Passivation of polysilicon material and selective deposition of dielectric material utilizing alkynes

Abstract

A method for selectively passivating a surface of a substrate, wherein the surface of the substrate includes at least a first surface comprising silicon and having Si-H groups and at least a second surface comprising a dielectric material or metal material that does not contain Si-H groups. The method includes the step of exposing the surface to at least one alkyne wherein the alkyne selectively reacts with the Si-H on the first surface to passivate the first surface thereby leaving the second surface substantially unpassivated.

Description

PASSIVATION OF POLYSILICON MATERIAL AND SELECTIVE DEPOSITION OF DIELECTRIC MATERIAL UTILIZING ALKYNESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to United States Provisional Patent Application number 63 / 639,527, filed on April 26, 2024, the entire contents of which are incorporated by reference.FIELD

[0002] The present application relates to selective passivation of a first surface of a substrate relative to a second surface thereof. In addition, further processing can be used to subsequently deposit a different material on the second surface relative to the first surface.BACKGROUND

[0003] Selective deposition processes are gaining a lot of momentum mostly because of the limitations of contemporary lithographic processes to enable the fabrication of advanced semiconductor devices based on ever diminishing physical dimensions. Traditionally, patterning in the microelectronics industry has been accomplished using various lithography and etch processes. However, since lithography is becoming exponentially more complex and expensive the use of selective deposition to form self-aligned features is becoming much more attractive. The fabrication of self-aligned via structures would benefit significantly from manufacturable selective deposition processes. Another potential application for selective deposition is gap fill. In gap fill, the dielectric “fill” film is grown selectively from the bottom of a trench towards the top. Selective deposition could be used for other applications such as selective sidewall deposition where films are selectively deposited on exposed surfaces of three dimensional FIN-FET structures. This would enable the deposition of a sidewall spacer without the need for complex patterning steps. Selective deposition processes for metal and metal oxide films that are used asgate dielectrics and capacitor dielectrics would also be of great utility in semiconductor device manufacturing.

[0004] There are previous examples within the technical literature related to the selective formation of surface passivation coatings on wafers with multiple, different chemical surfaces that are exposed. This has been done with the purpose of retarding or preventing the deposition of films through ALD processes on these passivated surfaces, but not preventing deposition on the surfaces where the ALD deposition process is desired to deposit a film. In general, the selectivity of the processes has been less than adequate due to incomplete passivation of the surfaces and / or due to physisorption of ALD precursor molecules and subsequent formation of the ALD film material either within the passivation layer itself or on the surfaces where deposition is not desired.

[0005] Selectively passivation of polysilicon over dielectric or metal to achieve area selective deposition (ASD) of dielectric on dielectric or metal remains great challenge due to the similarity in their surface chemistry natures, so far relatively few passivation chemistries have been reported that can selectively passivate polysilicon over dielectric or metal nitride at temperatures higher than 250 °C to successfully allow the atomic layer deposition of films on the dielectric or metal nitride.

[0006] The present disclosure seeks to overcome the limitations of the prior art and provide improved methods for selective deposition of ultra-thin film materials using ALD deposition processes.SUMMARY

[0007] In a first main aspect, a method is provided for forming a dielectric film selectively on a substrate. The method comprising: (a) providing the substrate in a reactor and heating to a temperature ranging from about 200 °C to about 700 °C, the substrate having a first surface comprising silicon and a second surface comprising a dielectric or a metal, wherein the first surface comprises Si-H groups and the second surface does not comprise Si-H 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 alkyne having one of the following formulae:wherein R1and R2are each selected from the group consisting of a linear, branched, or cyclic Cs to CM alkyl; a linear, branched, or cyclic Cs to Cu alkylsilyl; a Cg to Cu arylalkyl; a a linear, branched, or cyclic Ce to Cu alkynyl; and a Ge to C arylalkynyl; wherein R1and R2may have one or more carbon-carbon triple bonds; (c) purging the reactor with inert gas; (d) introducing a deposition precursor into the reactor to react with the second surface to form a deposition precursor-containing layer; (e) purging the reactor with inert gas; (f) introducing a vapor comprising an oxygen source or a nitrogen source into the reactor to react with the precursor-containing layer to form the dielectric film; (g) purging the reactor with inert gas; and (h) repeating steps (d) through (g) to deposit a desired thickness of the dielectric film on the second surface of the substrate. The oxygen source is selected from the group consisting of water, ozone, and combinations thereof. The nitrogen source is selected from the group consisting of ammonia, hydrazine, alkylsubstituted hydrazine, and combinations thereof.

[0008] In a further aspect of the first main aspect, the desired thickness of the dielectric film can range from about 1 A to about 100 A, or about 5 A to about 90 A, or about 5 A to about 80 A, or about 5 A to about 70 A or about 5 A to about 60 A, or about 5 A to about 50 A, or about 5 A to about 40 A, or about 5 A to about 30 A or about 5 A to about 20 A; wherein the dielectric film is selected from the group consisting of silicon nitride, metal oxide, silicon carbonitride, silicon oxynitride, and combinations thereof.

[0009] In a further aspect of the first main aspect, the temperatures for steps (a) to (c) range independently from about 250 °C to about 450 °C while temperatures for steps (d) to (g) range independently from about 300 °C to about 650 °C.

[0010] In a further aspect of the first main aspect, the deposition precursor is a silicon precursor selected from the group consisting of (i) hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane; (ii) hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octaclorotrisiloxane; (iii) 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-butyl- disilazane, 1 ,1 ,1 ,3,3,3-iodo-2-tert-butyl-disilazane, 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-methyl-disilazane, 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; (iv) 1 -chloro-1 ,3-disilacyclobutane, 1 -bromo-1 ,3- disilacyclobutane, 1 .3-dichloro- 1 ,3-1 ,3-disilacyclobutane, 1 ,3-dibromo-1 ,3- disilacyclobutane, 1 .1 .3-trichloro- 1 ,3-disilacyclobutane, 1 ,1 ,3-tribromo-1 ,3- disilacyclobutane, 1 ,1 ,3,3-tetrachloro-1 ,3-disilacyclobutane, 1 ,1 ,3,3-tetrabromo-1 ,3-disilacyclobutane, 1 ,3-dichloro-1 ,3-dimethyl-1 ,3-disilacyclobutane, 1 ,3-bromo-1 ,3- dimethyl-1 ,3-disilacyclobutane, 1 ,1 ,1 ,3,3,5,5,5-octachloro-1 ,3,5-trisilapentane,1 .1 .1 .3.3.5.5.5-octachloro-1 ,3,5-trisilapentane, 1 ,1 ,1 ,3,3,5,5,5-octachloro-1 ,5- dimethyl-1 ,3,5-trisilapentane, 1 ,1 ,1 ,5,5,5-hexachloro-3,3-dimethyl-1 ,3,5- trisilapentane, 1 ,1 ,3,5,5,5-pentachloro-1 ,3,5-tri methyl- 1 ,3,5-trisilapentane,1 .1 .1 .5.5.5-hexachloro-1 ,3,5-trisilapentane, and 1 ,1 ,5,5-tetraachloro-1 ,3,5- trisilapentane.

