US20060257570A1 - Deposition methods - Google Patents
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- US20060257570A1 US20060257570A1 US11/490,622 US49062206A US2006257570A1 US 20060257570 A1 US20060257570 A1 US 20060257570A1 US 49062206 A US49062206 A US 49062206A US 2006257570 A1 US2006257570 A1 US 2006257570A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/3141—Deposition using atomic layer deposition techniques [ALD]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31616—Deposition of Al2O3
- H01L21/3162—Deposition of Al2O3 on a silicon body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
Abstract
A deposition method includes contacting a substrate with a first initiation precursor and forming a first portion of an initiation layer on the substrate. At least a part of the substrate is contacted with a second initiation precursor different from the first initiation precursor and a second portion of the initiation layer is formed on the substrate. The substrate may be simultaneously contacted with a plurality of initiation precursors, forming on the substrate and initiation layer comprising components, derived from each of the plurality of initiation precursors. An initiation layer may be contacted with a deposition precursor, forming a deposition layer on the initiation layer. The deposition layer may be contacted with a second initiation precursor different from the first initiation precursor forming a second initiation layer over the substrate. Also, a first initiation layer may be formed substantially selectively on a first-type substrate surface relative to a second-type substrate surface and contacted with a deposition precursor, forming a deposition layer substantially selectively over the first-type substrate surface.
Description
- This invention relates to deposition methods including, but not limited to, atomic layer deposition.
- Atomic layer deposition (ALD) is recognized as a deposition technique that forms high quality materials with minimal defects and tight statistical process control. Even so, it is equally recognized that ALD can have limited application. In some circumstances, the theoretically expected quality of an ALD layer is not achieved.
- It can be seen that a need exists for an ALD method that forms a layer without introducing intolerable defects into the material.
- In accordance with an aspect of the invention, a deposition method includes contacting a substrate with a first initiation precursor and forming a first portion of an initiation layer on the substrate. At least a part of the substrate is contacted with a second initiation precursor different from the first initiation precursor and a second portion of the initiation layer is formed on the substrate. Another aspect of the invention includes simultaneously contacting a substrate with a plurality of initiation precursors, forming on the substrate an initiation layer comprising components derived from each of the plurality of initiation precursors. Also, in another aspect, a deposition method includes contacting a substrate with a first initiation precursor and forming a first initiation layer on the substrate. The first initiation layer is contacted with a deposition precursor and a deposition layer is formed on the first initiation layer. Next, at least the deposition layer is contacted with a second initiation precursor different from the first initiation precursor and a second initiation layer is formed over the substrate. In another aspect, a deposition method includes contacting a first-type surface of a substrate and a second-type surface of a substrate different from the first-type surface with a first initiation precursor and forming an initiation layer substantially selectively on the first-type surface relative to the second-type surface. The initiation layer is contacted with a deposition precursor and a deposition layer is formed substantially selectively over the first-type surface relative to the second-type surface.
- Preferred embodiments of the invention are described below with reference to the following accompanying drawings.
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FIG. 1 is an enlarged sectional view of a wafer portion at one processing step in the prior art. -
FIG. 2 is an enlarged sectional view of a wafer portion at one processing step in accordance with one aspect of the invention. -
FIG. 3 is an enlarged sectional view of a portion of theFIG. 2 wafer at a processing step subsequent to that depicted byFIG. 2 . -
FIG. 4 is an enlarged sectional view of a portion of theFIG. 3 wafer at a processing step subsequent to that depicted byFIG. 3 . -
FIG. 5 is an enlarged sectional view of a wafer portion at one processing step in accordance with another aspect of the invention. -
FIG. 6 is an enlarged sectional view of a portion of theFIG. 5 wafer at a processing step subsequent to that depicted byFIG. 5 . -
FIG. 7 is an enlarged sectional view of a wafer portion at one processing step in accordance with another aspect of the invention. -
FIG. 8 is a top view of a portion of theFIG. 7 wafer. -
FIG. 9 is an enlarged sectional view of a wafer portion at one processing step in accordance with another aspect of the invention. - This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws “to promote the progress of science and useful arts” (Article 1, Section 8).
