Selective deposition method for silicon-containing films using organic aminopolysiloxanes and organic aminopolysilazanes

Abstract

A method for selectively passivating the surface of a substrate, wherein the surface of the substrate comprises at least a first surface comprising a dielectric and at least a second surface comprising another material. The method comprises the step of exposing the first and second surfaces to at least one organic aminopolysiloxane or organic aminopolysilazane, wherein the organic aminopolysiloxane or organic aminopolysilazane selectively reacts with the dielectric to passivate the first surface, while leaving the second surface substantially unreacted.

Description

Cross-reference of related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 587,974 (Patent Document 1), filed on 4 October 2023, and U.S. Provisional Application No. 63 / 687,676 (Patent Document 2), filed on 27 August 2024. All of the contents of these documents are included herein. [Technical Field]

[0002] This application relates to a method for selectively forming a passivation layer on a first surface of a substrate relative to a second surface. In addition, further processing can be used to subsequently deposit a different material on the second surface relative to the first surface. [Background technology]

[0003] Selective deposition processes are gaining significant momentum, primarily because current lithography processes have limitations in enabling the manufacture of advanced semiconductor devices based on constantly shrinking physical dimensions. Traditionally, patterning in microelectronics engineering has been achieved using various lithography and etching processes. However, as lithography is rapidly becoming more complex and costly, the use of selective deposition for forming self-aligned shapes is becoming considerably more attractive. The manufacture of self-aligned via structures would greatly benefit from manufacturable selective deposition processes. One other potential application of selective deposition is gap filling, where a dielectric "filling" film is selectively grown from the bottom to the top of a trench. Selective deposition can also be used in other applications such as selective sidewall deposition, which selectively deposits films on exposed surfaces of three-dimensional FINFET structures. This would enable the deposition of sidewall spacers without requiring complex patterning steps. Selective deposition processes for metal and metal oxide films used as gate dielectrics and capacitor dielectrics would also be extremely useful in semiconductor device manufacturing.

[0004] Previous examples exist in the technical literature relating to the selective formation of surface passivation coatings on wafers with multiple exposed chemical surfaces. These were done with the aim of delaying or preventing film deposition via ALD on these passivation surfaces, and not to prevent deposition on surfaces where film deposition by the ALD deposition process is desired. Generally, process selectivity was insufficient due to incomplete passivation of the surface and / or due to the physical sorption of ALD precursor molecules within the passivation layer itself or on surfaces where deposition is undesirable, and the subsequent formation of the ALD film material.

[0005] Achieving ASD (Advanced Storage Deposition) of dielectrics on dielectrics presents significant challenges due to the similarity of their surface chemical properties, particularly in selectively passivating one dielectric relative to another. To date, relatively few passivation chemistry methods have been reported that successfully enable the selective passivation of one dielectric relative to another, thereby allowing for atomic layer deposition of dielectric films on other dielectrics. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Provisional Application No. 63 / 587,974 [Patent Document 2] U.S. Provisional Application No. 63 / 687,676 [Overview of the project] [Problems that the invention aims to solve]

[0007] This disclosure aims to overcome the limitations of the prior art and provide an improved method for the selective deposition of ultrathin films using the ALD deposition process. [Means for solving the problem]

[0008] In a first main aspect, a method for passivating a silicon-containing surface of a substrate is provided. The method comprises: (a) providing the substrate in a reaction vessel at a temperature ranging from 20°C to 800°C, wherein the substrate has a first surface comprising a dielectric material having hydroxyl groups and a second surface comprising a different material having fewer hydroxyl groups; (b) forming at least one passivation layer on the first surface by exposing the first surface and the second surface to a passivating composition comprising an organoaminoalkylpolysiloxane or organoaminoalkylpolysilazane having one of the following formulas;

[0009]

Chemical Formula

[0010] In still another aspect of the aforementioned first main aspect, steps (b) and (c) are repeated until a self-limiting monolayer coating of the first surface is achieved, i.e., until the passivating composition reacts with all chemically available hydroxyl groups on the first surface.

[0011] In still another aspect of the aforementioned first main aspect, the first surface is selected from the group consisting of silicon oxide, carbon-doped silicon oxide, metal oxides, and combinations thereof, and the second surface is selected from the group consisting of silicon nitride or metal nitrides.

[0012] In one of yet another aspects of the first main aspect, the second surface comprises a metal or metalloid selected from the group consisting of ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), silicon, and combinations thereof, or the second surface comprises a nitride selected from the group consisting of silicon nitride, germanium nitride, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and combinations thereof.

[0013] In one of the further aspects of the first main aspect, the first surface is selected from the group consisting of metal oxides such as hafnium oxide, zirconium oxide, titanium oxide, and combinations thereof, and the second surface is selected from the group consisting of metal nitrides such as titanium nitride, tantalum nitride, tungsten nitride, and combinations thereof.

[0014] In one further aspect of the first main aspect described above, the passivation composition comprises an organic aminoalkyl polysiloxane selected from the group consisting of 1-dimethylamino-1,1,3,3-tetramethyldisiloxane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-dimethylamino-1,1,3,3,5,5-hexamethyltrisiloxane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, and combinations thereof.

[0015] In one further aspect of the first main aspect mentioned above, the passivation composition includes an organic aminoalkyl polysilazane of formula IB selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisilazane, 1-dimethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-dimethylamino-1,1,3,3,5,5-hexamethyltrisilazane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisilazane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasilazane, 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasilazane, and combinations thereof.

[0016] In a second primary aspect, a method is provided for the selective deposition of silicon-containing and nitrogen films. The method comprises (a) providing a substrate in a reactor, wherein the substrate has a first surface comprising a dielectric material having hydroxyl groups and a second surface comprising a different dielectric material or metal having fewer hydroxyl groups or no hydroxyl groups compared to the first surface; (b) Exposing the first surface and the second surface to a passivation composition comprising an organic aminoalkylpolysiloxane or organic aminoalkylpolysilazane having one of the following formulas to form at least one self-limiting passivation layer on the first surface;

[0017] [ka] [In the formula, R 1 and R 2 R is independently selected from hydrogen and C1-C6 alkyl groups, however, 1 and R 2 Both cannot be hydrogen; R 3 And R are independently selected from hydrogen or methyl; n is 1, 2, or 3; and R 1 and R 2 They are connected to form an annular ring structure, or R 1 and R 2 They are not connected and do not form a ring-like structure. (c) Purge the reactor with an inert gas; (d) A halogenated silicon-containing precursor is introduced into the reactor to selectively form a silicon-containing layer on the second surface; (e) Purge the reactor with an inert gas; (f) Introducing a nitrogen source to react with the silicon-containing layer to form a silicon nitride layer, a carbon-doped silicon nitride layer, or a silicon oxynitride layer on the second surface; and (g) Purge the reactor with an inert gas; This includes, in this embodiment, steps (d) to (g) being repeated to selectively provide a silicon nitride layer of a certain thickness, or a carbon-doped silicon nitride layer, or a silicon oxynitride layer, on the second surface area.

[0018] In one further aspect of the second main aspect, the first surface is selected from the group consisting of silicon oxide and carbon-doped silicon oxide, and the second surface contains silicon nitride.

[0019] In one of yet another aspects of the second main aspect, the first surface is selected from the group consisting of metal oxides such as hafnium oxide, zirconium oxide, titanium oxide, and combinations thereof, and the second surface is selected from the group consisting of metal nitrides such as titanium nitride, tantalum nitride, tungsten nitride, and combinations thereof.

[0020] In one of yet another aspects of the second main aspect, the second surface comprises a metal selected from the group consisting of ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), and combinations thereof, or the second surface comprises a metal nitride selected from the group consisting of tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and combinations thereof.

[0021] In yet another perspective of the second main perspective, steps (b) and (c) are repeated to achieve a self-limiting single-layer immobilization layer before performing steps (d) through (g).

[0022] In one of yet another aspects of the second main aspect, the self-restricting monolayer passivation layer can be in the range of about 0.2 Å to about 3 Å. In one of yet another aspects of the second main aspect, the self-restricting monolayer passivation layer can be in the range of about 0.2 Å to about 5 Å. In one of yet another aspects of the second main aspect, the self-restricting monolayer passivation layer can be in the range of about 0.2 Å to about 10 Å.

[0023] In yet another aspect of the second main aspect, the aforementioned certain thickness of the silicon nitride or carbon-doped silicon nitride or silicon oxynitride film can be in the range of about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å.

[0024] In one of the further aspects of the second main aspect mentioned above, the organic aminopolysiloxane of formula IA is selected from the group consisting of 1-dimethylamino-1,1,3,3-tetramethyldisiloxane and 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.

[0025] In one of the further aspects of the second main aspect mentioned above, the organic aminopolysilazane of formula IB is selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisilazane and 1-dimethylamino-1,1,2,3,3,3-hexamethyldisilazane.

[0026] In one of yet another aspects of the second main aspect, the deposition selectivity of the second surface relative to the first surface is greater than about 0.3, more preferably greater than about 0.5, and most preferably greater than about 0.6.

[0027] In one of the further aspects of the second main aspect mentioned above, the nitrogen source is selected from the group consisting of, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, piperazine, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof.

[0028] In one further aspect of the second main aspect mentioned above, the halogenated silicon precursor is selected from the group consisting of (i) halogenated silane, (ii) halogenated siloxane, (iii) halogenated silazane, and (iv) halogenated carbosilane.

[0029] In one further aspect of the second main aspect mentioned above, the halogenated silicon precursor is a halogenated silane of group (i) selected from the group consisting of hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.