[0011] In a further aspect of the first main aspect, the deposition precursor is a metal precursor selected from the group consisting of trimethylaluminum, triethylaluminum, dimethylaluminum iso-propoxide, diethylaluminum iso-propoxide, tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe2)3), cyclopentadienyltris(methylethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyltris(methylethylamino)hafnium (MeCpHf(NMeEt)s), ethylcyclopentadienyltris(methylethylamino)hafnium (EtCpHf(NMeEt)s), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt2)3), methylcyclopentadienyltris(diethylamino)hafnium (MeCpHf(NEt2)3), ethylcyclopentadienyltris(diethylamino)hafnium (EtCpHf(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMe2)2), bis(cyclopentadienyl)bis(methylethylamino)hafnium (Cp2Hf(NMeEt)2), bis(methylcyclopentadienyl)bis(methylethylamino)hafnium ((MeCp)2Hf(NMeEt)2), bis(ethylcyclopentadienyl)bis(methylethylamino)hafnium ((EtCp)2Hf(NMeEt)2), bis(cyclopentadienyl)bis(diethylamino)hafnium ((Cp2Hf(NEt2)2), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp)2Hf(NEt2)3), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp)2Hf(NEt2)2) tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMe2)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMe2)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NMe2)3),cyclopentadienyltris(methylehtylamino)zirconium (CpZr(NMeEt)3), methylcyclopentadienyltris(methylethylamino)zirconium (MeCpZr(NMeEt)3), ethylcyclopentadienyltris(methylethylamino)zirconium (EtCpZr(NMeEt)s), cyclopentadienyltris(diethylamino)zirconium (CpZr(NEt2)3), methylcyclopentadienyltris(diethylamino)zirconium (MeCpZr(NEt2)3), ethylcyclopentadienyltris(diethylamino)zirconium (EtCpZr(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)zirconium (Op2Zr(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NMe2)2), bis(cyclopentadienyl)bis(methylethylamino)zirconium (Cp2Zr(NMeEt)2), bis(methylcyclopentadienyl)bis(methylethylamino)zirconium ((MeCp)2Zr(NMeEt)2), bis(ethylcyclopentadienyl)bis(methylethylamino)zirconium ((EtCp)2Zr(NMeEt)2), bis(cyclopentadienyl)bis(diethylamino)zirconium ((Cp2Zr(NEt2)2), bis(methylcyclopentadienyl)bis(diethylamino)zirconium ((MeCp)2Zr(NEt2)3), bis(ethylcyclopentadienyl)bis(diethylamino)zirconium ((EtCp)2Hf(NEt2)2),(MeNCH2CH2Cp)Hf(NMe2)2, (MeNCH2CH2CH2Cp)Hf(NMe2)2,(MeNCH2CH2Cp)Zr(NMe2)2, (MeNCH2CH2CH2Cp)Zr(NMe2)2, Cp2HfMe(OMe), Cp2ZrMe(OMe), (MeCp)2HfMe(OMe), (MeCp)2ZrMe(OMe), (EtCp)2HfMe(OMe)2, and (EtCp)2ZrMe(OMe).

[0012] In a further aspect of the first main aspect, the alkyne of Formula I A is selected from the group consisting of 1 -octyne, 1 -nonyne, 1 -decyne, 1 -undecyne, 1 -dodecyne,1 -tridecyne, 1 -tetradecyne, trimethylsilylacetylene, ethynylbenzene, cyclopropylacetylene, cyclobutylacetylene, cyclopentylacetylene, 3-phenyl-1 -propyne, 4-phenyl-1 -butyne, 5-phenyl-1 -pentyne, 6-phenyl-1 -hexyne, 1 ,3-octadiyne, 1 ,8- nonadiyne, and 1 ,3,5-triethynyl-benzene.

[0013] In a further aspect of the first main aspect, the alkyne of Formula IB is selected from the group consisting of 2-octyne, 2-nonyne, 2-decyne, 2-undecyne, 2-dodecyne,2-tridecyne, and 2-tetradecyne.

[0014] In a further aspect of the first main aspect, the passivating composition comprises 1 -decyne, 1 -dodecyne, 5-phenyl-1 -pentyne, 1 ,3-octadiyne, 1 ,8-nonadiyne, or 1 ,3,5-triethynyl-benzene.

[0015] In a further aspect of the first main aspect, a deposition selectivity of the second surface to the first surface is greater than about 0.3, more preferably greater than about 0.5, and most preferably greater than about 0.8.

[0016] In a further aspect of the first main aspect, a deposition selectivity of the second surface to the first surface is greater than about 0.8, and the thickness of the aluminum-containing dielectric film is about 50 A or less.

[0017] In a further aspect of the first main aspect, a preclean step is conducted prior to step (a), the preclean step comprising exposing the first surface to an acid, a reducing environment, heating, or a combination thereof.

[0018] In a further aspect of the first main aspect, the preclean step comprises exposing the substrate to citric acid, followed by exposing the substrate to H2 at a temperature ranging from about 250 to about 500 degrees Celsius.

[0019] In a further aspect of the first main aspect, the substrate is subjected to a chemical mechanical planarization step, wherein the chemical mechanical planarization step is conducted prior to the preclean step in order to provide coplanarity of the first surface and the second surface.

[0020] In a second main aspect, a method for passivating a silicon-containing surface of a substrate is provided. The method comprising: (a) providing the substrate in a reactor at temperatures ranging from about 200 °C to about 500 °C, the substrate having a first surface comprising a silicon-containing material and a second surface comprising a dielectric or a metal; (b) forming at least one passivation layer on the first surface by exposing both the first surface and the second surfaces to a passivating composition comprising an alkyne having one of the following formulae:IA IB; wherein R1and R2are each selected from the group consisting of a linear, branched, or cyclic C5to CM alkyl; a linear, branched, or cyclic Cs to Cu alkylsilyl; a Cg to Cu arylalkyl; a linear, branched, or cyclic C& to C14 alkynyl; a Ce to Cu arylalkynyl; wherein R1and R2may have one or more carbon-carbon triple bond; and (c) purging the reactor with inert gas.

[0021] In a further aspect of the second main aspect, steps (b) to (c) are repeated to provide a fully covered passivation layer on the first surface.

[0022] In a further aspect of the second main aspect, the first surface comprises polysilicon, amorphous silicon, crystalline silicon, amorphous silicon germanium, crystalline silicon germanium, polycrystalline silicon germanium, polycrystalline germanium, or crystalline germanium or wherein the second surface comprises anitride chosen from the group consisting of silicon nitride, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and combinations thereof; or wherein the second surface comprises a metal chosen from the group consisting of copper, cobalt, ruthenium, molybdenum, tungsten, and combination thereof.

[0023] In a further aspect of the second main aspect, the first surface is selected from the group consisting of polysilicon, crystalline silicon, amorphous silicon germanium, polycrystalline silicon germanium, or crystalline silicon germanium and wherein the second surface is selected from the group consisting of silicon nitride, silicon oxide, carbon doped silicon oxide, and combinations thereof.

[0024] In a further aspect of the second main aspect, the alkyne of Formula IA is selected from the group consisting of 1-octyne, 1-nonyne, 1-decyne, 1 -undecyne, 1 - dodecyne, 1 -tridecyne, 1 -tetradecyne, trimethylsilylacetylene, ethynylbenzene, cyclopropylacetylene, cyclobutylacetylene, cyclopentylacetylene, 3-phenyl-1 -propyne, 4-phenyl-1 -butyne, 5-phenyl-1 -pentyne, 6-phenyl-1 -hexyne, 1 ,3-octadiyne, 1 ,8- nonadiyne, and 1 ,3,5-triethynyl-benzene.

[0025] In a further aspect of the second main aspect, the alkyne of Formula IB is selected from the group consisting of 2-octyne, 2-nonyne, 2-decyne, 2-undecyne, 2- dodecyne, 2-tridecyne, and 2-tetradecyne.

[0026] In a further aspect of the second main aspect, the passivating composition comprises 1 -decyne, 1 -dodecyne, 5-phenyl-1 -pentyne, 1 ,3-octadiyne, 1 ,8-nonadiyne, or 1 ,3,5-triethynyl-benzene.

[0027] In a further aspect of the second main aspect, a preclean step is conducted prior to step (a), the preclean step comprising by exposing the substrate to H2 or hydrogen plasma at a temperature ranging from about 200 °C to about 500 °C.