- Atomic layer deposition (ALD) involves formation of successive atomic layers on a substrate. Such layers may comprise an epitaxial, polycrystalline, amorphous, etc. material. ALD may also be referred to as atomic layer epitaxy, atomic layer processing, etc. Further, the invention may encompass other deposition methods not traditionally referred to as ALD, for example, chemical vapor deposition (CVD), but nevertheless including the method steps described herein. The deposition methods herein may be described in the context of formation on a semiconductor wafer. However, the invention encompasses deposition on a variety of substrates besides semiconductor substrates.
- In the context of this document, the term “semiconductor substrate” or “semiconductive substrate” is defined to mean any construction comprising semiconductive material, including, but not limited to, bulk semiconductive materials such as a semiconductive wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure, including, but not limited to, the semiconductive substrates described above.
- Described in summary, ALD includes exposing an initial substrate to a first chemical specie to accomplish chemisorption of the specie onto the substrate. Theoretically, the chemisorption forms a monolayer that is uniformly one atom or molecule thick on the entire exposed initial substrate. Practically, as further described below, chemisorption might not occur on all portions of the substrate. Nevertheless, such an imperfect monolayer is still a monolayer in the context of this document. The first specie is purged from over the substrate and a second chemical specie is provided to chemisorb onto the first monolayer of the first specie. The second specie is then purged and the steps are repeated with exposure of the second specie monolayer to the first specie. In some cases, the two monolayers may be of the same specie. Also, additional species may be successively chemisorbed and purged just as described for the first and second species.
- ALD is often described as a self-limiting process, in that a finite number of sites exist on a substrate to which the first specie may form chemical bonds. The second species might only bond to the first specie and thus may also be self-limiting. Once all of the finite number of sites on a substrate are bonded with a first specie, the first specie will often not bond to other of the first specie already bonded with the substrate. However, process conditions can be varied in ALD as discussed below to promote such bonding and render ALD not self-limiting. Accordingly, ALD may also encompass a specie forming other than one monolayer at a time by stacking of a specie, forming a layer more than one atom or molecule thick. The various aspects of the present invention described herein are applicable to any circumstance where ALD may be desired. A few examples of materials that may be deposited by ALD include silicon nitride, zirconium oxide, tantalum oxide, aluminum oxide, and others.
- ALD offers a variety of advantages and improvements over other methods of forming materials on a substrate. However, ALD layers formed on a substrate may also possess thickness variations caused by variations in the composition and/or surface properties of the underlying substrate. Such disadvantage can limit the application of ALD methods to exclude applications where ALD might otherwise be particularly advantageous.
- For example, when a material is to be deposited simultaneously over multiple types of substrates or over a single type of substrate having different surface properties, ALD may be a poor candidate for forming the material. Experience indicates that material formed by ALD may not form at a uniform rate on differing types of substrates or on a single type of substrate having multiple surface properties in multiple areas. The different rates of formation produce defects and/or varying thicknesses in the deposited material. Accordingly, even though ALD may be used to form very thin layers of material, thickness variations may produce unacceptable defects.
- A deposition method according to one aspect of the invention comprises contacting a substrate with a first initiation precursor and forming a first portion of an initiation layer on the substrate. A
wafer portion 2 is shown inFIG. 1 , including asubstrate 4. As indicated above,substrate 4 may comprise a variety of materials, including a semiconductive, conductive, insulative, or other material. A layer of afirst initiation precursor 6 is formed on an outer surface ofsubstrate 4 as a first portion of an initiation layer. The initiation layer may not be formed uniformly acrosssubstrate 4, as shown.Substrate 4 is exposed through an opening in the initiation layer. One problem among conventional deposition methods is that such openings in an initiation layer can result in defects or unevenness as successive layers are formed on the initiation layer. - Failure of the
first initiation precursor 6 to form an initiation layer in certain regions may be caused by a variety of circumstances. For example, the amenability of a particular initiation precursor to form an initiation layer may depend on the type of substrate. Also, for example, even when the material from which a substrate is formed is substantially homogeneous, differences may exist in the type of surface provided with relation to the deposition method. Crystalline or other defects in a surface of a substrate may prevent a particular initiation precursor from forming an initiation layer uniformly across the substrate surface. It is further contemplated that yet other circumstances may prevent the formation of a uniform initiation layer onsubstrate 4. - Accordingly, in one aspect of the present invention, at least a part of
