# Patent

## Title
Atomic layer deposition methods

## Abstract

The invention includes an atomic layer deposition method of forming a layer of a deposited composition on a substrate. The method includes positioning a semiconductor substrate within an atomic layer deposition chamber. On the substrate, an intermediate composition monolayer is formed, followed by a desired deposited composition from reaction with the intermediate composition, collectively from flowing multiple different composition deposition precursors to the substrate within the deposition chamber. A material adheres to a chamber internal component surface from such sequentially forming. After such sequentially forming, a reactive gas flows to the chamber which is different in composition from the multiple different deposition precursors and which is effective to react with such adhering material. After the reactive gas flowing, such sequentially forming is repeated. Further implementations are contemplated.

## Background
RELATED PATENT DATA
This patent resulted from a divisional application of U.S. patent application Ser. No. 10/863,048, filed Jun. 7, 2004, entitled “Atomic Layer Deposition Methods”, naming Demetrius Sarigiannis, Garo J. Derderian, Gem Basceri, Gurtej S. Sandhu, F. Daniel Gealy and Chris M. Carlson as inventors, which is a continuation application of U.S. patent application Ser. No. 10/222,282, filed Aug. 15, 2002, entitled “Atomic Layer Deposition Methods”, naming Demetrius Sarigiannis, Garo J. Derderian, Gem Basceri, Gurtej S. Sandhu, F. Daniel Gealy and Chris M. Carlson as inventors, now U.S. Pat. No. 6,753,271, issued Jun. 22, 2004, the disclosures of which are incorporated by reference.


