WO2025210255A1 - Selective passivation of silicon oxide containing films utilizing organoamino-alkoxysilanes - Google Patents

Selective passivation of silicon oxide containing films utilizing organoamino-alkoxysilanes

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Publication number
WO2025210255A1
WO2025210255A1 PCT/EP2025/059336 EP2025059336W WO2025210255A1 WO 2025210255 A1 WO2025210255 A1 WO 2025210255A1 EP 2025059336 W EP2025059336 W EP 2025059336W WO 2025210255 A1 WO2025210255 A1 WO 2025210255A1
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Prior art keywords
dimethylsilane
iso
methylsilane
dimethylamino
propoxy
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French (fr)
Inventor
Xinjian Lei
Matthew R. Macdonald
Po-Chun Liu
Marisa GLIEGE
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Merck Patent GmbH
Versum Materials US LLC
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Merck Patent GmbH
Versum Materials US LLC
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Publication of WO2025210255A1 publication Critical patent/WO2025210255A1/en
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    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/61—Formation of materials, e.g. in the shape of layers or pillars of insulating materials using masks
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6336—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
    • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
    • H10P14/6681—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si
    • H10P14/6687—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/6903—Inorganic materials containing silicon
    • H10P14/6905—Inorganic materials containing silicon being a silicon carbide or silicon carbonitride and not containing oxygen, e.g. SiC or SiC:H
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/6922—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H10P14/6927—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/6928—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
    • H10P14/6929—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing aluminium, e.g. AlSiOx
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69391—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing aluminium, e.g. Al2O3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/694—Inorganic materials composed of nitrides
    • H10P14/6943—Inorganic materials composed of nitrides containing silicon
    • H10P14/69433—Inorganic materials composed of nitrides containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass

Definitions

  • the present application relates to selectively form a passivation layer on a first surface of a substrate relative to a second surface.
  • further processing can be used to subsequently deposit a different material on the second surface relative to the first.
  • steps (b) to (c) are repeated to provide a fully covered passivation layer on the first surface.
  • the first surface is selected from the group consisting of silicon oxide and carbon doped silicon oxide, and wherein the second surface is selected from the group consisting of silicon nitride.
  • the organoamino-alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, di-iso-propylamino(methoxy)dimethylsilane, pyrrolidino(methoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, cyclohexylmethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, diethylamino(phenoxy)dimethylsilane, di-iso-propylamino
  • the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethyl methylamino(dimethoxy) methylsilane, diethylamino(dimethoxy)methylsilane, di-iso-propylamino(dimethoxy)methylsilane, pyrrolidino(dimethoxy) methylsilane, piperidino(dimethoxy) methylsilane, pyrrolyl(dimethoxy)methylsilane, cyclohexylmethylamino(dimethoxy)methylsilane, dimethylamino(diphenoxy)methylsilane, ethylmethylamino(diphenoxy)methylsilane, diethylamino(diphenoxy)methylsilane, di-iso-propylamino(diphenoxy)methyls
  • the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethylmethylamino(dimethoxy) methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
  • the halides comprise chloride.
  • the chloride, if present are present at a concentration of 50 ppm or less as measured by IC.
  • the chloride, if present are present at a concentration of 10 ppm or less as measured by IC.
  • the chloride if present, are present at a concentration of 5 ppm or less as measured by IC.
  • the organoamino- alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dethylethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(sec-butoxy)
  • the organoamino- alkoxysilane is chosen from the group consisting of dimethylamino(dimethoxy)methylsilane, ethyl methylamino(dimethoxy) methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
  • the organoamino- alkoxysilane is chosen from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dimethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, and dimethylamino(diethoxy)methylsilane.
  • the embodiments of the disclosure can be used alone or in combination with each other.
  • FIG. 1 illustrates an exemplary embodiment of an area selective deposition method comprising: an optional surface pre-clean, selective passivation, and selective deposition wherein a dielectric film is selectively deposited on a dielectric film, while first surface (comprising a metal) and second surface (comprising a barrier material) are passivated;
  • FIG. 2 illustrates an exemplary process comprising: an optional surface preclean, selective passivation, and selective deposition wherein a dielectric film is selectively deposited on a silicon dioxide film, while the first surface (comprising copper) and the second surface (comprising tantalum nitride) are passivated;
  • FIG. 3 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 150°C deposition temperature;
  • FIG. 4 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 200°C deposition temperature;
  • FIG. 5 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 150°C deposition temperature; and
  • FIG. 6 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 200°C deposition temperature.
  • Embodiments of the disclosure are directed to methods that employ surface deactivation by taking advantage of the surface chemistry of two different surfaces. Since two different surfaces will have different reactive handles, the differences can be taken advantage of by utilizing molecules that will react with one surface (to deactivate that surface) and not react with the other surface.
  • 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 as gate dielectrics and capacitor dielectrics would also be of great utility in semiconductor device manufacturing.
  • a method for passivating a silicon-containing surface comprising predominantly hydroxyl groups comprises: (a) providing the substrate in a reaction vessel at temperatures ranging from 20°C to 800°C, the substrate having a first surface comprising a dielectric material with hydroxyl groups and a second surface comprising a dielectric material or metal with much less amount of hydroxyl groups; (b) forming at least one passivated layer on the first surface by exposing the first surface and the second surface to a passivating composition comprising an organoamino-alkoxysilane having one of the following formulae:
  • R 1 and R 2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R 3 and R 4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R 3 and R 4 cannot be both hydrogen; and either R 3 and R 4 are linked to form a cyclic ring structure or R 3 and R 4 are not linked to form a cyclic ring structure; (c) purging the reactor with inert gas; Steps (b) and (c) can be repeated to achieve self-limiting monolayer coverage of the first surface.
  • the organoamino-alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, di-iso-propylamino(methoxy)dimethylsilane, pyrrolidino(methoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, cyclohexylmethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, diethylamino(phenoxy)dimethylsilane, di-iso-propylamino(phenoxy)dimethyl
  • the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dethylethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(sec-butoxy)dimethylsilane,
  • the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethylmethylamino(dimethoxy)methylsilane, diethylamino(dimethoxy)methylsilane, di-iso-propylamino(dimethoxy)methylsilane, pyrrolidino(dimethoxy) methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, cyclohexylmethylamino(dimethoxy)methylsilane, dimethylamino(diphenoxy)methylsilane, ethylmethylamino(diphenoxy)methylsilane, diethylamino(diphenoxy)methylsilane, di-iso-propylamino(diphenoxy)methylsilane, pyrrolidino(
  • the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethylmethylamino(dimethoxy)methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
  • the passivating composition comprises an organoamino-alkoxysilane chosen from the group consisting of:
  • the first surface is a silicon-containing material comprising predominantly hydroxyl groups is selected from the group consisting of silicon oxide and carbon doped silicon oxide, while the second surface comprising a dielectric material is selected from the group consisting of silicon nitride, amorphous silicon.
  • the second surface may comprise a metal, including 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.
  • a method for selective deposition of silicon nitride, carbon doped silicon nitride, or silicon oxynitride comprises: (a) providing the substrate in a reaction vessel at temperature at 600 °C or higher, the substrate having a first surface comprising a dielectric material with hydroxyl groups and a second surface comprising a different dielectric material or metal with fewer hydroxyl groups, wherein the second surface preferably comprises silicon nitride;
  • R 1 and R 2 are each independently selected from a Ci to Cw alkyl group, a C3 to C10 cyclic alkyl group, Cg to Cw aryl group;
  • R 3 and R 4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R 3 and R 4 cannot be both hydrogen; and either R 3 and R 4 are linked to form a cyclic ring structure or R 3 and R 4 are not linked to form a cyclic ring structure;
  • 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 tertbutylamine, dimethylamine, diethylamine, iso-propylamine, diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and an alkoxyamine such as ethanolamine plasma, and mixtures thereof.
  • the nitrogen-containing source comprises an ammonia plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium or a plasma comprising hydrogen and nitrogen source gas.
  • the halogenated silicon-containing compounds can be selected from the group consisting of: (i) halogenated silanes, (ii) halogenated siloxanes, (iii) halogenated silazanes, and (iv) halogenated carbosilanes.
  • the halogenated silanes of group (i) include but are not limited to, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, trichlorosilane, tetrachlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.
  • dielectric materials such as silicon nitride
  • dielectric materials such as silicon nitride
  • SiN growth surface, GS is measured by XRF-XRR thickness calibration
  • the deposited film is a silicon-containing film.
  • the deposited dielectric materials include silicon nitride, carbon doped silicon nitride, and silicon dioxide films.
  • the deposited film is an aluminum-containing film.
  • the selectivity is defined as (the thickness of aluminum-containing film on the silicon nitride material - the thickness of aluminum-containing film on the silicon dioxide dielectric material)/(the thickness of aluminum-containing film on the silicon nitride material + the thickness of silicon-containing film on the silicon dioxide dielectric material).
  • the selectivity is preferred to be 30% or greater, or 40% or greater, or 50% or greater, 60% or greater.
  • a novel, and non- obvious, selective thermal atomic layer deposition process that selectively deposits aluminum-containing dielectric materials on top of a dielectric material relative to a metal, in an ALD reactor.
  • This method comprises:
  • R 1 and R 2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group;
  • R 3 and R 4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R 3 and R 4 cannot be both hydrogen; and either R 3 and R 4 are linked to form a cyclic ring structure or R 3 and R 4 are not linked to form a cyclic ring structure;
  • Steps (d) to (g) may be repeated to deposit a desired aluminum-containing dielectric films on top of the dielectric material.
  • step (b) and (c) can be repeated to allow a self-limiting monolayer passivation layer on the first surface before Step (d) to (g) are repeated to deposit a desired aluminum oxide.
  • step (b) and (c) can be conducted after Step (d) to (g) are repeated to deposit a desired aluminum oxide, followed by repeating Step (d) to (g) to provide a thicker aluminum oxide.
  • the alkoxysilanol is selected from the group consisting of tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, bis(tert-butoxy)(tert- pentoxy)silanol, and bis(tert-pentoxy)(tert-butoxy)silanol.
  • embodiment of the disclosure provides a process to deposit a silicon-containing film comprising steps of:
  • R 1 and R 2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R 3 and R 4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R 3 and R 4 cannot be both hydrogen; and either R 3 and R 4 are linked to form a cyclic ring structure or R 3 and R 4 are not linked to form a cyclic ring structure
  • steps b through e are repeated until a desired thickness of film is deposited.
  • the oxygen source is selected from water (H2O) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide, oxygen (O2), oxygen plasma, ozone (O3), N2O, N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma, hydrogen/oxygen, and combinations thereof.
  • H2O water
  • the organoamino-alkoxysilane precursor compound should have at least one anchoring functionality, which reacts with certain reactive sites on the substrate surface to anchor a monolayer of silicon species.
  • the anchoring functionality of a smaller organoamino group such as dimethylamino, ethylmethylamino or diethylamino allow the organoamino-alkoxysilane to have a relatively low boiling point and a relatively high reactivity.
  • the organoamino- alkoxysilane precursor compound should also have a passive functionality in that it is chemically stable to prevent further surface reaction, leading to a self-limiting process.
  • the passivating functionality is selected from different alkyl groups such methoxy groups. The remaining groups on the surface can then be oxidized to form silicon-containing layer as well as hydroxyl groups.
  • hydroxyl sources such as H2O or water plasma can also be introduced into the reactor to form more hydroxyl groups as reactive sites for the next ALD cycle.
  • the substrate temperatures for the method described herein use one or more of the following temperatures as endpoints: 20 °C, 50 °C, 75 °C, 100 °C, 125 °C, 150 °C, 175 °C, 200 °C, 225 °C, 250 °C, 275 °C, 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, 425 °C, 450 °C, 500 °C, 525 °C, 550 °C,
  • 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.
  • 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.
  • 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 bake the substrate surface.
  • 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.
  • the first substrate surface will comprise a metal
  • the second substrate surface will comprise a dielectric, or vice versa.
  • a substrate surface may comprise certain functionality (e.g., -OH, -NH, etc.).
  • the films that can be used in the methods described herein are quite varied.
  • the films may comprise, consist of, 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.
  • 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.
  • the film comprises a dielectric. Examples include, SiO 2 , carbon doped silicon oxide, SiN, HfO 2 , ZrO 2 etc.
  • 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 (non-passivated) 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.
  • 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.
  • the method of the present disclosure includes the optional step of contacting the surface of the substrate with a wet chemical composition to obtain a treated substrate.
  • exemplary wet chemical treatments include known chemical treatments such as, for example, RCA clean chemicals SC-1 and SC-2, aqueous HF, peroxide, H2SO4 / H2O2, NH4OH, buffered HF solutions, and mixtures thereof.
  • 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 hydrogen peroxide 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.
  • 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.
  • 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.
  • Embodiments also include the step of drying at least the surface of the substrate after the rinsing step.
  • the drying step is typically carried out by any suitable means, for example, the application of heat, iso-propyl alcohol (IPA) vapor drying, or by centripetal force.
  • IPA iso-propyl alcohol
  • 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, HF, CIF3, 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.
  • 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.
  • alkyl means a saturated hydrocarbon group which is straight-chained or branched.
  • 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.
  • 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.
  • alkenyl group denotes a group which has one or more carbon-carbon double bonds and has from 2 to 18 or from 2 to 10 carbon atoms.
  • alkenyl groups include, but are not limited to, vinyl or allyl groups.
  • a I kynyl means a straight or branched alkyl group having 2 to 20 carbon atoms and one or more triple carbon-carbon bonds.
  • 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.
  • alkynyl groups include, but are not limited to, acetylene, 1-propylene, 2-propylene, and the like.
  • the phrase "optionally substituted” means that a substitution is optional and, therefore, includes both unsubstituted and substituted atoms and moieties.
  • a "substituted" atom or moiety indicates that any hydrogen atom on the designated compound or moiety can be replaced with a selection from the indicated substituent groups, provided that the normal valency of the designated compound or moiety is not exceeded, and that the substitution results in a stable compound. For example, if a methyl group is optionally substituted, then 1, 2, or 3 hydrogen atoms on the carbon atom within the methyl group can be replaced with 1, 2, or 3 of the recited substituent groups.
  • phenyl means -CgHs.
  • a phenyl group can be unsubstituted or substituted with one, two, or three suitable substituents.
  • halo means halogen groups and includes, but is not limited to, fluoro, chloro, bromo, and iodo.
  • R 3 and R 4 are linked to form a cyclic ring structure
  • cyclic ring structures refers a cyclic ring via forming C-C bond.
  • cyclic ring structures include, but not limited to, pyrrolidino, pyrrolyl, piperidino.
  • 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.
  • reactive gas 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.
  • 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 conjunction with 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).
  • 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.
  • 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.
  • the temperature range of the reactions may be between room temperature and 800° C. In some cases, the temperature range of the reactions may be between room temperature and 650 °C. In yet other cases, the temperature range of the reactions may be between room temperature and 100° C.
  • the pressure may range from 10-10 Torr to 3000 Torr and may be maintained under dynamic flow conditions (i.e., with a valve and a butterfly valve type arrangement) or may be maintained under static conditions (i.e., an evacuated chamber is exposed to the desired precursor(s) and / or co-reactant(s) until a total desired pressure 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 evacuated fully and reexposed to fresh precursor(s) and / or co-reactants as many times as necessary. Precursor(s) and / or co-reactants may be introduced using any mixtures and / or concentrations desired.
  • 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, and Ar, but also other gases such as Hzmay be used.
  • 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.
  • 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.
  • 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.
  • the organoamino-alkoxysilane having formula IA or IB is substantially free of impurities that may react with metallic surface during a passivation process. In one embodiment, the organoamino-alkoxysilane having formula IA or IB is substantially free of impurities that react with precursors during a deposition process.
  • the organoamino-alkoxysilane having formula IA or IB is substantially free of impurities that passivate non-metallic surface and suppress growth on non-metallic surface.
  • the organoamino-alkoxysilane having formula IA or IB is substantially free of halogen-containing impurities.
  • the halogen-containing impurities are one or more of a fluorohydrocarbon, a chlorohydrocarbon, a bromohydrocarbon and an iodohydrocarbon.
  • the organoamino-alkoxysilane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 1000 ppm.
  • the organoamino-alkoxysilane 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 organoamino-alkoxysilane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 100 ppm. In one aspect of this embodiment, the organoamino-alkoxysilane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 50 ppm.
  • the organoamino-alkoxysilane 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 organoamino- alkoxysilane having formula IA or IB has a residual concentration of halogencontaining impurities of less than about 10 ppm. In one aspect of this embodiment, the organoamino-alkoxysilane having formula IA or IB is free of halogen-containing impurities.
  • the residual concentration of halogen-containing 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 (IR), 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
  • the residual concentration of halogencontaining impurities is detected by one or more of GC-MS, GC-ICP-MS, GC-ICP-OES, GC-FID, GC-ECD, HPLC and UV/Vis.
  • the organoamino-alkoxysilane having formula IA or IB is purified by exposure to molecular sieves. In one embodiment, the organoamino- alkoxysilane having formula IA or IB is purified by exposure to silica gel. In one embodiment, the organoamino-alkoxysilane having formula IA or IB is purified by exposure to one or more adsorbent materials.
  • the organoamino-alkoxysilane having formula IA or IB is purified by treatment with one or more group 1 metal followed by a distillation process.
  • the organoamino-alkoxysilane is treated with metallic sodium.
  • the metal and the organoamino-alkoxysilane are separated by filtration and the organoamino- alkoxysilane is distilled to remove non-volatile products of the reaction of impurities with metals.
  • the organoamino-alkoxysilane having formula IA or IB is purified by exposure to activated carbon.
  • the organoamino-alkoxysilane is separated by filtration and is distilled to remove nonvolatile products after treatment with activated carbon.
  • diethylamine 160 g, 2.2 mol was added dropwise over 6 hours to a stirred mixture of diethoxymethylsilane (267 g, 2.0 mol), THF (100 mL), and Ru3(CO)i2 (3.18 g, 0.00497 mol) at 45 °C in a 1-liter 3-neck roundbottom flask. The flask was vented to allow the hydrogen to be released. After the addition, the reaction mixture was continued to stir at 60 °C for 2 hours, then allowed to stir overnight at room temperature. The low-boilers were removed under reduced pressure, and crude product was collected by vacuum-transfer.
  • Silicon-containing film can be deposited via a typical ALD or PEALD process comprising the following steps: a. introducing vapors of DEADEOMS into an ALD chamber loaded with substrate for a layer of silicon-containing moieties on the substrate; b. purging with inert gas to remove any unreacted DEADEOMS; c. introducing ozone as oxygen-containing source to react with the layer of silicon- containing moieties to form a silicon-containing layer; d. purging with inert gas. Steps a to d are repeated until a desired thickness of silicon-containing film is achieved. It is expected the resulting silicon-containing film contains silicon, oxygen, and carbon depending on the deposition parameters, such as substrate temperature, ozone concentration.
  • Silicon-containing film can be deposited via a typical ALD or PEALD process comprising the following steps: a. introducing vapors of DMAMODMS into an ALD chamber loaded with substrate for a layer of silicon-containing moieties on the substrate; b. purging with inert gas to remove any unreacted DEADEOMS; c. introducing ozone as oxygen-containing source to react with the layer of silicon- containing moieties to form a silicon-containing layer; d. purging with inert gas. Steps a to d are repeated until a desired thickness of silicon-containing film is achieved. It is expected the resulting silicon-containing film contains silicon, oxygen, and carbon depending on the deposition parameters, such as substrate temperature, ozone concentration.
