Area-selective deposition of metal-containing films

Abstract

Methods for selectively depositing metal-containing films, the methods comprising: providing a surface having a plurality of materials simultaneously exposed thereon; and exposing the surface to a vapor of a metal-containing film-forming composition comprising a precursor having the formula: L x M(−N(R)−(CR’2) n −NR”2) wherein M is a Group 12, Group 13, Group 14, Group 15, Group IV or Group V element; x+1 is the oxidation state of M; L is an anionic ligand independently selected from dialkylamines, alkoxides, alkylimines, bis(trialkylsilylamines), amidinates, β-diketonates, keto-imines, halides, etc.; R, R” are each independently a C1-C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl; R’ is H or C1-C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl; n = 1-4, wherein at least one of these materials is at least partially blocked from deposition of the metal-containing film by a vapor deposition process.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority benefit of U.S. Patent Application No. 16 / 723,771, filed on December 20, 2019, under 35 U.S.C.§119(a) and (b), the entire content of which is incorporated herein by reference. Technical field

[0003] The present invention relates to a method for area - selective deposition (ASD) of a metal - containing film using a metal precursor. Specifically, the metal is a Group 12, Group 13, Group 14, Group 15, Group IV, or Group V metal. Background art

[0004] Due to the continuous shrinking of semiconductor devices, typical lithography is approaching its physical limit, at which structural defects such as contact misalignment will become inevitable. The difficulty of precise pattern alignment is increasing, and the biggest problem is "edge placement error (EPE)". Therefore, current top - down technologies need to use area - selective deposition (ASD) techniques combined with self - assembled monolayers (SAMs) or the formation of inhibitors on the surface to become bottom - up technologies.

[0005] In practice, achieving perfect growth selectivity is extremely difficult. This is explained by parasitic growth on the blocked surface, which starts from defects on the inhibited surface (available active sites, such as - OH, etc.). This effect limits the maximum thickness of growth on the unprotected surface before film growth occurs on the inhibited surface. For industrial benefit, this thickness on the unprotected surface should be maximized, and parasitic growth on the inhibited surface (i.e., turning into defect islands in the early stage of growth) should be suppressed at least to the extent of avoiding damage to the resulting structural function within the final device and ideally suppressed to the greatest possible extent.

[0006] Metal oxides are commonly used materials due to their specific physical properties (insulating properties, high dielectric constant, etch resistance, refractive index, etc.), and the selective growth of metal oxides has attracted attention in the semiconductor industry. Al2O3 is a common metal oxide material. A common precursor for forming Al2O3 is Al2Me6 (TMA) because it meets almost all the requirements of a perfect atomic layer deposition (ALD) precursor, such as volatility, rapid saturation, high surface reactivity, etc. However, for ASD, TMA is restricted by its extremely strong reactivity and oxygenophilic properties because it easily reacts with the oxygen that bridges the surface to the SAM, thus starting to grow a film on the protected area. Therefore, the use of O-containing inhibitors such as carboxylic acids, phosphonic acids, acetates, β-diketonates, etc., or O-bonded SAMs such as -O-TMS (trimethylsilane), O-DMS (dimethylsilane)-O, O-Si-R, etc. is incompatible with the use of highly oxygenophilic precursors like TMA.

[0007] Due to the above difficulties, it is challenging to find new and novel precursors suitable for ASD. Therefore, there is a need to provide such precursors to meet the requirements of ASD.

[0008] US2006193984 discloses methods for producing organoaluminum precursor compounds and methods for producing films or coatings from organoaluminum precursor compounds. The organoaluminum precursor compounds are represented by the following formula:

[0009]

[0010] wherein R1, R2, R3, and R4 are the same or different and each represents hydrogen or an alkyl group having from 1 to about 3 carbon atoms, and R5 represents an alkyl group having from 1 to about 3 carbon atoms.

[0011] US2015266904 discloses compounds having a low melting temperature, sufficient volatility, and high thermal stability, which are suitable for use as materials for forming thin films by CVD. The aluminum compounds are represented by the following general formula:

[0012]

[0013] wherein R1 and R2 each independently represent a straight-chain or branched-chain alkyl group having 2 to 5 carbon atoms; and R3 represents a methyl or ethyl group.

[0014] Beachley et al. (Inorganic Chemistry, Vol. 15, No. 9, 1976, 2110 - 2115) disclosed chelation in organoaluminum - nitrogen chemistry, including chelating monomers of compounds (CH3)2AI(C2H5)NC2H4N(C2H5)2, (C2H5)2Al(CH3)NC2H4N(CH3)2, (C6H5)2Al(C2H5)NC2H4N(CH3)2, Cl2Al(C2H5)NC2H4N(CH3)2, and (CH3)2AISC2H4N(CH3)2, having the following structures:

[0015]

[0016] Barry et al. (Mat.Res.Soc.Symp.Proc., Vol. 606, pp. 83 - 89, 2000) disclosed monomeric chelating amides of aluminum and gallium: volatile, miscible liquid precursors for CVD. Aluminum nitride (AIN) and gallium nitride (GaN) have the following structures:

[0017]

[0018] Blakeney et al. (Inorganic.Nucl.Chem.Lett., 9, 423 (1973)) disclosed the use of a thermally stable aluminum hydride reducing agent for ALD aluminum metal films, where a volatile dimeric dihydroaluminum complex coordinated by a simple amido - amine ligand of formula (RN)CH2CH2(NMe2) (R = Me, Et) has the following structure.

[0019]

[0020] McMahon et al. (J.Chem.,Soc., Dalton Trans., 1999, 67 - 72) disclosed aluminum compounds containing bidentate ligands: ligand base strength and long - range geometric control of the degree of association, where (tBu)2Al[N(Me)CH2CH2NMe2] was produced and has the following structure:

[0021]

[0022] Choi et al. (Chem. Mater. [Journal of Materials Chemistry], 10, 2323-2325, 1998) disclosed volatile amidoalane compounds H2Al{N(Et)C2H4NMe2} (1, DMEEDA), H2Al{N(Me)C2H4NMe2} (2, TRMEDA), and H2Al{N(Et)C2H4NEt2} (3, TREEDA) for CVD of aluminum.

[0023]

[0024] Wissing et al. (Journal of Organometallic Chemistry, 459, 11-16, 1993) disclosed 1,2-alkyl shift within chelate-bonded organoaluminum-enamines 1c-3c.

[0025] SUMMARY OF THE INVENTION

[0026] Disclosed is a method for selectively depositing a metal-containing film, the method comprising the steps of:

[0027] a) providing a surface having a plurality of materials simultaneously exposed thereon; and

[0028] b) exposing the surface to the vapor of a metal-containing film-forming composition, the composition containing a precursor having the following formula:

[0029] L x M(-N(R)-(CR’2) n -NR”2)

[0030] wherein M is a Group 12, Group 13, Group 14, Group 15, Group IV, or Group V element; x+1 is the oxidation state of M; L is an anionic ligand; R and R” are each independently a C1-C 10 linear, branched, or cyclic alkyl, alkenyl, or trialkylsilyl; R’ is H or a C1-C 10 linear, branched, or cyclic alkyl, alkenyl, or trialkylsilyl; n = 1-4; and

[0031] c) in a chemical vapor deposition process, preferentially or selectively depositing a film on one or more, but less than all, of the plurality of materials on the surface,

[0032] wherein at least one of the materials on the surface is at least partially blocked by a blocker, thereby reducing or preventing deposition of the metal-containing film on the blocked material.

[0033] In addition, a method for selectively depositing an Al2O3 film is disclosed, the method comprising the following steps:

[0034] a) providing a surface having at least one dielectric material and at least one metal material exposed thereon simultaneously;

[0035] b) exposing the surface to the vapor of (NMe2)2Al(-NEt-(CH2)2-NEt2); and

[0036] c) exposing the surface to the co-reactant H2O;

[0037] wherein the at least one dielectric material is at least partially blocked by the blocker dimethyldichlorosilane (DMDCS) from depositing the Al2O3 film by the ALD process.

