)2+nHX→[N(SiH 3-m (X)m]-SiH2-[SiH 3-n (X)n]+(m+n)H2, m=0 to 3, n=1 to 3.

[0231] The reaction is carried out in pure form or in an aprotic solvent, such as but not limited to C3-C 24 Hydrocarbon solvents, toluene, benzene, diethyl ether, acetonitrile, or THF.

[0232] The reaction is carried out at a temperature between room temperature and 150°C, preferably at 30°C-60°C.

[0233] - Optionally, the catalyst is filtered from the reaction mixture and the components of the remaining liquid composition are separated by distillation.

[0234] Optionally, the reaction mixture is treated with a reagent selected from, but not limited to, tertiary amines or coordination compounds such as XNR4 (X = F, Cl, Br, I; R = alkyl), R-CN, R2S, PR3 to deactivate the catalyst.

[0235] Optionally, the compound of BDSASi-X is purified by distillation to achieve an assay of >98%, more preferably or >99%, and even more preferably >99.5%, which is typical for semiconductor grade precursors Optionally, the product can be filtered to achieve typical specifications for products used in the semiconductor industry.

[0236] Example 6

[0237] Synthesis of diisobutylaminotrisilane (DIBATS, (iBu)2-N-SiH2-SiH2-SiH3)

[0238] The SAM precursor DIBATS is synthesized from trisilane (SiH3-SiH2-SiH3) and diisobutylamine ((iBu)2-NH3) in a pressurized reactor using a commercially available ruthenium / carbon catalyst. 6 g (0.003 mmol of ruthenium) of a 5% by weight ruthenium / carbon catalyst was added to a 0.3 L autoclave equipped with a mechanical stirrer, a thermocouple, a pressure gauge and a pressure sensor, and three metering valves. The reactor was then heated at 125°C for 3 hours under dynamic vacuum. After cooling to room temperature, the reactor was filled with 1 atm of helium, sealed, disconnected from the manifold, and placed in a glove box. Inside the glove box, 20.7 (0.205 mol) of diisobutylamine was added. The reactor was then removed from the glove box and reconnected to the manifold and cooled to -130°C in a liquid nitrogen bath. 40 g of trisilane (0.433 mol) was transferred to the reactor via the manifold. The reactor was then heated to 100°C. After stirring at 400 rpm for 23 hours, the reactor was cooled to room temperature. Volatiles were cryogenically collected in a stainless steel valve bottle (SSLB). The reaction vessel pressure was reduced to 20 Torr. DIBATS was recovered from the reaction vessel. The reaction solution contained 11.49 g of DIBATS. The unisolated yield was 29%. See, for example, US Pat. No. 10,494,387.

[0239] Example 7

[0240] Synthesis of amidino neopentylsilane (NPS-AMD, C5H 11 -SiH2-R 1 HN(CR 3 )═NR 2 )

[0241] The SAM precursor NPS-AMD was synthesized as follows.

[0242] a) making the reactant amidine (R 1 HN(CR 3 )═NR 2 ) and neopentylsilane (C5H 11 -SiH3) in the presence of a transition metal catalyst to form a reaction mixture; wherein R 1 、R 2 and R 3 independently selected from the group consisting of a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl ether, silyl, trimethylsilyl, or linear or branched C1 to C6 alkyl substituted silyl; wherein neopentylsilane (C5H 11 -SiH3) and (R 1 HN(CR3 )═NR 2 ) in a molar ratio of at least 1:1;

[0243] b) optionally adding a solvent to the reaction mixture;

[0244] c) maintaining the reaction mixture at a temperature between about 0° C. and about 300° C.;

[0245] d) Allow the reaction to proceed and form NPS-AMD (C5H 11 -SiH2-(R 1 N(CR 3 )═NR 2 ));

[0246] e) isolating the product NPS-AMD from the reaction mixture; wherein the reaction temperature may be varied during the synthesis and maintained such that the temperature of the reaction mixture is not allowed to drop below about 0° C. and does not exceed about 300° C. See, for example, US10494387.