  • Example 14 Deposition of silicon-containing film using dimethylamino(phenoxy)dimethylsilane (DMAPODMS)
  • Silicon-containing film can be deposited via a typical ALD or PEALD process comprising the following steps: a. introducing vapors of DMAPODMS into an ALD chamber loaded with substrate for a layer of silicon-containing moieties on the substrate; b. purging with inert gas to remove any unreacted DEADEOMS; c. introducing ozone as oxygen-containing source to react with the layer of si I iconcontaining moieties to form a silicon-containing layer; d. purging with inert gas. Steps a to d are repeated until a desired thickness of silicon-containing film is achieved. It is expected the resulting silicon-containing film contains silicon, oxygen, and carbon depending on the deposition parameters, such as substrate temperature, ozone concentration.
  • Organoamino-alkoxysilanes selectively passivates the dielectric layer surface (preferably SiOz) versus the second surface (which may be a different silicon- containing material or a metal). This process is depicted in FIG. 1. The process results in the selectivity to grow thicker dielectric film on the second surface.
  • the substrate 100 comprises: a dielectric layer, forming a first surface 102 and a different silicon-containing material or a metal, forming a second surface 104.
  • the first surface 102 and the second surface 104 are coplanar.
  • Step 1 comprises a precleaning of the first surface 102 (comprising a dielectric material) and the second surface 104 (comprising a different silicon- containing material or a metal) of a substrate 100, preferably with an acid, Hz, high temperature, or a combination thereof.
  • the first surface 102 and the second surface 104 are preferably coplanar, as a result of a chemical mechanical planarization (CMP) as shown in FIG. 1 prior to the precleaning step.
  • CMP chemical mechanical planarization
  • Step 2 comprises passivation of the first surface 102 and the second surface 104, which may be a metal nitride, by exposing the first surface 102 and the second surface 104 to the organoamino-alkoxysilane to form a passivating/blocking organic layer 106 employing a passivating composition.
  • Step 3 includes selectively depositing the aluminum containing dielectric layer 108 on the second surface 104 (comprising a dielectric), preferably by ALD of an aluminum precursor and a second precursor comprising oxygen or an alkoxysilanol.
  • the substrate 200 comprises: a dielectric layer (SiCh), forming a first surface 202 and a further silicon- containing material (SiN) forming a second surface 204.
  • SiCh dielectric layer
  • SiN silicon- containing material
  • the first surface 202 and the second surface 204 are coplanar.
  • Step 1 comprises a precleaning of the first surface (SiO?) 202 and the second surface (SiN) 204 of the substrate 200, preferably with an acid, H2, high temperature, or a combination thereof.
  • the first surface 202 and the second surface 204 are coplanar, as a result of a chemical mechanical planarization (CMP) as shown in FIG. 2 prior to the precleaning step.
  • CMP chemical mechanical planarization
  • Step 2 comprises passivation of the first surface comprising a dielectric (SiCh) and the second surface comprising a second material (silicon nitride) to form a passivating/blocking organic layer 206 employing a passivating composition.
  • Step 3 includes depositing the aluminum containing dielectric layer 208 on the second surface 204 (SiN), preferably by ALD of an aluminum precursor and a second precursor comprising oxygen or an alkoxysilanol.
  • the DFT calculations were carried out in Biovia Materials Studio R2022 and the Dmol3 application was used as the DFT calculator.
  • the BLYP functional and DNP basis set were chosen for the calculations.
  • a slab model of SiO2 was created with OH termination as the active sites. Periodic boundary conditions were included to capture the effects of multiple active sites.
  • Eproducts - EReactants was applied to the isolated reactants and formed products.
  • EA the energy of the transition state between the inhibitor and SiO? slab was first calculated and then the equation E-rransitionstate - EReactant was applied.
  • the surface coverage simulations were carried out using a semi-empirical method employed in the xTB-GFN software. To evaluate surface coverage, an SiO2 slab was created with 21 active sites. The inhibitor surface product was packed on the SiO2 slab, resembling a reacted inhibitor bonded with an active site. The surface product were packed as tightly as possible while considering steric effects. The initial models were then equilibrated in xTB-GFN and underwent a DFT-MD (molecular dynamics) simulation for lOps. The final trajectories were analyzed for successful surface coverage by various mechanisms.
  • DFT-MD molecular dynamics
  • Table 2 shows the results of the DFT calculations and surface coverage simulations for dimethylaminotrimethylsilane (DMATMS), dimethylamino(methoxy)dimethylsilane (DMAMODMS), dimethylamino(phenoxy)dimethylsilane (DMAPODMS), and dimethylamino(dimethoxy)methylsilane (DMADMOMS), indicating DMAMODMS and DMAPODMS are more reactive and provide much higher surface coverage than known passivation agent DMATMS, while DMADMOS provides similar surface coverage as DMATMS.
  • the total of reactive sites for the surface coverage simulations is 21 on silicon oxide surface.
  • the second surface comprising, for example, silicon oxide
  • the second surface comprising, for example, silicon oxide
  • the second surface is active for further selective reactions such as, for example, a selective ALD deposition of alumina-containing film on the silicon oxide surface.
  • 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.
  • Example 16 Selective deposition of a dielectric film on passivated vs non-passivated silicon oxide surfaces.
  • Thermal silicon oxide substrates were passivated by dimethylaminotrimethylsilane (DMATMS) and diethylamino(diethoxy)methylsilane (DEADEOMS), followed by atomic layer deposition of aluminum oxide using dimethylaluminum iso-propoxide (DMAI) and water ALD process at 150 and 200°C, respectively.
  • DMATMS dimethylaminotrimethylsilane
  • DEADEOMS diethylamino(diethoxy)methylsilane
  • DMAI dimethylaluminum iso-propoxide
  • the thickness of aluminum oxide on silicon oxide, DMATMS passivated silicon oxide and DEADEOMS passivated silicon oxide were measured by XRF-XRR thickness calibration, and selectivity was calculated by using formula:
  • FIG. 3 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide, and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 150°C deposition temperature;
  • FIG. 4 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide, and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 200°C deposition temperature;
  • FIG. 5 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 150°C deposition temperature; and
  • FIG. 6 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 200°C deposition temperature.

Abstract

A method for selectively passivating a surface of a substrate, wherein the surface of the substrate includes at least a first surface comprising a dielectric and at least a second surface comprising another dielectric material or metal. The method includes the step of exposing the first and second surfaces to at least one the organoamino-alkoxysilane selectively reacts with the dielectric to passivate the first surface thereby leaving the second surface substantially unreacted.

Description

SELECTIVE PASSIVATION OF SILICON OXIDE CONTAINING FILMS UTILIZING
ORGANOAMINO-ALKOXYSILANES
CROSS-REFERENCE TO RELATED APPLICATIONS
[001] This application claims priority to United States Provisional Patent Application number 63/575,106, filed on April 5, 2024, the entire contents of which are incorporated by reference.
FIELD
[002] The present application relates to selectively form 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.
BACKGROUND
[003] 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 as gate dielectrics and capacitor dielectrics would also be of great utility in semiconductor device manufacturing.
[004] 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.
[005] Selectively passivation of a dielectric comprising hydroxyls over another material to achieve ASD of dielectric on other materials 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 a dielectric comprising hydroxyls over another material to successfully allow the atomic layer deposition of dielectric films on the other dielectric.
[006] 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
[007] In a first main aspect, a method for passivation of a surface of dielectric having hydroxyl groups is provided. The method comprising: (a) providing the substrate in a reaction vessel at temperatures ranging from 20°C to 600°C, the substrate having a first surface comprising a dielectric material and a second surface comprising a different silicon-containing material or a metal; (b) forming at least one passivation layer on the first surface by exposing a composition comprising an organoamino-alkoxysilane having one of the following formulae:
IA IB wherein R1 and R2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; and (c) purging the reactor with inert gas.
[008] In a further aspect of the first main aspect, steps (b) to (c) are repeated to provide a fully covered passivation layer on the first surface.
[009] In a further aspect of the first main aspect, the second surface comprises a metal or metalloid chosen 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 wherein the second surface comprises a metal nitride chosen 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.
[0010] In a further aspect of the first main aspect, the first surface is selected from the group consisting of silicon oxide and carbon doped silicon oxide, and wherein the second surface is selected from the group consisting of silicon nitride.
[0011] In a further aspect of the first main aspect, the organoamino-alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, di-iso-propylamino(methoxy)dimethylsilane, pyrrolidino(methoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, cyclohexylmethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, diethylamino(phenoxy)dimethylsilane, di-iso-propylamino(phenoxy)dimethylsilane, pyrrolidino(phenoxy)dimethylsilane, piperidino(phenoxy)dimethylsilane, pyrrolyl(phenoxy)dimethylsilane, cyclohexylmethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, di-iso-propylamino(ethoxy)dimethylsilane, pyrrolidino(ethoxy)dimethylsilane, piperidino(ethoxy)dimethylsilane, pyrrolyl(ethoxy)dimethylsilane, cyclohexylmethylamino(ethoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, ethylmethylamino(n- propoxy)dimethylsilane, diethylamino(n-propoxy)dimethylsilane, di-iso- propylamino(n-propoxy)dimethylsilane, pyrrolidino(n-propoxy)dimethylsilane, piperidino(n-propoxy)dimethylsilane, pyrrolyl(n-propoxy)dimethylsilane, cyclohexylmethylamino(n-propoxy)dimethylsilane, dimethylamino(iso- propoxy)dimethylsilane, ethylmethylamino(iso-propoxy)dimethylsilane, diethylamino(iso-propoxy)dimethylsilane, di-iso-propylamino(iso- propoxy)dimethylsilane, pyrrolidino(iso-propoxy)dimethylsilane, piperidino(iso- propoxy)dimethylsilane, pyrrolyl(iso-propoxy)dimethylsilane, cyclohexylmethylamino(iso-propoxy)dimethylsilane, dimethylamino(sec- butoxy)dimethylsilane, ethylmethylamino(sec-butoxy)dimethylsilane, diethylamino(sec-butoxy)dimethylsilane, di-iso-propylamino(sec- butoxy)dimethylsilane, pyrrolidino(sec-butoxy)dimethylsilane, piperidino(sec- butoxy)dimethylsilane, pyrrolyl(sec-butoxy)dimethylsilane, cyclohexylmethylamino(sec-butoxy)dimethylsilane dimethylamino(cyclopentoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, diethylamino(cyclopentoxy)dimethylsilane, di-iso- propylamino(cyclopentoxy)dimethylsilane, pyrrolidino(cyclopentoxy)dimethylsilane, piperidino(cyclopentoxy)dimethylsilane, pyrrolyl(cyclopentoxy)dimethylsilane, cyclohexylmethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclohexoxy)dimethylsilane, diethylamino(cyclohexoxy)dimethylsilane, di-iso- propylamino(cyclohexoxy)dimethylsilane, pyrrolidino(cyclohexoxy)dimethylsilane, piperidino(cyclohexoxy)dimethylsilane, cyclohexylmethylamino(cyclohexoxy)dimethylsilane, dimethylamino(methoxy)diethylsilane, ethylmethylamino(methoxy)diethylsilane, diethylamino(methoxy)diethylsilane, di-iso-propylamino(methoxy)diethylsilane, pyrrolidino(methoxy)diethylsilane, piperidino(methoxy)diethylsilane, pyrrolyl(methoxy)diethylsilane, cyclohexylmethylamino(methoxy)diethylsilane, dimethylamino(phenoxy)diethylsilane, ethylmethylamino(phenoxy)diethylsilane, diethylamino(phenoxy)diethylsilane, di-iso-propylamino(phenoxy)diethylsilane, pyrrolidino(phenoxy)diethylsilane, piperidino(phenoxy)diethylsilane, pyrrolyl(phenoxy)diethylsilane, cyclohexyl methyla mi no(phenoxy)diethylsilane, dimet ylarriino(ethoxy)diethylsilane, ethylmet ylarriino(ethoxy)diethylsilane, diet ylarriino(ethoxy)diethylsilane, di-iso-propylarriino(ethoxy)diethylsilane, pyrrolidino(ethoxy)diethylsilane, piperidino(ethoxy)diethylsilane, pyrrolyl(ethoxy)diethylsilane, cyclohexylmet ylarriino(ethoxy)diethylsilane, diet ylamino(n-propoxy)diethylsilane, ethyl met y la mino(n-propoxy)diethylsilane, diethylarriino(n-propoxy)diethylsilane, di-iso-propylarriino(n-propoxy)diethylsilane, pyrrolidino(n-propoxy)diethylsilane, piperidino(n-propoxy)diethylsilane, pyrrolyl(n- propoxy)diethylsilane, cyclohexyl methyla mino(n-propoxy)diethylsilane, dimethylamino(iso-propoxy)diethylsilane, ethylmethylamino(iso- propoxy)diethylsilane, diethylamino(iso-propoxy)diethylsilane, di-iso- propylamino(iso-propoxy)diethylsilane, pyrrolidino(iso-propoxy)diethylsilane, piperidino(iso-propoxy)diethylsilane, pyrrolyl(iso-propoxy)diethylsilane, cyclohexyl methy la mino(iso-propoxy)diethylsilane, dimethylamino(sec- butoxy)diethylsilane, ethylmethylamino(sec-butoxy)diethylsilane, diethylamino(sec- butoxy)diethylsilane, di-iso-propylamino(sec-butoxy)diethylsilane, pyrrolidino(sec- butoxy)diethylsilane, piperidino(sec-butoxy)diethylsilane, pyrrolyl(sec- butoxy)diethylsilane, cyclohexylmethylamino(sec-butoxy)diethylsilane, dimethylamino(cyclopentoxy)diethylsilane, ethylmethylamino(cyclopentoxy)diethylsilane, diethylamino(cyclopentoxy)diethylsilane, di-iso- propylamino(cyclopentoxy)diethylsilane, pyrrolidino(cyclopentoxy)diethylsilane, piperidino(cyclopentoxy)diethylsilane, pyrrolyl(cyclopentoxy)diethylsilane, cyclohexylmethylamino(cyclopentoxy)diethylsilane, dimethylamino(cyclohexoxy)diethylsilane, ethylmethylamino(cyclohexoxy)diethylsilane, diethylamino(cyclohexoxy)diethylsilane, di-iso- propylamino(cyclohexoxy)diethylsilane, pyrrolidino(cyclohexoxy)diethylsilane, piperidino(cyclohexoxy)diethylsilane, cyclohexyl methy la mino(cyclohexoxy)diethylsilane, dimethylamino(methoxy)di-iso-propylsilane, ethyl met hyla mino(methoxy)di-iso- propylsilane, diethylamino(rriethoxy)di-iso-propylsilane, di-iso- propylamino(methoxy)di-iso-propylsilane, pyrrolidino(rriethoxy)di-iso-propylsilane, piperidino(methoxy)di-iso-propylsilane, pyrrolyl(rriethoxy)di-iso-propylsilane, cyclohexyl methy la rriino(rriethoxy)di-iso-propylsilane, dimethylamino(phenoxy)di-iso- propylsilane, ethylmethylamino(phenoxy)di-iso-propylsilane, diethylamino(phenoxy)di-iso-propylsilane, di-iso-propylamino(phenoxy)di-iso- propylsilane, pyrrolidino(phenoxy)di-iso-propylsilane, piperidino(phenoxy)di-iso- propylsilane, pyrrolyl(phenoxy)di-iso-propylsilane, cyclohexyl methy la mino(phenoxy)di-iso-propylsilane, dimethylamino(ethoxy)di-iso- propylsilane, ethyl methylamino(ethoxy)di-iso-propylsilane, diethylamino(ethoxy)di- iso-propylsilane, di-iso-propylamino(ethoxy)di-iso-propylsilane, pyrrolidino(ethoxy)di-iso-propylsilane, piperidino(ethoxy)di-iso-propylsilane, pyrrolyl(ethoxy)di-iso-propylsilane, cyclohexyl methylamino(ethoxy)di-iso- propylsila ne, diethylamino(n-propoxy)di-iso-propylsilane, ethylmethylamino(n- propoxy)di-iso-propylsilane, diethylamino(n-propoxy)di-iso-propylsilane, di-iso- propylamino(n-propoxy)di-iso-propylsilane, pyrrolidino(n-propoxy)di-iso- propylsilane, piperidino(n-propoxy)di-iso-propylsilane, pyrrolyl(n-propoxy)di-iso- propylsilane, cyclohexylmethylamino(n-propoxy)di-iso-propylsilane, dimethylamino(iso-propoxy)di-iso-propylsilane, ethylmethylamino(iso-propoxy)di- iso-propylsilane, diethylamino(iso-propoxy)di-iso-propylsilane, di-iso- propylamino(iso-propoxy)di-iso-propylsilane, pyrrolidino(iso-propoxy)di-iso- propylsilane, piperidino(iso-propoxy)di-iso-propylsilane, pyrrolyl(iso-propoxy)di-iso- propylsilane, cyclohexylmethylamino(iso-propoxy)di-iso-propylsilane, dimethylamino(sec-butoxy)di-iso-propylsilane, ethyl methy la mino(sec-butoxy)di-iso- propylsilane, diethylamino(sec-butoxy)di-iso-propylsilane, di-iso-propylamino(sec- butoxy)di-iso-propylsilane, pyrrolidino(sec-butoxy)di-iso-propylsilane, piperidino(sec- butoxy)di-iso-propylsilane, pyrrolyl(sec-butoxy)di-iso-propylsilane, cyclohexyl methy la mino(sec-butoxy)di-iso-propylsilane, dimethylamino(cyclopentoxy)di-iso-propylsilane, ethyl methylamino(cyclopentoxy)di- iso-propylsilane, diethylamino(cyclopentoxy)di-iso-propylsilane, di-iso- propylamino(cyclopentoxy)di-iso-propylsilane, pyrrolidino(cyclopentoxy)di-iso- propylsilane, piperidino(cyclopentoxy)di-iso-propylsilane, pyrrolyl(cyclopentoxy)di- iso-propylsilane, cyclohexylmethylamino(cyclopentoxy)di-iso-propylsilane, dimethylamino(cyclohexoxy)di-iso-propylsilane, ethylmethylamino(cyclohexoxy)di- iso-propylsilane, diethylamino(cyclohexoxy)di-iso-propylsilane, di-iso- propylamino(cyclohexoxy)di-iso-propylsilane, pyrrolidino(cyclohexoxy)di-iso- propylsilane, piperidino(cyclohexoxy)di-iso-propylsilane, cyclohexyl methy la mino(cyclohexoxy)di-iso-propylsilane, dimethylamino(methoxy)diphenylsilane, ethylmethylamino(methoxy)diphenylsilane, diethylamino(methoxy)diphenylsilane, di-iso-propylamino(methoxy)diphenylsilane, pyrrolidino(methoxy)diphenylsilane, piperidino(methoxy)diphenylsilane, pyrrolyl(methoxy)diphenylsilane, cyclohexylmethylamino(methoxy)diphenylsilane, dimethylamino(phenoxy)diphenylsilane, ethylmethylamino(phenoxy)diphenylsilane, diethylamino(phenoxy)diphenylsilane, di-iso-propylamino(phenoxy)diphenylsilane, pyrrolidino(phenoxy)diphenylsilane, piperidino(phenoxy)diphenylsilane, pyrrolyl(phenoxy)diphenylsilane, cyclohexyl methylamino(phenoxy)diphenylsilane, dimet ylamino(ethoxy)diphenylsilane, ethylmet ylamino(ethoxy)diphenylsilane, diet ylamino(ethoxy)diphenylsilane, di-iso-propylamino(ethoxy)diphenylsilane, pyrrolidino(ethoxy)diphenylsilane, piperidino(ethoxy)diphenylsilane, pyrrolyl(ethoxy)diphenylsilane, cyclohexyl met yla mi no(ethoxy)diphenylsilane, diethylamino(n-propoxy)diphenylsilane, ethylmethylamino(n- propoxy)diphenylsilane, diethylamino(n-propoxy)diphenylsilane, di-iso- propylamino(n-propoxy)diphenylsilane, pyrrolidino(n-propoxy)diphenylsilane, piperidino(n-propoxy)diphenylsilane, pyrrolyl(n-propoxy)diphenylsilane, cyclohexylmethylarriino(n-propoxy)diphenylsilane, dimethylamino(iso- propoxy)diphenylsilane, ethylmethylarriino(iso-propoxy)diphenylsilane, diethylarriino(iso-propoxy)diphenylsilane, di-iso-propylamino(iso- propoxy)diphenylsilane, pyrrolidino(iso-propoxy)diphenylsilane, piperidino(iso- propoxy)diphenylsilane, pyrrolyl(iso-propoxy)diphenylsilane, cyclohexylrriethylarriino(iso-propoxy)diphenylsilane, dimethylamino(sec- butoxy)diphenylsilane, ethylmethylarriino(sec-butoxy)diphenylsilane, diethylarriino(sec-butoxy)diphenylsilane, di-iso-propylamino(sec- butoxy)diphenylsilane, pyrrolidino(sec-butoxy)diphenylsilane, piperidino(sec- butoxy)diphenylsilane, pyrrolyl(sec-butoxy)diphenylsilane, cyclohexylrriethylarriino(sec-butoxy)diphenylsilane, dimethylarriino(cyclopentoxy)diphenylsilane, ethylmethylarriino(cyclopentoxy)diphenylsilane, diethylarriino(cyclopentoxy)diphenylsilane, di-iso- propylamino(cyclopentoxy)diphenylsilane, pyrrolidino(cyclopentoxy)diphenylsilane, piperidino(cyclopentoxy)diphenylsilane, pyrrolyl(cyclopentoxy)diphenylsilane, cyclohexyl methy la mino(cyclopentoxy)diphenylsilane, dimethylarriino(cyclohexoxy)diphenylsilane, ethylmethylarriino(cyclohexoxy)diphenylsilane, diethylamino(cyclohexoxy)diphenylsilane, di-iso- propylamino(cyclohexoxy)diphenylsilane, pyrrolidino(cyclohexoxy)diphenylsilane, piperidino(cyclohexoxy)diphenylsilane, and cyclohexylmethylamino(cyclohexoxy)diphenylsilane.