[0028] The embodiments of the disclosure can be used alone or in combination with each other.BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0030] FIG. 1A illustrates an exemplary method comprising: a surface pre-clean of substrate having a first surface and a second surface, passivation of the first surface, and selective deposition of a dielectric film on the second surface. The dielectric film is selectively deposited on the second surface, while the first surface is passivated;

[0031] FIG. 1 B illustrates an exemplary method comprising: a surface pre-clean of a first surface comprising polysilicon and a second surface comprising silicon nitride, passivation of polysilicon, and selective deposition of dielectric film. The dielectric film is selectively deposited on the silicon nitride surface, while the polysilicon surface is passivated;

[0032] FIG. 2 illustrates the XPS spectra confirming the formation of a carbon-rich passivation layer on polysilicon (PolySi) after the surface treatment to create Si-H groups on the surface of the polysilicon;

[0033] FIG. 3 illustrates selective deposition of aluminum oxide films on a substrate having polysilicon non-growth surface and a SiN growth surface. The substrate is passivated by two selected 1 -alkyne inhibitors at 250 °C and 350 °C;

[0034] FIG. 4 illustrates the selectivity comparison of a 5-phenyl-1 -pentyne and 1 - dodecyne at 250 °C and 350 °C, wherein the growth surface is OVD silicon nitride and the non-growth surface is OVD polysilicon;

[0035] FIG. 5 illustrates selective deposition of aluminum oxide films on a substrate having crystalline silicon and SiN surfaces, wherein the non-growth surface of the substrate is passivated by two selected 1 -alkyne inhibitors at 250 °C and 350 °C; and

[0036] FIG. 6 illustrates the selectivity comparison of a 5-phenyl-1 -pentyne and 1 - dodecyne at 250 °C and 350 °C, wherein the growth surface is CVD silicon nitride and the non-growth surface is crystalline silicon.DETAILED DESCRIPTION

[0037] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0038] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the disclosure (especially in the context of the following claims) are to beconstrued to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e. , meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the disclosure and does not pose a limitation on the scope of the claims unless otherwise stated explicitly. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the subject matter of this disclosure.

[0039] Preferred embodiments of this disclosure are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventor intends for the claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the claimed subject matter unless otherwise indicated herein or otherwise clearly contradicted by context.

[0040] Area selective deposition (ASD) has been envisioned as one of most promising integration approaches to reduce some of the semiconductor processing complexity caused by typical litho-etch steps. One of the applications for ASD is to selectively passivate the polysilicon therefore allows selective growth of nitride on nitrides, which is very challenging considering the similar surface chemistries on both nongrowth and growth substrates. To selectively passivate polysilicon, there are a few inhibitors candidates based on literatures, one of them is alkyne or alkene based molecules where carbon-carbon double / triple bonds can react with Si surface radical under UV radiation or photon initiator to form Si-C bonded monolayer at relatively short reaction time. Grafting these molecules to Si hydride surface by thermal activation arealso reported, but rather long reactions time more than 10 hours are needed under inert environment. This is not applicable to semiconductor integration process. Additionally, it is reported these carbon-based monolayers grafted on Si is not thermally stable up to 250 °C.

[0041] However, the present disclosure teaches that dodecyne can passivate polysilicon at 250 °C to 400 °C (relatively higher temperatures than thiol-based inhibitors) with strong surface hydrophobicity due to the molecular monolayer formation.

[0042] As such, alkynes such as dodecyne are relevant inhibitors for high temperature polysilicon ASD application. This high thermal stability mechanism is thought to be due to formation of double Si-C bond between carbon-carbon triple bond and Si surfaces at higher passivation temperatures, which enhance the thermal stability of this type of monolayer for passivation of silicon surface having Si-H groups.

[0043] Various aspects of the disclosure will now be described with reference to the drawings and tables disclosed herein, if applicable, with like reference numbers referring to like elements, unless specified otherwise. As described above, a need exists in the art to deposit silicon-containing materials, such as silicon oxide or silicon nitride, selectively on top of a silicon surface relative to another surface in a semiconductor manufacturing process using a thermal process without using a plasma at temperatures ranging from 150 °C to 700 °C with high selectivity. The selectivity is defined as (the thickness of silicon-containing film on the growth surface - the thickness of silicon-containing film on the non-growth surface) / (the thickness of silicon-containing film on the growth surface + the thickness of silicon-containing film on the non-growth surface). The preferred growth surface is silicon nitride and the preferred non-growth surface is polysilicon. The selectivity is preferred to be 80% or greater, or 85% or greater, or 90% or greater, 95% or greater.

[0044] Accordingly, disclosed herein is a novel, and non-obvious, selective thermal atomic layer deposition (ALD) process, that selectively deposits silicon-containing dielectric materials, such as silicon nitride, on top of a dielectric material, such as silicon nitride, relative to polysilicon, in an ALD reactor. This method comprises:(a) loading the substrate into a reactor, the substrate having a first surface comprising Si-H groups and a second surface that does not comprise Si-H groups;(b) introducing a passivating composition comprising an alkyne having one of the following formulae to selectively form a passivation layer on the polysilicon surface:IA IB; wherein R1and R2are each selected from the group consisting of a linear, branched, or cyclic C5to CM alkyl; a linear, branched, or cyclic Cs to CM alkylsilyl; a C& to CM arylalkyl; a linear, branched, or cyclic Ce to CM alkynyl; and a Ce to C arylalkynyl; wherein R1and R2may have one or more carbon-carbon triple bonds;(c) purging the reactor with inert gas;(d) introducing a deposition precursor into the reactor to react with the dielectric material to form a monolayer comprising a portion of deposition precursor;(e) purging the reactor with inert gas;(f) introducing a vapor comprising an oxygen source or a nitrogen source into the reactor to react with the monolayer to form the dielectric film; and(g) purging the reactor with inert gas.

[0045] Steps (d) to (g) may be repeated to deposit a desired dielectric film on top of the second surface. In some embodiments, step (b) and (c) can be conducted after Step (d) to (g) are repeated to deposit a desired dielectric film, followed by repeating Step (d) to (g) to provide a thicker dielectric film. The thickness of the dielectric film can range from about 1 A to about 100 A, or about 5 A to about 90 A, or about 5 A to about 80 A, or about 5 A to about 70 A or about 5 A to about 60 A, or about 5 A to about 50 A, or about 5 A to about 40 A, or about 5 A to about 30 A or about 5 A to about 20 A, depending on a targeted thickness for a required selectivity.

[0046] The deposition precursor can be a silicon-containing precursor selected from the group consisting of (i) hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane; (II) hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octaclorotrisiloxane; (ill) 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-butyl- disilazane, 1 ,1 ,1 ,3,3,3-iodo-2-tert-butyl-disilazane, 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-methyl-disilazane, 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; (iv) 1 -chloro-1 ,3-disilacyclobutane, 1 -bromo-1 ,3-disilacyclobutane, 1 .3-dichloro- 1 ,3-1 ,3-disilacyclobutane, 1 ,3-dibromo-1 ,3- disilacyclobutane, 1 .1 .3-trichloro- 1 ,3-disilacyclobutane, 1 ,1 ,3-tribromo-1 ,3- disilacyclobutane, 1 ,1 ,3,3-tetrachloro-1 ,3-disilacyclobutane, 1 ,1 ,3,3-tetrabromo-1 ,3- disilacyclobutane, 1 ,3-dichloro-1 ,3-dimethyl-1 ,3-disilacyclobutane, 1 ,3-bromo-1 ,3- dimethyl-1 ,3-disilacyclobutane, 1 ,1 ,1 ,3,3,5,5,5-octachloro-1 ,3,5-trisilapentane,1 .1 .1 .3.3.5.5.5-octachloro-1 ,3,5-trisilapentane, 1 ,1 ,1 ,3,3,5,5,5-octachloro-1 ,5- dimethyl-1 ,3,5-trisilapentane, 1 ,1 ,1 ,5,5,5-hexachloro-3,3-dimethyl-1 ,3,5- trisilapentane, 1 ,1 ,3,5,5,5-pentachloro-1 ,3,5-tri methyl- 1 ,3,5-trisilapentane,1 .1 .1 .5.5.5-hexachloro-1 ,3,5-trisilapentane, and 1 ,1 ,5,5-tetraachloro-1 ,3,5- trisilapentanewhen the dielectric film is silicon nitride.

[0047] The aluminum precursor can be selected from the group consisting of triethylaluminum, dimethylaluminum iso-propoxide, diethylaluminum iso-propoxide when the dielectric film is aluminum oxide.

