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  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
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  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6342—Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating
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  • H10P14/6516—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials
  • H10P14/6548—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials by forming intermediate materials, e.g. capping layers or diffusion barriers
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  • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
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  • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
  • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
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  • H10W20/031—Manufacture or treatment of conductive parts of the interconnections
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  • H10W20/071—Manufacture or treatment of dielectric parts thereof
  • H10W20/074—Manufacture or treatment of dielectric parts thereof of dielectric parts comprising thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
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  • H10W20/41—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their conductive parts
  • H10W20/44—Conductive materials thereof
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  • H10W20/48—Insulating materials thereof

Definitions

• Photoresist compositions are used in microlithographic processes for making miniaturized electronic components such as in the fabrication of computer chips and integrated circuits.
• a thin film of a photoresist composition is first applied to a substrate material, such as silicon wafers used for making integrated circuits.
• the coated substrate is then baked to evaporate solvent in the photoresist composition and to fix the coating onto the substrate.
• the baked, coated surface of the substrate is next subjected to an image-wise exposure to imaging radiation.
• This radiation exposure causes a chemical transformation in the exposed areas of the coated surface.
• Visible light, ultraviolet (UV) light, electron beam and X-ray radiant energy are imaging radiation types commonly used today in microlithographic processes.
• the coated substrate is treated with a developer solution to dissolve and remove either the radiation-exposed or the unexposed areas of the coated surface of the substrate.
• photoresist compositions there are two types, negative-working and positive-working.
• negative-working photoresist compositions When negative-working photoresist compositions are exposed image- wise to radiation, the areas of the resist composition exposed to the radiation become less soluble to a developer solution (e.g. a cross-linking reaction occurs) while the unexposed areas of the photoresist coating remain relatively soluble to such a solution.
• a developer solution e.g. a cross-linking reaction occurs
• treatment of an exposed negative-working resist with a developer causes removal of the non-exposed areas of the photoresist coating and the creation of a negative image in the coating, thereby uncovering a desired portion of the underlying substrate surface on which the photoresist composition was deposited.
• Electron beam physical vapor deposition is a form of physical vapor deposition in which a target anode is bombarded with an electron beam given off by a charged tungsten filament under high vacuum. The electron beam causes atoms from the target to transform into the gaseous phase. These atoms then precipitate into solid form, coating everything in the vacuum chamber (within line of sight) with a thin layer of the anode material.
• Sputtering metal deposition is done in a vacuum chamber where an electrically grounded metallic target wafer is bombarded with electrically charged Argon gas, sputtering away the metal atoms and depositing them on a target wafer.
• CVD metal deposition occurs by reaction of a reactive gas under reduced pressure with a either the semiconductor substrate, itself or by reaction with a second reactive gas producing in both scenarios a metal deposit.
• WF 6 may affect deposition on a Silicon substrate by reaction with Si to produce a metallic W deposits and producing as a reaction product gaseous SiF 6 which is pumped away.
• An example of the second scenario is the gaseous reaction of WF 6 with H 2 to deposit metallic W and producing as a reaction product gaseous HF which is pumped away.
• a low- ⁇ is a material with a small dielectric constant relative to bulk non-porous silicon dioxide which has a dielectric constant of 3.9.
• Low-K dielectric material implementation is one of several strategies used to allow continued scaling of microelectronic devices, colloquially referred to as extending Moore's law.
• insulating dielectrics separate the conducting parts (wire interconnects and transistors) from one another. As components have scaled and transistors have gotten closer together, the insulating dielectrics have thinned to the point where charge build up and crosstalk adversely affect the performance of the device.
• Approaches towards low-k materials include silicon dioxide doped with carbon or fluorine and silicon dioxide and doped silicon dioxide (a.k.a. doped S1O2) and silicon dioxide containing voids (a.k.a. porous S1O2) and the like.