[0030] In another aspect of the second main aspect mentioned above, the halogenated silicon precursor is a halogenated siloxane of group (ii) selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

[0031] In yet another aspect of the second main aspect mentioned above, the halogenated silicon precursor is a halogenated silazane of group (iii) selected from the group represented by the following formula I:

[0032] [ka] In the formula, R 4 This is hydrogen, linear or branched C1-C 10 Alkyl, linear or branched C3-C 10 Alkenyl group, linear or branched C3-C 10 Alkynyl group, C3-C 10 Cyclic alkyl groups, C2-C6 dialkylamino groups, electron-withdrawing groups, and C6-C 10 Selected from the group consisting of aryl groups; R 5 This is hydrogen, linear or branched C1-C 10 Alkyl groups, linear or branched C2-C6 alkenyl groups, linear or branched C3-C6 alkynyl groups, C3-C 10 Cyclic alkyl group, C2-C6 dialkylamino group, C6-C 10 Aryl group, linear or branched C1-C6 fluorinated alkyl group, electron-withdrawing group, C4-C 10 X is selected from the group consisting of an aryl group and halides selected from the group consisting of Cl, Br, and I; and X is a halide selected from the group consisting of C, Br, and I.

[0033] In one of yet another aspects of the second main aspect mentioned above, the halogenated silazane is selected from group (iii), which is selected from the group consisting of: 1,1,1,3,3,3-hexachloro-disilazane, 1,1,1,3,3-pentachloro-disilazane, 1,1,1,3,3,3-hexachloro-2-methyldisilazane, 1,1,1,3,3,3-hexachloro-2-ethyldisilazane, 1,1,1,3,3,3-hexachloro-2-n-propyldisilazane, 1, 1,1,3,3,3-Hexachloro-2-n-butyldisilazane, 1,1,1,3,3,3-Hexachloro-2-iso-butyldisilazane, 1,1,1,3,3,3-Hexachloro-2-sec-butyldisilazane, 1,1,1,3,3,3-Hexachloro-2-tert-butyldisilazane, 1,1,1,3,3,3-Hexabromo-2-methyldisilazane, 1,1,1,3,3,3-Bromo-2-ethyldisilazane, 1,1,1,3,3,3-Bromo-2-n-propyldisilazane, 1,1,1,3,3,3-Bromo-2-iso-propyldisilazane Zan, 1,1,1,3,3,3-bromo-2-n-butyldisilazane, 1,1,1,3,3,3-bromo-2-iso-butyldisilazane, 1,1,1,3,3,3-bromo-2-sec-butyldisilazane, 1,1,1,3,3,3-bromo-2-tert-butyldisilazane, 1,1,1,3,3,3-hexaiodo-2-methyldisilazane, 1,1,1,3,3,3-iodo-2-ethyldisilazane, 1,1,1,3,3,3-iodo-2-n-propyldisilazane, 1,1,1,3,3,3-iodo-2-iso-propyldisilazane, 1,1, 1,3,3,3-iodo-2-n-butyldisilazane, 1,1,1,3,3,3-iodo-2-iso-butyldisilazane, 1,1,1,3,3,3-iodo-2-sec-butyldisilazane, 1,1,1,3,3,3-iodo-2-tert-butyldisilazane, 1,1,1,3,3-pentachloro-2-methyldisilazane, 1,1,1,3,3-pentachloro-2-ethyldisilazane, 1,1,1,3,3-pentachloro-2-n-propyldisilazane, 1,1,1,3,3-pentachloro-2-iso-propyldisilazane, 1,1,1,3,3-Pentachloro-2-methyl-3-methyldisilazane, 1,1,1,3,3-Pentachloro-2-ethyl-3-methyldisilazane, 1,1,1,3,3-Pentachloro-2-n-propyl-3-methyldisilazane, 1,1,1,3,3-Pentachloro-2-iso-propyl-3-methyldisilazane, 1,1,3,3-Tetrachloro-2-methyldisilazane, 1,1,3,3-Tetrachloro-2-ethyldisilazane, 1,1,3,3-Tetrachloro-2-n-propyldisilazane, 1,1,3,3-Tetrachloro-2-iso-propyldisilazane , 1,1,3,3-tetrachloro-2-n-butyldisilazane, 1,1,3,3-tetrachloro-2-iso-butyldisilazane, 1,1,3,3-tetrachloro-2-sec-butyldisilazane, 1,1,3,3-tetrachloro-2-tert-butyldisilazane, 1,1,3,3-tetrabromo-2-methyldisilazane, 1,1,3,3-tetrabromo-2-ethyldisilazane, 1,1,3,3-tetrabromo-2-n-propyldisilazane, 1,1,3,3-tetrabromo-2-iso-propyldisilazane, 1,1,3,3-tetrabromo-2- n-butyldisilazane, 1,1,3,3-tetrabromo-2-iso-butyldisilazane, 1,1,3,3-tetrabromo-2-sec-butyldisilazane, 1,1,3,3-tetrachloro-2-tert-butyldisilazane, 1,1,3,3-tetraiodo-2-methyldisilazane, 1,1,3,3-tetraiodo-2-ethyldisilazane, 1,1,3,3-tetraiodo-2-n-propyldisilazane, 1,1,3,3-tetraiodo-2-iso-propyldisilazane, 1,1,3,3-tetraiodo-2-n-butyldisilazane, 1,1,3,3 -Tetraiodo-2-iso-butyldisilazane, 1,1,3,3-Tetraiodo-2-sec-butyldisilazane, 1,1,3,3-Tetraiodo-2-tert-butyldisilazane, 1,1,3,3-Tetrachloro-2-cyclopentyldisilazane, 1,1,3,3-Tetrachloro-2-cyclohexyldisilazane, 1,1,3,3-Tetrachloro-1,3-dimethyl-2-cyclopentyl-2-cyclopentyldisilazane, 1,1,3,3-Tetrachloro-1,3-dimethyl-2-cyclohexyldisilazane, 1,1,3,3-Tetrachloro-1,3-dimethyl-2-methyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-tetrachloro-2-ethyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-n-propyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-iso-propyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-n-butyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-iso-butyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-sec-butyldisilazane, and 1,1,3,3-tetrachloro-1,3-dimethyl-2-tert-butyldisilazane.

[0034] In another aspect of the second main aspect described above, the halogenated silicon precursor is a halogenated carbosilane of group (iv) selected from the group consisting of silicon compounds having one or two Si-C-Si linkages. Preferred carbosilanes of group iv include those represented by formulas II and III:

[0035] [ka] In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 Each is independently a H atom; a halide selected from F, Cl, Br, and I; an isocyanate; formula NR 5 R 6 An amino group having (wherein R 5 and R 6 These are, independently, hydrogen, C1- 10 Selected from the group consisting of linear alkyl groups); C 3-10 Branched alkyl group; C 3-10 Cyclic alkyl group; C 3-10 Alkenyl group; C 4-10 Aryl group; and C 4-10 Selected from heterocyclic groups. In some embodiments of formulas I, II, or both I and II, substituent X 1 , X2 , X 3 , X 4 , X 5 , and X 6 One or more of these are linked together to form a substituted or unsubstituted saturated or unsaturated cyclic group. In one particular embodiment of formulas II, III, or both II and III, substituent X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 One or more of these are the halide or amino groups described above. Regarding II, X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 Not all of them can be amino groups. In certain embodiments of formula II or III, formula NR 5 R 6 R in an amino group having 5 and R 6 They are connected to each other to form a ring. In one particular embodiment, R 5 and R 6 R is selected from linear or branched C3-C6 alkyl groups and linked together to form a cyclic ring. In alternative embodiments of formula II or III, R 5 and R 6 They are not connected to each other and do not form a ring. In one other embodiment, R 5 and R 6 They are different.

[0036] In one of the further aspects of the second main aspect mentioned above, the halogenated silicon-containing precursor is a halogenated carbosilane selected from the group consisting of: 1,1,1,3,3,3-hexachloro-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-ethyl-1,3-disilapropane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-tricilapropane 1,1,3,3,5,5-Hexachloro-1,5-dimethyl-1,3,5-Tricilapentane, 1,1,1,5,5,5-Hexachloro-3,3-dimethyl-1,3,5-Tricilapentane, 1,1,3,5,5-Pentachloro-1,3,5-Trimethyl-1,3,5-Tricilapentane, 1,1,1,5,5,5-Hexachloro-1,3,5-Tricilapentane, and 1,1,5,5-Tetrachloro-1,3,5-Tricilapentane, 1-Chloro-1,3-Disilacyclobutane, 1-Bromo-1,3-Disilacyclobutane, 1-Iodo-1, 3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3-triiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-di Silacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclohexane, 1,1,3,3-tetra(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane, 1,3-dichloro-1,3-demthyl-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-tricilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-tricilacyclohexane, 1,3,5-trichloro-1,3,5-tricilacyclohexane, and combinations thereof.

[0037] The embodiments of this disclosure can be used individually or in combination with each other.

[0038] The accompanying drawings, which provide a further understanding of the disclosed invention and are incorporated into this specification and constitute part thereof, illustrate aspects of the disclosed invention and, together with the detailed description of the invention, help to illustrate the principles of the disclosed invention. [Brief explanation of the drawing]

[0039] [Figure 1] Figure 1 shows an exemplary process including surface pre-cleaning, oxide passivation, and selective deposition, in which a dielectric film is selectively deposited on a nitride film, while a first surface (containing oxide) is passivated. [Figure 2] Figure 2 shows an exemplary process including surface pre-cleaning, silicon oxide passivation, and selective deposition, in which a dielectric film is selectively deposited on a silicon nitride film, while the first surface (silicon oxide) is passivated. [Figure 3] Figure 3 shows an exemplary process including surface pre-cleaning, zirconium oxide passivation, and selective deposition, in which a dielectric film is selectively deposited on a titanium nitride film, while the first surface (zirconium oxide) is passivated. [Modes for carrying out the invention]

[0040] All references cited herein, including publications, patent applications, and patents, are incorporated by reference as if each cited reference were individually and specifically indicated to be incorporated by reference and as if its entire content were contained herein.