[0048] Examples of the alkynes with Formula IA can be selected from the group consisting of 1 -octyne, 1 -nonyne, 1 -decyne, 1 -undecyne, 1 -dodecyne, 1 -tridecyne, 1 - tetradecyne, ethynylbenzene, 3-phenyl-1 -propyne, 4-phenyl-1 -butyne, 5-phenyl-1 - pentyne, and 6-phenyl-1 -hexyne. Examples of the alkynes with Formula IB can be selected from the group consisting of 2-octyne, 2-nonyne, 2-decyne, 2-undecyne, 2- dodecyne, 2-tridecyne, and 2-tetradecyne.

[0049] The silicon-containing film in a preferred embodiment is selected from the group consisting of silicon nitride, silicon carbonitride, silicon oxynitride, and combinations thereof.

[0050] In second aspect, a method of passivation a silicon-containing surface of a substrate process in an ALD reactor comprises:(a) loading the substrate comprising a first surface and a second surface into a reactor;(b) introducing a passivating composition comprising an alkyne to selectively form a passivation layer on the first surface, the alkyne having one of the following formulae:IA IB; wherein R1and R2are each selected from the group consisting of a linear, branched, or cyclic Cs to CM alkyl; a linear, branched, or cyclic Cs to Cu alkylsilyl; a Cs to Cuarylalkyl; a linear, branched, or cyclic Ce to Cu alkynyl; and a Ce to C arylalkynyl; wherein R1and R2may have one or more carbon-carbon triple bonds; and(c) purging the reactor with inert gas.

[0051] In some embodiments, step (b) and (c) can be repeated to deposit a desired thickness resulting in a fully covered passivation layer.

[0052] Examples of the alkynes with Formula I A include 1 -octyne, 1 -nonyne, 1 - decyne, 1 -undecyne, 1 -dodecyne, 1 -tridecyne, 1 -tetradecyne, trimethylsilylacetylene, ethynylbenzene, cyclopropylacetylene, cyclobutylacetylene, cyclopentylacetylene, 3- phenyl-1 -propyne, 4-phenyl-1 -butyne, 5-phenyl-1 -pentyne, 6-phenyl-1 -hexyne, 1 ,3- octadiyne, 1 ,8-nonadiyne, and 1 ,3,5-triethynyl-benzene.

[0053] Examples of the alkynes of Formula IB include of 2-octyne, 2-nonyne, 2- decyne, 2-undecyne, 2-dodecyne, 2-tridecyne, and 2-tetradecyne.

[0054] In a preferred embodiment of this method, the first surface includes polysilicon and the second surface includes silicon nitride.

[0055] The silicon-containing film in a preferred embodiment is selected from the group consisting of silicon nitride, silicon carbonitride, silicon oxynitride, and combinations thereof.

[0056] As used in this specification and the appended claims, the term “substrate” and “wafer” are used interchangeably, both referring to a surface, or portion of a surface, upon which a process acts. It will also be understood by those skilled in the art that reference to a substrate can also refer to only a portion of the substrate, unless the context clearly indicates otherwise. Additionally, reference to depositing on a substrate can mean both a bare substrate and a substrate with one or more films or features deposited or formed thereon.

[0057] A “substrate” as used herein, refers to any substrate or material surface formed on a substrate upon which film processing is performed during a fabrication process. For example, a substrate surface on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. Substrates include, without limitation, semiconductor wafers. Substrates may be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal and / or bakethe substrate surface. In addition to film processing directly on the surface of the substrate itself, in the present disclosure, any of the film processing steps disclosed may also be performed on an underlayer formed on the substrate as disclosed in more detail below, and the term “substrate surface” is intended to include such underlayer as the context indicates. For example, where a film / layer or partial film / layer has been deposited onto a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a given substrate surface comprises will depend on what films are to be deposited, as well as the particular chemistry used. In one or more embodiments, the first substrate surface will comprise a metal, and the second substrate surface will comprise a dielectric, or vice versa. In some embodiments, a substrate surface may comprise certain functionality (e.g., -OH, -NH, etc.).

[0058] Likewise, the films that can be used in the methods described herein are quite varied. In some embodiments, the films may comprise, or consist essentially of 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), etc., 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), etc., and combinations thereof. In some embodiments, the film comprises a dielectric. Examples include, SiOs, carbon doped silicon oxide, SiN, HfOs, ZrO2 etc.

[0059] In embodiments of the present disclosure, the substrate has at least two discrete surfaces wherein each discrete surface is characterized by a different chemistry. For example, in an embodiment, the surface of the substrate comprises at least a first surface comprising polysilicon and at least a second surface comprising a metal or a dielectric material such as silicon nitride.

[0060] The at least one second surface comprising a dielectric or metal material can be, for example, any of the materials selected from the group consisting of SiOg, a metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, monocrystalline silicon, germanium, and amorphous hydrogenated germanium. In some embodiments the at least one second surface comprises SiOa is a dielectric surface, such as a SiC>2 surface. In some embodiments the surface comprising SiC>2 may comprise silicon oxides, fluorinated silica glass (FSG), carbon doped silicon oxide (SiOC) and / ormaterials containing more than about 50% silicon oxide. In some embodiments the surface comprising SiOz comprises -OH groups and may also comprise, for example, an alumina (AI2O3) surface with -OH surface groups.

[0061] Embodiments of the disclosure provide methods of selectively depositing a film such as, for example, a metal film, onto one surface of a substrate over a second surface on the same substrate wherein the two surfaces are co-planar created by chemical mechanical planarization. As used in this specification and the appended claims, the term “selectively depositing a film on one surface over another surface,” and the like, means that one of the first or second surface is passivated to substantially prevent deposition on the passivated layer and a film is deposited on the second (nonpassivated) surface. The term “over” used in this regard does not imply a physical orientation of one surface on top of another surface, rather a relationship of the thermodynamic or kinetic properties of the chemical reaction with one surface relative to the other surface. For example, selectively depositing a cobalt film onto a copper surface over a dielectric surface means that the cobalt film deposits on the copper surface and less or no cobalt film deposits on the dielectric surface; or that the formation of the cobalt film on the copper surface is thermodynamically or kinetically favorable relative to the formation of a cobalt film on the dielectric surface.

[0062] The method of the present disclosure includes the optional step of contacting the surface of the substrate with hydrogen, a wet chemical composition, or a combination thereof to obtain a treated substrate. In a preferred embodiment, the substrate is exposed to hydrogen or hydrogen plasma at a temperature of between about 200 °C to about 500 °C. Exemplary wet chemical treatments include known chemical treatments such as, for example, RCA clean chemicals SC-1 and SC-2, aqueous HF, peroxide, H2SO4 1 H2O2, NH4OH, buffered HF solutions, and mixtures thereof.

[0063] In preferred embodiments, the wet chemical composition comprises at least one selected from the group consisting of a composition comprising H2O2 (28 % aq.), NH4OH (28-30 %), and H2O; HF (0.01 % - 10% (aq.)); peroxide; RCA clean chemicals SC-1 and SC-2; and a mixture of H2SO4 / H2O2.

[0064] As is known in the art, “RCA clean chemicals” refers to compositions comprising an ammonium hydroxide and hydrogen peroxide mixture wherein the basic cleaning procedure developed by the Radio Corporation of America in the 1960s. The RCA Standard-Clean-1 (SC-1 ) procedure uses an ammonium hydroxide and hydrogenperoxide solution and water heated to a temperature of about 70 °C. The SC-1 procedure dissolves films and removes Group I and II metals. The Group I and II metals are removed through complexing with the reagents in the SC-1 solution. The RCA Standard-Clean-2 (SC-2) procedure utilizes a mixture of hydrogen peroxide, hydrochloric acid, and water heated to a temperature of about 70 °C. The SC-2 procedure removes the metals that are not removed by the SC-1 procedure.

[0065] Contacting with the wet chemical composition can occur by any method known to those skilled in the art such as, for example, dipping or spraying. The contacting step can be one discrete step or more than one step.