substrate 4 is contacted with a second initiation precursor different from the first initiation precursor, forming a second portion of the initiation layer onsubstrate 4.FIG. 2 showswafer portion 2 wherein asecond initiation precursor 8 forms a second portion of the initiation layer on the substrate. The second portion fills the opening in the first portion of the initiation layer wherefirst initiation precursor 6 failed to form an initiation layer. The contacting ofsubstrate 4 withfirst initiation precursor 6 andsecond initiation precursor 8 may occur separately or simultaneously. When contacting occurs separately, the initiation layer may form in two different portions, the second portion filling openings in the first portion. When contacting occurs simultaneously, the first and second portions of the initiation layer may also be formed simultaneously. - It is conceivable that two or more initiation precursors may be desired to form an initiation layer having sufficient uniformity. Accordingly, another aspect of the invention involves simultaneously or otherwise contacting
substrate 4 with a plurality of initiation precursors and forming onsubstrate 4 an initiation layer comprising components derived from each of the plurality of initiation precursors. The plurality of initiation precursors could includefirst initiation precursor 6 andsecond initiation precursor 8, as well as other initiation precursors. As described above, a portion of the initiation layer derived from one of the plurality of initiation precursors may form on the substrate in a region less susceptible to formation of the initiation layer by another of the plurality of initiation precursors. Such may be the case where the portion of the initiation layer derived from the one initiation precursor substantially fillspinholes 24 in the initiation layer formed by the another initiation precursor.Pinholes 24 are shown inFIG. 8 and discussed below. - One characteristic of CVD is the simultaneous presence of multiple precursors in the deposition chamber that react to form the deposited material. Such condition is contrasted with the purging criteria for traditional ALD where a single deposition precursor is contacted with a substrate and chemisorbs to the substrate or previously deposited precursor. The deposition process regime described herein may provide simultaneously present precursors of a type or under conditions such that chemisorption, rather than CVD reaction occurs. The plurality of initiation precursors do not react together as in CVD. Rather, they chemisorb to the substrate, providing a surface onto which a deposition precursor may next chemisorb to form a complete layer of desired material.
- As shown in
FIG. 3 , the deposition method may further comprise contacting the first and second portions of the initiation layer with adeposition precursor 10 and forming a deposition layer on the first and second portions of the initiation layer. Accordingly, a deposition layer is formed on the portion of the initiation layer derived fromfirst initiation precursor 6 and another portion of the initiation layer derived fromsecond initiation precursor 8. A deposition method may additionally include contacting the deposition layer formed fromdeposition precursor 10 with athird initiation precursor 12 to form a second initiation layer, as shown inFIG. 4 .Third initiation precursor 12 may be different from bothfirst initiation precursor 6 andsecond initiation precursor 8. Alternatively,third initiation precursor 12 may be the same as either the first or second initiation precursors. - Another aspect of the invention includes a deposition method comprising contacting a substrate with
first initiation precursor 6 and forming a first initiation precursor layer onsubstrate 4. The first initiation layer is contacted withdeposition precursor 10, forming a deposition layer on the first initiation layer. At least the deposition layer is contacted withsecond initiation precursor 8, different fromfirst initiation precursor 6, forming a second initiation layer oversubstrate 4. -
FIG. 5 showssubstrate 4 having a first initiation layer derived fromfirst initiation precursor 6 on which a deposition layer is formed fromdeposition precursor 10. Notably,deposition precursor 10 did not form a deposition layer uniformly acrosssubstrate 4 since the initiation layer was not formed uniformly acrosssubstrate 4. A second initiation precursor may be used to form a second initiation layer on the deposition layer. The invention thus contemplates using a second initiation precursor different from the first initiation precursor even though the second initiation precursor might not fill openings in the first initiation layer. - However, the invention also contemplates that the contacting with the second initiation precursor further comprises contacting a portion of