• PECVD enhanced chemical vapor deposition
• Si0 2 silicon dioxide
• F-S1O2 fluorine-doped oxides
• OSG carbon-doped oxides
• Another approach is the introduction of pores in any of the above described materials deposited by CVD processes such as PECVD; this is accomplished by the introduction in this PECVD process of an additional poragen reagent material which will is incorporated into the bulk of the dielectric material, but that can be subsequently be removed by thermal processing, UV exposure, or a combination of thermal and UV processing to create voids in the dielectric material.
• Voids have a dielectric constant of approximately 1. Consequently, Silicon dioxide and Silicon dioxide doped with other elements, such as carbon, or fluorine, may have their dielectric constant further lowered by the introductions of these voids, increasing their porosity and consequently lowering their dielectric constants.
• porous dielectric with a k value lower than 2.4
• p-OSG Carbon-doped silicon oxides which contained poragens
• the poragens are removed from the OSG by either thermal, or photochemical means to produce additional porosity in the OSG.
• Surface roughness of the dielectric may also lead to undesirable metal diffusion into the surface pores of the porous dielectric during metallization processes employed in IC manufacturing.
• Surface roughness of the dielectric coupled with hydrophilicity may allow moisture to diffuse into the porous dielectric negatively affecting both the low k and uniformity of the dielectric constant in a layer of porous dielectric. Roughness of the dielectric coating and diffusion of metal into the dielectric coating may also negatively affect the performance properties of IC devices incorporating such low k dielectrics.
• the present invention relates to novel aromatic-amino functional compounds which are compound comprising a head group Xi of structure (1 ), one or two tail groups X 2 , and a linking group L, of structure (2), linking each said tail group to said head group.
• linking group L, L-i attaches it to said head group Xi and is selected from a direct valence bond, -CH 2 -, -S- and -0-; and within L, L 2 is a direct valence bond attaching it to each said tail group X 2 , and r designates the number of said tail groups X 2 attached to said head group Xi through said linking group L and is 1 or 2;
• n and n' are integers which independently range from 2 to 8.
• positions a, b, c, d and e are possible attachment positions of said head group Xi to each said tail group X 2 , through said linking group L, if these positions are not otherwise occupied by another moiety.
• Y in structure (1 ), is an optional bivalent organic moiety attaching positions b and d of structure (1 ), which forms a two carbon link containing either a single or double carbon to carbon bond.
• the two carbon positions on this linkage may be independently further substituted with hydrogen, an alkyl group, or an aryl group.
• the two carbon positions on this linkage may also be substituted in such a manner to be further joined together through a six membered saturated, or aromatic ring moiety.
• the linkage itself, its substituents, or any ring moieties joining the two positions in Y may be potential attachment points linking of said head group Xi to each said group X2 through said linking group L.
• positions a, b, d, e, if not otherwise substituted are possible attachment position of said head group Xi to each said tail group X 2 through said linking group L.
• these position may be independently substituted by hydrogen, an alkyl moiety or an aryl moiety.
• positions, a and b, a and f, d and e, or e and g may be substituted in a manner to further join them together through a six membered saturated, or aromatic ring moiety. If not part of said six membered ring system, positions e and g in structure (1 ) are independently substituted by hydrogen, an alkyl moiety, or an aryl moiety.
• X 2 is selected from the group consisting of, a moiety comprising a trialkyloxysilane group, a moiety comprising a dialkyloxysilane moiety group, a moiety comprising a monoalkyloxysilane; a moiety comprising a monoalkyloxyalkylsilane; a moiety comprising a monoalkyloxydialkylsilane; and a moiety comprising a dialkyloxymonoalkylsilane.
• Another aspect of this invention are compositions containing these novel aromatic amino functional siloxane, another aspect in the process for self-assembled monolayers of aromatic-amino functional siloxane.