[0066] In some embodiments, the temperature of the wet chemical composition during the contacting step can be, for example, from about ambient temperature to about 100 °C. In other embodiments, the temperature of the wet chemical composition during the contacting 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 contacting step can be, for example, from about 60 °C to about 90 °C.

[0067] Embodiments also include the step of rinsing the surface of the substrate with deionized water after the step of contacting the surface of the substrate with the wet chemical composition. The rinsing step is typically carried out by any suitable means, for example, rinsing the surface of the substrate with de-ionized water by immersion or spray techniques.

[0068] Embodiments also include the step of drying at least the surface of the substrate after the rinsing step, preferably in the presence of an inert atmosphere such as nitrogen. The drying step is typically carried out by any suitable means, for example, the application of heat, isopropyl alcohol (I PA) vapor drying, or by centripetal force.

[0069] Embodiments also optionally include the step of treating the surface with hydrogen plasma, argon plasma, or ammonia plasma. Suitable processes include plasma processes (hydrogen plasma, NH3 / NF3 plasmas, water plasmas, and the like). The optional plasma step functions to remove undesired deposits on the surface and activate the surface for subsequent deposition of passivation reagents. Such plasma treatments may be most preferably applied after some deposition on the surface has been performed in order to remove non-selectively deposited material from the previously passivated surface and to remove residual passivation reagents after the desired deposition thickness has been achieved.

[0070] As employed throughout the description, the term “alkyl” means a saturated hydrocarbon group which is straight-chained or branched. In some embodiments, the alkyl group has from 1 to 20 carbon atoms, from 2 to 20 carbon atoms, from 1 to 10 carbon atoms, from 2 to 10 carbon atoms, from 1 to 8 carbon atoms, from 2 to 8 carbon atoms, from 1 to 6 carbon atoms, from 2 to 6 carbon atoms, from 1 to 4 carbon atoms, from 2 to 4 carbon atoms, from 1 to 3 carbon atoms, or 2 or 3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (e.g., n- propyl and isopropyl), butyl (e.g., n-butyl, t-butyl, isobutyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), hexyl, isohexyl, heptyl, octyl, nonyl, 4,4dimethylpentyl, 2,2,4- trimethylpentyl, decyl, undecyl, dodecyl, 2-methyl-1 -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 the like.

[0071] As employed throughout the description, the term “alkylsilyl” denotes to a group derived from alkylsilane via removal of hydrogen from Si-H. Examples of alkylsilyl groups include, but are not limited to, trimethylsilyl, ethyldimethylsilyl, dimethylvinylsilyl.

[0072] As employed throughout the description, the term “cyclic alkyl” denotes a cyclic functional group having from 3 to 10 or from 4 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0073] As used herein, the term “aryl” means a monocyclic, bicyclic, or polycyclic (e.g., having 2, 3 or 4 fused rings) aromatic hydrocarbon. In some embodiments, the aryl group has from 6 to 20 carbon atoms or from 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, indenyl, and tetrahydronaphthyl, and the like.

[0074] As used herein, the term “arylalkyl” means a hydrogen in an alkyl group is substituted by an aryl. In some embodiments, the alkyl group is a Ci 6 alkyl group. It may be further substituted by a halide such as Cl, F, or Br. In other embodiments, one or more hydrogens in the aryl ring may be substituted by alkyl or halide or halide- containing alkyl.

[0075] As employed throughout the description, the term “alkenyl group” denotes a group which has one or more carbon-carbon double bonds and has from 2 to 18 orfrom 2 to 10 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl groups.

[0076] As used herein, the term “alkynyl” means a straight 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 from 2 to 10 carbon atoms, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, or from 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, acetylene, 1 -propylene, 2-propylene, and the like.

[0077] As used herein, the term “polysilicon material” refers a silicon-containing material having Si-H groups on the surface. Examples include polysilicon, crystalline silicon, polysilicon silicon germanium, crystalline silicon germanium, polycrystalline silicon germanium, or crystalline silicon germanium.

[0078] As used herein, the term “dielectric film” refers a silicon-containing or metal oxide dielectric material. Examples include silicon nitride, silicon oxide, carbon doped silicon oxide, aluminum oxide, hafnium oxide, zirconium oxide, and combination thereof.

[0079] As used herein, the term “metal material” refers a metal-containing material including pure metal, metal alloy, or metal nitride. Examples include copper, cobalt, ruthenium, molybdenum, tungsten, titanium nitride, tantalum nitride, molybdenum nitride, tungsten nitride, and combination thereof.

[0080] As used herein, the term “halo” means halogen groups and includes, but is not limited to, fluoro, chloro, bromo, and iodo.

[0081] Vapor phase or gas phase reactions include the exposure of the heated substrate to the precursor molecule(s) and / or co-reactants in a suitable chamber that must be capable of providing the necessary pressure control and that can also supply heat to the substrate and / or chamber walls; the chamber should also provide suitable purity for the reactions that will take place, generally through high leak integrity and the use of ultra-high purity carrier and reactive gases.

[0082] As used in this specification and the appended claims, the terms “reactive gas”, “precursor”, “reactant”, and the like, are used interchangeably to mean a gas that includes a species which is reactive with a substrate surface. For example, a first “reactive gas” may simply adsorb onto the surface of a substrate and be available for further chemical reaction with a second reactive gas. They may be used in conjunctionwith ultra-high purity carrier gases (as defined previously) and in any desired mixtures with one another (i.e. , more than one type of precursor can be used either together or in discrete, independent steps to form the desired passivation layer with whatever order of precursor introduction is desired).

[0083] The precursor(s) and / or co-reactants may be delivered to the reactor using mass flow controllers (perhaps with heated lines), liquid injection vaporizers (perhaps with heated lines) or with no metering device (i.e., neat introduction of the vapor and or gas from a vessel that is isolated from the reactor using a simple valve). Any of the foregoing may also be used in combination with one another. Any means of providing the gas and / or vapor(s) to the reaction chamber that provides sufficient purity and repeatability may be used.

[0084] The precursor(s) and / or co-reactants may be introduced independently to the reactor, mixed prior to introduction to the reactor, mixed in the reactor or in any combination of the preceding in multiple, independent steps that might include differences in how the precursors are introduced between steps.

[0085] The exposure of the surface can be conducted for 0.1 -60 minutes, preferably in 1 -5 minutes and most preferably for 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 up to almost 100% of its saturation vapor pressure. Most preferably, it will be between 20 and 50% of its saturation vapor pressure. The chamber pressure can be the same as the partial pressure of the organic halide vapors but can be higher with the balance of the atmosphere comprising a carrier gas. Preferred carrier gases include N2, He, Ar, and combinations thereof. The exposure vapors can be static (not flowing) for all or part of the exposure period. The preferred embodiment is to flow the vapors of the organic halide along with the optional carrier gas through the exposure chamber so that fresh vapors are exposed to the surface of the substrate for at least a portion of the exposure period.

[0086] Unreacted vapor of the at least one organic halide can then optionally be removed by evacuation or purging of the chamber with suitable inert gas before removing the substrate from the chamber or before chemical vapor or atomic-layer deposition processing. Optionally, the exposure chamber might also be used for subsequent processing steps to improve process efficiency so that the process may be repeated from step c), if necessary, to strip the protective film and any non-selective ALD deposit and then re-form a protective film.

[0087] Disclosed and Claimed Passivating Composition

[0088] Given the forgoing, in one embodiment the disclosed and claimed subject relates to passivating compositions that include, consist essentially of and / or consist of an alkyne. The passivating compositions are particularly well-suited for performing enhanced passivation of metallic substrates. In one aspect of this embodiment, the alkyne, consists essentially of or consists of one or more one 1 -alkyne (an alkyne having a triple bond and the 1 - position) or a 2-alkyne (an alkyne having a triple bond at the 2- position).