substrate 4 on which the first initiation layer did not form and wherein forming the second initiation layer occurs on at least such portion. Accordingly, forming the second initiation layer could also occur on the portion ofsubstrate 4 on which the first initiation layer did not form as well as on the deposition layer.FIG. 6 showssecond initiation precursor 8 forming a second initiation layer on the portion ofsubstrate 4 on which the first initiation layer did not form. Ifsecond initiation precursor 8 also formed an initiation layer on the deposition layer, then the second initiation layer would exist over the first initiation layer, as well as comprise part of the first initiation layer. - In another aspect of the invention, at least the deposition layer of
wafer portion 2 shown inFIG. 5 may be contacted with a plurality of initiation precursors. At least one of such plurality may be different from the first initiation precursor and the plurality may form a second initiation layer over the substrate. The contacting with the plurality of initiation precursors may further comprise contacting a portion of the substrate on which the first initiation layer did not form and the formation of the second initiation layer may occur on at least such portion. Also, the contacting with the plurality of initiation precursors may occur simultaneously or separately. Accordingly, one of the plurality of initiation precursors may comprisefirst initiation precursor 6, yetsecond initiation precursor 8 may be provided to form an initiation layer on a portion ofsubstrate 4 where the first initiation layer did not form. - A variety of particular initiation precursors and deposition precursors may be used in a variety of combinations according to the aspects of the present invention. Trimethyl aluminum (TMA) is one of several possible deposition precursors. TMA may be used beneficially with H2O, H2O2, CH3OH, or other alcohols as initiation precursors. In keeping with the above description, selection of particular precursors will depend on the properties of a surface upon which such precursor is to form an initiation or deposition layer. For example, H2O may be used as a first initiation precursor to chemisorb on a silicon surface to form an initiation layer of —OH groups, producing hydrogen gas (H2) as a byproduct. This is a self-limiting process, but it is contemplated that —OH groups might not form an initiation layer in select areas. Accordingly, H2O2, CH3OH, or other alcohols may be used to form an initiation layer also having an —OH termination to which TMA will chemisorb as the deposition precursor.
- The second initiation precursor different from the first initiation precursor may be contacted with the silicon surface simultaneously with the H2O, separately from the H2O, or after formation of the deposition layer. Contacting TMA with the —OH initiation layer will produce CH4 as a byproduct when the hydrogen atoms of the —OH groups chemisorb with one or more methyl groups of the TMA, resulting in aluminum bonding to one or more oxygen atoms on the silicon surface. H2O may then be contacted with the deposition layer to form a second initiation layer. In the alternative, a third initiation precursor different from either the first or second initiation precursor may contact the deposition layer to form the second initiation layer. The TMA and H2O (or alternative second initiation precursors) deposition method may be used to form an aluminum oxide (Al2O3) film.
- As shown in
FIGS. 1-7 and 9, initiation anddeposition precursors first initiation compound 16,second initiation compound 18, anddeposition compound 20, respectively. At least a portion of each precursor thus becomes a part of the final deposited material. For example, with H2O as an initiation precursor —OH forms on the silicon substrate asfirst initiation precursor 6 and —O— remains asfirst initiation compound 16 after chemisorption with a deposition precursor. Similarly, with TMA as a deposition precursor —Al(CH3)2 forms on the first initiation layer and remains as —Al— after chemisorption with a subsequent initiation precursor. - For an Al2O3 deposition from TMA/H2O, and perhaps other depositions, chamber temperature may be from about 250 to about 350° C., preferably about 300° C., and chamber pressure may be from about 100 milliTorr to about 10 Torr, preferably about 200 milliTorr. Using a GENUS™ ALD tool, deposition of aluminum oxide from TMA and H2O may be achieved at a rate of about 0.84 Angstroms per cycle. The first step of the cycle may include pulsing about 1 Liter of H2O at about 20 Torr for from about 200 to about 300 microseconds (μsec). About 1 Liter of a carrier at about 20 Torr may be pulsed for from about 500 to about 1000 μsec to purge the H2O. Next, about 1 Liter of TMA at about 20 Torr may be pulsed at for from about 100 to about 200 μsec followed by purging as indicated to complete the cycle. In keeping with the aspects of the present invention described herein, H2O2, CH3OH, or other alcohols may be used in the above method as second initiation precursors to reduce defect formation.
- Other types of film may be formed using deposition methods as disclosed herein. When SiH4 or SiCl4 are to be used as initiation precursors, alternate precursors include chlorosilanes (SiHCl3, SiH2Cl2, and SiH3Cl) and methysilanes (such as Si(CH3)nH4-n, wherein n=1 to 4). It is also contemplated that other alternatives to initiation precursors exist that may be used, depending on the corresponding deposition precursors and surface properties of a substrate.