[0038] The disclosed method may include one or more of the following aspects:

[0039] · The vapor deposition process is an ALD process;

[0040] · The method further includes exposing the surface to a co-reactant selected from an oxidizing agent or a nitrogen agent;

[0041] · The co-reactant is selected from O3, O2, H2O, H2O2, D2O, ROH where R = C1-C 10 a straight-chain or branched hydrocarbon or a combination thereof;

[0042] · The co-reactant is selected from NH3, NO, N2O, hydrazine, an amine or a combination thereof;

[0043] · The co-reactant is H2O;

[0044] · The blocker forms a SAM layer on at least one of these materials by dipping the surface into the blocker or spraying the surface with the vapor of the blocker;

[0045] · The plurality of materials on the surface includes at least a dielectric material and at least a metal material;

[0046] · The metal-containing film is deposited on the dielectric film rather than on the metal film by blocking the reactivity of the metal film with a metal blocker;

[0047] · The metal blocker is selected from alkyl or fluoroalkyl compounds having surface-reactive chemical functional groups, which are selected from phosphonic acid, carboxylic acid, thiol or triazole;

[0048] · The metal-containing film is deposited on the metal material rather than on the dielectric material by blocking the reactivity of the dielectric material with a dielectric blocker;

[0049] · The dielectric blocker has the formula R4-a SiX a compounds, where each X is independently a surface hydroxyl-reactive group (halide, alkylamino, alkoxy, acetamide, etc.), and each R is selected from H, C1-C 20 alkyl or fluoroalkyl or a mixture thereof;

[0050] · exposing the surface to the precursor at a temperature ranging from room temperature to about 500 °C;

[0051] · The method further comprises the steps of:

[0052] repeating the exposure to the vapor of the metal-containing film-forming composition and the exposure to the co-reactant until a metal-containing film of the desired thickness is formed; and

[0053] separately purging the excess vapor of the metal-containing film-forming composition and the excess co-reactant with an inert gas to separate each exposure, where the inert gas is N2, Ar, Kr, or Xe;

[0054] · The precursor is (NMe2)2Al(-NEt-(CH2)2-NEt2);

[0055] · The blocker is dimethyldichlorosilane (DMDCS); and

[0056] · The metal-containing film is an Al2O3 film.

[0057] In addition, a composition for selectively depositing a metal-containing film is disclosed, the composition comprising a precursor having the following formula:

[0058] L x M(-N(R)-(CR’2) n -NR”2)

[0059] where M is a Group 12, Group 13, Group 14, Group 15, Group IV, or Group V element; x + 1 is the oxidation state of M; L is an anionic ligand independently selected from dialkylamine, alkoxy, alkylimine, bis(trialkylsilylamine), amidinate, β-diketonate, ketimine, halide, etc.; R and R” are each independently a C1-C 10 linear, branched, or cyclic alkyl, alkenyl, or trialkylsilyl; R’ is H or C1-C 10 linear, branched, or cyclic alkyl, alkenyl, or trialkylsilyl; n = 1 - 4.

[0060] The disclosed composition includes one or more of the following aspects:

[0061] · M = Al;

[0062] · M = B, Ga, In, lanthanide elements, P, As, Sb or Bi;

[0063] · x = 2;

[0064] · L is a dialkylamino ligand -NR 1 R 2 , where R 1 , R 2 are each independently a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms;

[0065] · R 1 = R 2 = Me;

[0066] · n = 2;

[0067] · R = Me, Et, Pr, Bu;

[0068] · R' = H;

[0069] · R" = Me, Et;

[0070] · The precursor is (NMe2)2Al(-NEt-(CH2)2-NEt2);

[0071] · The Al-containing precursor is selected from (NMe2)2Al(-NMe-(CH2)2-NMe2), (NMe2)2Al(-NEt-(CH2)2-NMe2), (NMe2)2Al(-N i Pr-(CH2)2-NMe2), (NMe2)2Al(-N n Pr-(CH2)2-NMe2), (NMe2)2Al(-N i Bu-(CH2)2-NMe2), (NMe2)2Al(-N n Bu-(CH2)2-NMe2), (NMe2)2Al(-N t Bu-(CH2)2-NMe2), (NMe2)2Al(-N s Bu-(CH2)2-NMe2), (NEt2)2Al(-NMe-(CH2)2-NMe2), (NEt2)2Al(-NEt-(CH2)2-NMe2), (NEt2)2Al(-N i Pr-(CH2)2-NMe2), (NEt2)2Al(-N n Pr-(CH2)2-NMe2), (NEt2)2Al(-N i Bu-(CH2)2-NMe2), (NEt2)2Al(-N n<h2 style=";text-align:left;direction:ltr">Bu-(CH2)2-NMe2)、(NEt2)2Al(-N<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(NEt2)2Al(-N<h2 style=";text-align:left;direction:ltr"> s <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-NMe-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-NEt-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> s <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-NMe-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-NEt-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr2)2Al(-N<h2 style=";text-align:left;direction:ltr"> s <h2 style=";text-align:left;direction:ltr"> Bu-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Bu2)2Al(-NMe-(CH2)2-NMe2)、(N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Bu2)2Al(-NEt-(CH2)2-NMe2)、(Nn Bu2)2Al(-N i Pr-(CH2)2-NMe2), (N n Bu2)2Al(-N n Pr-(CH2)2-NMe2), (N n Bu2)2Al(-N i Bu-(CH2)2-NMe2), (N n Bu2)2Al(-N n Bu-(CH2)2-NMe2), (N n Bu2)2Al(-N t Bu-(CH2)2-NMe2), (N n Bu2)2Al(-N s Bu-(CH2)2-NMe2), (N i Bu2)2Al(-NMe-(CH2)2-NMe2), (N i Bu2)2Al(-NEt-(CH2)2-NMe2), (N i Bu2)2Al(-N i Pr-(CH2)2-NMe2), (N i Bu2)2Al(-N n Pr-(CH2)2-NMe2), (N i Bu2)2Al(-N i Bu-(CH2)2-NMe2), (N i Bu2)2Al(-N n Bu-(CH2)2-NMe2), (N i Bu2)2Al(-N t Bu-(CH2)2-NMe2), (N i Bu2)2Al(-N s Bu-(CH2)2-NMe2), (N t Bu2)2Al(-NMe-(CH2)2-NMe2), (N t Bu2)2Al(-NEt-(CH2)2-NMe2), (N t Bu2)2Al(-N i Pr-(CH2)2-NMe2), (N t Bu2)2Al(-N n Pr-(CH2)2-NMe2), (N t Bu2)2Al(-N i Bu-(CH2)2-NMe2), (N t Bu2)2Al(-Nn Bu-(CH2)2-NMe2), (N t Bu2)2Al(-N t Bu-(CH2)2-NMe2), (N t Bu2)2Al(-N s Bu-(CH2)2-NMe2), (N s Bu2)2Al(-NMe-(CH2)2-NMe2), (N s Bu2)2Al(-NEt-(CH2)2-NMe2), (N s Bu2)2Al(-N i Pr-(CH2)2-NMe2), (N s Bu2)2Al(-N n Pr-(CH2)2-NMe2), (N s Bu2)2Al(-N i Bu-(CH2)2-NMe2), (N s Bu2)2Al(-N n Bu-(CH2)2-NMe2), (N s Bu2)2Al(-N t Bu-(CH2)2-NMe2), (N s Bu2)2Al(-N s Bu-(CH2)2-NMe2), (NMe2)2Al(-NMe-(CH2)2-NEt2), (NMe2)2Al(-NEt-(CH2)2-NEt2), (NMe2)2Al(-N i Pr-(CH2)2-NEt2), (NMe2)2Al(-N n Pr-(CH2)2-NEt2), (NMe2)2Al(-N i Bu-(CH2)2-NEt2), (NMe2)2Al(-N n Bu-(CH2)2-NEt2), (NMe2)2Al(-N t Bu-(CH2)2-NEt2), (NMe2)2Al(-N s Bu-(CH2)2-NEt2), (NEt2)2Al(-NMe-(CH2)2-NEt2), (NEt2)2Al(-NEt-(CH2)2-NEt2), (NEt2)2Al(-N i Pr-(CH2)2-NEt2), (NEt2)2Al(-N n Pr-(CH2)2-NEt2), (NEt2)2Al(-Ni Bu-(CH2)2-NEt2), (NEt2)2Al(-N n Bu-(CH2)2-NEt2), (NEt2)2Al(-N t Bu-(CH2)2-NEt2), (NEt2)2Al(-N s Bu-(CH2)2-NEt2), (N i Pr2)2Al(-NMe-(CH2)2-NEt2), (N i Pr2)2Al(-NEt-(CH2)2-NEt2), (N i Pr2)2Al(-N i Pr-(CH2)2-NEt2), (N i Pr2)2Al(-N n Pr-(CH2)2-NEt2), (N i Pr2)2Al(-N i Bu-(CH2)2-NEt2), (N i Pr2)2Al(-N n Bu-(CH2)2-NEt2), (N i Pr2)2Al(-N t Bu-(CH2)2-NEt2), (N i Pr2)2Al(-N s Bu-(CH2)2-NEt2), (N n Pr2)2Al(-NMe-(CH2)2-NEt2), (N n Pr2)2Al(-NEt-(CH2)2-NEt2), (N n Pr2)2Al(-N i Pr-(CH2)2-NEt2), (N n Pr2)2Al(-N n Pr-(CH2)2-NEt2), (N n Pr2)2Al(-N i Bu-(CH2)2-NEt2), (N n Pr2)2Al(-N n Bu-(CH2)2-NEt2), (N n Pr2)2Al(-N t Bu-(CH2)2-NEt2), (N n Pr2)2Al(-N s Bu-(CH2)2-NEt2), (N nBu2)2Al(-NMe-(CH2)2-NEt2), (N n Bu2)2Al(-NEt-(CH2)2-NEt2), (N n Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N n Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N n Bu2)2Al(-N i Bu-(CH2)2-NEt2), (N n Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N n Bu2)2Al(-N t Bu-(CH2)2-NEt2), (N n Bu2)2Al(-N s Bu-(CH2)2-NEt2), (N i Bu2)2Al(-NMe-(CH2)2-NEt2), (N i Bu2)2Al(-NEt-(CH2)2-NEt2), (N i Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N i Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N i Bu2)2Al(-N i Bu-(CH2)2-NEt2), (N i Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N i Bu2)2Al(-N t Bu-(CH2)2-NEt2), (N i Bu2)2Al(-N s Bu-(CH2)2-NEt2), (N t Bu2)2Al(-NMe-(CH2)2-NEt2), (N t Bu2)2Al(-NEt-(CH2)2-NEt2), (N t Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N t Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N tBu2)2Al(-N i Bu-(CH2)2-NEt2), (N t Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N t Bu2)2Al(-N t Bu-(CH2)2-NEt2), (N t Bu2)2Al(-N s Bu-(CH2)2-NEt2), (N s Bu2)2Al(-NMe-(CH2)2-NEt2), (N s Bu2)2Al(-NEt-(CH2)2-NEt2), (N s Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N s Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N s Bu2)2Al(-N i Bu-(CH2)2-NEt2), (N s Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N s Bu2)2Al(-N t Bu-(CH2)2-NEt2), or (N s Bu2)2Al(-N s Bu-(CH2)2-NEt2);