[0089] In one embodiment, the alkyne having formula IA or IB is a high-purity alkyne that is substantially free of water. In one aspect of this embodiment, the high-purity alkyne has a residual concentration of water of less than about 500 ppm. In one aspect of this embodiment, the high-purity alkyne has a residual concentration of water of less than about 100 ppm. In one aspect of this embodiment, the high-purity alkyne has a residual concentration of water of less than about 50 ppm. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of water of less than about 25 ppm. In one aspect of this embodiment, the high-purity alkyne has a residual concentration of water of less than about 10 ppm. In one aspect of this embodiment, the high-purity alkyne is free of detectable water. In one aspect of this embodiment, the high-purity alkyne is free of water.

[0090] In one embodiment, the alkyne having formula IA or IB is substantially free of impurities that may react with metallic surface during a passivation process. In one embodiment, the alkyne having formula IA or IB is substantially free of impurities that react with precursors during a deposition process.

[0091] In one embodiment, the alkyne having formula IA or IB is substantially free of impurities that passivate non-metallic surface and suppress growth on non-metallic surface.

[0092] In one embodiment, the alkyne having formula IA or IB is substantially free of halogen-containing impurities. In one aspect of this embodiment, the halogencontaining impurities are one or more of a fluorohydrocarbon, a chlorohydrocarbon, a bromohydrocarbon and an iodohydrocarbon. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 1000 ppm. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 500 ppm. In one aspect of this embodiment, the alkyne havingformula IA or IB has a residual concentration of halogen-containing impurities of less than about 100 ppm. In one aspect of this embodiment, the alkyne 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 alkyne 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 alkyne 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 alkyne having formula IA or IB is free of halogencontaining impurities. In the forgoing aspects, the residual concentration of halogencontaining impurities is detected by one or more of the following: Gas Chromatography (GC) and its associated hyphenated techniques comprising but not limited to GC-FID, GC-ECD, GC-MS; Liquid Chromatography (as defined as to encompass LC, HPLC, or UPLC variations) and its associated hyphenated techniques comprising but not limited to LC-DAD and LC-MS; Ion Chromatography (IC) and its associated forms; Spectroscopic techniques comprising but not limited to infrared (I R), Ultraviolet / Visible (UV / Vis), Near infrared (NIR), Raman and Nuclear Magnetic Resonance (NMR) spectroscopies; Inductively Coupled Plasma spectroscopy or spectrometry (ICP) and their associated hyphenated techniques comprising but not limited to ICP-MS, ICP- OES, GC-ICP-MS, and GC-ICP-OES; Elemental analyses such as X-ray fluorescence spectroscopy (XRF) and its associated forms (example WD-XRF) or Atomic Absorbance spectroscopy (AA) and its forms; and finally wet chemical techniques comprising but not limited to Titration (example halogen titration by with silver nitrate) and electrochemical detection (examples, cyclic voltammetry, ion selective electrodes, etc.). In one embodiment of the forgoing aspects, 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.

[0093] In one embodiment, the alkyne having formula IA or IB is purified by exposure to molecular sieves. In one embodiment, the alkyne having formula IA or IB is purified by exposure to silica gel. In one embodiment, the alkyne having formula IA or IB is purified by exposure to one or more adsorbent materials.

[0094] In one embodiment, the alkyne having formula IA or IB is purified by treatment with one or more group 1 metal followed by a distillation process. In one aspect of this embodiment, the alkyne is treated with metallic sodium. In another aspect embodiment, the metal and the alkyne are separated by filtration and the alkyne is distilled to remove non-volatile products of the reaction of impurities with metals.

[0095] In one embodiment, the alkyne having formula IA or IB is purified by treatment with one or more group (II) metal followed by a distillation process. In one aspect of this embodiment, the alkyne is treated with metallic magnesium. In another aspect embodiment, the metal and the alkyne are separated by filtration and the alkyne is distilled to remove non-volatile products of the reaction of impurities with metals.

[0096] In one embodiment, the alkyne having formula IA or IB is purified by exposure to activated carbon. In one aspect of this embodiment the alkyne is separated by filtration and is distilled to remove non-volatile products after treatment with activated carbon.

[0097] Selective depositions according to the present disclosure can be, for example, metal and metal oxide layers disclosed in Hamalainen et al., “Atomic Layer Deposition of Noble Metals and Their Oxides,” Chem. Mater. 2014, 26, 786-801 ; and Johnson et al., “A Brief review of Atomic layer Deposition: From Fundamentals to Applications”, Materials Today, Volume 17, Number 5, June 2014, both of which are incorporated herein by reference in their entireties.

[0098] During the selective deposition process, the aforementioned protective surface previously deposited selectively on silicon nitride surfaces with the at least alkyne could begin to react or otherwise become less inert. An optional re-application of the at least one alkyne, either with or without any of the aqueous or plasma pretreatment steps may optionally be performed repeatedly to prevent or delay non- selective deposition on the silicon nitride surface.

[0099] In some embodiments passivation on a first surface of a substrate as described herein, such a polysilicon surface of the substrate, relative to a second surface of the substrate is at least about 90% selectivity, at least about 95% selectivity, at least about 96%, 97%, 98% or 99% or greater selectivity. In some embodiments passivation only occurs on the first surface and does not occur on the second surface. In some embodiments passivation on the first surface of the substrate relative to the second surface of the substrate is at least about 50% selectivity, or at least about 60% selectivity, which may be selective enough for some particular applications. In some embodiments passivation on the first surface of the substrate relative to the second surface of the substrate is at least about 50% selective, which may be selective enough for some particular applications.

[0100] Wet chemistry cleans may be used to remove the passivation layer. Example wet chemistry cleans include acidic, basic, and oxidative (e.g., peroxide-containing)wet chemistry compositions known in the art and described above for the optional step of contacting the substrate with a wet chemical composition. Another method to remove the passivation layer is via the application of heat or other energy.EXAMPLES

[0101] The goal of the area selective deposition (ASD) is to selectively passivate the polysilicon surface, which therefore allows selective growth of nitride on nitrides, which is very challenge considering the similar surface chemistries on both nongrowth and growth substrates. Surprisingly, alkynes (e.g., 1 -alkynes, 2-alkynes, or 1 -arylalkynes) selectively passivate the polysilicon surface versus the silicon nitride surface. This process is depicted in FIG. 1 B. The process results in the selectivity to grow thicker dielectric film on silicon nitride.

[0102] Processes:

[0103] An illustrative process is shown in FIG. 1 A. The process comprises providing a substrate 100 having first surface 102 and the second surface 104, that are precleaned. Following the pre-clean, the first surface 102 includes Si-H groups and the second surface 104 does not include Si-H groups. Preferably, the first surface 102 and the second surface 104 are coplanar, as a result of a chemical mechanical planarization (CMP) as shown in FIG. 1 A prior to the precleaning step.

[0104] Step 1 comprises passivation of the first surface 102 by exposing the substrate to form a passivating / blocking organic layer 106 employing a passivating composition preferably comprising a 1 -alkyne such as 1 -decyne or 1 -dodecyne and a 1 -arylalkyne such as 5-phenyl-1 -pentyne.

[0105] Following passivation of the first surface, Step 2 includes depositing a dielectric layer 108 or film on the second surface 104, preferably by ALD of a deposition precursor and an oxygen source or a nitrogen source.

[0106] A further illustrative process is shown in FIG. 1 B. Step 1 comprises a precleaning of the first surface 202 (polysilicon) and the second surface 204 (silicon nitride) of a substrate 200, preferably with an acid (such as dilute hydrofluoric acid (dHF)), H2, high temperature, or a combination thereof. Following the pre-clean, the polysilicon surface 202 includes Si-H groups and the silicon nitride surface 204 does not include Si-H groups. Rather, the second surface includes NH2groups. Preferably, the first surface 202 and the second surface 204 are coplanar, as a result of a chemical mechanical planarization (CMP) as shown in FIG. 1 B prior to the precleaning step.

[0107] Step 2 comprises passivation of the non-growth surface 202 by exposing the substrate to form a passivating / blocking organic layer 206 employing a passivating composition preferably comprising a 1 -alkyne such as 1 -decyne or 1 -dodecyne and a 1 -arylalkyne such as 5-phenyl-1 -pentyne.