[0247] Example 8

[0248] Synthesis of dialkylamino neopentylsilane (NPS-NR 4 R 5 )

[0249] In the above synthesis scheme of NPS-AMD in Example 7, the reactant amidine (R 1 HN(CR 3 )═NR 2 ) is replaced by amine R 4 R 5 NH, the product SAM precursor NPS-NR will be formed 4 R 5 , where R 4 and R 5 Each is independently: H, a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl. See, for example, US10494387.

[0250] Example 9

[0251] Synthesis of amidinocyclohexylsilane (CHS-AMD)

[0252] The SAM precursor CHS-AMD was synthesized as follows.

[0253] a) making the reactant amidine) (R 1 HN(CR 3 )═NR 2and cyclohexylsilane (C6H 11 -SiH 3) contacting in the presence of a transition metal catalyst to form a reaction mixture; wherein R 1 、R 2 and R 3 independently selected from the group consisting of a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl ether, silyl, trimethylsilyl, or linear or branched C1 to C6 alkyl substituted silyl; wherein cyclohexylsilane (C6H 11 -SiH3) and (R 1 HN(CR 3 )═NR 2 ) in a molar ratio of at least 1:1;

[0254] b) optionally adding a solvent to the reaction mixture;

[0255] c) maintaining the reaction mixture at a temperature between about 0° C. and about 300° C.;

[0256] d) Allow the reaction to proceed to form the SAM precursor CHS-AMD (C6H 11 -SiH2-(R 1 N(CR 3 )═NR 2 ));

[0257] e) isolating the product CHS-AMD from the reaction mixture; wherein the reaction temperature may be varied during the synthesis and maintained such that the temperature of the reaction mixture is not allowed to drop below about 0° C. and does not exceed about 300° C. See, for example, US10494387.

[0258] Example 10

[0259] Synthesis of dialkylaminocyclohexylsilane (CHS-NR 4 R 5 )

[0260] In Example 9, in the above synthesis scheme of CHS-AMD, the reactant amidine (R 1 HN(CR 3 )═NR 2 ) is replaced by amine R 4 R 5 NH, the product SAM precursor CHS-NR will be formed 4 R 5 , where R 4 and R5 Each is independently: H, a linear or branched C1 to C6 alkyl group, a linear or branched C1 to C8 alkenyl group, a linear or branched C1 to C8 alkynyl group, a C6 to C 10 Aryl, linear or branched C1 to C6 alkyl. See, for example, US10494387.

[0261] Example 11

[0262] Wet coating SiT-SAM

[0263] Pure SiT-SAM monomer (0.2mL) is deposited on SiO (thermal oxide) wafer under N atmosphere and room temperature.Then this wafer is rotated 60sec (that is, until this wafer is obviously dry) with 2000RPM.This wafer is received as is or carries out pre-treatment under O (5min, room temperature) to clean and hydroxylate this surface.Water contact angle (WCA) measurement is measured immediately in air.Then wafer is cured 10min at 300 ℃ under N, and WCA is remeasured after annealing.

[0264] The results are listed in Figure 2 and Figure 3 In the paper, it is shown that for monoaminotrisilane (Si3H7-NR2, where R 1 is a C2 to C5 alkyl) derivative and a monoaminotrimethylsilylamine derivative (Si3H8N-NR2, wherein R 1 After annealing, the WCA remains high at 300°C, indicating that the SiT-SAM monomers can withstand such high temperatures without decomposition and that wet exposure at room temperature is sufficient to chemically bind the SAMs to the surface.

[0265] Example 12

[0266] SiT SAM was applied as a SOD coating primer using (diisobutylamine)trisilane (DIBATS) as an adhesion promoter to deposit polycarbosilazane films

[0267] The same method as described in Comparative Example 1 was used, using DIBATS as an adhesion promoter instead of HDMS. A silicon wafer containing native oxide, cut into 2 x 2 cm specimens, was cleaned with UV-O3 for 10 minutes. The specimen was then placed in an N2 glove box and 200 μl of DIBATS solution was spin-coated at 2000 rpm for 60 seconds using a Brewer Science Cee 200X spin coater. After spin-coating the DIBATS adhesion promoter, the surface exhibited hydrophobic properties, with an average contact angle of 88°. Subsequently, 200 μl of a polycarbosilazane solution was spin-coated at 2000 rpm for 60 seconds. The spin-coating process was followed by a pre-bake step at 200°C for 5 minutes in an N2 glove box to promote evaporation of solvents and volatiles.