[0041] In the context of this disclosure (particularly in the context of the claims), the use of singular and similar nouns should be interpreted as including both singular and plural forms unless otherwise indicated or the context clearly contradicts it. Unless otherwise specified, the use of “includes,” “has,” “incorporates,” and “contains” should be interpreted as non-exclusive (i.e., “includes, but not limited to”) unless otherwise specified. The use of numerical ranges is intended, unless otherwise specified, simply as a convenient alternative to referring to each of the distinct values ​​that fall within that range, and each distinct value is to be presented in the specification as they are presented here. All methods described herein can be performed in any appropriate order unless otherwise specified or the context clearly contradicts it. The use of any and all examples or illustrative expressions (e.g., “etc.”) described herein is intended, unless otherwise expressly stated, simply as a better illustration of this disclosure and does not limit the claims. The descriptions herein should not be construed as indicating that any technical matters not described in the claims are essential to the implementation of the present invention.

[0042] Preferred embodiments of this disclosure are described herein, including the best modes known to the inventors for carrying out the claimed invention. Variations of these preferred embodiments will be apparent to those ordinary in the art upon reading the foregoing. The inventors anticipate that those skilled in the art may use such variations as appropriate, and they also intend that the claimed invention may be carried out in ways different from those specifically described herein. Therefore, this disclosure encompasses all improvements and equivalents / laws of the claimed invention to the extent permitted by applicable law. Furthermore, any combination of the foregoing in all possible variations is included in the claimed invention unless otherwise indicated or otherwise clearly contradictory to the context.

[0043] There are various methods that can be used for selective deposition. A part of this disclosure relates to a method for utilizing surface deactivation by taking advantage of surface chemistry between two different surfaces. Since the two different surfaces have different reactivity handles, such differences can be taken advantage of by using molecules that react with one surface (deactivating that surface) but not with the other surface.

[0044] In this disclosure, it has been devised and demonstrated that dielectric materials such as silicon dioxide can be selectively passivated using organic aminopolysiloxane or organic aminopolysilazane, thereby significantly preventing the growth of dielectric materials on the passivated silicon dioxide surface, while enabling highly selective growth of dielectric films such as silicon-containing dielectric films on dielectric surfaces such as silicon nitride at relatively high temperatures.

[0045] Various aspects of this disclosure are described below with reference to the drawings and tables disclosed herein, where applicable. Unless otherwise specified, the same reference numerals refer to the same element.

[0046] Selective deposition processes are gaining significant momentum, primarily because current lithography processes have limitations in enabling the manufacture of advanced semiconductor devices based on constantly shrinking physical dimensions. Traditionally, patterning in microelectronics engineering has been achieved using various lithography and etching processes. However, as lithography is rapidly becoming more complex and costly, the use of selective deposition for forming self-aligned shapes is becoming considerably more attractive. The fabrication of self-aligned via structures would greatly benefit from manufacturable selective deposition processes. One other potential application of selective deposition is gap filling, where a dielectric "filling" film is selectively grown from the bottom to the top of a trench. Selective deposition can also be used in other applications such as selective sidewall deposition, which selectively deposits films on exposed surfaces of three-dimensional FIN-FET structures. This would allow for the deposition of sidewall spacers without requiring complex patterning steps. Selective deposition processes for metal and metal oxide films used as gate dielectrics and capacitor dielectrics would also be extremely useful in semiconductor device manufacturing.

[0047] Previous examples exist in the technical literature relating to the selective formation of surface passivation coatings on wafers having multiple different exposed chemical surfaces. This was done with the aim of delaying or preventing film deposition via the ALD process on these passivation surfaces, and not to prevent deposition on surfaces on which film deposition by the ALD deposition process is desired. Generally, process selectivity was insufficient due to incomplete passivation of the surface and / or due to the physical sorption of ALD precursor molecules within the passivation layer itself or on surfaces on which deposition is undesirable, and the subsequent formation of the ALD film material.

[0048] In the first aspect, a method is provided for passivating a surface mainly containing hydroxyl groups. The method is (a) The substrate is placed in a reaction vessel at a temperature in the range of 20°C to 800°C, wherein the substrate has a first surface containing a dielectric material having hydroxyl groups and a second surface containing a material having a smaller amount of hydroxyl groups; (b) Expose the first surface and the second surface to a passivation composition comprising an organic aminoalkylpolysiloxane or organic aminoalkylpolysilazane having one of the following formulas to form at least one passivation layer on the first surface;

[0049] [ka] [In the formula, R 1 and R 2 Each is independently selected from hydrogen and a C1-C6 alkyl group, however, R 1 and R 2 Neither can become hydrogen; R 3 And R are independently selected from hydrogen or methyl, however R 1 and R 2 Neither can become hydrogen; n is 1, 2, or 3; and R 1 and R 2 They are connected to form an annular ring structure, or R 1 and R 2 They are not connected and do not form a ring-like structure. (c) Purge the reactor with an inert gas; Including; Steps (b) and (c) can be repeated to achieve a self-limiting monolayer coating of the first surface.

[0050] In one of the illustrated embodiments, organic aminopolysiloxanes and organic aminopolysilazanes are used to selectively passivate the oxide surface relative to the nitride surface. This process is illustrated in Figure 1. This process provides selectivity for growing a thicker dielectric film on the nitride surface.

[0051] process: An exemplary process 100 is shown in Figure 1. Step 1 includes pre-cleaning of a first surface 102 (containing an oxide, preferably SiO2) and a second surface 104 (containing a nitride, preferably silicon nitride). This pre-cleaning is preferably carried out using an acid, H2, high temperature, or a combination thereof. After this pre-cleaning, preferably the first surface 102 and the second surface 104 are coplanar as a result of chemical mechanical planarization (CMP) shown in Figure 1 prior to the pre-cleaning step.

[0052] Step 2 involves passivating the oxide surface 102 by exposing the dielectric to a passivation composition, preferably an organic aminopolysiloxane such as 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, to form a passivation / blocking organic layer 106. Following the passivation of the first surface 102, Step 3 involves depositing a dielectric film 108 on the nitride surface 104, preferably by ALD of silicon and nitrogen precursors.

[0053] Preferably, the first surface is an oxide, which can be a silicon-containing or metal-containing dielectric material mainly containing hydroxyl groups, selected from the group consisting of silicon oxide, carbon-doped silicon oxide, and metal oxides, while the second surface contains a dielectric material selected from the group consisting of silicon nitride and amorphous silicon.

[0054] The first surface may contain metal oxides such as hafnium oxide, zirconium oxide, titanium oxide, or a combination thereof.

[0055] The second surface may comprise a metal, including, but not limited to, ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), and the like, as well as combinations thereof. Examples of metal nitrides include, but are not limited to, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and the like, as well as combinations thereof.

[0056] The second surface may comprise a metal nitride such as titanium nitride, tantalum nitride, tungsten nitride, or a combination thereof.

[0057] R 1 and R 2 are both methyl, and R 3 is hydrogen or methyl, preferred examples of the organoaminoalkylpolysiloxane IA include, but are not limited to, the following compounds and the like:

[0058]

Chemical Formula

[0059]

Chemical Formula

[0060]

Chemical Formula

[0061] Steps (d) through (g) in this embodiment may be repeated to provide silicon nitride or carbon-doped silicon nitride or silicon oxynitride of a certain thickness. In some embodiments, steps (b) and (c) may be repeated to achieve a self-limiting monolayer passivation layer (i.e., a saturated passivation layer) before performing steps (d) through (g).

[0062] The nitrogen source is selected from the group consisting of, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof. In yet another embodiment, the nitrogen-containing source includes ammonia plasma, a plasma containing nitrogen and argon, a plasma containing nitrogen and helium, or a plasma containing hydrogen and a nitrogen source gas.

[0063] Preferably, the halogenated silicon-containing compound can be selected from the group consisting of (i) halogenated silane, (ii) halogenated siloxane, (iii) halogenated silazane, and (iv) halogenated carbosilane.

[0064] Examples of halogenated silanes in group (i) are, but are not limited to, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.

[0065] Examples of halogenated siloxanes in group (ii), though not limited to them, include hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

[0066] The silazane halides of group (iii) are selected from the group represented by the following formula I:

[0067] [ka] In the formula, R 4 This is hydrogen, linear or branched C1-C 10 Alkyl, linear or branched C3-C 10 Alkenyl group, linear or branched C3-C 10 Alkynyl group, C3-C 10 Cyclic alkyl groups, C2-C6 dialkylamino groups, electron-withdrawing groups, and C6-C 10 Selected from the group consisting of aryl groups; R 5 This is hydrogen, linear or branched C1-C 10 Alkyl groups, linear or branched C2-C6 alkenyl groups, linear or branched C3-C6 alkynyl groups, C3-C 10 Cyclic alkyl group, C2-C6 dialkylamino group, C6-C 10 Aryl group, linear or branched C1-C6 fluorinated alkyl group, electron-withdrawing group, C4-C 10 X is selected from the group consisting of aryl groups, Cl, Br, and I; and X is a halide selected from the group consisting of C, Br, and I.