[0012] In a further aspect of the first main aspect, the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethyl methylamino(dimethoxy) methylsilane, diethylamino(dimethoxy)methylsilane, di-iso-propylamino(dimethoxy)methylsilane, pyrrolidino(dimethoxy) methylsilane, piperidino(dimethoxy) methylsilane, pyrrolyl(dimethoxy)methylsilane, cyclohexylmethylamino(dimethoxy)methylsilane, dimethylamino(diphenoxy)methylsilane, ethylmethylamino(diphenoxy)methylsilane, diethylamino(diphenoxy)methylsilane, di-iso-propylamino(diphenoxy)methylsilane, pyrrolidino(diphenoxy)methylsilane, piperidino(diphenoxy)methylsilane, pyrrolyl(diphenoxy)methylsilane, cyclohexylmethylamino(diphenoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethylamino(diethoxy)methylsilane, diethylamino(diethoxy)methylsilane, di-iso-propylamino(diethoxy)methylsilane, pyrrolidino(diethoxy)methylsilane, piperidino(diethoxy)methylsilane, pyrrolyl(diethoxy)methylsilane, cyclohexylmethylamino(diethoxy)methylsilane, dimethylamino(di-n-propoxy) methylsilane, ethylmethylamino(di-n- propoxy)methylsilane, diethylamino(di-n-propoxy)methylsilane, di-iso- propylamino(di-n-propoxy)methylsilane, pyrrolidino(di-n-propoxy)methylsilane, piperidino(di-n-propoxy)methylsilane, pyrrolyl(di-n-propoxy)methylsilane, cyclohexylmethylamino(di-n-propoxy)methylsilane, dimethylamino(di-iso- propoxy)methylsilane, ethylmethylamino(di-iso-propoxy)methylsilane, diethylamino(di-iso-propoxy)methylsilane, di-iso-propylamino(di-iso- propoxy)methylsilane, pyrrolidino(di-iso-propoxy)methylsilane, piperidino(di-iso- propoxy)methylsilane, pyrrolyl(di-iso-propoxy)methylsilane, cyclohexylmethylamino(di-iso-propoxy)methylsilane, dimethylamino(di-sec- butoxy)methylsilane, ethylmethylamino(di-sec-butoxy)methylsilane, diethylamino(di-sec-butoxy)methylsilane, di-iso-propylamino(di-sec- butoxy) methylsilane, pyrrolidino(di-sec-butoxy)methylsilane, piperidino(di-sec- butoxy)methylsilane, pyrrolyl(di-sec-butoxy)methylsilane, cyclohexyl methylamino(di- sec-butoxy)methylsilane dimethylamino(dicyclopentoxy)methylsilane, ethylmethylamino(dicyclopentoxy)methylsilane, diethylamino(dicyclopentoxy)methylsilane, di-iso- propylamino(dicyclopentoxy)methylsilane, pyrrolidino(dicyclopentoxy)methylsilane, piperidino(dicyclopentoxy)methylsilane, pyrrolyl (dicyclopentoxy) methylsilane, cyclohexylmethylamino(dicyclopentoxy)methylsilane, dimethylamino(dicyclohexoxy)methylsilane, ethylmethylamino(dicyclohexoxy)methylsilane, diethylamino(dicyclohexoxy)methylsilane, di-iso- propylamino(dicyclohexoxy)methylsilane, pyrrolidino(dicyclohexoxy)methylsilane, piperidino(dicyclohexoxy)methylsilane, cyclohexylmethylamino(dicyclohexoxy)methylsilane, dirriethylarriino(dirnethoxy)ethylsilane, ethylrriethylarriino(dirriethoxy)ethylsilane, diethylamino(dimethoxy)ethylsilane, di-iso-propylamino(dimethoxy)ethylsilane, pyrrolidino(dimethoxy)ethylsilane, piperidino(dimethoxy)ethylsilane, pyrrolyl(dimethoxy)ethylsilane, cyclohexyl methylarriino(dirriethoxy)ethylsilane, dimethylamino(diphenoxy)ethylsilane, ethylmethylamino(diphenoxy)ethylsilane, diethylamino(diphenoxy)ethylsilane, di-iso-propylamino(diphenoxy)ethylsilane, pyrrolidino(diphenoxy)ethylsilane, piperidino(diphenoxy)ethylsilane, pyrrolyl(diphenoxy)ethylsilane, cyclohexyl methyla mi no(diphenoxy)ethylsilane, dimethylamino(diethoxy)ethylsilane, ethylmethylamino(diethoxy)ethylsilane, diethylamino(diethoxy)ethylsilane, di-iso-propylamino(diethoxy)ethylsilane, pyrrolidino(diethoxy)ethylsilane, piperidino(diethoxy)ethylsilane, pyrrolyl(diethoxy)ethylsilane, cyclohexylmethylamino(diethoxy)ethylsilane, diethylamino(di-n-propoxy)ethylsilane, ethylmethylamino(di-n-propoxy)ethylsilane, diethylamino(di-n-propoxy)ethylsilane, di-iso-propylamino(di-n-propoxy)ethylsilane, pyrrolidino(di-n-propoxy)ethylsilane, piperidino(di-n-propoxy)ethylsilane, pyrrolyl(di- n-propoxy)ethylsilane, cyclohexylmethylamino(di-n-propoxy)ethylsilane, dimethy lamino(di-iso-propoxy)ethylsilane, ethylmethylamino(di-iso- propoxy)ethylsilane, diethylamino(di-iso-propoxy)ethylsilane, di-iso-propylamino(di- iso-propoxy)ethylsilane, pyrrolidino(di-iso-propoxy)ethylsilane, piperidino(di-iso- propoxy)ethylsilane, pyrrolyl(di-iso-propoxy)ethylsilane, cyclohexyl methylamino(di- iso-propoxy)ethylsilane, dimethylamino(di-sec-butoxy)ethylsilane, ethylmethylamino(di-sec-butoxy)ethylsilane, diethylamino(di-sec-butoxy)ethylsilane, di-iso-propylamino(di-sec-butoxy)ethylsilane, pyrrolidino(di-sec-butoxy)ethylsilane, piperidino(di-sec-butoxy)ethylsilane, pyrrolyl(di-sec-butoxy)ethylsilane, cyclohexylmethylamino(di-sec-butoxy)ethylsilane, dimethylamino(dicyclopentoxy)ethylsilane, ethylmethylamino(dicyclopentoxy)ethylsilane, diethylamino(dicyclopentoxy)ethylsilane, di-iso- propylamino(dicyclopentoxy)ethylsilane, pyrrolidino(dicyclopentoxy)ethylsilane, piperidino(dicyclopentoxy)ethylsilane, pyrrolyl(dicyclopentoxy)ethylsilane, cyclohexylmethylamino(dicyclopentoxy)ethylsilane, dimethylamino(dicyclohexoxy)ethylsilane, ethylmethylamino(dicyclohexoxy)ethylsilane, diethylamino(dicyclohexoxy)ethylsilane, di-iso- propylamino(dicyclohexoxy)ethylsilane, pyrrolidino(dicyclohexoxy)ethylsilane, piperidino(dicyclohexoxy)ethylsilane, cyclohexyl methy la mino(dicyclohexoxy)ethylsilane, dimethylamino(dimethoxy)iso- propylsilane, ethylmethylamino(dimethoxy)iso-propylsilane, diethylamino(dimethoxy)iso-propylsilane, di-iso-propylamino(dimethoxy)iso- propylsilane, pyrrolidino(dimethoxy)iso-propylsilane, piperidino(dimethoxy)iso- propylsilane, pyrrolyl(dimethoxy)iso-propylsilane, cyclohexylmethylamino(dimethoxy)iso-propylsilane, dimethylamino(diphenoxy)iso- propylsilane, ethyl methylamino(diphenoxy)iso-propylsilane, diethylamino(diphenoxy)iso-propylsilane, di-iso-propylamino(diphenoxy)iso- propylsilane, pyrrolidino(diphenoxy)iso-propylsilane, piperidino(diphenoxy)iso- propylsilane, pyrrolyl(diphenoxy)iso-propylsilane, cyclohexylmethylarriino(diphenoxy)iso-propylsilane, dimethylamino(diethoxy)iso- propylsilane, ethylmethylamino(diethoxy)iso-propylsilane, diethylamino(diethoxy)iso-propylsilane, di-iso-propylamino(diethoxy)iso- propylsilane, pyrrolidino(diethoxy)iso-propylsilane, piperidino(diethoxy)iso- propylsilane, pyrrolyl(diethoxy)iso-propylsilane, cyclohexylmethylamino(diethoxy)iso-propylsilane, diethylamino(di-n-propoxy)iso- propylsilane, ethyl methylamino(di-n-propoxy)iso-propylsilane, diet ylamino(di-n- propoxy)iso-propylsilane, di-iso-propylamino(di-n-propoxy)iso-propylsilane, pyrrolidino(di-n-propoxy)iso-propylsilane, piperidino(di-n-propoxy)iso-propylsilane, pyrrolyl(di-n-propoxy)iso-propylsilane, cyclohexyl met ylamino(di-n-propoxy)iso- propylsilane, dimethylamino(di-iso-propoxy)iso-propylsilane, ethyl methylamino(di- iso-propoxy)iso-propylsilane, diethylamino(di-iso-propoxy)iso-propylsilane, di-iso- propylamino(di-iso-propoxy)iso-propylsilane, pyrrolidino(di-iso-propoxy)iso- propylsilane, piperidino(di-iso-propoxy)iso-propylsilane, pyrrolyl(di-iso-propoxy)iso- propylsilane, cyclohexylmethylamino(di-iso-propoxy)iso-propylsilane, dimethylamino(di-sec-butoxy)iso-propylsilane, ethyl methyla mino(di-sec-butoxy)iso- propylsilane, diethylamino(di-sec-butoxy)iso-propylsilane, di-iso-propylamino(di-sec- butoxy)iso-propylsilane, pyrrolidino(di-sec-butoxy)iso-propylsilane, piperidino(di-sec- butoxy)iso-propylsilane, pyrrolyl(di-sec-butoxy)iso-propylsilane, cyclohexyl methy la mino(di-sec-butoxy)iso-propylsilane, dimethylamino(dicyclopentoxy)iso-propylsilane, ethylmethylamino(dicyclopentoxy)iso-propylsilane, diethylamino(dicyclopentoxy)iso- propylsilane, di-iso-propylamino(dicyclopentoxy)iso-propylsilane, pyrrolidino(dicyclopentoxy)iso-propylsilane, piperidino(dicyclopentoxy)iso- propylsilane, pyrrolyl(dicyclopentoxy)iso-propylsilane, cyclohexyl methy la mino(dicyclopentoxy)iso-propylsilane, dimethylamino(dicyclohexoxy)iso-propylsilane, ethylrriethylamino(dicyclohexoxy)iso- propylsilane, diethylamino(dicyclohexoxy)iso-propylsilane, di-iso- propylamino(dicyclohexoxy)iso-propylsilane, pyrrolidino(dicyclohexoxy)iso- propylsilane, piperidino(dicyclohexoxy)iso-propylsilane, cyclohexyl methy la mino(dicyclohexoxy)iso-propylsilane, dimet ylamino(met oxy)phenylsilane, ethylmethylamino(met oxy)phenylsilane, diet ylamino(met oxy)phenylsilane, di-iso-propylamino(met oxy)phenylsilane, pyrrolidino(met oxy)phenylsilane, piperidino(met oxy)phenylsilane, pyrrolyl(met oxy)phenylsilane, cyclohexylmet ylamino(met oxy)phenylsilane, dimet ylamino(phenoxy)phenylsilane, ethylmethylamino(phenoxy)phenylsilane, diet ylamino(phenoxy)phenylsilane, di-iso-propylamino(phenoxy)phenylsilane, pyrrolidino(phenoxy)phenylsilane, piperidino(phenoxy)phenylsilane, pyrrolyl(phenoxy)phenylsilane, cyclohexylmet ylamino(phenoxy)phenylsilane, dimet ylamino(ethoxy)phenylsilane, ethylmet ylamino(ethoxy)phenylsilane, diet ylamino(ethoxy)phenylsilane, di-iso-propylamino(ethoxy)phenylsilane, pyrrolidino(ethoxy) phenylsilane, piperidino(ethoxy)phenylsilane, pyrrolyl (ethoxy) phenylsilane, cyclohexylmethylamino(ethoxy)phenylsilane, diethylamino(n-propoxy)phenylsilane, ethylmethylamino(n-propoxy)phenylsilane, diethylamino(n-propoxy)phenylsilane, di-iso-propylamino(n-propoxy)phenylsilane, pyrrolidino(n-propoxy) phenylsilane, piperidino(n-propoxy)phenylsilane, pyrrolyl(n- propoxy)phenylsilane, cyclohexylmethylamino(n-propoxy)phenylsilane, dimethylamino(iso-propoxy)phenylsilane, ethyl methylamino(iso- propoxy)phenylsilane, diethylamino(iso-propoxy)phenylsilane, di-iso- propylamino(iso-propoxy)phenylsilane, pyrrolidino(iso-propoxy)phenylsilane, piperidino(iso-propoxy) phenylsilane, pyrrolyl(iso-propoxy)phenylsilane, cyclohexyl methy la mino(iso-propoxy)phenylsilane, dimethylamino(sec- butoxy)phenylsilane, ethylmethylamino(sec-butoxy)phenylsilane, diethylamino(sec- butoxy)phenylsilane, di-iso-propylamino(sec-butoxy) phenylsilane, pyrrolidino(sec- butoxy)phenylsilane, piperidino(sec-butoxy)phenylsilane, pyrrolyl(sec- butoxy)phenylsilane, cyclohexylmethylamino(sec-butoxy)phenylsilane, dimethylamino(cyclopentoxy)phenyl, ethylmethylamino(cyclopentoxy)phenylsilane, diethylamino(cyclopentoxy)phenylsilane, di-iso- propy la mino(cyclopentoxy) phenylsilane, pyrrolidino(cyclopentoxy)phenylsilane, piperidino(cyclopentoxy)phenylsilane, pyrrolyl(cyclopentoxy)phenylsilane, cyclohexylmethylamino(cyclopentoxy)phenylsilane, dimethylamino(cyclohexoxy)phenylsilane, ethylmethylamino(cyclohexoxy)phenylsilane, diethylamino(cyclohexoxy)phenylsilane, di-iso- propylamino(cyclohexoxy)phenylsilane, pyrrolidino(cyclohexoxy)phenylsilane, piperidino(cyclohexoxy)phenylsilane, and cyclohexylmethylamino(cyclohexoxy)phenylsilane.
[0013] In a further aspect of the first main aspect, the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethylmethylamino(dimethoxy) methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
[0014] In a further aspect of the first main aspect, the organoamino-alkoxysilane having formula IA or IB is chosen from the group consisting of dimethylamino(methoxy)dimethylsilane (DMAMODMS), ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane (DEAMODMS), dimethylamino(phenoxy)dimethylsilane (DMAPODMS), ethylmethylamino(phenoxy)dimethylsilane, dimethylamino(dimethoxy)methylsilane (DMADMOMS), diethylamino(diethoxy)methylsilane (DEADEOMS), and dimethylamino(diethoxy)methylsilane (DMADEOMS).
[0015] In a second main aspect, a composition for a vapor deposition of a passivation layer on dielectric material is provided. The composition comprising an organoamino-alkoxysilane having one of the following formulae: wherein R1 and R2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure wherein the organoamino- alkoxysilane is substantially free of one or more impurities selected from the group consisting of a halide, water, and metals.
[0016] In a further aspect of the second main aspect, the halides comprise chloride. In a further aspect of the second main aspect, the chloride, if present, are present at a concentration of 50 ppm or less as measured by IC. In a further aspect of the second main aspect, the chloride, if present, are present at a concentration of 10 ppm or less as measured by IC.
[0017] In a further aspect of the second main aspect, the chloride, if present, are present at a concentration of 5 ppm or less as measured by IC.