[0072] · The composition comprises a precursor between about 95% by weight or w / w and about 100.0% w / w;

[0073] · The composition comprises a precursor between about 99% by weight or w / w and about 99.999% w / w;

[0074] · The composition comprises a precursor between about 99% by weight or w / w and about 100.0% w / w;

[0075] · The composition comprises impurities between about 0.0% by weight or w / w and about 5.0% w / w;

[0076] · The composition comprises impurities between about 0.0% by weight or w / w and about 0.1% w / w; and

[0077] · The composition comprises metal impurities between about 0 ppbw and about 500 ppbw.

[0078] Symbols and Nomenclature

[0079] The following detailed description and claims utilize many abbreviations, symbols, and terms that are well known in the art and include:

[0080] As used herein, the indefinite article "a" or "an" means one or more.

[0081] As used herein, "about" or "around / approximately" in the specification or claims means ±10% of the stated value.

[0082] As used herein, "room temperature" in the specification or claims means from about 20°C to about 25°C.

[0083] The term "ambient temperature" refers to the surrounding temperature of about 20°C to about 25°C.

[0084] 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 selected independently not only relative to other R groups with the same or different subscripts or superscripts, but also relative to any other species of the same R group. For example, in the formula MR 1 x (NR 2 R 3 ) (4-x) where x is 2 or 3, two or three R 1 groups may (but need not) be the same as each other or the same as R 2 or R 3 Further, it should be understood that unless specifically stated otherwise, when used in different formulas, the values of the R groups are independent of each other.

[0085] The term "substrate" refers to one or more materials on which a process is performed. The substrate can refer to a wafer having one or more materials on which a process is performed. The substrate can be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. The substrate can also have one or more different material layers that have been deposited on it from previous manufacturing steps. For example, the wafer can 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. Additionally, the substrate can be planar or patterned. The substrate can be an organic patterned photoresist film. The substrate can include an oxide layer used as a dielectric material (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. Those of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a certain thickness of a material placed or spread on a surface and that surface can range from as large as an entire wafer to as small as a trench or line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as the substrate.

[0086] The term "aspect ratio" refers to the ratio of the height of a trench (or hole) to the width of the trench (or the diameter of the hole).

[0087] It should be noted herein that the terms "film" and "layer" can be used interchangeably. It is understood that a film can correspond to or be related to a layer, and that layer can refer to the film. Additionally, those of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a certain thickness of a material placed or spread on a surface and that surface can range from as large as an entire wafer to as small as a trench or line.

[0088] The terms "via", "aperture", and "hole" are sometimes used interchangeably and generally refer to an opening in an interlayer insulator.

[0089] 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; the abbreviation "3D" refers to a 3-dimensional or vertical gate structure where the gate structures are stacked in the vertical direction.

[0090] Standard abbreviations for the elements of the periodic table 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.).

[0091] The unique CAS Registry Number (i.e., "CAS") assigned by the Chemical Abstract Service is provided to identify the specific molecules disclosed.

[0092] The term "wafer" or "patterned wafer" refers to a wafer having a stack of silicon-containing films on a substrate and having a patterned hard mask layer on the formed stack of silicon-containing films for pattern etching. The term "wafer" or "patterned wafer" can also refer to a trench wafer having a certain aspect ratio.

[0093] It should be noted herein that the terms "film" and "layer" can be used interchangeably. It should be understood that a film can correspond to or be related to a layer, and the layer can refer to the film. In addition, one of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a certain thickness of a material placed or spread on a surface and the surface can range from as large as an entire wafer to as small as a trench or line.

[0094] It should be noted herein that the terms "deposition temperature" and "substrate temperature" can be used interchangeably. It should be understood that the substrate temperature can correspond to or be related to the deposition temperature, and the deposition temperature can refer to the substrate temperature.

[0095] It should be noted herein that when the precursor is gaseous at room temperature and ambient pressure, the terms "precursor", "deposition compound", and "deposition gas" can be used interchangeably. It should be understood that the precursor can correspond to or be related to the deposition compound or deposition gas, and the deposition compound or deposition gas can refer to the precursor.

[0096] 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; the abbreviation "3D" refers to a 3-dimensional or vertical gate structure in which the gate structures are stacked in the vertical direction.

[0097] Standard abbreviations for the elements of the periodic table 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.).

[0098] The unique CAS Registry Number (i.e., “CAS”) assigned by the Chemical Abstract Service is provided to identify the specific molecule disclosed.

[0099] 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. Either of these two terms refers to straight-chain, branched-chain, or cyclic groups. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, etc. 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, cyclohexyl, etc.

[0100] As used in the disclosed embodiments, the abbreviation “Me” refers to methyl; the abbreviation “Et” refers to ethyl; the abbreviation “Pr” refers to propyl.

[0101] Ranges may be expressed herein as from about one specific value and / or to about another specific value. When such a range is expressed, it is to be understood that another embodiment is from the said one specific value and / or to the said another specific value, along with all combinations within the range. Any and all ranges recited herein include their endpoints (i.e., x = 1 to 4 or x is within the range from 1 to 4 includes x = 1, x = 4, and any value therebetween), whether or not the term “including endpoints” is used.