• Fluoroalkyloxy refers to a fluoroalkyl group as defined above on which is attached through an oxy (-0-) moiety it may be completed fluorinated (a.k.a. perfluorinated) or alternatively partially fluorinated (e.g. trifluoromethyoxy, perfluoroethyloxy, 2,2,2- trifluoroethoxy, perfluorocyclohexyloxy and the like). These fluoroalkyl moieties, if not pefluorinated may, be substituted or unsubstituted as described below.
• alkylene refers to hydrocarbon groups which can be a linear, branched or cyclic which has two (a.k.a. bivalent) or more (a.k.a. trivalent and higher) attachment points (e.g. of two attachment points: methylene, ethylene, 1 ,2-isopropylene, a 1 ,4-cyclohexylene and the like).
• this range encompasses linear alkylenes starting with C-1 but only designates branched alkylenes, or cycloalkylene starting with C-3.
• These alkylene moieties may be substituted or unsubstituted as described below.
• Aryl or aromatic groups refers to such groups which contain 6 to 24 carbon atoms including phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis- phenyls, tris-phenyls and the like. These aryl groups may further be substituted with any of the appropriate substituents e.g. alkyl, alkoxy, acyl or aryl groups mentioned hereinabove.
• arylene refers to a aromatic hydrocarbon moiety which has two or more attachment points (e.g. 2-5), this moiety may be a single benzene moiety (e.g. 1 ,4-phenylene, 1 ,3-phenylene and 1 ,2-phenylene), a polycyclic aromatic moiety with two attachment points such derived from napthtalene, anthracene, pyrene and the like, or a multiple benzene rings in a chain which have two attachment point (e.g. biphenylene).
• this moiety may be a single benzene moiety (e.g. 1 ,4-phenylene, 1 ,3-phenylene and 1 ,2-phenylene), a polycyclic aromatic moiety with two attachment points such derived from napthtalene, anthracene, pyrene and the like, or a multiple benzene rings in a chain which have two attachment point (e.g. biphenylene).
• fused ring arylenes In those instance where the aromatic moiety is a fused aromatic ring, these may be called fused ring arylenes, and more specifically named, for instance, napthalenylene, anthracenylene, pyrenylene, and the like.
• Fused ring arylenes may be substituted or unsubstituted as described below, additionally these fused ring arylenes may also contain a hydrocarbon substituent which has two attachment sites on the fused ring forming an additional aliphatic or unsaturated ring forming by attachment to the fused ring a ring having 5-10 carbon atoms.
• fused aromatic ring refers to a carbon based polycyclic aromatic compound containing 2-8 carbon based aromatic rings fused together (e.g. naphthalene, anthracene, and the like) these fused aromatic ring which may have a single attachment point to an organic moiety as part of an aryl moiety such as a pendant fused aromatic ring aryl group on a polymer or have two attachment points as part of an arylene moiety, such as, for instance, in the backbone of a polymer.
• substituted when referring to an aryl, alkyl, alkyloxy, fluoroalkyi, fluoroalkyloxy or fused aromatic ring refers to one of these moieties which also contain with one or more substituents, selected from the group consisting of unsubstituted alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, amino and amino alkyl.
• unsubstituted refers to these same moieties wherein no substituents apart from hydrogen is present.
• X 2 is selected from the group consisting of, a moiety comprising a trialkyloxysilane group, a moiety comprising a dialkyloxysilane moiety group, a moiety comprising a monoalkyloxysilane; a moiety comprising a monoalkyloxyalkylsilane; a moiety comprising a monoalkyloxydialkylsilane; and a moiety comprising a dialkyloxymonoalkylsilane.
• Another aspect of the above novel aromatic-amino functional siloxanes is one wherein said head group Xi is selected from the group consisting and a 1 ,10
• phenanthroline derivative group and a 2,2'-bipyridine derivative group.
• n ranges from 3 to 8.
• this embodiment is one wherein n' ranges from.
• this embodiment is one wherein n ranges from 4 to 8.
• this embodiment is one wherein n' ranges from 2 to 6.
• this embodiment is one wherein n ranges from 5 to 8.