[0018] In a further aspect of the second main aspect, the organoamino- alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, di-iso-propylamino(methoxy)dimethylsilane, pyrrolidino(methoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, cyclohexylmethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, diethylamino(phenoxy)dimethylsilane, di-iso-propylamino(phenoxy)dimethylsilane, pyrrolidino(phenoxy)dimethylsilane, piperidino(phenoxy)dimethylsilane, pyrrolyl(phenoxy)dimethy Isilane, cyclohexylmethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, di-iso-propylamino(ethoxy)dimethylsilane, pyrrolidino(ethoxy)dimethylsilane, piperidino(ethoxy)dimethylsilane, pyrrolyl(ethoxy)dimethylsilane, cyclohexylmethylamino(ethoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, ethylmethylamino(n- propoxy)dimethylsilane, diethylamino(n-propoxy)dimethylsilane, di-iso- propylamino(n-propoxy)dimethylsilane, pyrrolidino(n-propoxy)dimethylsilane, piperidino(n-propoxy)dimethylsilane, pyrrolyl(n-propoxy)dimethylsilane, cyclohexylmethylamino(n-propoxy)dimethylsilane, dimethylamino(iso- propoxy)dimethylsilane, ethylmethylamino(iso-propoxy)dimethylsilane, diethylamino(iso-propoxy)dimethylsilane, di-iso-propylamino(iso- propoxy)dimethylsilane, pyrrolidino(iso-propoxy)dimethylsilane, piperidino(iso- propoxy)dimethylsilane, pyrrolyl(iso-propoxy)dimethylsilane, cyclohexylmethylamino(iso-propoxy)dimethylsilane, dimethylamino(sec- butoxy)dimethylsilane, ethylmethylamino(sec-butoxy)dimethylsilane, diethylamino(sec-butoxy)dimethylsilane, di-iso-propylamino(sec- butoxy)dimethylsilane, pyrrolidino(sec-butoxy)dimethylsilane, piperidino(sec- butoxy)dimethylsilane, pyrrolyl(sec-butoxy)dimethylsilane, cyclohexylmethylamino(sec-butoxy)dimethylsilane dimethylamino(cyclopentoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, diethylamino(cyclopentoxy)dimethylsilane, di-iso- propylamino(cyclopentoxy)dimethylsilane, pyrrolidino(cyclopentoxy)dimethylsilane, piperidino(cyclopentoxy)dimethylsilane, pyrrolyl(cyclopentoxy)dimethylsilane, cyclohexylmethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclohexoxy)dimethylsilane, diethylamino(cyclohexoxy)dimethylsilane, di-iso- propylamino(cyclohexoxy)dimethylsilane, pyrrolidino(cyclohexoxy)dimethylsilane, piperidino(cyclohexoxy)dimethylsilane, cyclohexylmethylamino(cyclohexoxy)dimethylsilane, dimethylamino(methoxy)diethylsilane, ethylmethylamino(methoxy)diethylsilane, diethylamino(methoxy)diethylsilane, di-iso-propylamino(methoxy)diethylsilane, pyrrolidino(methoxy)diethylsilane, piperidino(methoxy)diethylsilane, pyrrolyl(methoxy)diethylsilane, cyclohexylmethylamino(methoxy)diethylsilane, dimethylamino(phenoxy)diethylsilane, ethylmethylamino(phenoxy)diethylsilane, diethylamino(phenoxy)diethylsilane, di-iso-propylamino(phenoxy)diethylsilane, pyrrolidino(phenoxy)diethylsilane, piperidino(phenoxy)diethylsilane, pyrrolyl(phenoxy)diethylsilane, cyclohexyl methyla mi no(phenoxy)diethylsilane, dimet ylarriino(ethoxy)diethylsilane, ethylmet ylarriino(ethoxy)diethylsilane, diet ylarriino(ethoxy)diethylsilane, di-iso-propylarriino(ethoxy)diethylsilane, pyrrolidino(ethoxy)diethylsilane, piperidino(ethoxy)diethylsilane, pyrrolyl(ethoxy)diethylsilane, cyclohexylmet ylarriino(ethoxy)diethylsilane, diet ylamino(n-propoxy)diethylsilane, ethyl met y la mino(n-propoxy)diethylsilane, diethylarriino(n-propoxy)diethylsilane, di-iso-propylarriino(n-propoxy)diethylsilane, pyrrolidino(n-propoxy)diethylsilane, piperidino(n-propoxy)diethylsilane, pyrrolyl(n- propoxy)diethylsilane, cyclohexyl methyla mino(n-propoxy)diethylsilane, dimethylamino(iso-propoxy)diethylsilane, ethylmethylamino(iso- propoxy)diethylsilane, diethylamino(iso-propoxy)diethylsilane, di-iso- propylamino(iso-propoxy)diethylsilane, pyrrolidino(iso-propoxy)diethylsilane, piperidino(iso-propoxy)diethylsilane, pyrrolyl(iso-propoxy)diethylsilane, cyclohexyl methy la mino(iso-propoxy)diethylsilane, dimethylamino(sec- butoxy)diethylsilane, ethylmethylamino(sec-butoxy)diethylsilane, diethylamino(sec- butoxy)diethylsilane, di-iso-propylamino(sec-butoxy)diethylsilane, pyrrolidino(sec- butoxy)diethylsilane, piperidino(sec-butoxy)diethylsilane, pyrrolyl(sec- butoxy)diethylsilane, cyclohexylmethylamino(sec-butoxy)diethylsilane, dimethylamino(cyclopentoxy)diethylsilane, ethylmethylamino(cyclopentoxy)diethylsilane, diethylamino(cyclopentoxy)diethylsilane, di-iso- propy la mino(cyclopentoxy)diethylsilane, pyrrolidino(cyclopentoxy)diethylsilane, piperidino(cyclopentoxy)diethylsilane, pyrrolyl(cyclopentoxy)diethylsilane, cyclohexylmethylamino(cyclopentoxy)diethylsilane, dimethylamino(cyclohexoxy)diethylsilane, ethylmethylamino(cyclohexoxy)diethylsilane, diethylamino(cyclohexoxy)diethylsilane, di-iso- propylamino(cyclohexoxy)diethylsilane, pyrrolidino(cyclohexoxy)diethylsilane, piperidino(cyclohexoxy)diethylsilane, cyclohexyl methy la mino(cyclohexoxy)diethylsilane, dimet ylamino(met oxy)di-iso- propylsilane, ethylmet ylamino(met oxy)di-iso-propylsilane, diet ylamino(met oxy)di-iso-propylsilane, di-iso-propylamino(met oxy)di-iso- propylsilane, pyrrolidino(met oxy)di-iso-propylsilane, piperidino(methoxy)di-iso- propylsilane, pyrrolyl(met oxy)di-iso-propylsilane, cyclohexylmet ylamino(met oxy)di-iso-propylsilane, dimet ylamino(phenoxy)di-iso- propylsilane, ethylmet ylamino(phenoxy)di-iso-propylsilane, diet ylamino(phenoxy)di-iso-propylsilane, di-iso-propylamino(phenoxy)di-iso- propylsilane, pyrrolidino(phenoxy)di-iso-propylsilane, piperidino(phenoxy)di-iso- propylsilane, pyrrolyl(phenoxy)di-iso-propylsilane, cyclohexyl methy la mino(phenoxy)di-iso-propylsilane, dimethylamino(ethoxy)di-iso- propylsilane, ethyl methylarriino(ethoxy)di-iso-propylsilane, diethylamino(ethoxy)di- iso-propylsilane, di-iso-propylamino(ethoxy)di-iso-propylsilane, pyrrolidino(ethoxy)di-iso-propylsilane, piperidino(ethoxy)di-iso-propylsilane, pyrrolyl(ethoxy)di-iso-propylsilane, cyclohexyl methyla mino(ethoxy)di-iso- propylsilane, diethylarriino(n-propoxy)di-iso-propylsilane, ethylmethylamino(n- propoxy)di-iso-propylsilane, diethylarriino(n-propoxy)di-iso-propylsilane, di-iso- propylamino(n-propoxy)di-iso-propylsilane, pyrrolidino(n-propoxy)di-iso- propylsilane, piperidino(n-propoxy)di-iso-propylsilane, pyrrolyl(n-propoxy)di-iso- propylsilane, cyclohexylrriethylarriino(n-propoxy)di-iso-propylsilane, dirriethylarriino(iso-propoxy)di-iso-propylsilane, ethylmethylamino(iso-propoxy)di- iso-propylsilane, diethylamino(iso-propoxy)di-iso-propylsilane, di-iso- propylamino(iso-propoxy)di-iso-propylsilane, pyrrolidino(iso-propoxy)di-iso- propylsilane, piperidino(iso-propoxy)di-iso-propylsilane, pyrrolyl(iso-propoxy)di-iso- propylsilane, cyclohexylmethylamino(iso-propoxy)di-iso-propylsilane, dimethylamino(sec-butoxy)di-iso-propylsilane, ethyl methy la mino(sec-butoxy)di-iso- propylsilane, diethylamino(sec-butoxy)di-iso-propylsilane, di-iso-propylamino(sec- butoxy)di-iso-propylsilane, pyrrolidino(sec-butoxy)di-iso-propylsilane, piperidino(sec- butoxy)di-iso-propylsilane, pyrrolyl(sec-butoxy)di-iso-propylsilane, cyclohexyl methy la mino(sec-butoxy)di-iso-propylsilane, dirriethylarriino(cyclopentoxy)di-iso-propylsilane, ethyl methylamino(cyclopentoxy)di- iso-propylsilane, diethylamino(cyclopentoxy)di-iso-propylsilane, di-iso- propylamino(cyclopentoxy)di-iso-propylsilane, pyrrolidino(cyclopentoxy)di-iso- propylsilane, piperidino(cyclopentoxy)di-iso-propylsilane, pyrrolyl(cyclopentoxy)di- iso-propylsilane, cyclohexylmethylamino(cyclopentoxy)di-iso-propylsilane, dirnethylamino(cyclohexoxy)di-iso-propylsilane, ethylmethylamino(cyclohexoxy)di- iso-propylsilane, diethylamino(cyclohexoxy)di-iso-propylsilane, di-iso- propylamino(cyclohexoxy)di-iso-propylsilane, pyrrolidino(cyclohexoxy)di-iso- propylsilane, piperidino(cyclohexoxy)di-iso-propylsilane, cyclohexyl methy la mino(cyclohexoxy)di-iso-propylsilane, dimethylamino(methoxy)diphenylsilane, ethylmethylamino(methoxy)diphenylsilane, diethylamino(methoxy)diphenylsilane, di-iso-propylamino(methoxy)diphenylsilane, pyrrolidino(methoxy)diphenylsilane, piperidino(methoxy)diphenylsilane, pyrrolyl(methoxy)diphenylsilane, cyclohexylmethylamino(methoxy)diphenylsilane, dimethylamino(phenoxy)diphenylsilane, ethylmethylamino(phenoxy)diphenylsilane, diethylamino(phenoxy)diphenylsilane, di-iso-propylamino(phenoxy)diphenylsilane, pyrrolidino(phenoxy)diphenylsilane, piperidino(phenoxy)diphenylsilane, pyrrolyl(phenoxy)diphenylsilane, cyclohexyl methylamino(phenoxy)diphenylsilane, dimethylamino(ethoxy)diphenylsilane, ethylmethylamino(ethoxy)diphenylsilane, diethylamino(ethoxy)diphenylsilane, di-iso-propylamino(ethoxy)diphenylsilane, pyrrolidino(ethoxy)diphenylsilane, piperidino(ethoxy)diphenylsilane, pyrrolyl(ethoxy)diphenylsilane, cyclohexylmethylamino(ethoxy)diphenylsilane, diethylamino(n-propoxy)diphenylsilane, ethyl methylamino(n- propoxy)diphenylsilane, diet ylamino(n-propoxy)diphenylsilane, di-iso- propylamino(n-propoxy)diphenylsilane, pyrrolidino(n-propoxy)diphenylsilane, piperidino(n-propoxy)diphenylsilane, pyrrolyl(n-propoxy)diphenylsilane, cyclohexylmet ylamino(n-propoxy)diphenylsilane, dimet ylamino(iso- propoxy)diphenylsilane, ethylmet ylamino(iso-propoxy)diphenylsilane, diet ylamino(iso-propoxy)diphenylsilane, di-iso-propylamino(iso- propoxy)diphenylsilane, pyrrolidino(iso-propoxy)dip enylsilane, piperidino(iso- propoxy)diphenylsilane, pyrrolyl(iso-propoxy)diphenylsilane, cyclohexylmet ylamino(iso-propoxy)diphenylsilane, dimet ylamino(sec- butoxy)diphenylsilane, ethylmethylamino(sec-butoxy)diphenylsilane, diethylamino(sec-butoxy)diphenylsilane, di-iso-propylamino(sec- butoxy)diphenylsilane, pyrrolidino(sec-butoxy)diphenylsilane, piperidino(sec- butoxy)diphenylsilane, pyrrolyl(sec-butoxy)diphenylsilane, cyclohexylmethylamino(sec-butoxy)diphenylsilane, dimethylamino(cyclopentoxy)diphenylsilane, ethylmethylamino(cyclopentoxy)diphenylsilane, diethylamino(cyclopentoxy)diphenylsilane, di-iso- propylamino(cyclopentoxy)diphenylsilane, pyrrolidino(cyclopentoxy)diphenylsilane, piperidino(cyclopentoxy)diphenylsilane, pyrrolyl(cyclopentoxy)diphenylsilane, cyclohexyl methy la mino(cyclopentoxy)diphenylsilane, dimethylamino(cyclohexoxy)diphenylsilane, ethylmethylamino(cyclohexoxy)diphenylsilane, diethylamino(cyclohexoxy)diphenylsilane, di-iso- propylamino(cyclohexoxy)diphenylsilane, pyrrolidino(cyclohexoxy)diphenylsilane, piperidino(cyclohexoxy)diphenylsilane, and cyclohexylmethylamino(cyclohexoxy)diphenylsilane.
[0019] In a further aspect of the second main aspect, the organoamino- alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dethylethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(sec-butoxy)dimethylsilane, dimethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, ethyl methylamino (cyclohexoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, and cyclohexylmethylamino(methoxy)dimethylsilane.
[0020] In a further aspect of the second main aspect, the organoamino- alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethyl methylamino(dimethoxy) methylsilane, diethylamino(dimethoxy)methylsilane, di-iso-propylamino(dimethoxy)methylsilane, pyrrolidino(dimethoxy) methylsilane, piperidino(dimethoxy) methylsilane, pyrrolyl(dimethoxy)methylsilane, cyclohexylmethylamino(dimethoxy)methylsilane, dimethylamino(diphenoxy)methylsilane, ethylmethylamino(diphenoxy)methylsilane, diethylamino(diphenoxy)methylsilane, di-iso-propylamino(diphenoxy)methylsilane, pyrrolidino(diphenoxy)methylsilane, piperidino(diphenoxy)methylsilane, pyrrolyl(diphenoxy)methylsilane, cyclohexylmethylamino(diphenoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethylamino(diethoxy)methylsilane, diethylamino(diethoxy)methylsilane, di-iso-propylamino(diethoxy)methylsilane, pyrrolidino(diethoxy)methylsilane, piperidino(diethoxy)methylsilane, pyrrolyl(diethoxy)methylsilane, cyclohexylmethylamino(diethoxy)methylsilane, dimethylamino(di-n-propoxy) methylsilane, ethylmethylamino(di-n- propoxy)methylsilane, diethylamino(di-n-propoxy)methylsilane, di-iso- propylamino(di-n-propoxy)methylsilane, pyrrolidino(di-n-propoxy)methylsilane, piperidino(di-n-propoxy)methylsilane, pyrrolyl(di-n-propoxy)methylsilane, cyclohexylmethylamino(di-n-propoxy)methylsilane, dimethylamino(di-iso- propoxy)methylsilane, ethylmethylamino(di-iso-propoxy)methylsilane, diethylamino(di-iso-propoxy)methylsilane, di-iso-propylamino(di-iso- propoxy)methylsilane, pyrrolidino(di-iso-propoxy)methylsilane, piperidino(di-iso- propoxy)methylsilane, pyrrolyl(di-iso-propoxy)methylsilane, cyclohexylmethylamino(di-iso-propoxy)methylsilane, dimethylamino(di-sec- butoxy)methylsilane, ethylmethylamino(di-sec-butoxy)methylsilane, diethylamino(di-sec-butoxy)methylsilane, di-iso-propylamino(di-sec- butoxy)methylsilane, pyrrolidino(di-sec-butoxy)methylsilane, piperidino(di-sec- butoxy)methylsilane, pyrrolyl(di-sec-butoxy)methylsilane, cyclohexyl methylamino(di- sec-butoxy)methylsilane dimethylamino(dicyclopentoxy)methylsilane, ethylmethylamino(dicyclopentoxy)methylsilane, diethylamino(dicyclopentoxy)methylsilane, di-iso- propylamino(dicyclopentoxy)methylsilane, pyrrolidino(dicyclopentoxy)methylsilane, piperidino(dicyclopentoxy)methylsilane, pyrrolyl (dicyclopentoxy) methylsilane, cyclohexylmethylamino(dicyclopentoxy)methylsilane, dimethylamino(dicyclohexoxy)methylsilane, ethylmethylamino(dicyclohexoxy)methylsilane, diethylamino(dicyclohexoxy)methylsilane, di-iso- propylamino(dicyclohexoxy)methylsilane, pyrrolidino(dicyclohexoxy)methylsilane, piperidino(dicyclohexoxy)methylsilane, cyclohexylmethylamino(dicyclohexoxy)methylsilane, dirriethylarriino(dirnethoxy)ethylsilane, ethylrriethylarriino(dirriethoxy)ethylsilane, diethylamino(dimethoxy)ethylsilane, di-iso-propylamino(dimethoxy)ethylsilane, pyrrolidino(dimethoxy)ethylsilane, piperidino(dimethoxy)ethylsilane, pyrrolyl(dimethoxy)ethylsilane, cyclohexyl methylarriino(dirriethoxy)ethylsilane, dimethylamino(diphenoxy)ethylsilane, ethylmethylamino(diphenoxy)ethylsilane, diethylamino(diphenoxy)ethylsilane, di-iso-propylamino(diphenoxy)ethylsilane, pyrrolidino(diphenoxy)ethylsilane, piperidino(diphenoxy)ethylsilane, pyrrolyl(diphenoxy)ethylsilane, cyclohexyl methyla mi no(diphenoxy)ethylsilane, dimethylamino(diethoxy)ethylsilane, ethylmethylamino(diethoxy)ethylsilane, diethylamino(diethoxy)ethylsilane, di-iso-propylamino(diethoxy)ethylsilane, pyrrolidino(diethoxy)ethylsilane, piperidino(diethoxy)ethylsilane, pyrrolyl(diethoxy)ethylsilane, cyclohexylmethylamino(diethoxy)ethylsilane, diethylamino(di-n-propoxy)ethylsilane, ethylmethylamino(di-n-propoxy)ethylsilane, diethylamino(di-n-propoxy)ethylsilane, di-iso-propylamino(di-n-propoxy)ethylsilane, pyrrolidino(di-n-propoxy)ethylsilane, piperidino(di-n-propoxy)ethylsilane, pyrrolyl(di- n-propoxy)ethylsilane, cyclohexylmethylamino(di-n-propoxy)ethylsilane, dimethylamino(di-iso-propoxy)ethylsilane, ethylmethylamino(di-iso- propoxy)ethylsilane, diethylamino(di-iso-propoxy)ethylsilane, di-iso-propylamino(di- iso-propoxy)ethylsilane, pyrrolidino(di-iso-propoxy)ethylsilane, piperidino(di-iso- propoxy)ethylsilane, pyrrolyl(di-iso-propoxy)ethylsilane, cyclohexyl methylamino(di- iso-propoxy)ethylsilane, dimethylamino(di-sec-butoxy)ethylsilane, ethylmethylamino(di-sec-butoxy)ethylsilane, diethylamino(di-sec-butoxy)ethylsilane, di-iso-propylamino(di-sec-butoxy)ethylsilane, pyrrolidino(di-sec-butoxy)ethylsilane, piperidino(di-sec-butoxy)ethylsilane, pyrrolyl(di-sec-butoxy)ethylsilane, cyclohexylmethylamino(di-sec-butoxy)ethylsilane, dimethylamino(dicyclopentoxy)ethylsilane, ethylmethylamino(dicyclopentoxy)ethylsilane, diethylamino(dicyclopentoxy)ethylsilane, di-iso- propylamino(dicyclopentoxy)ethylsilane, pyrrolidino(dicyclopentoxy)ethylsilane, piperidino(dicyclopentoxy)ethylsilane, pyrrolyl(dicyclopentoxy)ethylsilane, cyclohexylmethylamino(dicyclopentoxy)ethylsilane, dimethylamino(dicyclohexoxy)ethylsilane, ethylmethylamino(dicyclohexoxy)ethylsilane, diethylamino(dicyclohexoxy)ethylsilane, di-iso- propylamino(dicyclohexoxy)ethylsilane, pyrrolidino(dicyclohexoxy)ethylsilane, piperidino(dicyclohexoxy)ethylsilane, cyclohexyl methy la mino(dicyclohexoxy)ethylsilane, dimethylamino(dimethoxy)iso-propylsilane, ethyl methylamino(dimethoxy)iso- propylsilane, diethylamino(dimethoxy)iso-propylsilane, di-iso- propylamino(dimethoxy)iso-propylsilane, pyrrolidino(dimethoxy)iso-propylsilane, piperidino(dimet oxy)iso-propylsilane, pyrrolyl(dimet oxy)iso-propylsilane, cyclohexylmet ylamino(dimet oxy)iso-propylsilane, dimethylamino(diphenoxy)iso- propylsilane, ethyl met ylamino(diphenoxy)iso-propylsilane, diethylamino(diphenoxy)iso-propylsilane, di-iso-propylamino(diphenoxy)iso- propylsilane, pyrrolidino(diphenoxy)iso-propylsilane, piperidino(diphenoxy)iso- propylsilane, pyrrolyl(diphenoxy)iso-propylsilane, cyclohexylmethylamino(diphenoxy)iso-propylsilane, dimethylamino(diethoxy)iso- propylsilane, ethylmethylamino(diethoxy)iso-propylsilane, diethylamino(diethoxy)iso-propylsilane, di-iso-propylamino(diethoxy)iso- propylsilane, pyrrolidino(diethoxy)iso-propylsilane, piperidino(diethoxy)iso- propylsilane, pyrrolyl(diethoxy)iso-propylsilane, cyclohexylmethylamino(diethoxy)iso-propylsilane, diethylamino(di-n-propoxy)iso- propylsilane, ethyl methylamino(di-n-propoxy)iso-propylsilane, diethylamino(di-n- propoxy)iso-propylsilane, di-iso-propylamino(di-n-propoxy)iso-propylsilane, pyrrolidino(di-n-propoxy)iso-propylsilane, piperidino(di-n-propoxy)iso-propylsilane, pyrrolyl(di-n-propoxy)iso-propylsilane, cyclohexyl methylamino(di-n-propoxy)iso- propylsilane, dimethylamino(di-iso-propoxy)iso-propylsilane, ethyl methylamino(di- iso-propoxy)iso-propylsilane, diethylamino(di-iso-propoxy)iso-propylsilane, di-iso- propylamino(di-iso-propoxy)iso-propylsilane, pyrrolidino(di-iso-propoxy)iso- propylsilane, piperidino(di-iso-propoxy)iso-propylsilane, pyrrolyl(di-iso-propoxy)iso- propylsilane, cyclohexylmethylamino(di-iso-propoxy)iso-propylsilane, dimethylamino(di-sec-butoxy)iso-propylsilane, ethyl