- Turning to
FIG. 7 , awafer portion 20 is shown having afirst substrate region 26 and asecond substrate region 28. Each substrate region has a property causing a difference between the susceptibility of the first and second regions to formation of an initiation layer by a first initiation precursor. Accordingly, contactingfirst region 26 andsecond region 28 withfirst initiation precursor 6 forms an initiation layer onfirst region 26. Contacting at least a part of the substrate, includingsecond substrate region 28, withsecond initiation precursor 8 forms an initiation layer onsecond region 28. -
Second substrate region 28 may result from a defect in or contamination of an otherwise homogeneous substrate, causing the difference in susceptibility to formation of an initiation layer byfirst initiation precursor 6. Such difference may also be the product of two different materials forming each substrate region, such as borophosphosilicate glass (BPSG) and polysilicon: Accordingly, it may even be the case that either the first or second region is insulative and the other is conductive. Accordingly, a first portion of the first initiation layer may form on an insulative portion of a substrate, such asfirst substrate region 26. A second portion of the first initiation layer may form on a conductive portion of a substrate, such assecond substrate region 28. - In
FIG. 8 , a top view ofwafer portion 20 ofFIG. 7 shows a layer offirst initiation precursor 6 that is continuous across the substrate surface and a layer ofsecond initiation precursor 8 that is also continuous across the surface of the substrate.FIG. 8 also showspinholes 24 in the layer offirst initiation precursor 6 wherein no initiation layer was formed. Such pinholes are shown to not be continuous, since at least one pinhole exists that is not connected to a second pinhole by a region wherein no initiation layer was formed. - According to one aspect of the invention, substantially all of the first portion of the initiation layer may be continuous and at least some of a second portion of the initiation layer is not continuous. Such a result is produced when substantially all of
first region 26 is continuous and another region exists whereinpinholes 24 are formed in the initiation layer oversecond region 28. Such a region may also exist whensecond region 28 is intentionally not continuous. - Another aspect of the invention similarly includes
first initiation precursor 6 forming a negligible, if any, amount of an initiation layer onsecond region 28. In keeping with the present invention,second region 28 may comprise a variety of materials, including those intended to form a designated pattern such as shown inFIG. 8 and different from the material comprisingfirst substrate region 26. The deposition methods of the present invention may be helpful in forming such patterned areas by contacting a first-type surface of a substrate and a second-type surface of a substrate different from the first-type surface with a first initiation precursor and forming a first initiation layer substantially selectively on the first-type surface relative to the second-type surface. The initiation layer may then be contacted with a deposition precursor and a deposition layer formed substantially selectively over the first-type surface relative to the second-type surface. - Generally, substantially selective deposition is most desirable when substantially all of the first-type surface is continuous and substantially all of the second-type surface is also continuous. When multiple types of continuous surfaces are provided within a substrate, yet deposition is only desired on one such surface, such a method may be useful. According to the present invention, the first-type surface may even have a common border with the second-type surface. In the various types of arrangements of the first-type and second-type surfaces described above, it is desirable that the first initiation precursor form a negligible, if any, amount of the initiation layer on the second-type surface, surpassing mere substantial selectivity.
- Turning to
FIG. 9 , awafer portion 30 is shown having arecess 34 formed therein.Wafer portion 30 further comprises aninsulation material 36 and aconductive material 38, formed inrecess 34. In this regard,wafer portion 30 could exemplify a wafer portion having a BPSG layer and a container opening formed therein for a container capacitorconductive material 38 may comprise a storage node within the container opening. Such a conductive material may comprise polysilicon. As exemplified byFIG. 9 , afirst initiation precursor 6 may form an initiation layer oninsulative material 36 without forming an initiation layer onconductive material 38, and vice versa. A deposition precursor may then form a deposition layer substantially selectively overinsulative material 36. Alternatively,second initiation precursor 8 may form a second portion of the initiation layer onconductive material 38 when such is desired. - In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents.
Claims (25)
1-48. (canceled)
49. A deposition method comprising:
contacting a substrate with a first initiation precursor and forming a first portion of an initiation layer on at least a first region of the substrate, the substrate comprising a semiconductor material; and
contacting at least a second region of the substrate with a second initiation precursor different from the first initiation precursor and forming a second portion of the initiation layer on at least the second region, the second portion of the initiation layer forming at a greater rate over the second region than a rate at which the first portion of the initiation layer formed over the second region.