[0102] References herein to “an embodiment” or “embodiments” mean that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the invention. The appearances of the phrase “in an embodiment” in various places in the specification are not necessarily all referring to the same embodiment, and separate or alternative embodiments are not necessarily mutually exclusive of other embodiments. The same applies to the term “implement”. BRIEF DESCRIPTION OF THE DRAWINGS

[0103] 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:

[0104] Figure 1 is an exemplary flow chart of the ASD process;

[0105] Figure 2 are the X-ray photoelectron spectroscopy (XPS) results after ASD Al2O3 film on a W wafer using (NMe2)2Al(-NEt-(CH2)2-NEt2) at 150 °C;

[0106] Figure 3are the XPS results after ASD Al2O3 film on W wafer using (NMe2)2Al(-NEt-(CH2)2-NEt2) at 200 °C;

[0107] Figure 4 are the XPS results after ASD Al2O3 film on W wafer using (NMe2)2Al(-NEt-(CH2)2-NEt2) at 250 °C;

[0108] Figure 5 are the XPS results after ASD Al2O3 film on SiO2 wafer using (NMe2)2Al(-NEt-(CH2)2-NEt2) at 150 °C;

[0109] Figure 6 are the XPS results after ASD Al2O3 film on SiO2 wafer using (NMe2)2Al(-NEt-(CH2)2-NEt2) at 200 °C; and

[0110] Figure 7 are the XPS results after ASD Al2O3 film on SiO2 wafer using (NMe2)2Al(-NEt-(CH2)2-NEt2) at 250 °C. Detailed Description

[0111] Disclosed are metal-containing film-forming compositions comprising metal-containing precursors containing aminoamide ligands, methods of depositing metal-containing films using these film-forming compositions to fabricate semiconductor devices. More specifically, disclosed are methods of area-selective deposition (ASD) of metal-containing precursors containing aminoamide ligands to form metal-containing films. The aminoamide ligands that provide coordination bonds to the metal center can reduce the oxygenophilic nature of the metal center and limit the accessibility of the precursor to oxygen in the inhibitor by steric effects. The disclosed precursors are a new design of precursors containing Group 12, Group 13, Group 14, Group 15, Group IV, or Group V elements having heteroligands, one of which is a multidentate ligand. The disclosed methods are capable of fine-tuning selective deposition under mild process conditions such as deposition temperatures ranging from room temperature to about 500 °C. In addition, the disclosed ASD is highly selective deposition of thin films containing Group 12, Group 13, Group 14, Group 15, Group IV, or Group V elements on dielectric or metal substrates.

[0112] Even when an O-containing inhibitor such as an O-bound self-assembled monolayer (SAM) is used, the disclosed precursors are capable of selectively depositing metal oxide films.

[0113] The disclosed aminoamide ligands have the following general formula:

[0114] -N(R)-(CR’2)n -NR”2 (I)

[0115] wherein each of R and R” is independently a linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group; R’ is H or a linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group having 1 to 10 C carbon atoms; n = 1 - 4. Preferably, n = 2 or 3, R = Me, Et, Pr, Bu, and R” = Me, Et. 10 The disclosed aminoamide ligands can form metal-containing precursors for depositing metal-containing films using the ASD process, having the following formula:

[0116] L

[0117] L x M(-N(R)-(CR’2) n -NR”2) (II)

[0118] wherein M is a Group 12, Group 13, Group 14, Group 15, Group IV or Group V metal; x + 1 is the oxidation state of M; L is an anionic ligand independently selected from dialkylamines, alkoxides, alkylimines, bis(trialkylsilylamines), amidinates, β-diketonates, keto-imines, halides, etc.; each of R and R” is independently a linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group having 1 to 10 C carbon atoms; R’ is H or a linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group having 1 to 10 C carbon atoms; n = 1 - 4. Preferably, M = Al; x = 2; L is a dialkylamino ligand -NR 1 R 2 wherein each of R 1 and R 2 is independently a linear or branched alkyl group having 1 to 5 carbon atoms, preferably R 1 = R 2 = Me; n = 2; R = Me, Et, Pr, Bu; R’ = H; R” = Me, Et.