methyla mino(di-sec-butoxy)iso- propylsilane, diethylamino(di-sec-butoxy)iso-propylsilane, di-iso-propylamino(di-sec- butoxy)iso-propylsilane, pyrrolidino(di-sec-butoxy)iso-propylsilane, piperidino(di-sec- butoxy)iso-propylsilane, pyrrolyl(di-sec-butoxy)iso-propylsilane, cyclohexyl methy la mino(di-sec-butoxy)iso-propylsilane, dimethylamino(dicyclopentoxy)iso-propylsilane, ethylmethylamino(dicyclopentoxy)iso-propylsilane, diethylamino(dicyclopentoxy)iso- propylsilane, di-iso-propylamino(dicyclopentoxy)iso-propylsilane, pyrrolidino(dicyclopentoxy)iso-propylsilane, piperidino(dicyclopentoxy)iso- propylsilane, pyrrolyl(dicyclopentoxy)iso-propylsilane, cyclohexyl methy la mino(dicyclopentoxy)iso-propylsilane, dimet ylamino(dicyclohexoxy)iso-propylsilane, ethylmet ylamino(dicyclohexoxy)iso- propylsilane, diet ylamino(dicyclohexoxy)iso-propylsilane, di-iso- propylamino(dicyclohexoxy)iso-propylsilane, pyrrolidino(dicyclohexoxy)iso- propylsilane, piperidino(dicyclohexoxy)iso-propylsilane, cyclohexyl methy la mino(dicyclohexoxy)iso-propylsilane, dimethylamino(rriethoxy)phenylsilane, ethylmethylamino(rriethoxy)phenylsilane, diethylamino(rriethoxy)phenylsilane, di-iso-propylamino(rriethoxy)phenylsilane, pyrrolidino(rriethoxy)phenylsilane, piperidino(rriethoxy)phenylsilane, pyrrolyl(rriethoxy)phenylsilane, cyclohexylmethylarriino(rriethoxy)phenylsilane, dimethylarriino(phenoxy)phenylsilane, ethylmethylarriino(phenoxy)phenylsilane, diethylarriino(phenoxy)phenylsilane, di-iso-propylarriino(phenoxy)phenylsilane, pyrrolidino(phenoxy)phenylsilane, piperidino(phenoxy)phenylsilane, pyrrolyl(phenoxy)phenylsilane, cyclohexylmethylarriino(phenoxy)phenylsilane, dimethylarriino(ethoxy)phenylsilane, ethylmethylarriino(ethoxy)phenylsilane, diethylarriino(ethoxy)phenylsilane, di-iso-propylarriino(ethoxy)phenylsilane, pyrrolidino(ethoxy) phenylsilane, piperidino(ethoxy)phenylsilane, pyrrolyl (ethoxy) phenylsilane, cyclohexylmethylamino(ethoxy)phenylsilane, diethylamino(n-propoxy)phenylsilane, ethylmethylamino(n-propoxy)phenylsilane, diethylamino(n-propoxy)phenylsilane, di-iso-propylamino(n-propoxy)phenylsilane, pyrrolidino(n-propoxy) phenylsilane, piperidino(n-propoxy)phenylsilane, pyrrolyl(n- propoxy)phenylsilane, cyclohexylmethylamino(n-propoxy)phenylsilane, dimethylamino(iso-propoxy)phenylsilane, ethyl methylamino(iso- propoxy)phenylsilane, diethylamino(iso-propoxy)phenylsilane, di-iso- propylamino(iso-propoxy)phenylsilane, pyrrolidino(iso-propoxy)phenylsilane, piperidino(iso-propoxy) phenylsilane, pyrrolyl(iso-propoxy)phenylsilane, cyclohexyl methy la mino(iso-propoxy)phenylsilane, dimet ylamino(sec- butoxy)phenylsilane, ethylmethylamino(sec-butoxy)phenylsilane, diethylamino(sec- butoxy)phenylsilane, di-iso-propylamino(sec-butoxy) phenylsilane, pyrrolidino(sec- butoxy)phenylsilane, piperidino(sec-butoxy)phenylsilane, pyrrolyl(sec- butoxy)phenylsilane, cyclohexylmethylamino(sec-butoxy)phenylsilane, dimethylamino(cyclopentoxy)phenyl, ethylmethylamino(cyclopentoxy)phenylsilane, diethylamino(cyclopentoxy)phenylsilane, di-iso- propy la mino(cyclopentoxy) phenylsilane, pyrrolidino(cyclopentoxy)phenylsilane, piperidino(cyclopentoxy)phenylsilane, pyrrolyl(cyclopentoxy)phenylsilane, cyclohexylmethylamino(cyclopentoxy)phenylsilane, dimethylamino(cyclohexoxy)phenylsilane, ethylmethylamino(cyclohexoxy)phenylsilane, diethylamino(cyclohexoxy)phenylsilane, di-iso- propylamino(cyclohexoxy)phenylsilane, pyrrolidino(cyclohexoxy)phenylsilane, piperidino(cyclohexoxy)phenylsilane, and cyclohexylmethylamino(cyclohexoxy)phenylsilane.
[0021] In a further aspect of the second main aspect, the organoamino- alkoxysilane is chosen from the group consisting of dimethylamino(dimethoxy)methylsilane, ethyl methylamino(dimethoxy) methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
[0022] In a further aspect of the second main aspect, the organoamino- alkoxysilane is chosen from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dimethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, and dimethylamino(diethoxy)methylsilane. [0023] The embodiments of the disclosure can be used alone or in combination with each other.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] 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:
[0025] FIG. 1 illustrates an exemplary embodiment of an area selective deposition method comprising: an optional surface pre-clean, selective passivation, and selective deposition wherein a dielectric film is selectively deposited on a dielectric film, while first surface (comprising a metal) and second surface (comprising a barrier material) are passivated;
[0026] FIG. 2 illustrates an exemplary process comprising: an optional surface preclean, selective passivation, and selective deposition wherein a dielectric film is selectively deposited on a silicon dioxide film, while the first surface (comprising copper) and the second surface (comprising tantalum nitride) are passivated;
[0027] FIG. 3 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 150°C deposition temperature;
[0028] FIG. 4 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 200°C deposition temperature;
[0029] FIG. 5 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 150°C deposition temperature; and
[0030] FIG. 6 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 200°C deposition temperature.
DETAILED DESCRIPTION
[0031] 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.
[0032] 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 be construed 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.
[0033] 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.
[0034] There are a variety of methods that could be used for selective depositions. Embodiments of the disclosure are directed to methods that employ surface deactivation by taking advantage of the surface chemistry of two different surfaces. Since two different surfaces will have different reactive handles, the differences can be taken advantage of by utilizing molecules that will react with one surface (to deactivate that surface) and not react with the other surface.
[0035] 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.
[0036] 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 as gate dielectrics and capacitor dielectrics would also be of great utility in semiconductor device manufacturing.
[0037] 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.
[0038] In a first aspect, a method is provided for passivating a silicon-containing surface comprising predominantly hydroxyl groups. The method comprises: (a) providing the substrate in a reaction vessel at temperatures ranging from 20°C to 800°C, the substrate having a first surface comprising a dielectric material with hydroxyl groups and a second surface comprising a dielectric material or metal with much less amount of hydroxyl groups; (b) forming at least one passivated layer on the first surface by exposing the first surface and the second surface to a passivating composition comprising an organoamino-alkoxysilane having one of the following formulae:
IA IB wherein R1 and R2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; (c) purging the reactor with inert gas; Steps (b) and (c) can be repeated to achieve self-limiting monolayer coverage of the first surface.
[0039] In certain aspects, the organoamino-alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, di-iso-propylamino(methoxy)dimethylsilane, pyrrolidino(methoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, cyclohexylmethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, diethylamino(phenoxy)dimethylsilane, di-iso-propylamino(phenoxy)dimethylsilane, pyrrolidino(phenoxy)dimethylsilane, piperidino(phenoxy)dimethylsilane, pyrrolyl(phenoxy)dimethylsilane, cyclohexylmethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, di-iso-propylamino(ethoxy)dimethylsilane, pyrrolidino(ethoxy)dimethylsilane, piperidino(ethoxy)dimethylsilane, pyrrolyl(ethoxy)dimethylsilane, cyclohexylmethylamino(ethoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, ethylmethylamino(n- propoxy)dimethylsilane, diethylamino(n-propoxy)dimethylsilane, di-iso- propylamino(n-propoxy)dimethylsilane, pyrrolidino(n-propoxy)dimethylsilane, piperidino(n-propoxy)dirriethylsilane, pyrrolyl(n-propoxy)dimethylsilane, cyclohexylmethylamino(n-propoxy)dimethylsilane, dimethylamino(iso- propoxy)dimethylsilane, ethylmethylamino(iso-propoxy)dimethylsilane, diethylamino(iso-propoxy)dimethylsilane, di-iso-propylamino(iso- propoxy)dimethylsilane, pyrrolidino(iso-propoxy)dimethylsilane, piperidino(iso- propoxy)dimethylsilane, pyrrolyl(iso-propoxy)dimethylsilane, cyclohexylmethylamino(iso-propoxy)dimethylsilane, dimethylamino(sec- butoxy)dimethylsilane, ethylmethylamino(sec-butoxy)dimethylsilane, diethylamino(sec-butoxy)dimethylsilane, di-iso-propylamino(sec- butoxy)dimethylsilane, pyrrolidino(sec-butoxy)dimethylsilane, piperidino(sec- butoxy)dimethylsilane, pyrrolyl(sec-butoxy)dimethylsilane, cyclohexylmethylamino(sec-butoxy)dimethylsilane dimethylamino(cyclopentoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, diethylamino(cyclopentoxy)dimethylsilane, di-iso- propylamino(cyclopentoxy)dimethylsilane, pyrrolidino(cyclopentoxy)dimethylsilane, piperidino(cyclopentoxy)dimethylsilane, pyrrolyl(cyclopentoxy)dimethylsilane, cyclohexylmethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclohexoxy)dimethylsilane, diethylamino(cyclohexoxy)dimethylsilane, di-iso- propylamino(cyclohexoxy)dimethylsilane, pyrrolidino(cyclohexoxy)dimethylsilane, piperidino(cyclohexoxy)dimethylsilane, cyclohexylmethylamino(cyclohexoxy)dimethylsilane, dimethylamino(methoxy)diethylsilane, ethylmethylamino(methoxy)diethylsilane, diethylamino(methoxy)diethylsilane, di-iso-propylamino(methoxy)diethylsilane, pyrrolidino(methoxy)diethylsilane, piperidino(methoxy)diethylsilane, pyrrolyl(methoxy)diethylsilane, cyclohexylmethylamino(methoxy)diethylsilane, dimethylamino(phenoxy)diethylsilane, ethylmethylamino(phenoxy)diethylsilane, diethylamino(phenoxy)diethylsilane, di-iso-propylamino(phenoxy)diethylsilane, pyrrolidino(phenoxy)diethylsila ne, piperidino(phenoxy)diethylsilane, pyrrolyl(phenoxy)diethylsilane, cyclohexyl methyla mi no(phenoxy)diethylsilane, dimet ylarriino(ethoxy)diethylsilane, ethylmet ylarriino(ethoxy)diethylsilane, diet ylarriino(ethoxy)diethylsilane, di-iso-propylarriino(ethoxy)diethylsilane, pyrrolidino(ethoxy)diethylsilane, piperidino(ethoxy)diethylsilane, pyrrolyl(ethoxy)diethylsilane, cyclohexylmet ylarriino(ethoxy)diethylsilane, diet ylamino(n-propoxy)diethylsilane, ethylmet ylarriino(n-propoxy)diethylsilane, diet ylamino(n-propoxy)diethylsilane, di-iso-propylarriino(n-propoxy)diethylsilane, pyrrolidino(n-propoxy)diethylsilane, piperidino(n-propoxy)diethylsilane, pyrrolyl(n- propoxy)diethylsilane, cyclohexyl methyla mino(n-propoxy)diethylsilane, dimethylamino(iso-propoxy)diethylsilane, ethylmethylamino(iso- propoxy)diethylsilane, diethylamino(iso-propoxy)diethylsilane, di-iso- propylamino(iso-propoxy)diethylsilane, pyrrolidino(iso-propoxy)diethylsilane, piperidino(iso-propoxy)diethylsilane, pyrrolyl(iso-propoxy)diethylsilane, cyclohexyl methy la mino(iso-propoxy)diethylsilane, dimethylamino(sec- butoxy)diethylsilane, ethylmethylamino(sec-butoxy)diethylsilane, diethylamino(sec- butoxy)diethylsilane, di-iso-propylamino(sec-butoxy)diethylsilane, pyrrolidino(sec- butoxy)diethylsilane, piperidino(sec-butoxy)diethylsilane, pyrrolyl(sec- butoxy)diethylsilane, cyclohexylmethylamino(sec-butoxy)diethylsilane, dimethylamino(cyclopentoxy)diethylsilane, ethylmethylamino(cyclopentoxy)diethylsilane, diethylamino(cyclopentoxy)diethylsilane, di-iso- propylamino(cyclopentoxy)diethylsilane, pyrrolidino(cyclopentoxy)diethylsilane, piperidino(cyclopentoxy)diethylsilane, pyrrolyl(cyclopentoxy)diethylsilane, cyclohexylmethylamino(cyclopentoxy)diethylsilane, dimethylamino(cyclohexoxy)diethylsilane, ethylmethylamino(cyclohexoxy)diethylsilane, diethylamino(cyclohexoxy)diethylsilane, di-iso- propylamino(cyclohexoxy)diethylsilane, pyrrolidino(cyclohexoxy)diethylsilane, piperidino(cyclohexoxy)diethylsilane, cyclohexyl methy la mino(cyclohexoxy)diethylsilane, dimet ylamino(met oxy)di-iso- propylsilane, ethylmet ylamino(met oxy)di-iso-propylsilane, diet ylamino(met oxy)di-iso-propylsilane, di-iso-propylamino(met oxy)di-iso- propylsilane, pyrrolidino(met oxy)di-iso-propylsilane, piperidino(methoxy)di-iso- propylsilane, pyrrolyl(met oxy)di-iso-propylsilane, cyclohexylmet ylamino(met oxy)di-iso-propylsilane, dimet ylamino(phenoxy)di-iso- propylsilane, ethylmet ylamino(phenoxy)di-iso-propylsilane, diet ylamino(phenoxy)di-iso-propylsilane, di-iso-propylamino(phenoxy)di-iso- propylsilane, pyrrolidino(phenoxy)di-iso-propylsilane, piperidino(phenoxy)di-iso- propylsilane, pyrrolyl(phenoxy)di-iso-propylsilane, cyclohexyl methy la mino(phenoxy)di-iso-propylsilane, dimethylamino(ethoxy)di-iso- propylsilane, ethyl methylarriino(ethoxy)di-iso-propylsilane, diethylamino(ethoxy)di- iso-propylsilane, di-iso-propylamino(ethoxy)di-iso-propylsilane, pyrrolidino(ethoxy)di-iso-propylsilane, piperidino(ethoxy)di-iso-propylsilane, pyrrolyl(ethoxy)di-iso-propylsilane, cyclohexyl methyla mino(ethoxy)di-iso- propylsilane, diethylarriino(n-propoxy)di-iso-propylsilane, ethylmethylamino(n- propoxy)di-iso-propylsilane, diethylarriino(n-propoxy)di-iso-propylsilane, di-iso- propylamino(n-propoxy)di-iso-propylsilane, pyrrolidino(n-propoxy)di-iso- propylsilane, piperidino(n-propoxy)di-iso-propylsilane, pyrrolyl(n-propoxy)di-iso- propylsilane, cyclohexylrriethylarriino(n-propoxy)di-iso-propylsilane, dirriethylarriino(iso-propoxy)di-iso-propylsilane, ethylmethylamino(iso-propoxy)di- iso-propylsilane, diethylamino(iso-propoxy)di-iso-propylsilane, di-iso- propylamino(iso-propoxy)di-iso-propylsilane, pyrrolidino(iso-propoxy)di-iso- propylsilane, piperidino(iso-propoxy)di-iso-propylsilane, pyrrolyl(iso-propoxy)di-iso- propylsilane, cyclohexylmethylamino(iso-propoxy)di-iso-propylsilane, dimethylarriino(sec-butoxy)di-iso-propylsilane, ethyl methy la mino(sec-butoxy)di-iso- propylsilane, diethylamino(sec-butoxy)di-iso-propylsilane, di-iso-propylamino(sec- butoxy)di-iso-propylsilane, pyrrolidino(sec-butoxy)di-iso-propylsilane, piperidino(sec- butoxy)di-iso-propylsilane, pyrrolyl(sec-butoxy)di-iso-propylsilane, cyclohexyl methy la mino(sec-butoxy)di-iso-propylsilane, dimethy lamino(cyclopentoxy)di-iso-propylsilane, ethyl methylamino(cyclopentoxy)di- iso-propylsilane, diethylamino(cyclopentoxy)di-iso-propylsilane, di-iso- propylamino(cyclopentoxy)di-iso-propylsilane, pyrrolidino(cyclopentoxy)di-iso- propylsilane, piperidino(cyclopentoxy)di-iso-propylsilane, pyrrolyl(cyclopentoxy)di- iso-propylsilane, cyclohexylmet ylamino(cyclopentoxy)di-iso-propylsilane, dimet ylamino(cyclohexoxy)di-iso-propylsilane, ethylmethylamino(cyclohexoxy)di- iso-propylsilane, diethylamino(cyclohexoxy)di-iso-propylsilane, di-iso- propylamino(cyclohexoxy)di-iso-propylsilane, pyrrolidino(cyclohexoxy)di-iso- propylsilane, piperidino(cyclohexoxy)di-iso-propylsilane, cyclohexyl methy la mino(cyclohexoxy)di-iso-propylsilane, dimethylamino(methoxy)diphenylsilane, ethylmethylamino(methoxy)diphenylsilane, diethylamino(methoxy)diphenylsilane, di-iso-propylamino(methoxy)diphenylsilane, pyrrolidino(methoxy)diphenylsilane, piperidino(methoxy)diphenylsilane, pyrrolyl(methoxy)diphenylsilane, cyclohexylmethylamino(methoxy)diphenylsilane, dimethylamino(phenoxy)diphenylsilane, ethylmethylamino(phenoxy)diphenylsilane, diethylamino(phenoxy)diphenylsilane, di-iso-propylamino(phenoxy)diphenylsilane, pyrrolidino(phenoxy)diphenylsilane, piperidino(phenoxy)diphenylsilane, pyrrolyl(phenoxy)diphenylsilane, cyclohexyl methylamino(phenoxy)diphenylsilane, dimethylamino(ethoxy)diphenylsilane, ethylmethylamino(ethoxy)diphenylsilane, diethylamino(ethoxy)diphenylsilane, di-iso-propylamino(ethoxy)diphenylsilane, pyrrolidino(ethoxy)diphenylsilane, piperidino(ethoxy)diphenylsilane, pyrrolyl(ethoxy)diphenylsilane, cyclohexylmethylamino(ethoxy)diphenylsilane, diethylamino(n-propoxy)diphenylsilane, ethylmethylamino(n- propoxy)diphenylsilane, diethylamino(n-propoxy)diphenylsilane, di-iso- propylamino(n-propoxy)diphenylsilane, pyrrolidino(n-propoxy)diphenylsilane, piperidino(n-propoxy)diphenylsilane, pyrrolyl(n-propoxy)diphenylsilane, cyclohexylmethylamino(n-propoxy)diphenylsilane, dimethylamino(iso- propoxy)diphenylsilane, ethylmethylamino(iso-propoxy)diphenylsilane, diethylamino(iso-propoxy)diphenylsilane, di-iso-propylamino(iso- propoxy)diphenylsilane, pyrrolidino(iso-propoxy)diphenylsilane, piperidino(iso- propoxy)diphenylsilane, pyrrolyl(iso-propoxy)diphenylsilane, cyclohexylmethylamino(iso-propoxy)diphenylsilane, dimethylamino(sec- butoxy)diphenylsilane, ethylmethylamino(sec-butoxy)diphenylsilane, diethylamino(sec-butoxy)diphenylsilane, di-iso-propylamino(sec- butoxy)diphenylsilane, pyrrolidino(sec-butoxy)diphenylsilane, piperidino(sec- butoxy)diphenylsilane, pyrrolyl(sec-butoxy)diphenylsilane, cyclohexylmethylamino(sec-butoxy)diphenylsilane, dimethylamino(cyclopentoxy)diphenylsilane, ethylmethylamino(cyclopentoxy)diphenylsilane, diethylamino(cyclopentoxy)diphenylsilane, di-iso- propylamino(cyclopentoxy)diphenylsilane, pyrrolidino(cyclopentoxy)diphenylsilane, piperidino(cyclopentoxy)diphenylsilane, pyrrolyl(cyclopentoxy)diphenylsilane, cyclohexyl methy la mino(cyclopentoxy)diphenylsilane, dimethylamino(cyclohexoxy)diphenylsilane, ethylmethylamino(cyclohexoxy)diphenylsilane, diethylamino(cyclohexoxy)diphenylsilane, di-iso- propylamino(cyclohexoxy)diphenylsilane, pyrrolidino(cyclohexoxy)diphenylsilane, piperidino(cyclohexoxy)diphenylsilane, and cyclohexylmethylamino(cyclohexoxy)diphenylsilane.