[0068] An example of group (iii) of silazane halides can be represented by the following structure:

[0069] [ka] TIFF2026535036000012.tif248170TIFF2026535036000013.tif229170TIFF2026535036000014.tif248170TIFF2026535036000015.tif246170 Halide carbosilanes of group (iv) are selected from the group consisting of silicon compounds having one or two Si-C-Si linkages. Exemplary carbosilanes of group iv include those represented by formulas II and III:

[0070] [ka] In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 Each is independently a H atom; a halide selected from F, Cl, Br, and I; an isocyanate; formula NR 5 R 6 An amino group having (wherein R 5 and R 6 These are, independently, hydrogen, C1- 10 Selected from the group consisting of linear alkyl groups); C 3-10 Branched alkyl group; C 3-10 Cyclic alkyl group; C 3-10 Alkenyl group; C 4-10 Aryl group; and C 4-10 Selected from heterocyclic groups. In some embodiments of formulas I, II, or both I and II, substituent X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 One or more of these are linked together to form a substituted or unsubstituted saturated or unsaturated cyclic group. In one particular embodiment of formulas II, III, or both II and III, substituent X 1 , X 2 , X 3 , X 4 , X 5 , and X 6One or more of these are the halide or amino groups described above. Regarding II, X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 Not all of them can be amino groups. In certain embodiments of formula II or III, formula NR 5 R 6 R in an amino group having 5 and R 6 They are connected to each other to form a ring. In one particular embodiment, R 5 and R 2 R is selected from linear or branched C3-C6 alkyl groups and linked together to form a cyclic ring. In alternative embodiments of formula II or III, R 5 and R 6 They are not connected to each other and do not form a ring. In one other embodiment, R 5 and R 6 They are different.

[0071] An example of a halogenated carbosilane in group (iv) can be represented by the following structure:

[0072] [ka] As previously described, in semiconductor manufacturing processes using non-plasma thermal processes, there is a need to deposit dielectric materials such as silicon nitride or carbon-doped silicon nitride with high selectivity on the upper surface of a dielectric surface, relative to different dielectric surfaces, at temperatures ranging from 500°C to 800°C. Selectivity is defined as (thickness of silicon-containing film on the second surface - (minus) thickness of silicon-containing film on the first surface) / (thickness of silicon-containing film on the first surface + (plus) thickness of silicon-containing film on the second surface). Preferably, the selectivity is 30% or more, or 40% or more, or 50% or more, or 60% or more.

[0073] As previously mentioned, in semiconductor manufacturing processes using non-plasma thermal processes, there is a need to deposit silicon-containing dielectric materials such as silicon carbonitride, carbon-doped silicon oxide, and carbon-doped silicon oxynitride onto the upper surface of a second surface with high selectivity relative to the first surface of a different dielectric material, at temperatures ranging from 100°C to 800°C. Selectivity is defined as (thickness of the silicon-containing film on the second surface - (minus) thickness of the silicon-containing film on the first surface) / (thickness of the silicon-containing film on the first surface + (plus) thickness of the silicon-containing film on the second surface). Preferably, the selectivity is 30% or more, or 40% or more, or 50% or more, or 60% or more.

[0074] Therefore, in a first aspect of the present invention, a novel and non-trivial selective thermal atomic layer deposition (ALD) process is disclosed for selectively depositing a dielectric material onto the surface of a dielectric material in an ALD reactor.

[0075] In one preferred embodiment of this method, the dielectric material may be selected from the group consisting of silicon oxide, carbon-doped silicon oxide, silicon oxynitride, carbon-doped oxynitrides, silicon nitride, and metal oxides, such as zirconium oxide, hafnium oxide, silicon-doped zirconium oxide, silicon-doped hafnium oxide, or any other high-k material. In one preferred embodiment, the metal may be selected from the group consisting of cobalt, aluminum, copper, tantalum, ruthenium, molybdenum, tungsten, platinum, iridium, nickel, titanium, silver, gold, or combinations thereof.

[0076] As used herein and in the claims, the terms “substrate” and “wafer” are interchangeable and refer to both the surface on which the process is performed and a portion of the surface. Furthermore, it will be understood by those skilled in the art that when referring to a substrate, it may also refer to only a portion of the substrate unless the context clearly indicates otherwise. Additionally, when referring to depositing on a substrate, it may mean both a bare substrate and a substrate having one or more films or figures deposited or formed thereon.

[0077] As used herein, “substrate” refers to any substrate or any material surface formed on a substrate on which a film-forming process is carried out during the manufacturing process. For example, substrate surfaces on which film-forming can be carried out include, depending on the application, silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials, such as metals, metal nitrides, metal alloys, and other conductive materials. Semiconductor wafers are also included, but are not limited, as substrates. Substrates can be pre-treated to polish, etch, reduce, oxidize, introduce hydroxyl groups, anneal and / or bake the substrate surface. In this disclosure, in addition to directly carrying out film-forming on the substrate surface itself, any of the disclosed film-forming steps can also be carried out on underlying layers formed on the substrate as more detailed below, and the term “substrate surface” is intended to encompass such underlying layers as the context indicates. For example, when a film / layer or partial film / layer is deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a given substrate surface contains depends on the film to be deposited and the specific chemistry used. In one or more embodiments, the first substrate surface contains a metal and the second substrate surface contains a dielectric, or vice versa. In some embodiments, the substrate surface may contain certain functional groups (e.g., -OH, -NH, etc.).

[0078] Similarly, there are a wide variety of films that can be used in the methods described herein. In some embodiments, the film may contain or be essentially made from a metal or metal nitride. Examples of metal films include, but are not limited to, ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), and combinations thereof. Examples of metal nitride films include, but are not limited to, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and combinations thereof. In some embodiments, the film contains a dielectric. Examples include silicon oxide, carbon-doped silicon oxide, silicon nitride, hafnium oxide, zirconium oxide, and the like.

[0079] In aspects of the present disclosure, the substrate has at least two separate surfaces, each of which is characterized by a different chemistry. For example, in one aspect, the surface of the substrate includes at least a first surface containing a dielectric material such as silicon dioxide, and at least a second surface containing yet another dielectric material such as silicon nitride.

[0080] In some embodiments, the Disclosure provides a method for selectively depositing a film, such as silicon nitride, on the same substrate, on one surface of the substrate, relative to a second surface, wherein the two surfaces are formed on the same plane by chemical mechanical planarization. In other embodiments, the Disclosure provides a method for selectively depositing a film, such as silicon nitride, on the same substrate, on one surface of the substrate, relative to a second surface, wherein the two surfaces are not on the same plane. As used herein and in the claims, phrases such as “selectively depositing on one surface, relative to another” mean that one of the first or second surfaces is passivated, substantially preventing deposition on the passivated layer, and the film is deposited on the second (unpassivated) surface. The phrase “relative to” as used herein does not mean a physical orientation in which one surface is on top of the other, but rather a relationship of thermodynamic or kinetic properties of the chemical reaction with one surface relative to the other surface. For example, selective deposition of a cobalt film on a copper surface compared to a dielectric surface means that a cobalt film is deposited on the copper surface, while a smaller amount of cobalt film is deposited on the dielectric surface, or that no cobalt film is deposited on the dielectric surface; or that the formation of a cobalt film on the copper surface is thermodynamically or kinetically superior to the formation of a cobalt film on the dielectric surface.

[0081] The method disclosed herein includes an optional step of bringing the surface of a substrate into contact with a wet chemical composition to obtain a substrate to be treated. Exemplary wet chemical treatments include known chemical treatments, such as RCA cleaning solutions SC-1 and SC-2, aqueous HF solutions, peroxides, H2SO4 / H2O2, NH4OH, buffered HF solutions, and mixtures thereof.

[0082] In a preferred embodiment, the wet chemical composition comprises at least one selected from the group consisting of a composition containing H2O2 (28% aqueous solution), NH4OH (28-30%) and H2O; HF (0.01%-10% (aqueous solution)); peroxides; RCA cleaning solutions SC-1 and SC-2; and a mixture of H2SO4 / H2O2.

[0083] As is well known in the art, "RCA cleaning solution" refers to a composition containing a mixture of ammonium hydroxide and hydrogen peroxide, and is a basic cleaning method developed by Radio Corporation of America in the 1960s. The RCA Standard-Clean-1 (SC-1) method uses a solution of ammonium hydroxide and hydrogen peroxide, as well as water heated to approximately 70°C. The SC-1 method dissolves films and removes Group I and Group II metals. Group I and Group II metals are removed through complexation with the agents in the SC-1 solution. The RCA Standard-Clean-2 (SC-2) method utilizes a mixture of hydrogen peroxide, hydrochloric acid, and water heated to approximately 70°C. The SC-2 method removes metals that are not removed by the SC-1 method.

[0084] Contact with a wet chemical composition can be carried out by any method known to those skilled in the art, such as immersion or spraying. The contact step can be one separate step or more than one step.

[0085] In some embodiments, the temperature of the wet chemical composition during the contact step can be, for example, approximately from ambient temperature to about 100°C. In other embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from about 55°C to about 95°C. In other embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from about 60°C to about 90°C.

[0086] The embodiment also includes a step of washing the surface of the substrate with deionized water after the step of bringing the surface of the substrate into contact with the wet chemical composition. The washing step is typically carried out by any suitable means, for example, washing the surface of the substrate with deionized water by impregnation or spraying techniques.

[0087] The embodiment also includes a step of drying at least the surface of the substrate after the washing step. The drying step is typically carried out by any suitable means, such as the use of heat, isopropyl alcohol (IPA) vapor drying, or centripetal force.

[0088] The embodiment optionally includes a step of treating the surface with a hydrogen plasma, argon plasma, or ammonia plasma. Suitable processes include plasma processes (hydrogen plasma, NH3 / NF3 plasma, HF, ClF3, water plasma, and similar). This optional plasma step serves to remove undesirable deposits on the surface and to activate the surface for subsequent deposition of a passivator. Such plasma treatment can be applied most preferably to remove non-selectively deposited material from a pre-passivated surface after some deposition has been performed on the surface and to remove residual passivator after a desired deposition thickness has been achieved.