TECHNICAL FIELD
This invention relates to atomic layer deposition methods.
BACKGROUND OF THE INVENTION
Semiconductor processing in the fabrication of integrated circuitry typically includes the deposition of layers on semiconductor substrates. One such method is atomic layer deposition (ALD) which involves the deposition of successive monolayers over a substrate within a deposition chamber typically maintained at subatmospheric pressure. With typical ALD, successive mono-atomic layers are adsorbed to a substrate and/or reacted with the outer layer on the substrate, typically by successive feeding of different deposition precursors to the substrate surface.
Atomic layer depositions are typically conducted within chambers or reactors which retain a single substrate upon a wafer holder or susceptor. The chambers include internal walls and other internal components which can undesirably have deposition product deposited thereupon in addition to the substrate. One existing method of protecting or preserving the internal chamber walls and other components is to shield such from the deposition material with one or more removable liners or shields. The liners might be received immediately adjacent or against the internal chamber walls or other surfaces. Alternately, the liners might be displaced from the wall or other surfaces, thereby defining an appreciably reduced volume chamber, or subchamber, within which the substrate is received for deposition. One advantage of using liners and shields is that they can be periodically replaced with new or cleaned liners, thereby extending the life of the deposition chambers and components therein. Further and regardless, the spent liners and shields can typically be removed and replaced much more quickly than the time it would take to clean the internal chamber walls and other components at given cleaning intervals.
An exemplary ALD method includes feeding a single vaporized precursor to a deposition chamber effective to form a first monolayer over a substrate received therein. Thereafter, the flow of the first deposition precursor is ceased and an inert purge gas is flowed through the chamber effective to remove any remaining first precursor which is not adhering to the substrate from the chamber. Subsequently, a second vapor precursor different from the first is flowed to the chamber effective to form a second monolayer on/with the first monolayer. The second monolayer might react with the first monolayer. Additional precursors can form successive monolayers, or the above process can be repeated until a desired thickness and composition layer has been formed over the substrate.
It is a desired intent or effect of the purging to remove unreacted gas or reaction by-products from the chamber to provide a clean reactive surface on the substrate for the subsequent precursor. In the context of this document, a reaction by-product is any substance (whether gas, liquid, solid or mixture thereof) which results from reaction of any deposition precursor flowing to the chamber and that is not desired to be deposited on the substrate. Further in the context of this document, an intermediate reaction by-product or reaction intermediate by-product is a reaction by-product formed by less than desired complete reaction of a precursor to form a desired monolayer on the substrate. Where there is a great degree of varying topography and/or there are high aspect ratio features on the substrate, it can be difficult to move the unreacted gases or reaction by-products from deep within openings for ultimate removal from the chamber. Further, certain reaction by-products, particularly intermediate reaction by-products, may not be gaseous and may not completely react to form gaseous reaction by-products in the typical short precursor pulse times. Accordingly, the purge gas pulse may not be effective or sufficient in removing such intermediate reaction by-products from the substrate and chamber.
For example, consider that in an atomic layer deposition of titanium nitride using TiCl4 and NH3, the desired deposition product is TiN with HCl gas being the desired principle gaseous by-product. Consider also that there might be reaction intermediate by-products which might, even if gaseous, be difficult to remove from substrate openings. Further, if certain reaction intermediate by-products are solid and/or liquid phase prior to HCl formation, complete removal can be even more problematic where less than complete reaction to TiN and HCl occurs.
Consider also the atomic layer deposition of Al2O3 using trimethylaluminum (TMA) and ozone as alternating deposition precursors. Apparently in such deposition, achieving an effective ozone precursor feed can be somewhat of a challenge due to the limited lifetime of ozone within the chamber. Specifically, an ozone molecule is in an inherently unstable, reactive form of oxygen which can rapidly dissociate and/or combine with another ozone molecule to form three O2 molecules. Regardless, a desired goal in the ozone feed is to result in oxygen atoms from the O3 bonding to the surface of the substrate with O2 as the reaction by-product which is driven off. Of course, the O2 which forms deep within openings on the substrate has to be removed therefrom while more O3 needs to get into the openings to desirable form a complete monolayer of oxygen atoms adhered and projecting from the substrate. In other words, the O2 which forms is trying to get out while more O3 is desirably trying to get in.
While the invention was motivated in addressing the above issues and improving upon the above-described drawbacks, it is in no way so limited. The invention is only limited by the accompanying claims as literally worded (without interpretative or other limiting reference to the above background art description, remaining portions of the specification or the drawings) and in accordance with the doctrine of equivalents.
SUMMARY
The invention includes an atomic layer deposition method of forming a layer of a deposited composition on a substrate. The method includes positioning a semiconductor substrate within an atomic layer deposition chamber. On the substrate, an intermediate composition monolayer is formed, followed by a desired deposited composition from reaction with the intermediate composition, collectively from flowing multiple different composition deposition precursors to the substrate within the deposition chamber. A material adheres to a chamber internal component surface from such sequential forming. After such sequential forming, a reactive gas flows to the chamber which is different in composition from the multiple different deposition precursors and which is effective to react with such adhering material. After the reactive gas flowing, such sequential forming is repeated.
Further implementations are contemplated.



BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are described below with reference to the following accompanying drawings.
FIG. 1 is a diagrammatic depiction of flow versus time of one atomic layer deposition process in accordance with an aspect of the invention.
FIG. 2 is a diagrammatic depiction of flow versus time of one atomic layer deposition process in accordance with an aspect of the invention.
FIG. 3 is a diagrammatic depiction of flow versus time of one atomic layer deposition process in accordance with an aspect of the invention.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
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).
An atomic layer deposition method in accordance with an aspect of the invention includes positioning a semiconductor substrate within an atomic layer deposition chamber. 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.
An intermediate composition monolayer is formed on the substrate from one or more deposition precursors flowed to the substrate within the deposition chamber. Then, one or more different composition deposition precursors is flowed to the substrate within the deposition chamber effective to react with the first monolayer and form a monolayer comprising a desired deposited composition of the ultimate layer being formed, with “desired” herein referring to at least at this point in time with respect to the preferred method. In other words, such deposited layer might be subsequently annealed, implanted, exposed to plasma, or otherwise processed in a manner which does not significantly modify its overall composition. Any deposition precursor gases are contemplated whether existing or yet-to-be developed. By way of example only where a desired ultimate deposition product or layer is TiN, exemplary different composition precursors include TiCl4 or NH3 to deposit a TiN comprising layer. Further by way of example only where the ultimate layer or product being formed is to be Al2O3, exemplary different composition deposition precursors include trimethylaluminum and ozone. Further by way of example only, an exemplary first monolayer intermediate composition utilizing TiCl4 would include titanium or a titanium complex, whereas with respect to NH3 such would at least include nitrogen. With respect to trimethylaluminum, the first monolayer intermediate composition would include an aluminum complex, and with ozone typically adhered oxygen atoms. Any suitable temperature, pressure, flow rate or other operating parameters, with or without plasma, can be selected and optimized by the artisan, of course, with no particular set of the same being preferred or constituting a part of the invention.
By way of example only, FIG. 1 depicts an exemplary plot of flow rate versus time of but one process in accordance with an aspect of the invention. A first precursor gas is flowed to the substrate within the atomic layer deposition chamber effective to form a first monolayer on the substrate. Such is designated by a precursor flowing P1. After forming the first monolayer of intermediate composition on the substrate, a second precursor gas, different in composition from the first precursor gas, is flowed to the substrate within the deposition chamber effective to react with the first monolayer and form a monolayer comprising the desired deposited composition. Such second precursor gas flowing is designated by P2. The particular lengths and rates of the respective flowings, and the times therebetween, can also be optimized by the artisan, of course, and do not constitute material or preferred aspects of the inventions disclosed herein. Further, the exemplary FIG. 1 and other figure depictions contemplate any processing occurring before or after the depicted flowings, including any additional processing intermediate the respective gas pulses, unless such is specifically precluded by the particular claim under analysis as literally worded, without interpretative or limiting reference to the background art description, remaining portions of the specification or the drawings, and yet in accordance with the doctrine of equivalents.
In the course of one or both of the above-described precursor flowings, some material may adhere to a chamber internal component surface. In the context of this document, a “chamber internal component surface” comprises any surface of hardware received within the deposition chamber that is subjected to multiple processings of semiconductor substrates within the chamber. Examples include an actual internal wall surface of the chamber, a surface of a chamber liner apparatus which forms a deposition subchamber within the chamber, and a surface of a portion of a substrate support received internally of the chamber walls.
By way of example only, the adhering material might be derived totally or at least primarily from a deposition precursor flow which forms the intermediate composition monolayer. Alternately by way of example only, such material might be derived totally or at least primarily from a deposition precursor flow which reacts with the intermediate composition monolayer and forms the desired deposited composition. The adhering material and the intermediate composition might be of a common composition relative one another or of different composition. The material might also adhere to the substrate within the chamber which is the focus of the deposition, although the invention is principally directed to contending with material which adheres to chamber internal component surfaces. Further by way of example only, and during the formation of the intermediate composition monolayer, intermediate reaction by-product might be formed, for example in any of gaseous, liquid and deposited states. Such adhering material might be of common composition with one or more of the intermediate reaction by-products, or be different in composition from all intermediate reaction by-products.