[0040] In certain aspects, the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dethylethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(sec-butoxy)dimethylsilane, dimethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, ethylmethylamino (cyclohexoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, and cyclohexylmethylamino(methoxy)dimethylsilane.
[0041] In certain aspects, the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethylmethylamino(dimethoxy)methylsilane, diethylamino(dimethoxy)methylsilane, di-iso-propylamino(dimethoxy)methylsilane, pyrrolidino(dimethoxy) methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, cyclohexylmethylamino(dimethoxy)methylsilane, dimethylamino(diphenoxy)methylsilane, ethylmethylamino(diphenoxy)methylsilane, diethylamino(diphenoxy)methylsilane, di-iso-propylamino(diphenoxy)methylsilane, pyrrolidino(diphenoxy)methylsilane, piperidino(diphenoxy)methylsilane, pyrrolyl(diphenoxy)methylsilane, cyclohexylmethylamino(diphenoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethylamino(diethoxy)methylsilane, diethylamino(diethoxy)methylsilane, di-iso-propylamino(diethoxy)methylsilane, pyrrolidino(diethoxy)methylsilane, piperidino(diethoxy)methylsilane, pyrrolyl(diethoxy)methylsilane, cyclohexylmethylamino(diethoxy)methylsilane, dimethylamino(di-n-propoxy) methylsilane, ethylmethylamino(di-n- propoxy)methylsilane, diethylamino(di-n-propoxy)methylsilane, di-iso- propylamino(di-n-propoxy)methylsilane, pyrrolidino(di-n-propoxy)methylsilane, piperidino(di-n-propoxy)methylsilane, pyrrolyl(di-n-propoxy)methylsilane, cyclohexylmethylamino(di-n-propoxy)methylsilane, dimethylamino(di-iso- propoxy)methylsilane, ethylmethylamino(di-iso-propoxy)methylsilane, diethylamino(di-iso-propoxy)methylsilane, di-iso-propylamino(di-iso- propoxy)methylsilane, pyrrolidino(di-iso-propoxy)methylsilane, piperidino(di-iso- propoxy)methylsilane, pyrrolyl(di-iso-propoxy)methylsilane, cyclohexylmethylamino(di-iso-propoxy)methylsilane, dimethylamino(di-sec- butoxy)methylsilane, ethylmethylamino(di-sec-butoxy)methylsilane, diethylamino(di-sec-butoxy)methylsilane, di-iso-propylamino(di-sec- butoxy)methylsilane, pyrrolidino(di-sec-butoxy)methylsilane, piperidino(di-sec- butoxy) methylsilane, pyrrolyl(di-sec-butoxy)methylsilane, cyclohexyl methylamino(di- sec-butoxy)methylsilane dimethylamino(dicyclopentoxy)methylsilane, ethylmethylamino(dicyclopentoxy)methylsilane, diethylamino(dicyclopentoxy)methylsilane, di-iso- propylamino(dicyclopentoxy)methylsilane, pyrrolidino(dicyclopentoxy)methylsilane, piperidino(dicyclopentoxy)methylsilane, pyrrolyl (dicyclopentoxy) methylsilane, cyclohexylmethylamino(dicyclopentoxy)methylsilane, dimethylamino(dicyclohexoxy)methylsilane, ethylmethylamino(dicyclohexoxy)methylsilane, diethylamino(dicyclohexoxy)methylsilane, di-iso- propylamino(dicyclohexoxy)methylsilane, pyrrolidino(dicyclohexoxy)methylsilane, piperidino(dicyclohexoxy)methylsilane, cyclohexylmethylamino(dicyclohexoxy)methylsilane, dirriethylarriino(dirnethoxy)ethylsilane, ethylrriethylarriino(dirriethoxy)ethylsilane, diethylamino(dimethoxy)ethylsilane, di-iso-propylamino(dimethoxy)ethylsilane, pyrrolidino(dimethoxy)ethylsilane, piperidino(dimethoxy)ethylsilane, pyrrolyl(dimethoxy)ethylsilane, cyclohexyl methylarriino(dirriethoxy)ethylsilane, dimethylamino(diphenoxy)ethylsilane, ethylmethylamino(diphenoxy)ethylsilane, diethylamino(diphenoxy)ethylsilane, di-iso-propylamino(diphenoxy)ethylsilane, pyrrolidino(diphenoxy)ethylsilane, piperidino(diphenoxy)ethylsilane, pyrrolyl(diphenoxy)ethylsilane, cyclohexyl methyla mi no(diphenoxy)ethylsilane, dimethylamino(diethoxy)ethylsilane, ethylmethylamino(diethoxy)ethylsilane, diethylamino(diethoxy)ethylsilane, di-iso-propylamino(diethoxy)ethylsilane, pyrrolidino(diethoxy)ethylsilane, piperidino(diethoxy)ethylsilane, pyrrolyl(diethoxy)ethylsilane, cyclohexylmethylamino(diethoxy)ethylsilane, diethylamino(di-n-propoxy)ethylsilane, ethylmethylamino(di-n-propoxy)ethylsilane, diethylamino(di-n-propoxy)ethylsilane, di-iso-propylamino(di-n-propoxy)ethylsilane, pyrrolidino(di-n-propoxy)ethylsilane, piperidino(di-n-propoxy)ethylsilane, pyrrolyl(di- n-propoxy)ethylsilane, cyclohexylmethylamino(di-n-propoxy)ethylsilane, dimethylamino(di-iso-propoxy)ethylsilane, ethylmethylamino(di-iso- propoxy)ethylsilane, diethylamino(di-iso-propoxy)ethylsilane, di-iso-propylamino(di- iso-propoxy)ethylsilane, pyrrolidino(di-iso-propoxy)ethylsilane, piperidino(di-iso- propoxy)ethylsilane, pyrrolyl(di-iso-propoxy)ethylsilane, cyclohexyl methylamino(di- iso-propoxy)ethylsilane, dimethylamino(di-sec-butoxy)ethylsilane, ethylmethylamino(di-sec-butoxy)ethylsilane, diethylamino(di-sec-butoxy)ethylsilane, di-iso-propylamino(di-sec-butoxy)ethylsilane, pyrrolidino(di-sec-butoxy)ethylsilane, piperidino(di-sec-butoxy)ethylsilane, pyrrolyl(di-sec-butoxy)ethylsilane, cyclohexylmethylamino(di-sec-butoxy)ethylsilane, dimethylamino(dicyclopentoxy)ethylsilane, ethylmethylamino(dicyclopentoxy)ethylsilane, diethylamino(dicyclopentoxy)ethylsilane, di-iso- propylamino(dicyclopentoxy)ethylsilane, pyrrolidino(dicyclopentoxy)ethylsilane, piperidino(dicyclopentoxy)ethylsilane, pyrrolyl(dicyclopentoxy)ethylsilane, cyclohexylmethylamino(dicyclopentoxy)ethylsilane, dimethylamino(dicyclohexoxy)ethylsilane, ethylmethylamino(dicyclohexoxy)ethylsilane, diethylamino(dicyclohexoxy)ethylsilane, di-iso- propylamino(dicyclohexoxy)ethylsilane, pyrrolidino(dicyclohexoxy)ethylsilane, piperidino(dicyclohexoxy)ethylsilane, cyclohexyl methy la mino(dicyclohexoxy)ethylsilane, dimethylamino(dimethoxy)iso- propylsilane, ethylmethylamino(dimethoxy)iso-propylsilane, diethylamino(dimethoxy)iso-propylsilane, di-iso-propylamino(dimethoxy)iso- propylsilane, pyrrolidino(dimethoxy)iso-propylsilane, piperidino(dimethoxy)iso- propylsilane, pyrrolyl(dimethoxy)iso-propylsilane, cyclohexylmethylamino(dimethoxy)iso-propylsilane, dimethylamino(diphenoxy)iso- propylsilane, ethyl methylamino(diphenoxy)iso-propylsilane, diethylamino(diphenoxy)iso-propylsilane, di-iso-propylamino(diphenoxy)iso- propylsilane, pyrrolidino(diphenoxy)iso-propylsilane, piperidino(diphenoxy)iso- propylsilane, pyrrolyl(diphenoxy)iso-propylsilane, cyclohexylmethylamino(diphenoxy)iso-propylsilane, dimethylamino(diethoxy)iso- propylsila ne, ethylmethylamino(diethoxy)iso-propylsilane, diethylamino(diethoxy)iso-propylsilane, di-iso-propylamino(diethoxy)iso- propylsilane, pyrrolidino(diethoxy)iso-propylsilane, piperidino(diethoxy)iso- propylsilane, pyrrolyl(diethoxy)iso-propylsilane, cyclohexylmethylamino(diethoxy)iso-propylsilane, diethylamino(di-n-propoxy)iso- propylsilane, ethyl methylamino(di-n-propoxy)iso-propylsilane, diet ylamino(di-n- propoxy)iso-propylsilane, di-iso-propylamino(di-n-propoxy)iso-propylsilane, pyrrolidino(di-n-propoxy)iso-propylsilane, piperidino(di-n-propoxy)iso-propylsilane, pyrrolyl(di-n-propoxy)iso-propylsilane, cyclohexyl methylamino(di-n-propoxy)iso- propylsilane, dimethylamino(di-iso-propoxy)iso-propylsilane, ethyl methylamino(di- iso-propoxy)iso-propylsilane, diethylamino(di-iso-propoxy)iso-propylsilane, di-iso- propylamino(di-iso-propoxy)iso-propylsilane, pyrrolidino(di-iso-propoxy)iso- propylsilane, piperidino(di-iso-propoxy)iso-propylsilane, pyrrolyl(di-iso-propoxy)iso- propylsilane, cyclohexylmethylamino(di-iso-propoxy)iso-propylsilane, dimethylamino(di-sec-butoxy)iso-propylsilane, ethyl methyla mino(di-sec-butoxy)iso- propylsilane, diethylamino(di-sec-butoxy)iso-propylsilane, di-iso-propylamino(di-sec- butoxy)iso-propylsilane, pyrrolidino(di-sec-butoxy)iso-propylsilane, piperidino(di-sec- butoxy)iso-propylsilane, pyrrolyl(di-sec-butoxy)iso-propylsilane, cyclohexyl methy la mino(di-sec-butoxy)iso-propylsilane, dimethylamino(dicyclopentoxy)iso-propylsilane, ethylmethylamino(dicyclopentoxy)iso-propylsilane, diethylamino(dicyclopentoxy)iso- propylsilane, di-iso-propylamino(dicyclopentoxy)iso-propylsilane, pyrrolidino(dicyclopentoxy)iso-propylsilane, piperidino(dicyclopentoxy)iso- propylsilane, pyrrolyl(dicyclopentoxy)iso-propylsilane, cyclohexyl methy la mino(dicyclopentoxy)iso-propylsilane, dimethylamino(dicyclohexoxy)iso-propylsilane, ethylmethylamino(dicyclohexoxy)iso- propylsilane, diethylamino(dicyclohexoxy)iso-propylsilane, di-iso- propylamino(dicyclohexoxy)iso-propylsilane, pyrrolidino(dicyclohexoxy)iso- propylsilane, piperidino(dicyclohexoxy)iso-propylsilane, cyclohexyl methy la mino(dicyclohexoxy)iso-propylsilane, dimethy lamino(methoxy)phenylsilane, ethylmethylamino(methoxy)phenylsilane, diethylamino(methoxy)phenylsilane, di-iso-propylamino(methoxy)phenylsilane, pyrrolidino(methoxy)phenylsilane, piperidino(methoxy)phenylsilane, pyrrolyl(methoxy)phenylsilane, cyclohexylmethylamino(methoxy)phenylsilane, dimethylamino(phenoxy)phenylsilane, ethylmethylamino(phenoxy)phenylsilane, diethylamino(phenoxy)phenylsilane, di-iso-propylamino(phenoxy)phenylsilane, pyrrolidino(phenoxy)phenylsilane, piperidino(phenoxy)phenylsilane, pyrrolyl(phenoxy)phenylsilane, cyclohexylmethylamino(phenoxy)phenylsilane, dimethylamino(ethoxy)phenylsilane, ethylmethylamino(ethoxy)phenylsilane, diethylamino(ethoxy)phenylsilane, di-iso-propylamino(ethoxy)phenylsilane, pyrrolidino(ethoxy) phenylsilane, piperidino(ethoxy)phenylsilane, pyrrolyl (ethoxy) phenylsilane, cyclohexylmethylamino(ethoxy)phenylsilane, diethylamino(n-propoxy)phenylsilane, ethylmethylamino(n-propoxy)phenylsilane, diethylamino(n-propoxy)phenylsilane, di-iso-propylamino(n-propoxy)phenylsilane, pyrrolidino(n-propoxy) phenylsilane, piperidino(n-propoxy)phenylsilane, pyrrolyl(n- propoxy)phenylsilane, cyclohexylmethylamino(n-propoxy)phenylsilane, dimethylamino(iso-propoxy)phenylsilane, ethyl methylamino(iso- propoxy)phenylsilane, diethylamino(iso-propoxy)phenylsilane, di-iso- propylamino(iso-propoxy)phenylsilane, pyrrolidino(iso-propoxy)phenylsilane, piperidino(iso-propoxy) phenylsilane, pyrrolyl(iso-propoxy)phenylsilane, cyclohexyl methy la mino(iso-propoxy)phenylsilane, dimethylamino(sec- butoxy)phenylsilane, ethylmethylamino(sec-butoxy)phenylsilane, diethylamino(sec- butoxy)phenylsilane, di-iso-propylamino(sec-butoxy) phenylsilane, pyrrolidino(sec- butoxy)phenylsilane, piperidino(sec-butoxy)phenylsilane, pyrrolyl(sec- butoxy)phenylsilane, cyclohexylmethylamino(sec-butoxy)phenylsilane, dimethylamino(cyclopentoxy)phenyl, ethylmethylamino(cyclopentoxy)phenylsilane, diethylamino(cyclopentoxy)phenylsilane, di-iso- propy la mino(cyclopentoxy) phenylsilane, pyrrolidino(cyclopentoxy)phenylsilane, piperidino(cyclopentoxy)phenylsilane, pyrrolyl(cyclopentoxy)phenylsilane, cyclohexylmethylamino(cyclopentoxy)phenylsilane, dimethylamino(cyclohexoxy)phenylsilane, ethylmethylamino(cyclohexoxy)phenylsilane, diethylamino(cyclohexoxy)phenylsilane, di-iso- propylamino(cyclohexoxy)phenylsilane, pyrrolidino(cyclohexoxy)phenylsilane, piperidino(cyclohexoxy)phenylsilane, and cyclohexylmethylamino(cyclohexoxy)phenylsilane.