[0268] Figure 4 Shown is a deposited film spin-coated using DIBATS as a binder. The film was maintained and uniform across the sample. After the prebake step, a 260nm thick polycarbosilazane film was maintained. The film exhibited good uniformity across the film, with few voids and defects. Therefore, this example demonstrates that DIBATS can strongly bond to polycarbosilazane and maintain this bond after the prebake heat treatment. To test the adhesion of polycarbosilazane to a silicon substrate, a scotch tape test was performed. The film did not peel or detach. After repeating the scotch tape test multiple times (greater than 5 times) on the same sample, no visual difference was observed.

[0269] Example 13

[0270] SiT SAM was applied as a SOD coating primer using (diisopropylamine)trimethylsilylamine (TSA-N(CHMe2)2) as an adhesion promoter to deposit polycarbosilazane films.

[0271] TSA-N(CHMe2)2 was used as an adhesion promoter instead of DIBATS, following the same method described in Example 12 using DIBATS as the adhesion promoter. Silicon wafers containing native oxide, cut into 2 x 2 cm samples, were cleaned with UV-O3 for 10 minutes. The samples were then placed in an N2 glove box and 200 μl of TSA-N(CHMe2)2 solution was spin-coated at 2000 rpm over 60 seconds using a Brewer Science Cee 200X spin coater. After spin-coating the TSA-N(CHMe2)2 adhesion promoter, the surface exhibited hydrophobic properties with an average contact angle of 98°. Subsequently, 200 μl of polycarbosilazane solution was spin-coated at 2000 rpm over 60 seconds. The spin-coating process was followed by a prebake step at 200°C for 5 minutes in an N2 glove box to facilitate evaporation of solvent and volatiles.

[0272] Figure 5 Shown is a deposited film spin-coated using TSA-NH(CHMe2)2 as a binder. The film was maintained and uniform across the sample. After the prebake step, a 260nm thick polycarbosilazane film was maintained. The film exhibited good uniformity across the film with very few voids and defects. Therefore, this example demonstrates that TSA-NH(CHMe2)2 is able to bond strongly to polycarbosilazane and maintain that bond after the prebake heat treatment. To test the adhesion of polycarbosilazane to a silicon substrate, a scotch tape test was performed. The film did not peel or detach. After repeating the scotch tape test multiple times (greater than 5 times) on the same sample, no visual difference was observed.

[0273] Example 14

[0274] Vapor-coated SiT-SAM

[0275] SiO2 (thermal oxide) wafers were exposed to SiT-SAM monomer DIBATS (0.02 Torr partial pressure) vapor at 100°C under vacuum (9.5F). The wafers were exposed to SiT SAM vapor for 5 minutes. The wafers were received as is (original) or pretreated with O3 (10 min, room temperature) to clean and hydroxylate the surface. Water contact angle (WCA) measurements were performed immediately in air. The wafers were stored at ambient temperature (23-24°C) and humidity (41%-56% RH) and the WCA was remeasured after aging for 24 and 48 hours.

[0276] The results are listed in Figure 6 Figure 3 shows that the WCA of both pristine and pre-treated SiO substrates exposed to vapor SiT-SAM, DIBATS, increased significantly. After aging for 24 and 48 hours under ambient conditions, the WCA remained high (>70 degrees), indicating that the SiT-SAM monomer may be stable under ambient conditions and can withstand exposure.

[0277] Prophetic Example 1

[0278] Dry coating of SiT-SAM

[0279] The disclosed SiT-SAM monomers used in the dry coating process are volatile enough to evaporate and reach sufficient vapor pressure to react with the surface of the substrate / wafer within a reasonable time. The surface to be treated is exposed to the vapor of the SiT-SAM monomer and reacts with it. CVD or ALD processes can be used to dry-coat the SiT-SAM. 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 can be achieved under atmospheric pressure (e.g., APCVD) or in vacuum.