[0119] Exemplary Al-containing precursors include

[0120] (NMe2)2Al(-NMe-(CH2)2-NMe2), (NMe2)2Al(-NEt-(CH2)2-NMe2), (NMe2)2Al(-N i Pr-(CH2)2-NMe2), (NMe2)2Al(-N n Pr-(CH2)2-NMe2), (NMe2)2Al(-N i Bu-(CH2)2-NMe2), (NMe2)2Al(-N nBu-(CH2)2-NMe2), (NMe2)2Al(-N t Bu-(CH2)2-NMe2), (NMe2)2Al(-N s Bu-(CH2)2-NMe2), (NEt2)2Al(-NMe-(CH2)2-NMe2), (NEt2)2Al(-NEt-(CH2)2-NMe2), (NEt2)2Al(-N i Pr-(CH2)2-NMe2), (NEt2)2Al(-N n Pr-(CH2)2-NMe2), (NEt2)2Al(-N i Bu-(CH2)2-NMe2), (NEt2)2Al(-N n Bu-(CH2)2-NMe2), (NEt2)2Al(-N t Bu-(CH2)2-NMe2), (NEt2)2Al(-N s Bu-(CH2)2-NMe2), (N i Pr2)2Al(-NMe-(CH2)2-NMe2), (N i Pr2)2Al(-NEt-(CH2)2-NMe2), (N i Pr2)2Al(-N i Pr-(CH2)2-NMe2), (N i Pr2)2Al(-N n Pr-(CH2)2-NMe2), (N i Pr2)2Al(-N i Bu-(CH2)2-NMe2), (N i Pr2)2Al(-N n Bu-(CH2)2-NMe2), (N i Pr2)2Al(-N t Bu-(CH2)2-NMe2), (N i Pr2)2Al(-N s Bu-(CH2)2-NMe2), (N n Pr2)2Al(-NMe-(CH2)2-NMe2), (N n Pr2)2Al(-NEt-(CH2)2-NMe2), (N n Pr2)2Al(-N i Pr-(CH2)2-NMe2), (N n Pr2)2Al(-N n Pr-(CH2)2-NMe2), (Nn Pr2)2Al(-N i Bu-(CH2)2-NMe2)、(N n Pr2)2Al(-N n Bu-(CH2)2-NMe2)、(N n Pr2)2Al(-N t Bu-(CH2)2-NMe2)、(N n Pr2)2Al(-N s Bu-(CH2)2-NMe2)、(N n Bu2)2Al(-NMe-(CH2)2-NMe2)、(N n Bu2)2Al(-NEt-(CH2)2-NMe2)、(N n Bu2)2Al(-N i Pr-(CH2)2-NMe2)、(N n Bu2)2Al(-N n Pr-(CH2)2-NMe2)、(N n Bu2)2Al(-N i Bu-(CH2)2-NMe2)、(N n Bu2)2Al(-N n Bu-(CH2)2-NMe2)、(N n Bu2)2Al(-N t Bu-(CH2)2-NMe2)、(N n Bu2)2Al(-N s Bu-(CH2)2-NMe2)、(N i Bu2)2Al(-NMe-(CH2)2-NMe2)、(N i Bu2)2Al(-NEt-(CH2)2-NMe2)、(N i Bu2)2Al(-N i Pr-(CH2)2-NMe2)、(N i Bu2)2Al(-N n Pr-(CH2)2-NMe2)、(N i Bu2)2Al(-N i Bu-(CH2)2-NMe2)、(N i Bu2)2Al(-N n Bu-(CH2)2-NMe2)、(N i Bu2)2Al(-N t Bu-(CH2)2-NMe2)、(N i Bu2)2Al(-Ns Bu-(CH2)2-NMe2), (N t (Bu2)2Al(-NMe-(CH2)2-NMe2), (N t (Bu2)2Al(-NEt-(CH2)2-NMe2), (N t (Bu2)2Al(-N i Pr-(CH2)2-NMe2), (N t (Bu2)2Al(-N n Pr-(CH2)2-NMe2), (N t (Bu2)2Al(-N i Bu-(CH2)2-NMe2), (N t (Bu2)2Al(-N n Bu-(CH2)2-NMe2), (N t (Bu2)2Al(-N t Bu-(CH2)2-NMe2), (N t (Bu2)2Al(-N s Bu-(CH2)2-NMe2), (N s (Bu2)2Al(-NMe-(CH2)2-NMe2), (N s (Bu2)2Al(-NEt-(CH2)2-NMe2), (N s (Bu2)2Al(-N i Pr-(CH2)2-NMe2), (N s (Bu2)2Al(-N n Pr-(CH2)2-NMe2), (N s (Bu2)2Al(-N i Bu-(CH2)2-NMe2), (N s (Bu2)2Al(-N n Bu-(CH2)2-NMe2), (N s (Bu2)2Al(-N t Bu-(CH2)2-NMe2), (N s (Bu2)2Al(-N s Bu-(CH2)2-NMe2), (NMe2)2Al(-NMe-(CH2)2-NEt2), (NMe2)2Al(-NEt-(CH2)2-NEt2), (NMe2)2Al(-N i Pr-(CH2)2-NEt2), (NMe2)2Al(-N n Pr-(CH2)2-NEt2), (NMe2)2Al(-N iBu-(CH2)2-NEt2), (NMe2)2Al(-N n Bu-(CH2)2-NEt2), (NMe2)2Al(-N t Bu-(CH2)2-NEt2), (NMe2)2Al(-N s Bu-(CH2)2-NEt2), (NEt2)2Al(-NMe-(CH2)2-NEt2), (NEt2)2Al(-NEt-(CH2)2-NEt2), (NEt2)2Al(-N i Pr-(CH2)2-NEt2), (NEt2)2Al(-N n Pr-(CH2)2-NEt2), (NEt2)2Al(-N i Bu-(CH2)2-NEt2), (NEt2)2Al(-N n Bu-(CH2)2-NEt2), (NEt2)2Al(-N t Bu-(CH2)2-NEt2), (NEt2)2Al(-N s Bu-(CH2)2-NEt2), (N i Pr2)2Al(-NMe-(CH2)2-NEt2), (N i Pr2)2Al(-NEt-(CH2)2-NEt2), (N i Pr2)2Al(-N i Pr-(CH2)2-NEt2), (N i Pr2)2Al(-N n Pr-(CH2)2-NEt2), (N i Pr2)2Al(-N i Bu-(CH2)2-NEt2), (N i Pr2)2Al(-N n Bu-(CH2)2-NEt2), (N i Pr2)2Al(-N t Bu-(CH2)2-NEt2), (N i Pr2)2Al(-N s Bu-(CH2)2-NEt2), (N n Pr2)2Al(-NMe-(CH2)2-NEt2), (N n Pr2)2Al(-NEt-(CH2)2-NEt2), (N n Pr2)2Al(-N i Pr-(CH2)2-NEt2), (N nPr2)2Al(-N n Pr-(CH2)2-NEt2), (N n Pr2)2Al(-N i Bu-(CH2)2-NEt2), (N n Pr2)2Al(-N n Bu-(CH2)2-NEt2), (N n Pr2)2Al(-N t Bu-(CH2)2-NEt2), (N n Pr2)2Al(-N s Bu-(CH2)2-NEt2), (N n Bu2)2Al(-NMe-(CH2)2-NEt2), (N n Bu2)2Al(-NEt-(CH2)2-NEt2), (N n Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N n Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N n Bu2)2Al(-N i Bu-(CH2)2-NEt2), (N n Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N n Bu2)2Al(-N t Bu-(CH2)2-NEt2), (N n Bu2)2Al(-N s Bu-(CH2)2-NEt2), (N i Bu2)2Al(-NMe-(CH2)2-NEt2), (N i Bu2)2Al(-NEt-(CH2)2-NEt2), (N i Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N i Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N i Bu2)2Al(-N i Bu-(CH2)2-NEt2), (N i Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N i Bu2)2Al(-N tBu-(CH2)2-NEt2), (N i Bu2)2Al(-N s Bu-(CH2)2-NEt2), (N t Bu2)2Al(-NMe-(CH2)2-NEt2), (N t Bu2)2Al(-NEt-(CH2)2-NEt2), (N t Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N t Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N t Bu2)2Al(-N i Bu-(CH2)2-NEt2), (N t Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N t Bu2)2Al(-N t Bu-(CH2)2-NEt2), (N t Bu2)2Al(-N s Bu-(CH2)2-NEt2), (N s Bu2)2Al(-NMe-(CH2)2-NEt2), (N s Bu2)2Al(-NEt-(CH2)2-NEt2), (N s Bu2)2Al(-N i Pr-(CH2)2-NEt2), (N s Bu2)2Al(-N n Pr-(CH2)2-NEt2), (N s Bu2)2Al(-N i Bu-(CH2)2-NEt2), (N s Bu2)2Al(-N n Bu-(CH2)2-NEt2), (N s Bu2)2Al(-N t Bu-(CH2)2-NEt2), and (N s Bu2)2Al(-N s Bu-(CH2)2-NEt2).

[0121] Other exemplary metal-containing precursors can be listed by replacing Al in the above molecules with B, Ga, In, lanthanide elements, P, As, Sb, or Bi.

[0122] A preferred metal precursor is (NMe2)2Al(-NEt-(CH2)2-NEt2) and has the following structure:

[0123]

[0124] The disclosed metal precursors contain heteroligands, one of which is a polydentate ligand. The disclosed metal precursors provide unique regioselectivity on various substrates.

[0125] The disclosed metal precursors containing Group 12 metals have the following general formula:

[0126]

[0127] where M = Zn, and L is independently selected from H, C1-C5 straight or branched alkyl, alkoxy - OR group (where R is H, alkyl), -NR a R b group (where R a 、R b are independently H, C1-C5 straight or branched alkyl), or SiR’3 group (where each R’ is independently H or alkyl); R1 to R7 are independently selected from H or C1-C5 straight or branched alkyl; n is an integer > 0, and 0 < m < 6 is an integer.

[0128] The disclosed metal precursors containing Group 13 and Group 15 metals have the following general formula:

[0129]

[0130] where M is B, Al, Ga, In, Tl, P, As, Sb or Bi; L is independently selected from H, C1-C5 straight or branched alkyl, alkoxy - OR group (where R is H, alkyl), -NR a R b group (where R a 、R b are independently H, C1-C5 straight or branched alkyl), or SiR’3 group (where each R’ is independently H or alkyl); R1 to R7 are independently selected from H or C1-C5 straight or branched alkyl; n is an integer > 0, and 0 < m < 6 is an integer.

[0131] The disclosed metal precursors containing Group IV and Group 14 metals have the following general formula:

[0132]

[0133] where M is Ti, Zr, Hf, Si, Ge, Sn or Pb; L is independently selected from H, C1-C5 straight or branched alkyl, alkoxy - OR group (where R is H, alkyl), -NRa R b group (wherein R a and R b are independently H, a C1-C5 straight or branched alkyl group), or a SiR'3 group (wherein each R' is independently H or an alkyl group); R1 to R7 are independently selected from H or a C1-C5 straight or branched alkyl group; n is an integer greater than 0, and 0 < m < 6 is an integer.

[0134] The disclosed metal-containing precursor containing a Group V metal has the following general formula:

[0135]

[0136] wherein M is V, Nb, Ta; L is independently selected from H, a C1-C5 straight or branched alkyl group, an alkoxy -OR group (wherein R is H, an alkyl group), -NR a R b group (wherein R a and R b are independently H, a C1-C5 straight or branched alkyl group), or a SiR'3 group (wherein each R' is independently H or an alkyl group); R1 to R7 are independently selected from H or a C1-C5 straight or branched alkyl group; n is an integer greater than 0, and 0 < m < 6 is an integer.