• this embodiment is one wherein n' ranges from 2 to 5.
• this embodiment is one wherein n ranges from 6 to 8.
• this embodiment is one wherein n' ranges from 3 to 5.
• this embodiment is one wherein n ranges from 7 to 8.
• this embodiment is one wherein n' ranges from 4 to 5.
• this embodiment is one wherein n' is 8.
• this embodiment is one wherein n' is 4.
• l_i is -CH 2 - or -S-.
• l_i is -CH 2 - or -0-.
• l_i is a direct valence bond or -0-.
• Li is a direct valence bond or -S-.
• l_i is a direct valence bond or - CH 2 -.
• l_i is a direct valence bond.
• l_i is -CH 2 -.
• l_i is -0-.
• Li is -S- .
• this embodiment is one wherein X is a direct valence bond or a bivalent moiety selected from the group consisting
• this embodiment is one wherein X is a direct valence bond.
• said tail group X 2 is a moiety comprising a trialkyloxysilane group. Another aspect, of the above, is one wherein said tail group X 2 is a moiety comprising a dialkyloxysilane group. Another aspect, of any of the above, is one wherein said tail group X2 is a moiety comprising a monoalkyloxysilane group. In another aspect, of any of the above, is one is one wherein said tail group X 2 is a moiety comprising a monoalkyloxydialkylsilane group. In another aspect, this embodiment is one wherein said tail group X 2 is moiety comprising a dialkyloxymonoalkylsilane group.
• this embodiment is one wherein bivalent organic moiety Y is present and is comprised of a two carbon alkylene moiety. In another aspect, this embodiment is one wherein bivalent organic moiety Y is present and comprised of a two carbon alkenylene moiety. In another aspect, this embodiment is one wherein bivalent organic moiety Y is present is comprised of an arylene moiety which is attached through two adjacent vicinal ring carbons of the arylene.
• Another aspect of the above novel aromatic-amino functional siloxanes is one wherein, two said tail groups X2, each are individually attached through said linking group L, to said head group X-i .
• Another aspect of the above novel aromatic-amino functional siloxanes is one where the above compounds have the more specific structure (1 a), wherein Xi a is a head group selected from the group consisting of (3), (3a) and (3b); X 2a is a tail group selected from the group consisting of (4), and (4a); » w r represents a point of attachment; Q and Qi are independently selected from hydrogen or Ci to C- 6 to alkyl group; wherein m is a integer ranging from 2 to 8, r' is the number of tail groups attached to the head group, r' is 1 if the head group Xi a is selected from (3) or (3b), and r' is 2 if the head group Xi a is (3a), and ml and m2 are integers independently ranging from 2 to 8; y and y1 independently are 0, 1 or 2; and further wherein R and Ri are independently selected from a Ci to Ce alkyl group;
• Another aspect of the above novel aromatic-amino functional siloxanes having structure (1 a) is one wherein m ranges from 3 to 8. In yet another, m ranges from 4 to 8. In another, m ranges from 5 to 8. In still another, m ranges from 6 to 8. In yet another, m ranges from 7 to 8. In a final embodiment of this aspect of the inventive compound in structure (1 a) m is 8. [0070] In another embodiment of the inventive compound having structure (1 a) the tail group X2a has structure (4), ml ranges from 2 to 7. In yet another, ml ranges from 2 to 6. In still another, ml ranges from 2 to 5. In yet another, ml ranges from 2 to 4. In still another, ml ranges from 3 to 4. In a final embodiment of this aspect of the inventive compound in the tail group of structure (4) ml is 4.
• the tail group X2a has structure (4a), m2 ranges from 2 to 7. In yet another, m2 ranges from 2 to 6. In still another, m2 ranges from 2 to 5. In yet another, m2 ranges from 2 to 4. In still another, m2 ranges from 3 to 4. In a final embodiment of this aspect of the inventive compound in the tail group of structure (4a) m2 is 4.
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the head group has structure (3).