[0280] Prophetic Example 2

[0281] Applying SiT-SAM as an enhancement layer for thin film deposition

[0282] Exemplary applications for Si anodes in the cell space can be made by comparing the growth of polySi on (diisobutylamine)trisilane-coated SiO with that on SiO without (diisobutylamine)trisilane coating (gas / liquid), and by comparing the growth of porous Si on (diisobutylamine)trisilane-coated Ni (with native oxide)O with that on Ni without (diisobutylamine)trisilane coating (gas / liquid). The disclosed SiT-SAM monomers can be used as seeds for metal barriers using metal halides (W, Mo, Ti, Ta, ...) at temperatures below 600°C, preferably below 500°C.

[0283] Prophetic Example 3

[0284] SiT-SAM for powder coating

[0285] The disclosed SiT-SAM monomers can be used to wet-coat SiO2 powders / filter / wet-oxidize (HO+IPA) on the surface of the powder. The disclosed SiT-SAM monomers can be used to vapor-coat carbon-free, hydrophobic-enhanced powders (e.g., Al2O3, SiO2 powders, Si powders containing native oxides, any metal powders containing native or ALD oxides, such as Al, W, Ti, Cu).

[0286] Although the subject matter described herein may be described in the context of illustrative implementations for processing one or more computing application features / operations of a computing application having a user interaction component, the subject matter is not limited to these specific embodiments. Rather, the techniques described herein may be applied to any suitable type of user interaction component execution management method, system, platform, and / or apparatus.

[0287] It should be understood that many additional changes in the details, materials, steps, and arrangements of parts described and illustrated herein to explain the essence of the present invention may be made by those skilled in the art within the principles and scope of the present invention as expressed in the appended claims. Therefore, the present invention is not intended to be limited to the specific embodiments shown in the examples and / or drawings given above.

[0288] Although embodiments of the present invention have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit or teachings of the present invention. The embodiments described herein are intended to be illustrative only 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 only by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims.

Claims

1. A method for forming a film, the method comprising the following steps: A surface on a substrate is prepared so as to expose the surface to a self-assembled monolayer (SAM) forming composition comprising A SAM precursor having a main chain with surface reactive groups X, wherein the main chain does not contain Si-C bonds and is a group consisting of Si-C-free polysilane and trisilylamine, Wherein the surface reactive group X is selected from: - halogen selected from Cl, Br, I; - cyanate, isocyanate or thiocyanate groups; -Amino-NR 1 R 2 , where R 1 Selected from H, linear, branched or cyclic C1-C 10 Alkyl or alkenyl or alkylsilyl; R 2 Selected from linear, branched or cyclic C2-C 10 alkyl or alkenyl, provided that R 1 =R 2 ≠Et; or alkylsilyl; or R 1 and R 2 Bridge, thus NR 1 R 2 Formation of a cyclic ligand, provided that the cyclic ligand contains a heteroatom S, N or O; -amidino-R 3 -NC(R 4 )=NR 5 , where R 3 and R 5 Each independently selected from C1 to C 10 a linear or branched alkyl or trialkylsilyl group; and R 4 Selected from H, C1 to C 10 a straight-chain or branched alkyl group; or - mercapto -SH, phosphonic acid or carboxylic acid; exposing the surface to the SAM-forming composition; forming the SAM on the surface by liquid or vapor phase exposure; as well as A film is grown on the SAM by a wet deposition process or a dry deposition process using a film-forming precursor, wherein the film-forming precursor is 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 a combination thereof.

2. The method of claim 1, wherein the film-forming precursor is selected from the group consisting of: WF6, WOF4, WOCl4, WCl6, WCl5, MoCl5, MoOCl4, MoO2Cl2, TiCl4, TiBr4, TiI4, TaCl5, AlCl3, VCl4, NbCl5, BCl3, BBr3, GeCl4, GeBr4 or GeCl2, GeBr2, and combinations thereof. The method according to claim 1 , wherein the dry deposition process is an ALD or CVD process.