[0137] Preferably, the disclosed metal-containing precursor has suitable properties for the ASD metal-containing film. Figure 1 An exemplary flow chart of the ASD process is depicted. The process starts with a surface cleaning and preparation step (Step 1) for the substrate to be used. The wafer or substrate for depositing the metal-containing film has at least two different surfaces simultaneously exposed. For example, the wafer or substrate has at least one first surface (which is a metal surface), such as a W (tungsten) surface, and at least one second surface (which is a dielectric surface), such as a SiO2 surface. In this step, the wafer or substrate is cleaned to remove native oxides or residues. For example, the wafer or substrate is cleaned with diluted HF (1%) for about 1 min to remove native oxides or residues, and then rinsed with deionized water. Those of ordinary skill in the art will recognize that any solvent or solution for cleaning and removing chemicals can be used here to clean the wafer or substrate. Thereafter, N2 gas is blown onto the wafer or substrate to dry the wafer.

[0138] Next, step 2, is a step of performing SAM modification or SAM pretreatment on the wafer or substrate according to the surface on which the desired metal-containing film is to be deposited. If the metal-containing film is to be deposited on a metal surface, a dielectric barrier SAM layer is formed using a dielectric barrier agent to modify the dielectric surface to prevent the metal-containing film from being deposited thereon. If the metal-containing film is to be deposited on a dielectric surface, a metal barrier SAM layer is formed using a metal barrier agent to modify the metal surface to prevent the metal-containing film from being deposited thereon. To form the SAM layer, the cleaned and dried wafer or substrate is immersed or dipped into a pure SAM solution for about 24 hours and then rinsed with acetone, IPA, and deionized water. After that, N2 gas is blown onto the wafer or substrate to dry the wafer. Then, the wafer or substrate is dried under vacuum for about 4 hours. Alternatively, instead of dipping the wafer into a pure SAM agent, the SAM layer formed on the wafer or substrate can be formed by vapor spraying a pure chemical solution thereon and then dried by blowing dry with N2. By this step, depending on the type of SAM solution selected, a SAM layer is grown on the dielectric surface or the metal surface. If the SAM solution is a metal barrier agent, the SAM layer will grow on the metal surface. If the SAM solution is a dielectric barrier agent, the SAM layer will grow on the dielectric surface.

[0139] Dielectric barrier agents for blocking dielectric surfaces include, but are not limited to, compounds having the formula R 4-a SiX a , where each X is independently a surface hydroxyl-reactive group (halide, alkylamino, alkoxy, acetamide, etc.), and each R is selected from H, C1-C 20 alkyl or fluoroalkyl or mixtures thereof. Examples of dielectric barrier agents include dimethyldichlorosilane (DMDCS); trichlorosilane derivatives, X(CH2) n SiCl3, where X = CH3, Br, CN; n = 7-17, such as n-octadecyltrichlorosilane (OTS, CH3(CH2) 17 SiCl3), octadecylsiloxane (ODS), tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS), alkyltrichlorosilane (CH3(CH2) n SiCl3), bromoundecyltrichlorosilane (Br(CH2) 11 SiCl3), cyanoundecylchlorosilane (CN(CH2) 11 SiCl3); phenyl- and pentafluorophenyl-based silanes; octadecylsiloxane (ODS), etc.

[0140] Metal barrier agents are typically alkyl or fluoroalkyl compounds having surface-reactive chemical functional groups selected from phosphonic acid, carboxylic acid, thiol, or triazole.

[0141] If a dielectric blocker is applied, the SAM layer will grow on the dielectric SiO2 surface due to the -OH (hydroxyl)-terminated groups on the SiO2 surface. However, no SAM will grow on the metal surface. The SAM formed on the dielectric SiO2 surface will protect the dielectric SiO2 surface from the ALD metal-containing film, as shown in the next step.

[0142] The third step (step 3) of the ASD process is an ALD process, which is area-selective ALD. The substrate pretreated with the dielectric blocker in step 2 is placed in an ALD processing chamber for ALD of the metal-containing film using the disclosed metal-containing precursor. The metal-containing film is selectively deposited on the metal surface relative to the dielectric SiO2 surface. Conversely, by using a metal blocker to block the metal surface, such as Cu, Co, Ru, Pt, etc., to form a metal-blocking SAM layer on the surface, the ALD metal-containing film can be selectively deposited on the dielectric surface. Those of ordinary skill in the art will recognize that the substrate can have multiple first surfaces and second surfaces, where after SAM pretreatment on the substrate, by blocking the second surface, the first surface is selectively deposited with the metal-containing film. Those of ordinary skill in the art will also recognize that more than one SAM-pretreated substrate can be applied in the ALD processing chamber for ASD, each pretreated substrate having at least two different surfaces, and one surface is selectively deposited with the metal-containing film relative to the other surface.

[0143] The disclosed metal-containing precursor is applicable to depositing metal-containing films, such as Al2O3, by the ASD process and has the following advantages:

[0144] a. Being liquid at room temperature or having a melting point below 50 °C;

[0145] b. Thermally stable to enable proper distribution and evaporation using industrial standard methods (bubbler, direct liquid injection, vapor extraction) without particle generation and product decomposition;

[0146] c. Appropriate reactivity with the substrate to allow a wide self-limiting ALD window, thus allowing the deposition of various metal-containing films, such as Al2O3, NbN, Nb2O5, etc.;

[0147] d. Appropriate reactivity of the chemisorbed precursor with the co-reactant to form the metal-containing film in the ALD process; and

[0148] e. High thermal stability of the chemisorbed substance to prevent self-decomposition and parasitic CVD growth on the substrate surface.

[0149] While the disclosed metal-containing precursors are ideally liquids and are evaporated in bubblers or direct liquid injection systems, it is also possible to use sublimators (such as those disclosed in PCT Publication WO 2009 / 087609 by Xu et al.) for ALD precursor evaporation using solid precursors. Alternatively, solid precursors can be mixed or dissolved in a solvent to achieve a usable melting point and viscosity for use through a direct liquid injection system.

[0150] To ensure process reliability, the disclosed metal-containing precursors can be purified by continuous or fractional batch distillation or sublimation prior to use 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.

[0151] The disclosed metal-containing precursors can contain any of the following impurities: unwanted homologues; solvents; chlorinated metal compounds; or other reaction products. In an alternative, the total amount of these impurities is less than 5.0% w / w, preferably less than 0.1% w / w.

[0152] Solvents such as hexane, pentane, dimethyl ether, or anisole can be used in the synthesis of the precursors. The concentration range of the solvent in the disclosed metal-containing precursors can be 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, it may be difficult to separate the solvent from the precursor. 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 about its decomposition point.

[0153] In an alternative, the disclosed metal-containing precursors contain less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably less than 0.01% v / v of any of their unwanted homologues, reactants, or other reaction products. This alternative can provide better process reproducibility. This alternative can be achieved by distillation of the disclosed metal-containing precursors.

[0154] In another alternative, the disclosed metal-containing precursors can contain one or more of the same metal-containing precursors, reactants, or other reaction products in the range of 5% v / v to 50% v / v, especially when the mixture provides improved process parameters or when separating the target compound is too difficult or expensive. For example, a mixture of two metal-containing precursors can produce a stable liquid mixture suitable for vapor deposition.

[0155] In another alternative, the disclosed metal-containing precursor can contain metal impurities in the range of from about 0 ppbw to about 500 ppbw.

[0156] The concentration ranges of trace metals and metalloids in the disclosed metal-containing precursors can each be from about 0 ppb to about 100 ppb, and more preferably from about 0 ppb to about 10 ppb.

[0157] In addition to the disclosed metal-containing precursor, reactants or co-reactants can be introduced into the reactor. The co-reactant can be an oxygen-containing gas or a nitrogen-containing gas for metal oxide film deposition. Co-reactants include, but are not limited to, oxidants such as O3, O2, H2O, H2O2, D2O, ROH (R = C1-C 10 linear or branched hydrocarbons), etc. H2O and ROH (R = C1-C 10 linear or branched hydrocarbons) are preferred oxidation sources to avoid reaction with the SAM layer formed on the substrate.

[0158] The ALD sequence can include sequential pulses of several compounds. For example, the surface can be exposed to O2 / O3 and then to H2O to increase the density of hydroxyl groups on the surface.