[0089] As used throughout this specification, the term "alkyl" means a saturated hydrocarbon group that is linear or branched. In some embodiments, the alkyl group has one to twenty carbon atoms, two to twenty carbon atoms, one to ten carbon atoms, two to ten carbon atoms, one to eight carbon atoms, two to eight carbon atoms, one to six carbon atoms, two to six carbon atoms, one to four carbon atoms, two to four carbon atoms, one to three carbon atoms, or two or three carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (e.g., n-propyl and iso-propyl), butyl (e.g., n-butyl, t-butyl, iso-butyl), pentyl (e.g., n-pentyl, iso-pentyl, neo-pentyl), hexyl, iso-hexyl, heptyl, octyl, nonyl, 4,4-dimethylpentyl, 2,2,4-trimethylpentyl, decyl, undecyl, dodecyl, and 2-methyl-1 Examples include propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2-methyl-1-pentyl, 2,2-dimethyl-1-propyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, and similar compounds.

[0090] As used throughout this specification, the term “cyclic alkyl” refers to a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms. Examples of cyclic alkyls include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0091] As used herein, the term "aryl" refers to monocyclic, bicyclic, or polycyclic (e.g., with 2, 3, or 4 fused rings) aromatic hydrocarbons. In some embodiments, aryl groups have 6 to 20 carbon atoms or 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthrasyl, phenantrenyl, indanyl, indenyl, and tetrahydronaphthyl, and their analogues.

[0092] As used throughout this specification, the term “alkenyl group” means a group having one or more carbon-carbon double bonds and containing 2 to 18 or 2 to 10 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl or allyl groups.

[0093] As used herein, the term "alkynyl" refers to a linear or branched alkyl group having 2 to 20 carbon atoms and one or more triple carbon-carbon bonds. In some embodiments, the alkynyl group has 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, acetylene, 1-propylene, 2-propylene, and analogues.

[0094] The phrase "optionally substituted" as used herein means that the substitution is optional and therefore includes both unsubstituted and substituted atoms and parts. A "substituted" atom or part means that a hydrogen atom on a given compound or part can be replaced with a group selected from the substituents listed, provided that the standard valence of the given compound or part is not exceeded and the substitution results in a stable compound. For example, when a methyl group is optionally substituted, one, two, or three hydrogen atoms on the carbon atoms within the methyl group can be replaced with one, two, or three groups from the substituents listed.

[0095] The term "phenyl" used here refers to -C6H5. The phenyl group may be unsubstituted, or it may be substituted with one, two, or three appropriate substituents.

[0096] The term "halo" used here refers to a halogen group, which includes, but is not limited to, fluorine, chlorine, bromine, and iodine.

[0097] The term "dielectric material" as used herein refers to silicon-containing or metal-containing films. Examples of dielectric materials, but are not limited to, silicon oxide, carbon-doped silicon oxide, metal oxides such as hafnium oxide, zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, tungsten oxide, and combinations thereof.

[0098] The vapor-phase or gas-phase reaction involves exposing a heated substrate to precursor molecules(s) and / or co-reactants in a suitable chamber, the chamber of which must be capable of providing the necessary pressure control and also supplying heat to the substrate and / or chamber walls; furthermore, the chamber should generally provide high leak integrity and adequate purity for the reaction to occur, through the use of ultra-high purity carriers and reactive gases.

[0099] As used herein and in the claims, terms such as “reactive gas,” “precursor,” and “reactant” refer to gases containing chemical species that are reactive to the substrate surface and are used interchangeably. For example, the first “reactive gas” may readily adsorb to the substrate surface and be used for further chemical reactions with a second reactive gas. These may be used in combination with (previously defined) ultra-high purity carrier gases and in any desired mixture of each other (i.e., more than one precursor may be used together or in separate independent steps to form a desired passivation layer, in which case the introduction of the precursors may be in any desired order).

[0100] Precursors(s) and / or co-reactants may be delivered to the reactor using a mass flow controller (with heating element if applicable) or an injection-type liquid material vaporizer (with heating element if applicable), or without a metering device (i.e., directly introducing vapor and / or gas from a container isolated from the reactor using a simple valve). Any of the above may be used in combination with each other. Any means of supplying gas and / or vapor(s) to the reaction chamber that provides sufficient purity and repeatability may be used.

[0101] The precursor(s) and / or co-reactants may be introduced into the reactor independently in multiple separate steps, mixed before introduction into the reactor, mixed in the reactor, or a combination of these. In this case, the method of introducing the precursors between steps may differ.

[0102] The temperature range of the substrate in the reactor may be between room temperature and 800°C. In some cases, the temperature range of the substrate in the reactor may be between room temperature and 650°C. In yet another case, the temperature range of the substrate in the reactor may be between room temperature and 100°C. The pressure may be in the range of 10-10 Torr to 3000 Torr and may be maintained under dynamic flow conditions (i.e., using valve and butterfly valve type equipment) or under static conditions (i.e., the evacuated chamber is exposed to the desired precursor(s) and / or co-reactants(s) until the desired total thickness is achieved, and then the chamber is isolated from both the precursor(s) and / or co-reactant(s) source(s) and the vacuum pump). The reactor can be completely evacuated and re-exposed to fresh precursor(s) and / or co-reactants as many times as necessary. The precursor(s) and / or co-reactants can be introduced using any desired mixture and / or concentrate.

[0103] Surface exposure can be carried out for 0.1 to 60 minutes, preferably 1 to 5 minutes, most preferably 1 minute. The partial pressure of the organic halide in the reaction chamber can vary from about 1% of its saturated vapor pressure at the substrate temperature to nearly 100% of its vapor pressure. Most preferably, this is between 20% and 50% of its saturated vapor pressure. The chamber pressure can be the same as the partial pressure of the organic halide vapor, but can be higher, balanced by an atmosphere containing a carrier gas. Preferred carrier gases include N2, He, and Ar, but other gases such as H2 may also be used. The exposure vapor can be static (non-flowing) for all or part of the exposure period. A preferred embodiment is to circulate the organic halide vapor in the exposure chamber with an optional carrier gas so that fresh vapor is exposed to the surface of the substrate for at least part of the exposure period.

[0104] The exposure chamber can be maintained at approximately ambient temperature or optionally heated. Heat can be supplied to the outer wall of the chamber (hot wall) or only to the substrate (cold wall reactor). Heating of the substrate in the cold wall reactor can be achieved by the use of incident radiation through a transparent window (lamp heating), by resistance heating of the substrate itself, or by induction from a resistance heating element on a platform in contact with the substrate, or by other known means in the art. The temperature of the treatment is preferably between about 20°C and about 400°C, preferably between 20°C and about 200°C, and most preferably between 20°C and about 100°C. This temperature can be constant during the exposure period or can vary within the aforementioned specific temperature range.

[0105] Next, optionally, unreacted vapors of at least one organic halide can be removed by exhausting or purging the chamber with a suitable inert gas before removing the substrate from the chamber or before chemical vapor deposition or atomic layer deposition. Optionally, the exposure chamber can also be used for subsequent processing steps to improve process efficiency, in which case the process can be repeated from step c) as needed to remove the protective film and non-selective ALD deposits, and then the protective film can be reformed.

[0106] The selection of at least one organic aminopolysiloxane or organic aminopolysilazane and exposure conditions used in this method should be optimized by standard experiments to optimize the selectivity of protection imparted to silicon nitride against possible non-selective passivation, processing time, and chemical costs, depending on the requirements imposed by the subsequent processing steps. For example, selectivity is determined by the R of at least one organic aminopolysiloxane or organic aminopolysilazane having a structure represented by structure IA or IB. 1 or R 2 It can be adjusted / optimized by changing the type of group. Typically, reactivity and selectivity are often inversely related, so if the chemistry of the two surfaces is similar, R 1 or R 2 Experiments using the underlying principles may be necessary for process optimization.

[0107] Disclosed and claimed passivation compositions Based on the foregoing, in one aspect, the disclosed and claimed invention relates to a passivation composition or passivating agent comprising, or essentially comprising and / or comprising an organic aminopolysiloxane or organic aminopolysilazane. The passivation composition is particularly well suited for enhanced passivation of metal substrates. In one aspect of this aspect, the organic aminopolysiloxane or organic aminopolysilazane comprises or essentially comprises one or more organic aminopolysiloxanes or organic aminopolysilazanes.

[0108] In one embodiment, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is substantially free of impurities that may react with the metal surface during the passivation process. In one embodiment, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is substantially free of impurities that may react with the precursor during the deposition process.

[0109] In one embodiment, an organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is substantially free of impurities that passivate nonmetallic surfaces and inhibit growth on nonmetallic surfaces.

[0110] In one aspect, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is substantially free of halogen-containing impurities. In one aspect of this aspect, the halogen-containing impurities are one or more of fluorinated hydrocarbons, chlorinated hydrocarbons, bromide hydrocarbons, and iodide hydrocarbons. In one aspect of this aspect, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 1000 ppm. In one aspect of this aspect, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 500 ppm. In one aspect of this aspect, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 100 ppm. In one aspect of this aspect, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 50 ppm. In one aspect of this embodiment, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 25 ppm. In one aspect of this embodiment, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 10 ppm. In one aspect of this embodiment, the organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is free from halogen-containing impurities.In the above view, the residual concentration of halogen-containing impurities is detected by one or more of the following: gas chromatography (GC) and related combined techniques, e.g., GC-FID, GC-ECD, GC-MS; liquid chromatography (defined as including variations such as LC, HPLC, or UPLC) and related combined techniques, e.g., LC-DAD and LC-MS; ion chromatography (IC) and related forms; spectroscopic techniques, e.g., infrared (IR), ultraviolet / visible light (UV / Vis), near-infrared (N) light. IR), Raman and nuclear magnetic resonance (NMR) spectroscopy; inductively coupled plasma spectroscopy or spectroscopy (ICP) and related combined techniques, e.g., ICP-MS, ICP-OES, GC-ICP-MS, and GC-ICP-OES; elemental analysis, e.g., X-ray fluorescence spectroscopy (XRF) and related forms thereof (e.g., WD-XRF) or atomic absorption spectroscopy (AA) and its forms; and finally, wet chemical techniques, e.g., titration (e.g., halogen titration with silver nitrate), and electrochemical detection methods (e.g., cyclic voltammetry, ion-selective electrodes, etc.). In one aspect of the above, the residual concentration of halogen-containing impurities is detected by one or more of GC-MS, GC-ICP-MS, GC-ICP-OES, GC-FID, GC-ECD, HPLC, and UV / Vis.