4. The method of claim 1, wherein X is a dialkylamino-NR 1 R 2 , where R 1 is H, C2 to C5 alkyl, and R 2 is C1 to C5 alkyl, provided that if R 1 =H, then R 2 is C3 to C5 alkyl; and if R 1 If not H, then R 1 and R 2 are the same.

5. The method of claim 1, wherein X is amidino-NR 3 -C(R 4 )=NR 5 , where R 3 and R 5 are each independently selected from Et, nPr, iPr, nBu, tBu, sBu, iBu, and R 4 It is H or Me.

6. The method of claim 1, wherein the Si-C-free polysilane backbone of the SAM precursor is selected from -SiH2-SiH3 or -SiH2-SiH2-SiH3.

7. The method of claim 1, wherein the SAM precursor having a Si-C-free polysilane backbone is selected from X-(SiH2) n -SiH3, wherein n=1 to 3, X-(Si n H 2n-1 ), where Si n H 2n-1 represents a cyclic hydrosilane backbone, wherein n=5, 6, 7, X-(SiH(SiH3)2), or X-SiH2-Si(SiH3)3.

8. The method of any one of claims 1 to 6, wherein the SAM precursor having a Si-C-free polysilane backbone is selected from the group consisting of: NiPr2-(SiH2)-SiH3, NnBu2-(SiH2)-SiH3, NtBu2-(SiH2)-SiH3, NsBu2-(SiH2)-SiH3, NiBu2-(SiH2)-SiH3, NPen2-(SiH2)-SiH3, NnPr2-(SiH2)2-SiH3, NiPr2-(SiH2)-SiH3, H2)2-SiH3, NnBu2-(SiH2)2-SiH3, NtBu2-(SiH2)2-SiH3, NsBu2-(SiH2)2-SiH3, NiBu2-(SiH2)2-SiH3, NsPen 2-(SiH2)2-SiH3, NHtBu-(SiH2)2-SiH3, NHPen-(SiH2)2-SiH3, NHsBu-(SiH2)2-SiH3, NHiBu-(SiH2)2-SiH3, NnPr2-(SiH2)3-SiH3, NiPr2-(SiH2)3-SiH3, NnBu2-(SiH2)3-SiH3, NtBu2-(SiH2)3-SiH3, NsBu2-(SiH2)3-S iH3, NiBu2-(SiH2)3-SiH3, NsPen2-(SiH2)3-SiH3, NEt2-(SiH(SiH3)2), NiPr2-(SiH(SiH3)2), NnPr2-(SiH( SiH3)2), NiBu2-(SiH(SiH3)2), NtBu2-(SiH(SiH3)2), NnBu2-(SiH(SiH3)2), NsBu2-(SiH(SiH3)2), NsPen2- (SiH(SiH3)2), NHtBu-(SiH(SiH3)2), NHnBu-(SiH(SiH3)2), NHiBu-(SiH(SiH3)2), or NHPen-(SiH(SiH3)2).

9. The method of any one of claims 1-6, wherein the SAM precursor is a bis-disilylaminohalosilane (BDSASi-X), wherein X = F, Cl, Br or I.

10. The method of any one of claims 1-6, wherein the SAM precursor is (diisobutylamino)trisilane (DIBATS, (iBu)2-N-SiH2-SiH2-SiH3).

11. The method of any one of claims 1 to 6, wherein the SAM precursor is amidino neopentylsilane (NPS-AMD, C5H 11 -SiH2-R 1 HN(CR 3 )═NR 2 ).

12. The method of any one of claims 1 to 6, wherein the SAM precursor is dialkylamino neopentylsilane (NPS-NR 4 R 5 ).

13. The method of any one of claims 1-6, wherein the SAM precursor is amidinocyclohexylsilane (CHS-AMD).

14. The method of any one of claims 1 to 6, wherein the SAM precursor is dialkylaminocyclohexylsilane (CHS-NR 4 R 5 ).

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