[0159] Alternatively, the co-reactant can be a nitrogen-containing gas for nitrogen-containing film deposition. Nitrogen-containing gases include, but are not limited to, NH3, NO, N2O, hydrazine, primary amines such as methylamine, ethylamine, tert-butylamine; secondary amines such as dimethylamine, diethylamine, diisopropylamine, ethylmethylamine, pyrrolidine; tertiary amines such as trimethylamine, triethylamine, trimethylsilylamine, N2, its N2 / H2 mixture, preferably NH3. The co-reactant can be selected from NH3, NO, N2O, hydrazine, amines or combinations thereof. Preferably, plasma-treated co-reactants are avoided because they are prone to damage the SAM layer, unless the SAM layer is reformed in each ALD cycle.

[0160] Also disclosed is a method or process for forming a metal-containing film on a substrate using an ASD process. In one embodiment, the method for forming a metal-containing film on a substrate comprises the steps of: a) providing a substrate having a first surface and a second surface, b) exposing the substrate to a SAM solution or precursor to form a SAM layer on the second surface, c) exposing the substrate to a vapor of a disclosed metal-containing film-forming composition comprising a disclosed precursor, d) selectively depositing at least a portion of a deposition precursor onto the first surface (i.e., depositing selectively on the first surface relative to the second surface) by a vapor deposition process to form a metal-containing film, and repeating c) and d) until a metal-containing film of a desired thickness is formed. The method further comprises the step of exposing the substrate to a co-reactant after c), wherein the co-reactant is selected from O3, O2, H2O, H2O2, D2O, ROH (R = C1-C 10 (linear or branched) hydrocarbon), NH3, NO, N2O, hydrazine, amine, or a combination thereof. For example, one or a combination of the above co-reactants can be used for depositing a silicon oxynitride film by co-flowing or sequentially flowing the co-reactant. In an alternative embodiment, the method for forming a metal-containing film on a substrate comprises the steps of: a) providing a surface having a plurality of materials simultaneously exposed thereon, b) exposing the surface to a vapor of a disclosed metal-containing film-forming composition comprising a disclosed precursor as shown in formula (II), and c) in a vapor deposition process, preferentially or selectively depositing a film on one or more, but less than all, of the plurality of materials on the surface, wherein at least one of the materials on the surface is at least partially blocked by a blocker, thereby reducing or preventing the deposition of a metal-containing film on the blocked material.

[0161] The method further comprises the step of exposing the substrate to a co-reactant after step b), wherein the co-reactant is selected from O3, O2, H2O, H2O2, D2O, ROH (R = C1-C 10 (linear or branched) hydrocarbon), NH3, NO, N2O, hydrazine, amine, or a combination thereof. The method further comprises the steps of: repeating the exposure to the vapor of the metal-containing film-forming composition and the exposure to the co-reactant until a metal-containing film of a desired thickness is formed, and purging excess vapor of the metal-containing film-forming composition and excess co-reactant with an inert gas, respectively, to separate each exposure, wherein the inert gas is N2, Ar, Kr, or Xe.

[0162] The disclosed processes using the disclosed metal precursors include ALD processes for selectively depositing metal-containing films. Suitable ALD methods include thermal ALD, spatial ALD, and temporal ALD methods. Preferably, the suitable ALD methods do not use plasma because it is extremely difficult to grow conformal films with high aspect ratios using this type of ALD. It should be understood that suitable ALD can operate in a non-ideal self-limiting growth mode, allowing some parasitic CVD to occur. As long as the deposited film meets the conformality requirements, such parasitic CVD may not be a problem.

[0163] The reaction chamber can be any enclosed chamber or cavity of a device in which the deposition method is carried out, such as but not limited to a parallel plate type reactor, a hot wall type reactor, a single wafer reactor, a multi-wafer reactor, or other such types of deposition systems. All of these exemplary reaction chambers are capable of being used as ALD reaction chambers.

[0164] The reactor contains one or more substrates on which a thin film is selectively deposited. A substrate is generally defined as the material on which a process is carried out. The substrate is cleaned to remove native oxides and dried prior to SAM pretreatment. The substrate can be any suitable substrate used in the manufacture of semiconductor, photovoltaic, flat panel, or LCD-TFT devices. Examples of suitable substrates include wafers such as metals (e.g., W, Ge, etc.), silicon, SiGe, silicon dioxide, or glass. The substrate can also have one or more surface regions of different materials that have been deposited thereon from previous manufacturing steps. For example, a wafer can include simultaneously exposed dielectric surfaces and conductive or electrode surfaces such as metal surfaces, metal oxide surfaces, silicon surfaces, silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layer / surfaces, silicon nitride layer / surfaces, silicon oxynitride layer / surfaces, carbon-doped silicon oxide (SiCOH) layer / surfaces, or combinations thereof. Additionally, the wafer can include copper, cobalt, ruthenium, tungsten, and / or other metal layers (e.g., platinum, palladium, nickel, ruthenium, or gold). The wafer can include barrier layers or electrodes such as tantalum, tantalum nitride, etc. The wafer can be planar or patterned. The substrate can include an oxide layer having an exposed oxide surface that serves as a dielectric material in 3D NAND, MIM, DRAM, or FeRam technologies (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) or a nitride-based film that serves as an electrode (e.g., TaN, TiN, NbN). The disclosed process can selectively deposit a metal-containing layer directly on the wafer or directly on one or more than one (when the patterned layer forms the substrate) layer on top of the wafer. Additionally, those of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a certain thickness of some material placed or spread on a surface and that surface can be a trench or a line. Throughout the specification and claims, the wafer and any associated layer / surface thereon are referred to as the substrate. The actual substrate utilized can also depend on the particular precursor embodiment utilized.

[0165] The disclosed ASD process using the disclosed metal-containing precursor can be carried out on substrates having a temperature range from room temperature to about 500 °C. The ASD processing temperature range is from room temperature to about 500 °C, which is typically lower than the self-decomposition temperature of SAM.

[0166] In the disclosed ASD process using the disclosed precursor, the substrate exposure time range in the ALD reaction chamber can be from 1 millisecond to 5 minutes, preferably from 1 second to 60 seconds. In the disclosed ASD process, the co-reactant exposure time range in the ALD reaction chamber can be from 1 millisecond to 1 minute, preferably from 100 milliseconds to 30 seconds.

[0167] Maintain the pressure in the reaction chamber under conditions suitable for the reaction of the precursor with the surface. For example, the pressure in the chamber can be maintained between about 0.1 millitorr and about 1000 torr, preferably between about 1 millitorr and about 400 torr, more preferably between about 1 torr and about 100 torr, and even more preferably between about 1 torr and about 10 torr.

[0168] The temperature of the reactor chamber can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor wall. Devices for heating the substrate are known in the art. The reactor wall is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the reactor wall can be heated include from room temperature to about 600 °C, preferably from room temperature to about 500 °C.

[0169] The disclosed ALD process or sequence typically includes a step of removing excess precursor and excess co-reactant from the deposition surface by providing a purge step, which is accomplished by purging the reactor with an inert gas or by passing the substrate through a section under high vacuum and / or a carrier gas curtain. The inert gas is N2, Ne, Ar, Kr, or Xe, preferably N2 or Ar.

[0170] The disclosed metal-containing precursors and co-reactants can be introduced into the reactor sequentially (ALD). The reactor can be purged with an inert gas between the introduction of the precursor and the introduction of the co-reactant and after the introduction of the co-reactant. Alternatively, the substrate can be moved from one area for precursor exposure to another area for co-reactant exposure (spatial ALD).

[0171] Depending on the specific process parameters, the deposition may proceed for different lengths of time. Generally, the deposition can be continued for the desired or necessary length of time to produce a film with the necessary thickness. Depending on the specific deposition process, typical film thicknesses can vary from atomic monolayers to several hundred micrometers, preferably between 0.5 and 100 nm, more preferably between 1 and 50 nm. The deposition process can also be carried out many times as necessary to obtain the desired film.

[0172] In a non-limiting, exemplary ASD-type process, the disclosed metal-containing precursor in vapor phase is introduced into a reactor, where the metal-containing precursor selectively physically adsorbs or chemically adsorbs onto the SAM-pretreated substrate. Excess composition can then be removed from the reactor by purging and / or evacuating the reactor. A desired gas (e.g., H2O or O3) is introduced into the reactor, where it selectively reacts in a self-limiting manner with the physically or chemically adsorbed precursor. Any excess reducing gas is removed from the reactor by purging and / or evacuating the reactor. If the desired film is a metal-containing film, this four-step process can provide the desired film thickness or can be repeated until a film with the requisite thickness is obtained.