[0111] In one embodiment, an organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is purified by exposure to a molecular sieve. In another embodiment, an organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is purified by exposure to silica gel. In yet another embodiment, an organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is purified by exposure to one or more adsorbent materials.

[0112] In one embodiment, an organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is purified by treatment with one or more group 1 metals, followed by a distillation process. In one aspect of this embodiment, the organic aminopolysiloxane or organic aminopolysilazane is treated with metallic sodium. In one other aspect of this embodiment, the metal and the organic aminopolysiloxane or organic aminopolysilazane are separated by filtration, and the organic aminopolysiloxane or organic aminopolysilazane is distilled to remove impurities and non-volatile reaction products with the metal.

[0113] In one embodiment, an organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is purified by treatment with one or more group (II) metals, followed by a distillation process. In one aspect of this embodiment, the organic aminopolysiloxane or organic aminopolysilazane is treated with metallic magnesium. In one other aspect of this embodiment, the metal and the organic aminopolysiloxane or organic aminopolysilazane are separated by filtration, and the organic aminopolysiloxane or organic aminopolysilazane is distilled to remove impurities and non-volatile reaction products of the metal.

[0114] In one embodiment, an organic aminopolysiloxane or organic aminopolysilazane having formula IA or IB is purified by exposure to activated carbon. In one aspect of this embodiment, after treatment with activated carbon, the organic aminopolysiloxane or organic aminopolysilazane is separated by filtration and then distilled to remove non-volatile products. [Examples]

[0115] Example 1: Growth of silicon-containing and nitrogen films on a silicon oxide surface passivated with 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane Silicon-containing films (i.e., silicon carbonitride) were deposited on a silicon oxide surface in a screening ALD reactor. Both the passivation layer and film growth were evaluated in real time using an in-situ ellipsometer. The films were deposited thermally using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and NH3. The passivation layer was formed using 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane as the passivating agent. A passivation layer using dimethylaminotrimethylsilane was also used for comparison. The substrate temperature was 300°C.

[0116] The silicon oxide surface was prepared by exposing a silicon coupon to an oxygen plasma for 180 seconds. This plasma consisted of 200 sccm of O2 and 100 sccm of Ar. The plasma power used was 3000 W at 2 GHz.

[0117] The detailed process steps are as follows:

[0118] [Table 1]

[0119] Steps 6 through 9 were repeated multiple times to achieve the desired thickness.

[0120] The saturated passivation layer from 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane saturated at 4±0.5 Å, while the saturated passivation layer using dimethylaminotrimethylsilane saturated at only 2.5±0.5 Å. This demonstrates that 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane is a better passivating agent than dimethylaminotrimethylsilane.

[0121] [Table 2]

[0122] A saturated passivation layer from 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane provides better passivation protection than well-known dimethylaminotrimethylsilanes, i.e., relatively less film growth as shown in the table above.

[0123] Example 2: Growth of silicon and nitrogen-containing silicon films on a silicon oxide surface passivated with 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane A silicon-containing film (i.e., silicon carbonitride) containing silicon and nitrogen was deposited on a silicon oxide surface using a screening ALD reactor. The inventors evaluated both the passivation layer and film growth in real time using an in-situ ellipsometer. The film was thermally deposited using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and NH3. The passivation layer was formed using 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane. A passivation layer using dimethylaminotrimethylsilane was also used for comparison. The substrate temperature was 300°C.

[0124] The silicon oxide surface was prepared by exposing a silicon coupon to an oxygen plasma for 180 seconds. This plasma consisted of 200 sccm of O2 and 100 sccm of Ar. The plasma power used was 3000 W at 2 GHz.

[0125] The deposition process was carried out according to the steps listed in Table 1. Steps 6 through 9 were repeated multiple times to obtain the desired thickness.

[0126] The saturated passivation layer from 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane saturated at 5.5 ± 0.5 Å, while the saturated passivation layer using dimethylaminotrimethylsilane saturated at only 2.5 ± 0.5 Å.

[0127] [Table 3]

[0128] The table above shows that film growth on silicon oxide surfaces with a passivation layer from 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane is considerably less than in the case of (dimethylamino)trimethylsilane, demonstrating that 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane is a better passivation agent than dimethylaminotrimethylsilane.

[0129] Example 3: Growth of silicon and nitrogen-containing silicon films on a silicon oxide surface passivated with 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane A silicon-containing film (i.e., silicon nitride) containing silicon and nitrogen was deposited on a silicon oxide surface with a passivation layer in a screening ALD reactor. The inventors evaluated both the passivation layer and film growth in real time using an in-situ ellipsometer. The film was deposited using 1,1,1,3,3,3-hexachlorodisilazane and ammonia. The passivation layer was formed using 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, and a passivation layer using dimethylaminotrimethylsilane was also used for comparison. The substrate temperature was 400°C.

[0130] The silicon oxide surface was prepared by exposing a silicon coupon to an oxygen plasma for 180 seconds. This plasma consisted of 200 sccm of O2 and 100 sccm of Ar. The plasma power used was 3000 W at 2 GHz. The detailed process steps are described below.

[0131] [Table 4]

[0132] Steps 6 through 9 were repeated multiple times to obtain the desired thickness.

[0133] The saturated passivation layer from 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane saturated at 4±0.5 Å, while the saturated passivation layer using dimethylaminotrimethylsilane saturated at only 2.5±0.5 Å.

[0134] [Table 5]

[0135] A thicker passivation layer from 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane provides better passivation, i.e., less film growth, compared to a surface passivated with dimethylaminotrimethylsilane.

[0136] Example 4: Growth of silicon-containing and nitrogen films on a silicon oxide surface passivated with 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane Silicon-containing and nitrogen-containing films (e.g., silicon nitride) were deposited on a silicon oxide surface with a single layer of inhibitor in a screening ALD reactor. The inventors evaluated both the passivation layer and film growth in real time using an in-situ ellipsometer. Films were thermally deposited using 1,1,1,3,3,3-hexachlorodisilazane and NH3. The selected passivation layer was 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane. Dimethylaminotrimethylsilane passivation was also used for comparison. The process temperature was 400°C.

[0137] To prepare the silicon oxide surface, Si coupons were exposed to an oxygen plasma for 180 seconds. This plasma consisted of 200 sccm of O2 and 100 sccm of Ar. The plasma power used was 3000 W at 2 GHz.

[0138] The deposition was carried out according to the steps described in Table 1. Steps 6 through 9 were repeated multiple times to obtain the desired thickness.

[0139] The passivation layer from 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane saturated at 5.3 Å ± 0.5 Å, while the passivation layer using dimethylaminotrimethylsilane saturated at 2.5 Å ± 0.5 Å.

[0140] [Table 6]

[0141] A thicker passivation layer from 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane provides better passivation, i.e., less film growth, compared to a surface passivated with dimethylaminotrimethylsilane.

[0142] Example 5: Growth of silicon-containing and nitrogen films on a silicon oxide surface passivated with 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane. Silicon-containing and nitrogen (e.g., silicon nitride) films were deposited on a silicon oxide surface having a single layer of inhibitor in a screening ALD reactor. The inventors evaluated both the passivation layer and film growth in real time using an in-situ ellipsometer. The films were thermally deposited using 1,1,1,3,3,3-hexachloromethyldisilazane and NH3. The selected passivation layer was 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.

[0143] The silicon oxide surface was prepared by exposing a silicon coupon to an oxygen plasma for 180 seconds. This plasma consisted of 200 sccm of O2 and 100 sccm of Ar. The plasma power used was 3000 W at 2 GHz. The process temperature was 600°C.

[0144] The detailed deposition steps are as follows:

[0145] [Table 7]

[0146] Steps 6 through 9 were repeated multiple times to obtain the desired thickness.

[0147] The passivation layer from 1-(dimethylamino)-1,1,3,3,3-pentamethyldisiloxane was saturated at 3.2 Å ± 0.5 Å.

[0148] [Table 8]

[0149] Film growth on a surface immobilized with 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane is thinner compared to growth without a passivation layer.

[0150] Example 6: Growth of silicon-containing and nitrogen films on a silicon oxide surface passivated with 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane Silicon-containing and nitrogen-containing films (e.g., silicon nitride) were deposited on a silicon oxide surface having a single layer of inhibitor in a screening ALD reactor. The inventors evaluated both the passivation layer and film growth in real time using an in-situ ellipsometer. The selected inhibitor layer was 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane. The process temperature was 600°C.

[0151] The silicon oxide surface was prepared by exposing a silicon coupon to an oxygen plasma for 180 seconds. This plasma consisted of 200 sccm of O2 and 100 sccm of Ar. The plasma power used was 3000 W at 2 GHz.

[0152] The deposition process was carried out according to the steps described in Table 3. Steps 6 through 9 were repeated multiple times to obtain the desired thickness.

[0153] A 4.3 Å ± 0.5 Å inhibitory layer derived from 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane.

[0154] [Table 9]

[0155] Film growth on a surface passivated with 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane is thinner compared to growth on a surface without a passivation layer.