[0042] In certain aspects, the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy)methylsilane, ethylmethylamino(dimethoxy)methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
[0043] In a further aspect of the first main aspect, wherein the passivating composition comprises an organoamino-alkoxysilane chosen from the group consisting of:
[0044] Preferably, the first surface is a silicon-containing material comprising predominantly hydroxyl groups is selected from the group consisting of silicon oxide and carbon doped silicon oxide, while the second surface comprising a dielectric material is selected from the group consisting of silicon nitride, amorphous silicon. The second surface may comprise a metal, including 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.
[0045] In a second aspect of this disclosure, a method is provided for selective deposition of silicon nitride, carbon doped silicon nitride, or silicon oxynitride. The method comprises: (a) providing the substrate in a reaction vessel at temperature at 600 °C or higher, the substrate having a first surface comprising a dielectric material with hydroxyl groups and a second surface comprising a different dielectric material or metal with fewer hydroxyl groups, wherein the second surface preferably comprises silicon nitride;
(b) forming at least one passivated layer on the first surface by exposing the first surface and the second surface to a passivating composition comprising an organoamino-alkoxysilane having one of the following formulae:
IA IB wherein R1 and R2 are each independently selected from a Ci to Cw alkyl group, a C3 to C10 cyclic alkyl group, Cg to Cw aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure;
(c) purging the reactor with inert gas;
(d) introducing a halogenated silicon-containing precursor into the reactor to react with the silicon nitride or carbon doped silicon nitride film to form a silicon-containing layer;
(e) purging the reactor using inert gas;
(f) introducing a nitrogen source to react with the silicon-containing layer to form a silicon nitride or carbon doped silicon nitride layer;
(g) purging the reactor using inert gas [0046] Steps (d) to (g) in this embodiment may be repeated to provide a certain thickness of silicon nitride or carbon doped silicon nitride or silicon oxynitride. In some embodiments, step (b) and (c) can be repeated to achieve a self-limiting monolayer passivation layer on the first surface before Steps (d) to (g) are conducted.
[0047] 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 tertbutylamine, dimethylamine, diethylamine, iso-propylamine, diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and an alkoxyamine such as ethanolamine plasma, and mixtures thereof. In yet other embodiments, the nitrogen-containing source comprises an ammonia plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium or a plasma comprising hydrogen and nitrogen source gas.
[0048] Preferably, the halogenated silicon-containing compounds can be selected from the group consisting of: (i) halogenated silanes, (ii) halogenated siloxanes, (iii) halogenated silazanes, and (iv) halogenated carbosilanes.
[0049] The halogenated silanes of group (i) include but are not limited to, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, trichlorosilane, tetrachlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.
[0050] As described above, a need exists in the art to deposit dielectric materials, such as silicon nitride, selectively on top of a dielectric surface relative to a different dielectric surface in a semiconductor manufacturing process using a thermal process without using a plasma at temperatures ranging from 500 to 800 °C with high selectivity. [0051] The thickness of aluminum oxide on SiO? (non-growth surface, NGS) and
SiN (growth surface, GS) is measured by XRF-XRR thickness calibration, and
I . . .. . I I . . , . , Thk GS ]-Thk NGS selectivity
1 is calculated by 1 using b formula: - - — - - . Thk [GS]+Thk [NGS]
[0052] In a preferred embodiment, the deposited film is a silicon-containing film. Preferably, the deposited dielectric materials include silicon nitride, carbon doped silicon nitride, and silicon dioxide films. In the illustrated embodiment, the deposited film is an aluminum-containing film.
[0053] The selectivity is defined as (the thickness of aluminum-containing film on the silicon nitride material - the thickness of aluminum-containing film on the silicon dioxide dielectric material)/(the thickness of aluminum-containing film on the silicon nitride material + the thickness of silicon-containing film on the silicon dioxide dielectric material). The selectivity is preferred to be 30% or greater, or 40% or greater, or 50% or greater, 60% or greater.
[0054] Accordingly, In a second aspect, disclosed herein in, is a novel, and non- obvious, selective thermal atomic layer deposition process, that selectively deposits aluminum-containing dielectric materials on top of a dielectric material relative to a metal, in an ALD reactor. This method comprises:
(a) providing the substrate in a reaction vessel at temperature at 600 °C or higher, the substrate having a first surface comprising a dielectric material with hydroxyl groups and a second surface comprising a different dielectric material or metal with fewer hydroxyl groups, wherein the second surface preferably comprises metal;
(b) introducing a passivating composition comprising an organoamino- alkoxysilane having one of the following formulae:
IA IB wherein R1 and R2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure;
(c) purging the reactor with inert gas;
(d) Introducing an aluminum precursor into the reactor to react with the dielectric material to form an aluminum-containing layer;
(e) purging the reactor with inert gas;
(f) introducing a vapor comprising water into the reactor to react with the aluminum-containing layer to form an aluminum oxide layer; and
(g) purging the reactor with inert gas.
[0055] Steps (d) to (g) may be repeated to deposit a desired aluminum-containing dielectric films on top of the dielectric material. In some embodiments, step (b) and (c) can be repeated to allow a self-limiting monolayer passivation layer on the first surface before Step (d) to (g) are repeated to deposit a desired aluminum oxide. In other embodiments, step (b) and (c) can be conducted after Step (d) to (g) are repeated to deposit a desired aluminum oxide, followed by repeating Step (d) to (g) to provide a thicker aluminum oxide. The thickness of the aluminum-containing dielectric films 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 which is preferred to be 30% or greater, or 40% or greater, or 50% or greater, 60% or greater. The aluminum precursor can be selected from the group consisting of triethylaluminum, dimethylaluminum iso-propoxide, and diethylaluminum iso- propoxide.
[0056] In second aspect, a thermal atomic layer deposition (ALD) process, that selectively deposits aluminum-containing dielectric materials on top of a dielectric material relative to a metal, in an ALD reactor. This method comprises:
(a) providing the substrate in a reaction vessel at temperature at 400 °C or lower, the substrate having a first surface comprising a dielectric material with hydroxyl groups and a second surface comprising a different dielectric material or metal with fewer hydroxyl groups, wherein the second surface preferably comprises metal;
(b) introducing a passivating composition comprising an organoamino- alkoxysilane having one of the following formulae: IB wherein R1 and R2 are each independently selected from a Ci to Cw alkyl group, a C3 to C10 cyclic alkyl group, Cg to Cw aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure;
(c) Purging the reactor with inert gas;
(d) introducing an aluminum precursor into the reactor to react with the dielectric material to form an aluminum-containing layer; (e) purging the reactor with inert gas;
(f) introducing a vapor comprising an alkoxysilanol into the reactor to react with the aluminum-containing layer to form an aluminum silicon oxide layer; and
(g) purging the reactor with inert gas.
[0057] Steps (d) to (g) may be repeated to deposit a desired thickness of the aluminum doped silicon oxide dielectric film on top of the dielectric material. In some embodiments, step (b) and (c) can be repeated to allow a self-limiting monolayer passivation layer on the first surface before Step (d) to (g) are repeated to deposit a desired aluminum oxide, followed by repeating Step (d) to (g) to provide a thicker aluminum oxide. In other embodiments, step (b) and (c) can be conducted after Step (d) to (g) are repeated to deposit a desired aluminum oxide, followed by repeating Step (d) to (g) to provide a thicker aluminum oxide. The thickness of the aluminum- containing dielectric films 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 what targeted thickness for a required selectivity which is preferred to be 60% or greater, or 70% or greater, or 80% or greater, 90% or greater. The aluminum precursor is selected from the group consisting of triethylaluminum, dimethylaluminum iso-propoxide (DMAI), diethylaluminum iso-propoxide. The alkoxysilanol is selected from the group consisting of tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, bis(tert-butoxy)(tert- pentoxy)silanol, and bis(tert-pentoxy)(tert-butoxy)silanol.
[0058] In a 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 oxynitride, silicon nitride, and metal oxide such as zirconium oxide, hafnium oxide, silicon doped zirconium oxide, silicon doped hafnium oxide, or any other high k materials. The metal in a preferred embodiment may be selected from selected from the group consisting of cobalt, aluminum, copper, tantalum, ruthenium, molybdenum, tungsten, platinum, iridium, nickel, titanium, silver, gold, or a combination thereof.
[0059] Accordingly, disclosed herein in a first aspect, is a novel, and non-obvious, selective thermal atomic layer deposition (ALD) process, that selectively deposits dielectric materials on top of a dielectric material, in an ALD reactor.
[0060] In a 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 oxynitride, silicon nitride, and metal oxide such as zirconium oxide, hafnium oxide, silicon doped zirconium oxide, silicon doped hafnium oxide, or any other high k materials. The metal in a preferred embodiment may be selected from selected from the group consisting of cobalt, aluminum, copper, tantalum, ruthenium, molybdenum, tungsten, platinum, iridium, nickel, titanium, silver, gold, or a combination thereof.
[0061] In a third aspect, embodiment of the disclosure provides a process to deposit a silicon-containing film comprising steps of:
(a) providing a substrate in a reactor with temperature ranging from 20 °C to 800 °C;
(b) introducing into the reactor at least one organoamino-alkoxysilane precursor compound according to Formula IA or IB as defined herein; wherein R1 and R2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure
(c) purging the reactor with purge gas;
(d) introducing an oxygen source into the reactor; and
(e) purging the reactor with purge gas, wherein steps b through e are repeated until a desired thickness of film is deposited.
[0062] The oxygen source is selected from water (H2O) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide, oxygen (O2), oxygen plasma, ozone (O3), N2O, N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma, hydrogen/oxygen, and combinations thereof. Not being bound by theory, for ALD or ALD-like deposition process at one or more temperatures less than 700 °C, the organoamino-alkoxysilane precursor compound should have at least one anchoring functionality, which reacts with certain reactive sites on the substrate surface to anchor a monolayer of silicon species. The anchoring functionality of a smaller organoamino group such as dimethylamino, ethylmethylamino or diethylamino allow the organoamino-alkoxysilane to have a relatively low boiling point and a relatively high reactivity. The organoamino- alkoxysilane precursor compound should also have a passive functionality in that it is chemically stable to prevent further surface reaction, leading to a self-limiting process. The passivating functionality is selected from different alkyl groups such methoxy groups. The remaining groups on the surface can then be oxidized to form silicon-containing layer as well as hydroxyl groups. In addition, hydroxyl sources such as H2O or water plasma can also be introduced into the reactor to form more hydroxyl groups as reactive sites for the next ALD cycle. The substrate temperatures for the method described herein use one or more of the following temperatures as endpoints: 20 °C, 50 °C, 75 °C, 100 °C, 125 °C, 150 °C, 175 °C, 200 °C, 225 °C, 250 °C, 275 °C, 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, 425 °C, 450 °C, 500 °C, 525 °C, 550 °C,
600 °C, 650 °C, 700 °C, 750 °C, 760 °C, and 800 °C.
[0063] 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.
[0064] 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 bake the 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.). [0065] Likewise, the films that can be used in the methods described herein are quite varied. In some embodiments, the films may comprise, consist of, 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, SiO2, carbon doped silicon oxide, SiN, HfO2, ZrO2 etc.
[0066] 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 a dielectric such as silicon dioxide and at least a second surface comprising a further dielectric material such as silicon nitride.
[0067] In some embodiments, the disclosure provides methods of selectively depositing a film such as, for example, a silicon nitride, 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. In other embodiments, the disclosure provides methods of selectively depositing a film such as, for example, a silicon nitride, onto one surface of a substrate over a second surface on the same substrate wherein the two surfaces are not co-planar. 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 (non-passivated) 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.
[0068] The method of the present disclosure includes the optional step of contacting the surface of the substrate with a wet chemical composition to obtain a treated substrate. Exemplary wet chemical treatments include known chemical treatments such as, for example, RCA clean chemicals SC-1 and SC-2, aqueous HF, peroxide, H2SO4 / H2O2, NH4OH, buffered HF solutions, and mixtures thereof.
[0069] 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.
[0070] 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 hydrogen peroxide 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.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] Embodiments also include the step of drying at least the surface of the substrate after the rinsing step. The drying step is typically carried out by any suitable means, for example, the application of heat, iso-propyl alcohol (IPA) vapor drying, or by centripetal force.
[0075] 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, HF, CIF3, 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.
[0076] 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 iso-propyl), 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-l-propyl, 2-methyl-2-propyl, 2-methyl-l-butyl, 3-methyl-l-butyl, 2-methyl-3- butyl, 2-methyl-l-pentyl, 2,2-dimethyl-l-propyl, 3-methyl-l-pentyl, 4-methyl-l- pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-l- butyl, 3,3-dimethyl-l-butyl, 2-ethyl-l-butyl, and the like.
[0077] 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.
[0078] 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.
[0079] 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 or from 2 to 10 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl groups.
[0080] As used herein, the term "a I kynyl" 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.
[0081] As used herein, the phrase "optionally substituted" means that a substitution is optional and, therefore, includes both unsubstituted and substituted atoms and moieties. A "substituted" atom or moiety indicates that any hydrogen atom on the designated compound or moiety can be replaced with a selection from the indicated substituent groups, provided that the normal valency of the designated compound or moiety is not exceeded, and that the substitution results in a stable compound. For example, if a methyl group is optionally substituted, then 1, 2, or 3 hydrogen atoms on the carbon atom within the methyl group can be replaced with 1, 2, or 3 of the recited substituent groups.
[0082] As used herein, the term "phenyl" means -CgHs. A phenyl group can be unsubstituted or substituted with one, two, or three suitable substituents.
[0083] As used herein, the term "halo" means halogen groups and includes, but is not limited to, fluoro, chloro, bromo, and iodo.
[0084] As used herein, the term "R3 and R4 are linked to form a cyclic ring structure" refers a cyclic ring via forming C-C bond. Examples of cyclic ring structures include, but not limited to, pyrrolidino, pyrrolyl, piperidino.
[0085] 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.
[0086] 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 conjunction with 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). [0087] 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.
[0088] 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.
[0089] The temperature range of the reactions may be between room temperature and 800° C. In some cases, the temperature range of the reactions may be between room temperature and 650 °C. In yet other cases, the temperature range of the reactions may be between room temperature and 100° C. The pressure may range from 10-10 Torr to 3000 Torr and may be maintained under dynamic flow conditions (i.e., with a valve and a butterfly valve type arrangement) or may be maintained under static conditions (i.e., an evacuated chamber is exposed to the desired precursor(s) and / or co-reactant(s) until a total desired pressure 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 evacuated fully and reexposed to fresh precursor(s) and / or co-reactants as many times as necessary. Precursor(s) and / or co-reactants may be introduced using any mixtures and / or concentrations desired.
[0090] 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, and Ar, but also other gases such as Hzmay be used. 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.
[0091] The exposure chamber can be kept at near ambient temperature or can optionally be heated. Heat can be supplied to the outer walls of the chamber (hot wall) or only to the substrate (cold-wall reactor). Substrate heating in a cold wall reactor can be achieved by use of incident radiation through a transparent window (lamp heating), by resistive heating of the substrate itself or from resistive heating elements in the platform that the substrate is contacting, through induction or by other means known in the art. The temperature of the treatment is preferably between about 20 °C to about 400 °C, preferably between 20°C to about 200 °C, and most preferably between 20 °C to about 100 °C. The temperature can be constant during the exposure period or can vary within the specified temperature range.
[0092] 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.
[0093] The choice of the at least one organoamino-alkoxysilane and the exposing conditions used in this method should be optimized by standard experimentation to optimize selectivity of the protection afforded the silicon nitride surface against potential non-selective passivation, processing time, reagent cost, etc. depending on the requirements imposed by subsequent processing steps. For example, selectivity can be adjusted/optimized by varying the nature of the R1 or R2 group of the at least one organoamino-alkoxysilane having the structure represented by Formula IA or IB. Typically, since reactivity and selectivity are often inversely related, if the two surfaces are similar in chemistry, experimenting with the R1 or R2 group may be required to optimize the process.
Disclosed and Claimed Passivating Composition
[0094] Given the forgoing, in one embodiment the disclosed and claimed subject relates to passivating composition that include, consist essentially of and/or consist of an organoamino-alkoxysilane. The passivating composition is particularly well- suited for performing enhanced passivation of metallic substrates. In one aspect of this embodiment, the organoamino-alkoxysilane consists essentially of or consists of one or more organoamino-alkoxysilane.
[0095] In one embodiment, the organoamino-alkoxysilane having formula IA or IB is substantially free of impurities that may react with metallic surface during a passivation process. In one embodiment, the organoamino-alkoxysilane having formula IA or IB is substantially free of impurities that react with precursors during a deposition process.
[0096] In one embodiment, the organoamino-alkoxysilane having formula IA or IB is substantially free of impurities that passivate non-metallic surface and suppress growth on non-metallic surface.
[0097] In one embodiment, the organoamino-alkoxysilane having formula IA or IB is substantially free of halogen-containing impurities. In one aspect of this embodiment, the halogen-containing impurities are one or more of a fluorohydrocarbon, a chlorohydrocarbon, a bromohydrocarbon and an iodohydrocarbon. In one aspect of this embodiment, the organoamino-alkoxysilane 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 organoamino-alkoxysilane 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 organoamino-alkoxysilane having formula IA or IB has a residual concentration of halogen-containing impurities of less than about 100 ppm. In one aspect of this embodiment, the organoamino-alkoxysilane 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 organoamino-alkoxysilane 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 organoamino- alkoxysilane having formula IA or IB has a residual concentration of halogencontaining impurities of less than about 10 ppm. In one aspect of this embodiment, the organoamino-alkoxysilane having formula IA or IB is free of halogen-containing impurities. In the forgoing aspects, the residual concentration of halogen-containing 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 (IR), 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 halogencontaining impurities is detected by one or more of GC-MS, GC-ICP-MS, GC-ICP-OES, GC-FID, GC-ECD, HPLC and UV/Vis.
[0098] In one embodiment, the organoamino-alkoxysilane having formula IA or IB is purified by exposure to molecular sieves. In one embodiment, the organoamino- alkoxysilane having formula IA or IB is purified by exposure to silica gel. In one embodiment, the organoamino-alkoxysilane having formula IA or IB is purified by exposure to one or more adsorbent materials.
[0099] In one embodiment, the organoamino-alkoxysilane 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 organoamino-alkoxysilane is treated with metallic sodium. In another aspect embodiment, the metal and the organoamino-alkoxysilane are separated by filtration and the organoamino- alkoxysilane is distilled to remove non-volatile products of the reaction of impurities with metals.
[00100] In one embodiment, the organoamino-alkoxysilane having formula IA or IB is purified by exposure to activated carbon. In one aspect of this embodiment the organoamino-alkoxysilane is separated by filtration and is distilled to remove nonvolatile products after treatment with activated carbon.
EXAMPLES
Example 1. Synthesis of diethylamino(diethoxy)methylsilane (DEADEOMS).
[00101] Under the protection of nitrogen, diethylamine (160 g, 2.2 mol) was added dropwise over 6 hours to a stirred mixture of diethoxymethylsilane (267 g, 2.0 mol), THF (100 mL), and Ru3(CO)i2 (3.18 g, 0.00497 mol) at 45 °C in a 1-liter 3-neck roundbottom flask. The flask was vented to allow the hydrogen to be released. After the addition, the reaction mixture was continued to stir at 60 °C for 2 hours, then allowed to stir overnight at room temperature. The low-boilers were removed under reduced pressure, and crude product was collected by vacuum-transfer. The crude product was purified by vacuum-distillation to yield 361 g of 98.6% pure DEADEOMS, as analyzed by GC-TCD. The chemical structure was confirmed by GC-MS analysis. GC-MS showed the following mass peaks: 205 (M+), 190 (M-15), 174, 160, 146, 133, 119, 105, 89, 77, 61, 45. Example 2. Synthesis of dimethylamino(methoxy)dimethylsilane (DMAMODMS).