[0173] Examples

[0174] The following non-limiting examples are provided to further illustrate embodiments of the present invention. However, these examples are not intended to include all examples and are not intended to limit the scope of the invention described herein.

[0175] Example 1: Use of (NMe2)2Al(-NEt-(CH2)2-NEt2) for ASD Al2O3 films on W and SiO2 wafers at different deposition temperatures

[0176] Tungsten (W) wafers and SiO2 wafers were placed in a container containing diluted HF (1%) for 1 min, then rinsed with DI water and dried with N2 gas. Thereafter, the two wafers were immersed in pure dimethyldichlorosilane (DMDCS) for 24 hours. As a result of this step, a SAM layer grew on the surface of the SiO2 wafer and did not grow on the surface of the W wafer. Then, the two wafers were rinsed with acetone, ethanol, and DI water and dried with N2 gas. After that, the two wafers were dried under vacuum for 4 hours. Next, ALD metal-containing films were deposited on the W wafers and SiO2 wafers using (NMe2)2Al(-NEt-(CH2)2-NEt2) as a precursor and H2O as a co-reactant at temperatures of 150 °C, 200 °C, and 250 °C for 50 cycles, resulting in Al2O3 films selectively deposited on the W wafers. After the first 50 cycles, the formed Al2O3 films had a thickness of approximately 5 nm. Figures 2 to 4 Are the XPS results after ASD Al2O3 films on W wafers using (NMe2)2Al(-NEt-(CH2)2-NEt2) at temperatures of 150 °C, 200 °C, and 2�0 °C, respectively. Figures 5 to 7XPS results after ASD Al2O3 films on SiO2 wafers using (NMe2)2Al(-NEt-(CH2)2-NEt2) at 150 °C, 200 °C, and 250 °C, respectively. XPS results of Al content on W wafers and SiO2 wafers at different temperatures show that selective deposition was achieved between W wafers and SiO2 wafers up to 250 °C. These figures depict that the Al content on W wafers is much higher than that on SiO2 wafers. That is, the Al2O3 film was selectively deposited on W wafers relative to SiO2 wafers. Since the SAM formation step produced a protective SAM layer on the SiO2 wafer, the Al2O3 deposition that occurred was preferentially on the W wafer.

[0177] Although the subject matter described herein may be described in the context of illustrative implementations to address one or more computing application features / operations of a computing application with user interaction components, the subject matter is not limited to these particular embodiments. Rather, the techniques described herein can be applied to any suitable type of user interaction component for performing management methods, systems, platforms, and / or devices.

[0178] It should be understood that many additional changes in details, materials, steps, and arrangements of parts, which have been described and elucidated herein to explain the nature of the invention, can be made by those skilled in the art within the principles and scope of the invention as set forth in the appended claims. Therefore, the invention is not intended to be limited to the specific embodiments given in the examples and / or drawings above.

[0179] Although embodiments of the invention have been shown and described, they can be modified by those skilled in the art without departing from the spirit or teachings of the invention. The embodiments described herein are merely exemplary and non-limiting. Many variations and modifications of the compositions and methods are possible and within the scope of the invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is only defined by the subsequent claims, the scope of which should include all equivalents of the subject matter of the claims.

Claims

1. A method for selectively depositing a metal-containing film, the method comprising the following steps: a) Providing a surface having a plurality of materials simultaneously exposed thereon; And b) Exposing the surface to a vapor of a metal-containing film-forming composition, the composition comprising a precursor having the following formula: L x M(-N(R)-(CR’2) n -NR”2) where M is a Group 12, 13, 14, 15, IV or V element; x+1 is the oxidation state of M; L is an anionic ligand; R and R” are each independently a C1-C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group; R’ is H or C1-C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group; n = 1-4; and c) In a chemical vapor deposition process, preferentially or selectively depositing a film on one or more, but less than all, of the plurality of materials on the surface, Wherein at least one of these materials on the surface is at least partially blocked by a blocker, thereby reducing or preventing the deposition of the metal-containing film on the blocked material.

2. The method according to claim 1, wherein The chemical vapor deposition process is an ALD process.

3. The method according to claim 1, further comprising Exposing the surface to a co-reactant selected from an oxidant or a nitrogen agent.

4. The method according to claim 3, further comprising the following steps: Repeating the exposure to the vapor of the metal-containing film-forming composition and the exposure to the co-reactant until a metal-containing film of a desired thickness is formed; And Respectively purging excess vapor of the metal-containing film-forming composition and excess co-reactant with an inert gas to separate each exposure, wherein the inert gas is N2, Ar, Kr or Xe.

5. The method according to claim 3, wherein, The co-reactant is selected from O3, O2, H2O, H2O2, D2O, ROH where R = C1-C 10 straight-chain or branched hydrocarbon, NH3, NO, N2O, hydrazine, amine, or a combination thereof.

6. The method according to claim 3, wherein, The co-reactant is H2O.

7. The method according to claim 1, wherein The blocker forms a SAM layer on at least one of these materials by dipping the surface into the blocker or spraying the surface with the blocker vapor.

8. The method according to claim 1, wherein, The plurality of materials on the surface includes at least one dielectric material and at least one metal material.

9. The method according to claim 8, wherein, By blocking the reactivity of the metal material with a blocker, the metal-containing film is deposited on the dielectric material rather than on the metal material, and the blocker is a metal blocker.

10. The method according to any one of claims 1, 8, and 9, wherein, The blocker is selected from alkyl or fluoroalkyl compounds having surface-reactive chemical functional groups, which are selected from phosphonic acid, carboxylic acid, thiol or triazole.

11. The method according to claim 8, wherein By blocking the reactivity of the dielectric material with a blocker, the metal-containing film is deposited on the metal material rather than on the dielectric material, wherein the blocker is a dielectric blocker.

12. The method according to any one of claims 1, 8, and 11, wherein The blocking agent is a compound having the formula R 4-a SiX a wherein each X is independently a surface hydroxyl-reactive group, and each R is selected from H, C1-C 20 alkyl or fluoroalkyl or a mixture thereof.

13. The method according to claim 12, wherein, Each X is independently a halide, alkylamino, alkoxy or acetamide.

14. The method according to claim 1, wherein, The surface is exposed to the precursor at a temperature ranging from room temperature to 500 °C.

15. The method according to claim 1, wherein The precursor is (NMe2)2Al(-NEt-(CH2)2-NEt2).

16. The method according to claim 15, wherein, The metal-containing film is an Al2O3 film.

17. A composition for selectively depositing a metal-containing film, the composition comprising a precursor having the following formula: L x M(-N(R)-(CR’2) n -NR”2) where M is a Group 12, Group 13, Group 14, Group 15, Group IV or Group V element; x+1 is the oxidation state of M; L is an anionic ligand independently selected from dialkylamines, alkoxides, alkylimines, bis(trialkylsilylamines), amidinates, β-diketonates, keto-imines, halides; R and R” are each independently a C1-C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl; R’ is H or C1-C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl; n = 1-4.

18. The composition according to claim 17, wherein, The precursor is (NMe2)2Al(-NEt-(CH2)2-NEt2).

19. The composition according to claim 17 or claim 18, wherein, The composition comprises between 95% w / w and 100.0% w / w of the precursor.

20. The composition according to claim 17 or claim 18, wherein The composition comprises between 0.0% w / w and 5.0% w / w of impurities.

21. A method for selectively depositing an Al2O3 film, the method comprising the following steps: a) Providing a surface having at least one dielectric material and at least one metal material simultaneously exposed thereon; b) Exposing the surface to the vapor of (NMe2)2Al(-NEt-(CH2)2-NEt2); And c) Expose the surface to co-reactant H2O, wherein the at least one dielectric material is at least partially blocked from deposition of the Al2O3 film by ALD process by blocker dimethyldichlorosilane (DMDCS).

Images