[0156] Example 7. Selective deposition of silicon nitride (growth surface) on silicon oxide (non-growth surface) using 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane In this example, the inventors demonstrated selective deposition on a growth surface (e.g., silicon nitride) and a non-growth surface (e.g., silicon oxide). Both the growth and non-growth surfaces were prepared in situ without interrupting the vacuum before film deposition. The growth surface was prepared by depositing silicon nitride approximately 100 Å thick using chlorosilane and ammonia plasma at 400°C. A passivation layer was introduced by exposing a Si coupon to 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane for 100 seconds. The non-growth surface was prepared by exposing a silicon coupon with native oxides to oxygen plasma for 180 seconds. Films were thermally deposited with 1,1,1,3,3,3-hexachlorodisilazane and ammonia. The process temperature was 400°C.

[0157] Details regarding both surface preparation and film deposition are described in Table 4.

[0158] The saturation of the passivation layer using 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane on the non-growth surface (silicon oxide) was confirmed after exposure by measuring with an in-situ ellipsometer via in-situ ellipsometry, resulting in a total thickness of 4.2 Å ± 0.5 Å. The thickness of the passivation layer on the growth surface was 1.0 Å after the same exposure time.

[0159] [Table 10]

[0160] Steps 6 through 9 were repeated until the desired thickness was reached.

[0161] [Table 11]

[0162] Table 11 demonstrates that the silicon nitride film (growth surface) has a thickness of 32 Å compared to 10 Å on the silicon oxide (non-growth) surface. This confirms that the 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane passivation layer enables selective film growth on different surfaces.

[0163] Example 8. Selective deposition of silicon nitride (growth surface) on silicon oxide (non-growth surface) using 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane In this example, the inventors demonstrated selective deposition on a growth surface (e.g., silicon nitride) and a non-growth surface (e.g., silicon oxide). Both the growth and non-growth surfaces were prepared in situ without interrupting the vacuum before film deposition. The growth surface was prepared by depositing silicon nitride approximately 100 Å thick using chlorosilane and ammonia plasma at 500°C. The passivation layer was introduced by exposing a Si coupon to 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane for 100 seconds. The non-growth surface was prepared by exposing a silicon coupon with native oxides to oxygen plasma for 180 seconds. The film was thermally deposited using 1,1,1,3,3,3-hexachlorodisilazane and ammonia. The process temperature was 500°C.

[0164] Details regarding both surface preparation and film deposition are described in Table 12. A 5.3 Å ± 0.5 Å monolayer of 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane was deposited on a passivated non-growth surface (silicon oxide). The thickness of the passivation agent on the growth surface (silicon nitride) was 2.0 Å ± 0.5 Å after the same exposure time.

[0165] [Table 12]

[0166] Steps 6 through 9 were repeated until the desired thickness was reached.

[0167] [Table 13]

[0168] Table 13 confirms that the silicon nitride film (on the growing surface) has a thickness of 14 Å compared to 2 Å on the silicon oxide (non-growing) surface. This confirms that the 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane passivation layer enables selective film growth on different surfaces.

[0169] An exemplary process 300 is shown in Figure 3. Step 1 includes pre-cleaning of the first surface 302 (containing zirconium oxide) and the second surface 304 (containing titanium nitride), preferably with an acid, H2, high temperature, or a combination thereof. After this pre-cleaning, preferably the first surface 302 and the second surface 304 are coplanar as a result of chemical mechanical planarization (CMP) shown in Figure 3 prior to the pre-cleaning step.

[0170] Step 2 involves passivating the ZrO2 surface 302 by exposing the dielectric to a passivation composition, preferably an organic aminopolysiloxane such as 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, to form a passivation / blocking organic layer 306. Following the passivation of the first surface 302, Step 3 involves depositing a SiN-containing dielectric layer 108 on the second surface 304 (TiN) preferably by ALD of silicon and nitrogen precursors.

[0171] The disclosed and claimed methods can be used with deposition tools commonly found at semiconductor manufacturing sites for producing molybdenum-containing layers for logic applications and other potential functionalities.

[0172] The above description is intended primarily for illustrative purposes. While the disclosed and claimed invention has been shown and described in exemplary embodiments thereof, it should be understood by those skilled in the art that various other modifications, omissions, and additions can be made to the above and various other modifications in form and detail without departing from the spirit and scope of the disclosed and claimed invention.

[0173] Although the principles of the present invention have been described above in relation to preferred embodiments, it is clear that these are merely illustrative examples and do not limit the scope of the claimed invention.

Claims

1. A method for passivating the silicon-containing or metal-containing surface of a substrate, (a) The substrate is placed in a reaction vessel at a temperature in the range of 20°C to 800°C, the substrate having a first surface containing a dielectric material having hydroxyl groups and a second surface containing a different material having fewer hydroxyl groups than the first surface; (b) Expose the first surface and the second surface to a passivation composition comprising an organic aminoalkylpolysiloxane or organic aminoalkylpolysilazane having one of the following formulas to form at least one passivation layer on the first surface; 【Chemistry 1】 [In the formula, R １ and R ２ are each independently selected from hydrogen, C １ -C ６ alkyl groups, provided that R １ and R ２ cannot both be hydrogen; R ３ and R are each independently selected from hydrogen or methyl; n is 1, 2, 3; and R １ and R ２ are linked to form a cyclic ring structure, or R １ and R ２ are not linked and do not form a cyclic ring structure.]] (c) Purge the reactor with an inert gas; A method that includes doing so.

2. The method according to claim 1, wherein steps (b) and (c) are repeated to achieve a self-limiting monolayer coating of the first surface.

3. The method according to claim 1, wherein the first surface is selected from the group consisting of silicon oxide, carbon-doped silicon oxide, metal oxides, and combinations thereof, and the second surface is selected from the group consisting of silicon nitride or metal nitride.

4. The method according to claim 1, wherein the second surface comprises a metal or metalloid selected from the group consisting of ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), silicon, and combinations thereof, or the second surface comprises a nitride selected from the group consisting of silicon nitride, germanium nitride, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and combinations thereof.

5. The method according to claim 1, wherein the passivation composition comprises an organic aminoalkyl polysiloxane IA selected from the group consisting of 1-dimethylamino-1,1,3,3-tetramethyldisiloxane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-dimethylamino-1,1,3,3,5,5-hexamethyltrisiloxane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, and combinations thereof.

6. The method according to claim 1, wherein the passivation composition comprises an organic aminoalkyl polysilazane IB selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisilazane, 1-dimethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-dimethylamino-1,1,3,3,5,5-hexamethyltrisilazane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisilazane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasilazane, 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasilazane, and combinations thereof.

7. In a method for selective deposition of silicon-containing and nitrogen-containing films, (a) A substrate is placed in a reaction vessel, the substrate having a first surface comprising a dielectric material having hydroxyl groups, and a second surface comprising a different material having fewer hydroxyl groups than the first surface or having no hydroxyl groups at all; (b) Expose the first surface and the second surface to a passivation composition comprising an organic aminoalkylpolysiloxane or organic aminoalkylpolysilazane having one of the following formulas to form at least one self-limiting passivation layer on the first surface; 【Chemistry 2】 [In the formula, R １ and R ２ These are, independently, hydrogen and C １ -C ６ Selected from alkyl groups, however, R １ and R ２ Neither can become hydrogen; R ３ And R are independently selected from hydrogen or methyl; n is 1, 2, or 3; and R １ and R ２ They are connected to form an annular ring structure, or R １ and R ２ They are not connected and do not form a ring-like structure. (c) Purge the reactor with an inert gas; (d) A silicon halogenated precursor is introduced into the reactor to selectively form a silicon-containing layer on the second surface; (e) Purge the reactor with an inert gas; (f) Introducing a nitrogen source to react with the silicon-containing layer to form a silicon nitride layer, a carbon-doped silicon nitride layer, or a silicon oxynitride layer on the second surface; and (g) Purge the reactor with an inert gas; A method that includes, A method comprising repeating steps (d) to (g) in this embodiment to selectively provide a silicon nitride layer or a carbon-doped silicon nitride layer or silicon oxynitride layer of a certain thickness onto a second surface region.

8. The method according to claim 7, wherein the first surface is selected from the group consisting of silicon oxide, carbon-doped silicon oxide, metal oxides, and combinations thereof, and the second surface comprises silicon nitride or a metal nitride.

9. The method according to claim 7, wherein the second surface comprises a metal or metalloid selected from the group consisting of ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), and combinations thereof, or the second surface comprises a metal nitride selected from the group consisting of tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper-silicon nitride (CuSiN), silicon, germanium, and combinations thereof.

10. The method according to claim 7, wherein steps (b) and (c) are repeated to achieve a self-limiting monolayer immobilization layer before performing steps (d) through (g).

11. The method according to claim 10, wherein the self-limiting monolayer passivation layer may preferably be in the range of about 0.2 Å to about 10 Å, more preferably about 0.2 Å to about 5 Å, and most preferably about 0.2 Å to about 3 Å.

12. The method according to claim 7, wherein the aforementioned certain thickness of the silicon nitride film or carbon-doped silicon nitride film or silicon oxynitride film can be in the range of about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å.

13. The method according to claim 7, wherein the organic aminopolysiloxane of formula IA is selected from the group consisting of 1-dimethylamino-1,1,3,3-tetramethyldisiloxane and 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.

14. The method according to claim 7, wherein the organic aminopolysilazane of formula IB is selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisilazane and 1-dimethylamino-1,1,2,3,3,3-hexamethyldisilazane.

15. The method according to claim 7, wherein the deposition selectivity of the second surface relative to the first surface is greater than about 0.3, more preferably greater than about 0.5, and most preferably greater than about 0.

6.

16. The method according to claim 7, wherein the nitrogen source is selected from the group consisting of, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, piperazine, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof.