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the head group has structure (3a).
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the tail group has structure (4).
• Another aspect of this aspect is one wherein in structure (4), y is 0, another where y is 1 , another where y is 2.
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the tail group has structure wherein the tail group has structure (4a).
• Another aspect of this aspect is one wherein in structure (4a), y1 is 0, another where y1 is 1 , another where y1 is 2.
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the tail group has structure (4) and where Q is hydrogen and R is methyl, ethyl or propyl, in another where Q is hydrogen and R is methyl or ethyl, in another where Q is hydrogen and R is ethyl.
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the tail group has structure (4) and where Q is methyl and R is methyl, ethyl or propyl, in another where Q is methyl and R is methyl or ethyl, in another where Q is methyl and R is ethyl.
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the tail group has structure (4a) and where Qi is hydrogen and Ri is methyl, ethyl or propyl, in another where Qi is hydrogen and Ri is methyl or ethyl, in another where Qi is hydrogen and Ri is ethyl.
• Another aspect of the above novel aromatic-amino functional siloxanes having more specific structure (1 a) is one wherein the tail group has structure (4a) and where Qi is methyl and Ri is methyl, ethyl or propyl, in another where Qi is methyl and Ri is methyl or ethyl, in another where Qi is methyl and Ri is ethyl.
• preferred ones are one which have a molecular volume ranging from about 350 cubic A to about 580 cubic A. In another preferred embodiment this range is about 420 cubic A to about 570 cubic A.
• the volume calculated these ranges is half the actual volume.
• Non Limiting Examples of such bifunctional materials are shown in structures (5)-(12), (13), (14), (22)-(27), (CgDBSI) and (C12DBSi). Although not bound by theory it is believed that these molecular volumes are particularly preferred for capping pore sizes in porous S1O2 which have a diameter from about 10 to about 20 A.
• oligomerization reactions of the above novel aromatic-amino functional siloxanes An example of a suitable range would be one which would range from about 0.25 to about 2.5 wt % water in another embodiment from about 0.5 to about 2.5 wt %.. This said, amount higher or lower than this range are not precluded, as long as it allows in a given solvent for enough hydrolysis and oligomerization of the novel aromatic-amino functional siloxanes in the composition to occur without causing any particulates to precipitate from the
• C1 -C8 halogenated solvent examples include methylene chloride chloroform.
• Examples of C3-C12 amides and C5-C12 cyclic amides- are dimethylformamide and N-methyl- pyrrolidone, N-butyl-pyrrolidone.
• Examples of C2-C8 sulfoxide are dimethyl sulfoxide, and diethyl sulfoxide.
• Suitable solvent are propyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether and ethyl lactate.
• propylene glycol monomethyl ether (1 -methoxypropan-2- yl acetate) (PGMEA) is employed.
• Non limiting examples of suitable NMBC materials are amines, organic ammonium hydroxides, and ammonium aryloxides (aryl-O " ) bases as follows:
• Amines having a pK a from about 9 to about 15.7 such as alkylamines, dialkyl amines, trialkyl amines, this denotation also includes, branched, and cyclic saturated aliphatic amines either when the amine nitrogen is within the cycle or external to it; this denotation also further includes amines that have more than one amino
• Alkyl amines containing benzyl or other alkylaryl moieties in which a alkylene moiety is present between the nitrogen atom and the aryl moiety, allowing for a higher pK a such as the non-limiting examples of diethyl, benzylamine (N-benzyl-N-ethylethanamine), benzylamine (phenylmethamine), phenethylamine (phenethyl- '-azane), ((2-naphthalen-1 - yl)-ethyl)amine ((2-(napthathalene-1 -yl)ethyl)- l -azane), dimethyl, isopropylamine (N,N- dimethylpropan-2 -amine).
• aforementioned amines may be substituted with other moieties which do not hinder their required pK a range such as aryl, alkyloxy, aryloxy and the like.