[0108] Following passivation of the first surface 202, Step 3 includes depositing the dielectric film 208 on the second surface 204 (silicon nitride), preferably by ALD of a deposition precursor and an oxygen source or a nitrogen.

[0109] In the exemplary embodiment below, Step 3 includes depositing an aluminum containing dielectric layer 208 on the second surface 204 (silicon nitride), preferably by ALD of an aluminum precursor and an oxygen source.

[0110] Table 1 shows the water contact angle of passivation layer on polysilicon or crystalline silicon (c-Si) vs SiN as function of passivation temperature, which suggests dodecyne selectively passivate polysilicon at above 350 °C.TABLE 1

[0111] FIG. 2 illustrate XPS spectra, which confirms formation of the carbon-rich passivation layer only on H terminated polysilicon which was generated by dipping in diluted HF solution and dried with nitrogen.

[0112] As shown in FIG. 3, both dodecyne and 5-phenyl-1 -pentyne show selective passivation on polysilicon allowing selective deposition of aluminum oxide on silicon nitride at 250 °C to 350 °C. FIG. 4 illustrates the selectivity comparison of an alkyne having Formula IA HC^=CR1wherein R1a linear or branched Ge to CM alkyne or arylalkyl such as 5-phenyl-1 -pentyne and 1 -dodecyne at 250 °C with various thickness of aluminum oxide films, demonstrating that the polysilicon surface passivated with 5- phenyl-1 -pentyne shows DoD selectivity up to 80% for 21 A aluminum oxide at 250 °C deposition temperature, which is comparable to 1 -dodecyne.

[0113] The thickness of aluminum oxide on polysilicon (non-growth surface, NGS) and silicon nitride (growth surface, GS) is measured by XRF-XRR thickness calibration, and selectivity is calculated by using formula:„ ,rz.c1„ ,r

[0114] Both FIG. 3 and FIG. 4 indicate 1 -alkynes and 1 -arylalkylalkynes are useful passivating compositions for polysilicon at higher temperatures.

[0115] For purposes of this disclosure and claims, selectivity of the second surface to the first surface is found by the following equation: selectivity = (thickness of film on the second surface (silicon nitride) - thickness of film on the first surface (polysilicon)) / (thickness of film on the second surface (silicon nitride) + thickness of film on the first surface (polysilicon)). In the illustrated embodiments, the deposition selectivity of the second surface to the first surface is greater than about 0.3, more preferably greater than about 0.5 and most preferably greater than about 0.8. Ideally a selectivity of 1 .0 is required for semi-conductor fabrication process.

[0116] FIG. 5 illustrates selective deposition of aluminum oxide films on crystalline silicon and SiN surfaces passivated by two selected 1 -alkyne inhibitors at 250 °C and 350 °C, demonstrating that 1 -alkyne inhibitors successfully passivate crystalline silicon surface while allow deposition of aluminum oxide on silicon nitride surface at both temperatures.

[0117] FIG. 6 illustrates the selectivity comparison of a 5-phenyl-1 -pentyne and 1 - dodecyne at 250 °C and 350 °C, wherein the growth surface is OVD silicon nitride and the non-growth surface is crystalline silicon, demonstrating deposition selectivity is about 0.8 or greater. Surprisingly, 5-phenyl-1 -pentyne shows deposition selectivity is 1 .0 at 250 °G.

[0118] The foregoing description is intended primarily for purposes of illustration. Although the disclosed and claimed subject matter has been shown and described with respect to an exemplary embodiment thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in the form and detail thereof may be made therein without departing from the spirit and scope of the disclosed and claimed subject matter.

[0119] While the principles of the disclosure have been described above in connection with preferred embodiments, it is to be clearly understood that this description is made only by way of example and not as a limitation of the scope of the claimed subject matter.

Claims

CLAIMSWe claim:1 . A method for forming a dielectric film selectively on a substrate comprising:(a) providing the substrate in a reactor and heating to a temperature ranging from about 200 °C to about 700 °C, the substrate having a first surface comprising silicon and a second surface comprising a dielectric or a metal, wherein the first surface comprises Si- H groups and the second surface does not comprise Si-H 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 alkyne having one of the following formulae:wherein R1and R2are each selected from the group consisting of a linear, branched, or cyclic Csto C14 alkyl; a linear, branched, or cyclic C3to Cu alkylsilyl; a Ceto Cu arylalkyl; a linear, branched, or cyclic Ce to Cu alkynyl; and a Ce to Cu arylalkynyl; wherein R1and R2may have one or more carbon-carbon triple bonds;(c) purging the reactor with inert gas;(d) introducing a deposition precursor into the reactor to react with the second surface to form a deposition precursor-containing layer;(e) purging the reactor with inert gas;(f) introducing a vapor comprising an oxygen source or a nitrogen source into the reactor to react with the deposition precursor-containing layer to form the dielectric film;(g) purging the reactor with inert gas; and(h) repeating steps (d) through (g) to deposit a desired thickness of the dielectric film on the second surface of the substrate.

2. The method of claim 1 , wherein the desired thickness of the dielectric film can range from about 1 A to about 100 A, or about 5 A to about 90 A, or about 5 A to about 80 A, or about 5 A to about 70 A or about 5 A to about 60 A, or about 5 A to about 50 A, or about 5 A to about 40 A, or about 5 A to about 30 A or about 5 A to about 20 A.

3. The method of claim 1 , wherein the dielectric film is selected from the group consisting of silicon nitride, silicon carbonitride, silicon oxynitride, aluminum oxide, and combinations thereof.

4. The method of claim 1 , where temperatures for steps (a) to (c) independently range from about 250 °C to about 450 °C, and wherein temperatures for steps (d) to (g) independently range from about 200 °C to about 650 °C.