17. The method according to claim 7, wherein the halogenated silicon-containing precursor is selected from the group consisting of (i) halogenated silane, (ii) halogenated siloxane, (iii) halogenated silazane, and (iv) halogenated carbosilane.

18. The method according to claim 17, wherein the halogenated silicon precursor is a halogenated silane of group (i) selected from the group consisting of hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.

19. The method according to claim 17, wherein the halogenated silicon precursor is a halogenated siloxane of group (ii) selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

20. The method according to claim 17, wherein the halogenated silicon-containing precursor is a halogenated silazane of group (iii) selected from the group represented by the following formula I. 【Transformation 3】 In the formula, R ４ is hydrogen, linear or branched C １ -C １０ Alkyl, linear or branched C ３ -C １０ Alkenyl group, linear or branched C ３ -C １０ Alkynyl group, C ３ -C １０ Cyclic alkyl group, C ２ -C ６ Dialkylamino group, electron-withdrawing group, and C ６ -C １０ Selected from the group consisting of aryl groups; R ５ is hydrogen, linear or branched C １ -C １０ Alkyl, linear or branched C ２ -C ６ Alkenyl group, linear or branched C ３ -C ６ Alkynyl group, C ３ -C １０ Cyclic alkyl group, C ２ -C ６ Dialkylamino group, C ６ -C １０ Aryl group, linear or branched C １ -C ６ Fluorinated alkyl group, electron-withdrawing group, C ４ -C １０ X is selected from the group consisting of an aryl group and halides selected from the group consisting of Cl, Br, and I; and X is a halide selected from the group consisting of C, Br, and I.

21. Halide silazanes are selected from group (iii), and 1,1,1,3,3,3-hexachloro-disilazane, 1,1,1,3,3-pentachloro-disilazane, 1,1,1,3,3,3-hexachloro-2-methyldisilazane, 1,1,1,3,3,3-hexachloro-2-ethyldisilazane, 1,1,1,3,3,3-hexachloro-2-n-propyldisilazane, 1,1,1,3,3,3-hexachloro-2-iso-propyldisilazane, 1,1,1,3,3,3-hexachloro-2-n-butyldisilazane, 1,1,1,3,3, 3-Hexachloro-2-iso-butyldisilazane, 1,1,1,3,3,3-Hexachloro-2-sec-butyldisilazane, 1,1,1,3,3,3-Hexachloro-2-tert-butyldisilazane, 1,1,1,3,3,3-Hexabromo-2-methyldisilazane, 1,1,1,3,3,3-Bromo-2-ethyldisilazane, 1,1,1,3,3,3-Bromo-2-n-propyldisilazane, 1,1,1,3,3,3-Bromo-2-iso-propyldisilazane, 1,1,1,3,3,3-Bromo-2-n-butyldisilazane, 1,1,1, 3,3,3-bromo-2-iso-butyldisilazane, 1,1,1,3,3,3-bromo-2-sec-butyldisilazane, 1,1,1,3,3,3-bromo-2-tert-butyldisilazane, 1,1,1,3,3,3-hexaiodo-2-methyldisilazane, 1,1,1,3,3,3-iodo-2-ethyldisilazane, 1,1,1,3,3,3-iodo-2-n-propyldisilazane, 1,1,1,3,3,3-iodo-2-iso-propyldisilazane, 1,1,1,3,3,3-iodo-2-n-butyldisilazane, 1,1,1,3,3,3 -iodo-2-iso-butyldisilazane, 1,1,1,3,3,3-iodo-2-sec-butyldisilazane, 1,1,1,3,3,3-iodo-2-tert-butyldisilazane, 1,1,1,3,3-pentachloro-2-methyldisilazane, 1,1,1,3,3-pentachloro-2-ethyldisilazane, 1,1,1,3,3-pentachloro-2-n-propyldisilazane, 1,1,1,3,3-pentachloro-2-iso-propyldisilazane, 1,1,1,3,3-pentachloro-2-methyl-3-methyldisilazane, 1,1,1,3,3-Pentachloro-2-ethyl-3-methyldisilazane, 1,1,1,3,3-Pentachloro-2-n-propyl-3-methyldisilazane, 1,1,1,3,3-Pentachloro-2-iso-propyl-3-methyldisilazane, 1,1,3,3-Tetrachloro-2-methyldisilazane, 1,1,3,3-Tetrachloro-2-ethyldisilazane, 1,1,3,3-Tetrachloro-2-n-propyldisilazane, 1,1,3,3-Tetrachloro-2-iso-propyldisilazane, 1,1,3,3-Tetrachloro-2-n-butyldisilazane, 1,1,3, 3-tetrachloro-2-iso-butyldisilazane, 1,1,3,3-tetrachloro-2-sec-butyldisilazane, 1,1,3,3-tetrachloro-2-tert-butyldisilazane, 1,1,3,3-tetrabromo-2-methyldisilazane, 1,1,3,3-tetrabromo-2-ethyldisilazane, 1,1,3,3-tetrabromo-2-n-propyldisilazane, 1,1,3,3-tetrabromo-2-iso-propyldisilazane, 1,1,3,3-tetrabromo-2-n-butyldisilazane, 1,1,3,3-tetrabromo-2-iso-butyl Disilazane, 1,1,3,3-tetrabromo-2-sec-butyldisilazane, 1,1,3,3-tetrachloro-2-tert-butyldisilazane, 1,1,3,3-tetraiodo-2-methyldisilazane, 1,1,3,3-tetraiodo-2-ethyldisilazane, 1,1,3,3-tetraiodo-2-n-propyldisilazane, 1,1,3,3-tetraiodo-2-iso-propyldisilazane, 1,1,3,3-tetraiodo-2-n-butyldisilazane, 1,1,3,3-tetraiodo-2-iso-butyldisilazane, 1,1,3,3-tetraiodo 1,1,3,3-tetraiodo-2-tert-butyldisilazane, 1,1,3,3-tetrachloro-2-cyclopentyldisilazane, 1,1,3,3-tetrachloro-2-cyclohexyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-cyclopentyl-2-cyclopentyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-cyclohexyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-methyldisilazane, 1,1,3,3-tetrachloro-1,The method according to claim 20, selected from the group consisting of 3-dimethyltetrachloro-2-ethyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-n-propyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-iso-propyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-n-butyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-iso-butyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-sec-butyldisilazane, and 1,1,3,3-tetrachloro-1,3-dimethyl-2-tert-butyldisilazane, and combinations thereof.

22. The method according to claim 17, wherein the halogenated silicon-containing precursor is a halogenated carbosilane of group (iv) selected from the group consisting of silicon compounds having one or two Si-C-Si linkages. Preferred carbosilanes in group iv include those represented by formulas II and III: 【Chemistry 4】 In the formula, X １ , X ２ , X ３ , X ４ , X ５ , and X ６ are each independently selected from: an H atom; a halide selected from F, Cl, Br, and I; an isocyanate; an amino group having the formula NR ５ R ６ (wherein R in the formula ５ and R ６ are independently selected from the group consisting of hydrogen, C １ - １０ linear alkyl groups); a C ３－１０ branched alkyl group; a C ３－１０ cyclic alkyl group; a C ３－１０ alkenyl group; a C ４－１０ aryl group; and a C ４－１０ heterocyclic group. In some embodiments of Formula I, Formula II, or both Formula I and II, the substituents X １ , X ２ , X ３ , X ４ , X ５ , and X ６ one or more of them are linked to form a substituted or unsubstituted saturated or unsaturated cyclic group. In one specific embodiment of Formula II, Formula III, or both Formula II and III, the substituents X １ , X ２ , X ３ , X ４ , X ５ , and X ６ one or more of are the halide or amino group described above. Regarding Formula II, X １ , X ２ , X ３ , X ４ , X ５ , and X ６ cannot all be amino groups. In certain embodiments of Formula II or Formula III, R in the amino group having the formula NR ５ R ６ in the amino group ５ and R ６ are linked to each other to form a ring. In one specific embodiment, R ５ and R ２ are linear or branched C ３ -C ６ are selected from alkyl groups, and are linked to form a cyclic ring. In an alternative embodiment of Formula II or III, R ５ and R ６ are not linked to each other and do not form a ring. In another embodiment, R ５ and R ６ are different.

23. The halogenated silicon-containing precursors are 1,1,1,3,3,3-hexachloro-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-ethyl-1,3-disilapropane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-tricilapentane, 1,1,1,5, 5,5-Hexachloro-3,3-dimethyl-1,3,5-Tricilapentane, 1,1,3,5,5-Pentachloro-1,3,5-Trimethyl-1,3,5-Tricilapentane, 1,1,1,5,5,5-Hexachloro-1,3,5-Tricilapentane, and 1,1,5,5-Tetrachloro-1,3,5-Tricilapentane, 1-Chloro-1,3-Disilacyclobutane, 1-Bromo-1,3-Disilacyclobutane, 1-Iodo-1,3-Disilacyclobutane, 1,3-Dichloro-1,3-Disilacyclobutane, 1,3-Dibromo-1,3-Disilacyclobutane Tan, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3-triiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1, 3-disilacyclohexane, 1,1,3,3-tetra(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane, 1,3-dichloro-1,3-demthyl-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-tricilacyclohexane, 1,1,3,The method according to claim 17, wherein the halogenated carbosilane is selected from the group consisting of 3-tetrachloro-1,3,5-tricilacyclohexane, 1,3,5-trichloro-1,3,5-tricilacyclohexane, and combinations thereof.

24. The method according to claim 1, wherein a pre-cleaning step is performed prior to step (a), and the pre-cleaning step includes exposing the surface to alcohol, hydrogen-containing plasma, or a fluorine-containing composition.

25. R １ and R ２ Both are methyl groups, or R １ is hydrogen and R ２ The method according to claim 1, wherein is a methyl group.

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