• the amine is an alkyl amine having at least one alkyl group which has 4 carbons or more; a non-limiting embodiment of this aspect of the inventive composition is when the amine is n-butylamine.
• Organic ammonium hydroxides (organic aminium hydroxides) having a pK a from about 9 to about 15.7, such as the hydroxide salts of tetraalkylammonium,
• trialkylammonium, dialkylammonium, alkylammonium (alkanaminium), and other ammonium cations which contain aryl moieties (phenyl, benzyl and the like) or mixtures of aryl moieties with alkyl moieties or mixtures of these quaternary ammonium hydroxide salts.
• Organic aryloxides having a pK a from about 9 to about 15.7 such as aryloxides salts with tetraalkylammonium, trialkylammonium, dialkylammonium, alkylammonium (alkanaminium), and other ammonium cations which contain aryl moieties (phenyl, benzyl and the like) or mixtures of aryl moieties with alkyl moieties and the like, or mixtures of these quaternary ammonium hydroxide salts.
• aryloxides salts with tetraalkylammonium, trialkylammonium, dialkylammonium, alkylammonium (alkanaminium), and other ammonium cations which contain aryl moieties (phenyl, benzyl and the like) or mixtures of aryl moieties with alkyl moieties and the like, or mixtures of these quaternary ammonium hydroxide salts.
• tetrabutylammonium phenolate tetrapropylammonium phenolate, tetraethylammonium hydroxide, tetramethylammonium phenolate, benzyldiethylammonium phenolate (N-benzyl-N,N-diethylethanaminium phenolate) tetrabutylammonium 2-naphtholate, tetrapropylammonium 2-naphtholate, tetraethylammonium 2-naphtholate, tetramethylammonium 2-naphtholate,
• benzyldiethylammonium 2-naphtholate N-benzyl-N,N-diethylethanaminium naphthalen-1 - olate
• organic phenolate may be substituted with other moieties which donot hinder their required pK a range such as aryl and alkyl.
• the solution may contain from about 0.5 to about 4 wt% of total solids (a.k.a aromatic-amino functional siloxane+ NMBC) in the solution with the solvent component containing a trace of water. In another embodiment it may contain from about 0.75 to about 3 wt% solids in this solvent. In yet another embodiment it may contain from about 1 to about 2 wt% in this solvent.
• the molar ratio of aromatic-amino functional siloxane to NMBC ranges from about 0.333 to about 3.
• the molar ratio of aromatic-amino functional siloxane to NMBC ranges from about 0.5 to about 2.5.
• the molar ratio of aromatic-amino functional siloxane to NMBC ranges from about 0.90 to about 1.2.
• the molar ratio of aromatic-amino functional siloxane to NMBC ranges is about 1 to about 1.
• any of the above novel compositions may be aged at about room temperature in the solution comprising the above described solvent containing a trace of water to produce an new novel composition is which part of the aromatic-amino functionalized siloxane has undergone hydrolysis and oligomerization to produce respectively hydrolyzed aromatic-amino functionalized siloxane containing Si-OH and aromatic-amino functionalized siloxane which have oligomerized through the formation of Si-O-Si moieties
• the solution composition is aged at about room temperature
• the solution composition is aged at about room temperature for about 2 days to about 3 weeks in order to partially hydrolyze and oligomerize the alkoxy silyl moieties in said compound.
• the solution composition is aged at about room temperature for about 3 days to about 3 weeks in order to partially hydrolyze and oligomerize the alkoxy silyl moieties in said compound.
• the solution composition is aged at about room temperature for about 1 week to about 3 weeks in order to partially hydrolyze and oligomerize the alkoxy silyl moieties in said compound.
• the solution composition is aged at about room temperature for about 2 weeks in order to partially hydrolyze and oligomerize the alkoxy silyl moieties in said compound.