5. The method of claim 1 , wherein the deposition precursor is a silicon precursor selected from the group consisting of (i) hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane; (ii) hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octaclorotrisiloxane; (iii) 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-butyl-disilazane, 1 ,1 ,1 ,3,3,3-iodo-2-tert-butyl-disilazane,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- methyl-disilazane, 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, and1 ,1 ,3,3-tetrachloro-1 ,3-dimethyl-2-tert-butyldisilazane; (iv) 1 -chloro-1 ,3- disilacyclobutane, 1 -bromo-1 ,3-disilacyclobutane, 1 ,3-dichloro-1 ,3-1 ,3- disilacyclobutane, 1 ,3-dibromo-1 ,3-disilacyclobutane, 1 ,1 ,3-trichloro- 1 ,3- disilacyclobutane, 1 ,1 ,3-tribromo-1 ,3-disilacyclobutane, 1 ,1 ,3,3- tetrachloro-1 ,3-disilacyclobutane, 1 ,1 ,3,3-tetrabromo-1 ,3- disilacyclobutane, 1 ,3-dichloro-1 ,3-dimethyl-1 ,3-disilacyclobutane, 1 ,3- bromo-1 ,3-di methyl-1 ,3-disilacyclobutane, 1 ,1 ,1 ,3,3,5,5,5-octachloro-1 .3.5-trisilapentane, 1 ,1 ,1 ,3,3,5,5,5-octachloro-1 ,3,5-trisilapentane,1 .1 .1 .3.3.5.5.5-octachloro-1 ,5-dimethyl-1 ,3,5-trisilapentane, 1 ,1 ,1 ,5,5,5- hexachloro-3,3-dimethyl-1 ,3,5-trisilapentane, 1 ,1 , 3,5,5, 5-pentachloro-1 .3.5-trimethyl- 1 ,3,5-trisilapentane, 1 ,1 ,1 ,5,5,5-hexachloro-1 ,3,5- trisilapentane, and 1 ,1 ,5,5-tetraachloro-1 ,3,5-trisilapentane.The method of claim 1 , wherein the deposition precursor is a metal precursor selected from the group consisting of trimethylaluminum, triethylaluminum, dimethylaluminum iso-propoxide, diethylaluminum iso- propoxide, tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe2)3), cyclopentadienyltris(methylethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyltris(methylethylamino)hafnium i (MeCpHf(NMeEt)3), ethylcyclopentadienyltris(methylethylamino)hafnium (EtCpHf(NMeEt)3), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt2)3), methylcyclopentadienyltris(diethylamino)hafnium (MeCpHf(NEt2)3), ethylcyclopentadienyltris(diethylamino)hafnium (EtCpHf(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMe2)2), bis(cyclopentadienyl)bis(methylethylamino)hafnium (Cp2Hf(NMeEt)2), bis(methylcyclopentadienyl)bis(methylethylamino)hafnium ((MeCp)2Hf(NMeEt)2), bis(ethylcyclopentadienyl)bis(methylethylamino)hafnium ((EtCp)2Hf(NMeEt)2), bis(cyclopentadienyl)bis(diethylamino)hafnium ((Cp2Hf(NEt2)2), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp)2Hf(NEt2)3), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp)2Hf(NEt2)2), tetrakis(dimethylamino)zirconium (TDM AZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMe2)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMe2)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NMe2)3), cyclopentadienyltris(methylethylamino)zirconium (CpZr(NMeEt)3),methylcyclopentadienyltris(methylethylamino)zirconium(MeCpZr(NMeEt)3), ethylcyclopentadienyltris(methylethylamino)zirconium(EtCpZr(NMeEt)3), cyclopentadienyltris(diethylamino)zirconium(CpZr(NEt2)3), methylcyclopentadienyltris(diethylamino)zirconium(MeCpZr(NEt2)3), ethylcyclopentadienyltris(diethylamino)zirconium(EtCpZr(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)zirconium(Cp2Zr(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NMe2)2), bis(cyclopentadienyl)bis(methylethylamino)zirconium (Cp2Zr(NMeEt)2), bis(methylcyclopentadienyl)bis(methylethylamino)zirconium ((MeCp)2Zr(NMeEt)2), bis(ethylcyclopentadienyl)bis(methylethylamino)zirconium ((EtCp)2Zr(NMeEt)2), bis(cyclopentadienyl)bis(diethylamino)zirconium ((Cp2Zr(NEt2)2), bis(methylcyclopentadienyl)bis(diethylamino)zirconium ((MeCp)2Zr(NEt2)3), bis(ethylcyclopentadienyl)bis(diethylamino)zirconium ((EtCp)2Hf(NEt2)2),(MeNCH2CH2Cp)Hf(NMe2)2, (MeNCH2CH2CH2Cp)Hf(NMe2)2,(MeNCH2CH2Cp)Zr(NMe2)2, (MeNCH2CH2CH2Cp)Zr(NMe2)2,Cp2HfMe(OMe), Cp2ZrMe(OMe), (MeCp)2HfMe(OMe),(MeCp)2ZrMe(OMe), (EtCp)2HfMe(OMe)2, and (EtCp)2ZrMe(OMe).

7. The method of claim 1 , wherein the deposition precursor is an aluminum precursor selected from the group consisting of triethylaluminum, dimethylaluminum iso-propoxide, and diethylaluminum iso-propoxide.

8. The method of claim 1 , wherein the oxygen source is selected from the group consisting of water, ozone, and combinations thereof; or wherein the nitrogen source is selected from the group consisting of ammonia, hydrazine, alkylsubstituted hydrazine, and combinations thereof.

9. The method of claim 1 , wherein the alkyne of Formula IA is selected from the group consisting of 1 -octyne, 1 -nonyne, 1 -decyne, 1 -undecyne, 1 - dodecyne, 1 -tridecyne, 1 -tetradecyne, trimethylsilylacetylene,ethynylbenzene, cyclopropylacetylene, cyclobutylacetylene, cyclopentylacetylene, 3-phenyl-1 -propyne, 4-phenyl-1 -butyne, 5-phenyl-1 - pentyne, 6-phenyl-1 -hexyne, 1 ,3-octadiyne, 1 ,8-nonadiyne, and 1 ,3,5- triethynyl-benzene.

10. The method of claim 1 , wherein the alkyne of Formula IB is selected from the group consisting of 2-octyne, 2-nonyne, 2-decyne, 2-undecyne, 2- dodecyne, 2-tridecyne, and 2-tetradecyne.1 1 . The method of claim 1 , wherein the passivating composition comprises 1 - decyne, 1 -dodecyne, 5-phenyl-1 -pentyne, 1 ,3-octadiyne, 1 ,8-nonadiyne, or 1 ,3,5-triethynyl-benzene.

12. The method of claim 1 , wherein a deposition selectivity of the second surface to the first surface is greater than about 0.3, more preferably greater than about 0.5, and most preferably greater than about 0.8.

13. The method of claim 1 , wherein a preclean step is conducted prior to step (a), the preclean step comprising exposing the first surface to an acid, a reducing environment, heating, or a combination thereof.

14. A method for passivating a silicon-containing surface of a substrate comprising:(a) providing the substrate in a reactor at temperatures ranging from about 200 °C to about 500 °C, the substrate having a first surface comprising a silicon-containing material and a second surface comprising a dielectric or a metal;(b) forming at least one passivation layer on the first surface by exposing both the first surface and the second surfaces to a passivating composition comprising an alkyne having one of the following formulae:IA IB; wherein R1and R2are each selected from the group consisting of a linear, branched, or cyclic C5to C14 alkyl, a linear, branched, or cyclic Cato C14 alkylsilyl; a Ceto C14 arylalkyl; a linear, branched,or cyclic Ce to Cu alkynyl; a Ce to Cu arylalkynyl; wherein R1and R2may have one or more carbon-carbon triple bond; and (c) purging the reactor with inert gas.

15. The method of claim 14, wherein steps (b) to (c) are repeated to provide a fully covered passivation layer on the first surface.

16. The method of claim 14, wherein the first surface comprises polysilicon, amorphous silicon, crystalline silicon, amorphous silicon germanium, polycrystalline silicon germanium, crystalline silicon germanium polycrystalline germanium, or crystalline germanium.

17. The method of claim 14, wherein the second surface comprises a nitride chosen from the group consisting of silicon nitride, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and combinations thereof; or wherein the second surface comprises a metal chosen from the group consisting of copper, cobalt, ruthenium, molybdenum, tungsten, and combination thereof.

18. The method of claim 14, wherein the first surface is selected from the group consisting of polysilicon, amorphous silicon, crystalline silicon, amorphous silicon germanium, polycrystalline silicon germanium, and crystalline silicon germanium; and wherein the second surface is selected from the group consisting of silicon nitride, silicon oxide, carbon doped silicon oxide, and combinations thereof.

19. The method of claim 14, wherein the alkyne of Formula IA is selected from the group consisting of 1 -octyne, 1 -nonyne, 1 -decyne, 1 -undecyne, 1 - dodecyne, 1 -tridecyne, 1 -tetradecyne, trimethylsilylacetylene, ethynylbenzene, cyclopropylacetylene, cyclobutylacetylene, cyclopentylacetylene, 3-phenyl-1 -propyne, 4-phenyl-1 -butyne, 5-phenyl-1 - pentyne, 6-phenyl-1 -hexyne, 1 ,3-octadiyne, 1 ,8-nonadiyne, and 1 ,3,5-triethynyl-benzene.

20. The method of claim 14, wherein the alkyne of Formula IB is selected from the group consisting of 2-octyne, 2-nonyne, 2-decyne, 2-undecyne, 2- dodecyne, 2-tridecyne, and 2-tetradecyne.21 . The method of claim 14, wherein the passivating composition comprises 1 - decyne, 1 -dodecyne, 5-phenyl-1 -pentyne, 1 ,3-octadiyne, 1 ,8-nonadiyne, or 1 ,3,5-triethynyl-benzene.

22. The method of claim 14, wherein a preclean step is conducted prior to step (a), the preclean step comprising by exposing the substrate to H2or hydrogen plasma at a temperature ranging from about 200 °C to about 500 °C .

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