50. The deposition method of claim 49 , wherein the initiation layer consists essentially of a monolayer of the first and second initiation precursors.
51. The deposition method of claim 49 , wherein the contacting with the first initiation precursor and the contacting with the second initiation precursor occur simultaneously.
52. The deposition method of claim 49 , wherein substantially all of the first portion of the initiation layer is continuous and at least some of the second portion of the initiation layer is not continuous.
53. The deposition method of claim 49 , wherein the second portion of the initiation layer does not form over the first portion of the initiation layer.
54. The deposition method of claim 49 , wherein forming the second portion of the initiation layer substantially fills holes in the first portion of the initiation layer.
55. The deposition method of claim 49 , further comprising contacting the first and second portions of the initiation layer with a deposition precursor and forming a deposition layer on the first and second portions of the initiation layer.
56. The deposition method of claim 55 , further comprising contacting the deposition layer with a third initiation precursor different from both the first and second initiation precursor and forming a second initiation layer on the deposition layer.
57. The deposition method of claim 49 , wherein the first portion of the initiation layer forms to a greater degree over the first region of the substrate than over the second region.
58. The deposition method of claim 49 , wherein the first portion of the initiation layer forms at a greater rate over the first region of the substrate than over the second region.
59. The deposition method of claim 49 , wherein the first portion forms more uniformly over the first region of the substrate than over the second region.
60. A deposition method comprising:
providing a substrate having a first region and second region, the first and second regions each having a property causing a difference between formation rates of an initiation layer by a first initiation precursor over the first region compared to the second region, the substrate comprising a semiconductor material;
contacting the substrate with the first initiation precursor and forming the initiation layer on the first region; and
contacting at least the second region with a second initiation precursor and forming the initiation layer on the second region, but not over the first region.
61. The deposition method of claim 60 , wherein the semiconductor material comprises a bulk silicon wafer, the first region comprises an insulative material, and the second region comprises a capacitor storage node.
62. The deposition method of claim 60 , wherein the initiation layer consists essentially of a monolayer on the first and second region.
63. The deposition method of claim 60 , wherein the first initiation precursor forms a negligible, if any, amount of the initiation layer on the second region.
64. The deposition method of claim 60 , wherein contacting with the first initiation precursor and contacting with the second initiation precursor occur simultaneously.
65. The deposition method of claim 60 , wherein either the first or the second region is insulative and the other is conductive.
66. The deposition method of claim 60 , wherein forming the initiation layer on the second region substantially fills holes in the initiation layer on the first region.
67. The deposition method of claim 60 , further comprising contacting the initiation layer on the first and second regions with a deposition precursor and forming a deposition layer on the initiation layer on the first and second regions.
68. The deposition method of claim 67 , further comprising contacting the deposition layer with a third initiation precursor different from both the first and second initiation precursor and forming a second initiation layer on the deposition layer.
69. The deposition method of claim 67 , wherein the deposition layer comprises aluminum oxide.
70. A deposition method comprising:
contacting a substrate containing a semiconductor material with a first initiation precursor and forming a first portion of an initiation layer on at least a first region of the substrate, the first portion of the initiation layer forming to a greater degree over the first region than over a second region of the substrate; and
contacting at least the second region with a second initiation precursor different from the first initiation precursor and forming a second portion of the initiation layer on at least the second region.
71. A deposition method comprising:
contacting a substrate containing a semiconductor material with a first initiation precursor and forming a first portion of an initiation layer on at least a first region of the substrate, the first portion forming at a greater rate over the first region than over a second region of the substrate; and
contacting at least the second region with a second initiation precursor different from the first initiation precursor and forming a second portion of the initiation layer on at least the second region.
72. A deposition method comprising:
contacting a substrate containing a semiconductor material with a first initiation precursor and forming a first portion of an initiation layer on at least a first region of the substrate, the first portion forming more uniformly over the first region than over a second region of the substrate; and
contacting at least the second region with a second initiation precursor different from the first initiation precursor and forming a second portion of the initiation layer on at least the second region.
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Also Published As
Publication number | Publication date |
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US20030044538A1 (en) | 2003-03-06 |
US20040062863A1 (en) | 2004-04-01 |
US7087535B2 (en) | 2006-08-08 |
US6458416B1 (en) | 2002-10-01 |
US6627260B2 (en) | 2003-09-30 |
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