• the solution composition is aged at about room temperature for about 3 weeks in order to partially hydrolyze and oligomerize the alkoxy silyl moieties in said compound. [01 18] In all embodiments aging these formulations, beyond 4 weeks does not cause any significant change in solution stability up to 1 year with no aggregation and
• any of the above novel compositions may be aged at about room temperature in the solution comprising the above described solvent containing about 0.5 to about 2.5 wt% water; an organic nonmetallic basic compound having a pK a in water from about 9 to about 15.7.
• any of the above novel an aged composition is produced by the following steps at about room temperature:
• a process for forming a self-assembled monolayer on an unpatterned substrate comprising the steps:
• a process for forming a self-assembled monolayer on a patterned dielectric substrate having a k value which ranges from about 2.2 to about 2.55, to cap pores in said patterned dielectric comprising the steps
• a process for copper metallization of a capped patterned dielectric substrate having a k value which ranges from about 2.2 to about 2.55 comprising the steps
• FIG. 1 shows the 1 H NMR spectrum of (8-bromooctyl) triethoxysilane.
• FIG. 2 shows the 1 H NMR spectrum of 4-methyl-4'-(12-(triethoxysilyl)dodecyl)-2,2'-bipyridine.
• Example 5b Transmetallation of 4, 4'dimethyl bipyridine with (11 -bromoundecyl) triethoxysilane using LDA to make 4,4'-bis(12-(triethoxysilyl)dodecyl)-2,2'-bipyridine
• FIG. 3 shows the 1 H NMR spectrum of 4,4'-bis(12-(triethoxysilyl)dodecyl)-2,2'-bipyridine [4,4'-bis(12-(triethoxysilyl)dodecyl)-2,2'-bipyridine].
• Example 7 Transmetallation of 4, 4'dimethyl bipyridine with (8-bromooctyl) triethoxysilane using LDA to make 4,4'-bis(9-(triethoxysilyl)nonyl)-2,2'-bipyridine (C9DBSi)
• Table 1 Types of SAM com ounds and their characterization
• Table 2 shows the thickness obtained after rinse of the layer before and after rinse, using, either 1 or a 2 wt% solution of CgMBSi. This formulation hereafter referred as FORMULATION 1 , and similar FORMULATION 2 formulation was made using example 8.
• Example 13 Solution reaction with triethylaluminum [0150]
• reference and SAM coated substrates, coated with either Formulation 1 or Formulation 2 were treated with triethylaluminum.
• Manipulations were carried out in glovebox as follow: 1 mL of triethylaluminum (TEA) (25 wt% solution in toluene) was puddled on the 1.5 x1.5 inch coupon for one minute and then rinsed with excess cyclohexane. After removing the coupons from the glovebox these immediately underwent hydrolysis on exposure to air. Next, the coupons were further washed under a stream of deionized water to hydrolyze deposited TEA and remove any physi-absorbed byproducts of TEA.
• TEA triethylaluminum
• SAM not only prevented diffusion of metal oxides to the surface, but also helped in the deposition of MO on top of SAM layer. Although not bound by theory this may be due to presence of aromatic amino tail-groups which can complex well with metals.
• Example 14 ALD reaction with trimethylaluminum
• ALD was used to deposit a thin film of hafnium oxide by using precursor's tetrakis (dimethylamido) hafnium (IV) (TDMA Hf) for hafnium, and water for oxygen.
• the substrate temperature used was 200 °C and a total 35 ALD cycles were applied which grew a Hf0 2 thin film of -3.5 nm.
• Elemental compositions were calculated using XPS (Table 7). Small difference of Hf at% were noted between reference and FORMULATION 1 and FORMULATION 2. These results follow the same trends as was observed using ALD grown of AI 2 O 3 .
• the inventive composition are not only the first report such materials, but also unexpectedly shows the property of being spin coatable, forming a self-assembled monolayer on a porous dielectric which can then acts as a barrier towards undesirable diffusion into the pores of metals oxide during deposition. Such diffusion, if not suppressed would lead to a degradation of the performance of the porous dielectric in microelectronic devices.

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