[00102] Under the protection of nitrogen, dimethylamino(chloro)dimethylsilane (1.00 g, 7.26 mmol) was quickly added to a stirred suspension of lithium methoxide (0.27 g, 7.1 mmol) in THF (2 g) and hexanes (2 g). After stirring the mixture overnight at room temperature, the reaction solution was filtered to remove the white lithium chloride solids and was determined by GC/GC-MS analysis to contain DMAMODMS as a major product. GC-MS showed the following mass peaks: 133 (M+), 118 (M-15), 102, 89, 75, 59, 45.
Example 3. Synthesis of dimethylamino(phenoxy)dimethylsilane (DMAPODMS).
[00103] Under the protection of nitrogen, a solution of lithium phenoxide in hexanes and THF was generated by adding dropwise n-butyllithium solution (2.5M in hexanes) to a stirred solution of phenol (0.68 g, 7.2 mmol) in THF (2 g) at room temperature. This solution was then added dropwise to a stirred solution of dimethylamino(chloro)dimethylsilane (1.00 g, 7.26 mmol) in THF (1 g) at room temperature. After stirring the mixture for 2 hours, the reaction solution was filtered to remove the lithium chloride solids and was determined by GC/GC-MS analysis to contain DMAPODMS as the major product. GC-MS showed the following mass peaks: 195 (M+), 180 (M-15), 165, 151, 137, 121, 102, 91, 77, 59, 42.
Examples 4-11. Synthesis of other organoamino-alkoxysilanes having Formula IA and IB.
[00104] Several other organoamino-alkoxysilane analogs were synthesized according to the general procedures described in Examples 1-3 above. The molecular structures were confirmed by GC-MS analysis of the reaction solutions, and the results are summarized in Table 1. TABLE 1. Exemplary Organoamino-alkoxysilanes Synthesized Example 12. Deposition of silicon-containing film using diethylamino(diethoxy)methylsilane (DEADEOMS)
[00105] Silicon-containing film can be deposited via a typical ALD or PEALD process comprising the following steps: a. introducing vapors of DEADEOMS into an ALD chamber loaded with substrate for a layer of silicon-containing moieties on the substrate; b. purging with inert gas to remove any unreacted DEADEOMS; c. introducing ozone as oxygen-containing source to react with the layer of silicon- containing moieties to form a silicon-containing layer; d. purging with inert gas. Steps a to d are repeated until a desired thickness of silicon-containing film is achieved. It is expected the resulting silicon-containing film contains silicon, oxygen, and carbon depending on the deposition parameters, such as substrate temperature, ozone concentration.
Example 13. Deposition of silicon-containing film using dimethylamino(methoxy)dimethylsilane (DMAMODMS)
[00106] Silicon-containing film can be deposited via a typical ALD or PEALD process comprising the following steps: a. introducing vapors of DMAMODMS into an ALD chamber loaded with substrate for a layer of silicon-containing moieties on the substrate; b. purging with inert gas to remove any unreacted DEADEOMS; c. introducing ozone as oxygen-containing source to react with the layer of silicon- containing moieties to form a silicon-containing layer; d. purging with inert gas. Steps a to d are repeated until a desired thickness of silicon-containing film is achieved. It is expected the resulting silicon-containing film contains silicon, oxygen, and carbon depending on the deposition parameters, such as substrate temperature, ozone concentration.
Example 14. Deposition of silicon-containing film using dimethylamino(phenoxy)dimethylsilane (DMAPODMS)
[00107] Silicon-containing film can be deposited via a typical ALD or PEALD process comprising the following steps: a. introducing vapors of DMAPODMS into an ALD chamber loaded with substrate for a layer of silicon-containing moieties on the substrate; b. purging with inert gas to remove any unreacted DEADEOMS; c. introducing ozone as oxygen-containing source to react with the layer of si I iconcontaining moieties to form a silicon-containing layer; d. purging with inert gas. Steps a to d are repeated until a desired thickness of silicon-containing film is achieved. It is expected the resulting silicon-containing film contains silicon, oxygen, and carbon depending on the deposition parameters, such as substrate temperature, ozone concentration.
Example 15. Selective Passivation of Silicon Oxide with Organoamino-alkoxysilanes.
[00108] Organoamino-alkoxysilanes selectively passivates the dielectric layer surface (preferably SiOz) versus the second surface (which may be a different silicon- containing material or a metal). This process is depicted in FIG. 1. The process results in the selectivity to grow thicker dielectric film on the second surface.
[00109] A first illustrative process is shown in FIG. 1. The substrate 100 comprises: a dielectric layer, forming a first surface 102 and a different silicon-containing material or a metal, forming a second surface 104. In the illustrated embodiment, the first surface 102 and the second surface 104 are coplanar.
[00110] Step 1 comprises a precleaning of the first surface 102 (comprising a dielectric material) and the second surface 104 (comprising a different silicon- containing material or a metal) of a substrate 100, preferably with an acid, Hz, high temperature, or a combination thereof. The first surface 102 and the second surface 104 are preferably coplanar, as a result of a chemical mechanical planarization (CMP) as shown in FIG. 1 prior to the precleaning step.
[00111] Step 2 comprises passivation of the first surface 102 and the second surface 104, which may be a metal nitride, by exposing the first surface 102 and the second surface 104 to the organoamino-alkoxysilane to form a passivating/blocking organic layer 106 employing a passivating composition. Following passivation of the first surface 102 and the second surface 104, Step 3 includes selectively depositing the aluminum containing dielectric layer 108 on the second surface 104 (comprising a dielectric), preferably by ALD of an aluminum precursor and a second precursor comprising oxygen or an alkoxysilanol.
[00112] A second illustrative process is shown in FIG. 2. The substrate 200 comprises: a dielectric layer (SiCh), forming a first surface 202 and a further silicon- containing material (SiN) forming a second surface 204. In the illustrated embodiment, the first surface 202 and the second surface 204 are coplanar.
[00113] Step 1 comprises a precleaning of the first surface (SiO?) 202 and the second surface (SiN) 204 of the substrate 200, preferably with an acid, H2, high temperature, or a combination thereof. 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. 2 prior to the precleaning step.
[00114] Step 2 comprises passivation of the first surface comprising a dielectric (SiCh) and the second surface comprising a second material (silicon nitride) to form a passivating/blocking organic layer 206 employing a passivating composition.
Following passivation of the first surface 202, Step 3 includes depositing the aluminum containing dielectric layer 208 on the second surface 204 (SiN), preferably by ALD of an aluminum precursor and a second precursor comprising oxygen or an alkoxysilanol.
[00115] Investigations of reactivity and surface coverage of amino-alkoxysilanes dimethylaminotrimethylsilane and dimethylamino(methoxy)dimethylsilane (DMAMODMS) on the silicon oxide surface were conducted using density functional theory (DFT) and semi-empirical molecular modeling.
[00116] The DFT calculations were carried out in Biovia Materials Studio R2022 and the Dmol3 application was used as the DFT calculator. The BLYP functional and DNP basis set were chosen for the calculations. A slab model of SiO2 was created with OH termination as the active sites. Periodic boundary conditions were included to capture the effects of multiple active sites. To calculate the ERXN, the equation Eproducts - EReactants was applied to the isolated reactants and formed products. To calculate EA, the energy of the transition state between the inhibitor and SiO? slab was first calculated and then the equation E-rransitionstate - EReactant was applied.
[00117] The surface coverage simulations were carried out using a semi-empirical method employed in the xTB-GFN software. To evaluate surface coverage, an SiO2 slab was created with 21 active sites. The inhibitor surface product was packed on the SiO2 slab, resembling a reacted inhibitor bonded with an active site. The surface product were packed as tightly as possible while considering steric effects. The initial models were then equilibrated in xTB-GFN and underwent a DFT-MD (molecular dynamics) simulation for lOps. The final trajectories were analyzed for successful surface coverage by various mechanisms. Surface coverage is achieved by inhibitors reacting with as many active sites as possible, in addition, if the inhibitor can cover unreacted active sites, then it makes them sterica lly unavailable and protected during deposition. The coverage percents on SiO? were calculated using the r .. . . # active sites -covered/reacted sites „ following equation coverages = - x 100.
It active sites
[00118] Table 2 shows the results of the DFT calculations and surface coverage simulations for dimethylaminotrimethylsilane (DMATMS), dimethylamino(methoxy)dimethylsilane (DMAMODMS), dimethylamino(phenoxy)dimethylsilane (DMAPODMS), and dimethylamino(dimethoxy)methylsilane (DMADMOMS), indicating DMAMODMS and DMAPODMS are more reactive and provide much higher surface coverage than known passivation agent DMATMS, while DMADMOS provides similar surface coverage as DMATMS. The total of reactive sites for the surface coverage simulations is 21 on silicon oxide surface.
TABLE 2
[00119] Once the dielectric surface is passivated, the second surface comprising, for example, silicon oxide, is active for further selective reactions such as, for example, a selective ALD deposition of alumina-containing film on the silicon oxide surface.
[00120] 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.
Example 16. Selective deposition of a dielectric film on passivated vs non-passivated silicon oxide surfaces.
[00121] Thermal silicon oxide substrates were passivated by dimethylaminotrimethylsilane (DMATMS) and diethylamino(diethoxy)methylsilane (DEADEOMS), followed by atomic layer deposition of aluminum oxide using dimethylaluminum iso-propoxide (DMAI) and water ALD process at 150 and 200°C, respectively. The thickness of aluminum oxide on silicon oxide, DMATMS passivated silicon oxide and DEADEOMS passivated silicon oxide were measured by XRF-XRR thickness calibration, and selectivity was calculated by using formula:
Thk [SiO2]-Thk[PassivatedSiO2]
Thk [SiO2]+77ifc [Passivated SiO2]'
[00122] FIG. 3 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide, and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 150°C deposition temperature;
[00123] FIG. 4 illustrates the thickness of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide, dimethylaminotrimethylsilane passivated silicon oxide, and diethylamino(diethoxy)methylsilane passivated silicon oxide vs number of cycles at 200°C deposition temperature;
[00124] FIG. 5 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 150°C deposition temperature; and
[00125] FIG. 6 illustrates the selectivity of atomic layer deposition of aluminum oxide employing dimethyl aluminum iso-propoxide and water on unpassivated silicon oxide vs dimethylaminotrimethylsilane passivated silicon oxide and unpassivated silicon oxide vs diethylamino(diethoxy)methylsilane passivated silicon oxide, respectively, for number of cycles at 200°C deposition temperature.
[00126] Those results demonstrate that diethylamino(diethoxy)methylsilane provides better passivation protection at less ALD cycles, i.e., thicker aluminum oxide and higher selectivity with ALD cycles less than 15 cycles which are consistent with the modeling results, i.e., the organoamino-alkoxysilane provides high surface coverage. It is believed that the organoamino groups react with the hydroxyl group to anchor the remaining moiety of the organoamino-alkoxysilane on the surface because the alkoxy groups help the reaction between the surface hydroxyl groups and organoamino groups to provide higher surface coverage and may also form hydrogen bond with remaining unreacted hydroxyl group on the surface to reduce the interaction between DMAI and hydroxyl groups. On the other hand, the alkoxy groups remained on the surface may also interact with DMAI to allow deposition of aluminum oxide when the number of ALD cycles is increased to more than 15.
[00127] It is anticipated that the disclosed and claimed methods could be used in conjunction with deposition tools commonly found at semiconductor manufacturing sites to produce molybdenum-containing layers for logic applications and other potential functions.
[00128] 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.
[00129] 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

CLAIMS What is claimed is:
1. A method for passivation of a surface of dielectric having hydroxyl groups comprising:
(a) providing the substrate in a reaction vessel at temperatures ranging from 20°C to 600°C, the substrate having a first surface comprising a dielectric material and a second surface comprising a different silicon- containing material or a metal;
(b) forming at least one passivation layer on the first surface by exposing a composition comprising an organoamino-alkoxysilane having one of the following formulae:
IA IB wherein R1 and R2 are each independently selected from a Ci to Cw alkyl group, a C3 to Cw cyclic alkyl group, Cg to Cw aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; and
(c) purging the reactor with inert gas.
2. The method of claim 1, wherein steps (b) to (c) are repeated to provide a fully covered passivation layer on the first surface.
3. The method of claim 1, wherein the second surface comprises a metal or metalloid chosen 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 wherein the second surface comprises a metal nitride chosen 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.
4. The method of claim 1, wherein the first surface is selected from the group consisting of silicon oxide and carbon doped silicon oxide, and wherein the second surface is selected from the group consisting of silicon nitride.
5. The method of claim 1, wherein the organoamino-alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dethylethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, dimethylamino(n- propoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(sec-butoxy)dimethylsilane, dimethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, ethyl methylamino (cyclohexoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, and cyclohexylmethylamino(methoxy)dimethylsilane.
6. The method of claim 1, wherein the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy) methylsilane, ethylmethylamino(dimethoxy)methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
7. The method of claim 1, wherein the organoamino-alkoxysilane is chosen from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dimethylamino(dimethoxy) methylsilane, diethylamino(diethoxy)methylsilane, and dimethylamino(diethoxy)methylsilane.
8. A composition for a vapor deposition of a passivation layer on dielectric material, the composition comprising an organoamino-alkoxysilane having one of the following formulae:
IA IB wherein R1 and R2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cio aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure wherein the organoamino-alkoxysilane is substantially free of one or more impurities selected from the group consisting of a halide, water, and metals.
9. The composition of claim 8, wherein the halides comprise chloride.
10. The composition of claim 9, wherein the chloride, if present, are present at a concentration of 50 ppm or less as measured by IC.
11. The composition of claim 9, wherein the chloride, if present, are present at a concentration of 10 ppm or less as measured by IC.
12. The composition of claim 9, wherein the chloride, if present, are present at a concentration of 5 ppm or less as measured by IC.
13. The composition of claim 8, wherein the organoamino-alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dethylethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, dimethylamino(n- propoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(sec-butoxy)dimethylsilane, dimethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, ethylmethylamino (cyclohexoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, and cyclohexylmethylamino(methoxy)dimethylsilane.
14. The composition of claim 8, wherein the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy) methylsilane, ethylmethylamino(dimethoxy)methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
15. The composition of claim 8, wherein the organoamino-alkoxysilane is chosen from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dimethylamino(dimethoxy) methylsilane, diethylamino(diethoxy)methylsilane, and dimethylamino(diethoxy)methylsilane.
16. A composition for a deposition of a silicon-containing film, the composition comprising an organoamino-alkoxysilane having one of the following formulae:
IA IB wherein R1 and R2 are each independently selected from a Ci to Cio alkyl group, a C3 to Cio cyclic alkyl group, Cg to Cw aryl group; R3 and R4 are each independently selected from a hydrogen, Ci to Cg alkyl group with a proviso that R3 and R4 cannot be both hydrogen; and either R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure wherein the organoamino-alkoxysilane is substantially free of one or more impurities selected from the group consisting of a halide, water, and metals.
17. The composition of claim 16, wherein the halides comprise chloride.
18. The composition of claim 17, wherein the chloride, if present, are present at a concentration of 50 ppm or less as measured by IC.
19. The composition of claim 17, wherein the chloride, if present, are present at a concentration of 10 ppm or less as measured by IC.
20. The composition of claim 17, wherein the chloride, if present, are present at a concentration of 5 ppm or less as measured by IC.
21. The composition of claim 16, wherein the organoamino-alkoxysilane having formula IA is selected from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dethylethylamino(phenoxy)dimethylsilane, dimethylamino(ethoxy)dimethylsilane, ethylmethylamino(ethoxy)dimethylsilane, diethylamino(ethoxy)dimethylsilane, dimethylamino(n- propoxy)dimethylsilane, dimethylamino(n-propoxy)dimethylsilane, dimethylamino(sec-butoxy)dimethylsilane, dimethylamino(cyclopentoxy)dimethylsilane, dimethylamino(cyclohexoxy)dimethylsilane, ethylmethylamino(cyclopentoxy)dimethylsilane, ethylmethylamino (cyclohexoxy)dimethylsilane, piperidino(methoxy)dimethylsilane, pyrrolyl(methoxy)dimethylsilane, and cyclohexylmethylamino(methoxy)dimethylsilane.
22. The composition of claim 16, wherein the organoamino-alkoxysilane having formula IB is selected from the group consisting of dimethylamino(dimethoxy) methylsilane, ethylmethylamino(dimethoxy)methylsilane, diethylamino(dimethoxy)methylsilane, diethylamino(diethoxy)methylsilane, dimethylamino(diethoxy)methylsilane, ethylmethyl(diethoxy)methylsilane, piperidino(dimethoxy)methylsilane, pyrrolyl(dimethoxy)methylsilane, and cyclohexylmethylamino(dimethoxy)methylsilane.
23. The composition of claim 16, wherein the organoamino-alkoxysilane is chosen from the group consisting of dimethylamino(methoxy)dimethylsilane, ethylmethylamino(methoxy)dimethylsilane, diethylamino(methoxy)dimethylsilane, dimethylamino(phenoxy)dimethylsilane, ethylmethylamino(phenoxy)dimethylsilane, dimethylamino(dimethoxy) methylsilane, diethylamino(diethoxy)methylsilane, and dimethylamino(diethoxy)methylsilane.
24. The composition of claim 16, wherein the deposition is plasma enhanced atomic layer deposition to form the silicon-containing film.
PCT/EP2025/059336 2024-04-05 2025-04-04 Selective passivation of silicon oxide containing films utilizing organoamino-alkoxysilanes Pending WO2025210255A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006210791A (en) * 2005-01-31 2006-08-10 Tosoh Corp Si-containing film forming material and use thereof
US20150004806A1 (en) * 2006-11-01 2015-01-01 Lam Research Corporation Low-k oxide deposition by hydrolysis and condensation
US20210301394A1 (en) * 2020-03-30 2021-09-30 Asm Ip Holding B.V. Selective deposition of silicon oxide on metal surfaces
US20240052490A1 (en) * 2019-09-13 2024-02-15 Versum Materials Us, Llc Monoalkoxysilanes and dialkoxysilanes and dense organosilica films made therefrom

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006210791A (en) * 2005-01-31 2006-08-10 Tosoh Corp Si-containing film forming material and use thereof
US20150004806A1 (en) * 2006-11-01 2015-01-01 Lam Research Corporation Low-k oxide deposition by hydrolysis and condensation
US20240052490A1 (en) * 2019-09-13 2024-02-15 Versum Materials Us, Llc Monoalkoxysilanes and dialkoxysilanes and dense organosilica films made therefrom
US20210301394A1 (en) * 2020-03-30 2021-09-30 Asm Ip Holding B.V. Selective deposition of silicon oxide on metal surfaces

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAMALAINEN ET AL.: "Atomic Layer Deposition of Noble Metals and Their Oxides", CHEM. MATER., vol. 26, 2014, pages 786 - 801
JOHNSON ET AL.: "A Brief review of Atomic layer Deposition: From Fundamentals to Applications", MATERIALS TODAY, vol. 17, no. 5, June 2014 (2014-06-01), XP055238259, DOI: 10.1016/j.mattod.2014.04.026

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