In one non-limiting consideration, such adhering material might be reactive with one or a multiple of the deposition precursors. In such event, it might be desirable to remove such adhering material from the substrate so it will not react with subsequent flowing precursor, or at least in some way passivate such adhering material to preclude its reaction with subsequently flowing deposition precursors. Further by way of example only, the adhering material might result, in part, from the reaction of deposition precursor with material of the chamber internal component surface, thus forming material adhering thereto. Such might constitute a monolayer or eventually considerably thicker layers from the successive formation of repeated monolayers.
By way of example only, an exemplary adhered material might comprise oxygen atoms adhering to a metal internal surface of a deposition chamber. Such could manifest by the feeding of ozone in any of the above-described exemplary processes involving the deposition of Al2O3. Alternately by way of example only, such might encompass any of TiCl2, TiCl3 and NH3 complexes with respect to TiCl4 and NH3 deposition precursor flows.
After forming at least the initially desired deposited composition of the layer being formed, a reactive gas is flowed to the chamber which is different in composition from the multiple different deposition precursors effective to react with the adhering material. Further in one preferred embodiment, such reactive gas flowing preferably occurs prior to forming any further monolayer on the substrate.
In one aspect, the reactive gas reacts to modify the composition of the adhering material, with such modified composition material adhering to the chamber internal component surface(s). By way of example only, and where the adhering material comprises TiCl, TiCl2 and/or TiCl3, an exemplary reactive gas would be O2 to modify the adhering material composition to TiO2, which still adheres to the chamber internal component surface.
In one aspect, the reactive gas reacts to effectively remove the adhered material, and any reaction by-product thereof, from adhering to the chamber internal component surface. For example and by way of example only, where the adhering material comprises TiCl, TiCl2 and/or TiCl3, an exemplary reactive gas includes Cl2, which would effectively etch or otherwise vaporize the adhering material from the substrate (i.e., to TiCl4) and be exhausted from the chamber.
In one aspect, the reactive gas is not capable under conditions of the reactive gas flowing of reaction with the desired deposited composition. In one aspect, and under conditions of the reactive gas flowing, the reactive gas is capable of reaction with the intermediate composition, and regardless of whether any intermediate composition is exposed during the reactive gas flowing, either on the substrate or on any chamber internal component surface.
The conditions (i.e., temperature, pressure, flow rate, etc.) of the reactive gas flowing can be optimized by the artisan and are not otherwise particularly germane or preferred to any aspect of the invention. By way of example only, such conditions might be the same as, or different from, any of a first precursor gas flow, a second precursor gas flow and/or inert purge gas flow. In one aspect, the reactive gas flow is plasma-enhanced, for example either by plasma generation within the chamber, plasma generation remote of the chamber, or both.
The particular reactive gas selected, whether a single constituent or a mixture of constituents, will depend as a minimum upon at least some portion or component of the adhering material which will be capable of reaction with the reactive gas under conditions of the reactive gas flowing. By way of example only, possible reactive gases components include Cl2, O2 and H2. For example and by way of example only where the adhering material comprises oxygen atoms, such might be removed in the presence of O2 to form ozone and/or with H2 to form H2O which is exhausted from the chamber.
FIG. 1 depicts an exemplary such reactive gas flowing in the form of a discrete pulse RG. After the reactive gas flowing, the sequential forming is repeated, whereby an intermediate composition monolayer is formed, then a desired deposited composition from reaction with the intermediate composition collectively from flowing multiple different composition deposition precursors to the substrate within the deposition chamber. FIG. 1 depicts such exemplary processing by subsequent P1 and P2 pulsings. In one preferred embodiment, thereafter the reactive gas flowing is repeated (FIG. 2). Further in one aspect, the repeating of one or both of the sequential formings, as just so stated, and/or the reactive gas flowing, are sequentially repeated multiple times. Further in one aspect, the invention contemplates repeating the sequentially forming multiple times and repeating the reactive gas flowing only periodically after a plurality of consecutive sequential forming repetitions. In other words, such reactive gas flowing does not necessarily occur intermediate each desired deposited composition monolayer forming, but rather after multiple formings thereof.
Further more typically and preferably, inert gas flows are interposed between some or all of the respective deposition precursor and reactive gas flowings. By way of example only, such is depicted in FIG. 3. There illustrated is a two-sequence repetition, with inert gas flows being indicated by IN and which are interposed between the respective precursor and reactive gas flows.
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

1. A method of performing atomic layer deposition on a substrate, comprising the steps of:
placing said substrate in a deposition chamber;
flowing at least a first precursor gas into said chamber to form a first layer on said substrate by atomic layer deposition;
flowing at least a second precursor gas into said chamber, said second precursor being reactive with said first layer to form a second layer therewith by atomic layer deposition, at least one of said first and second precursors leaving a deposited residue upon surfaces within said chamber; and
purging said chamber with a reactive gas which is reactive with said residue and differs from all precursors utilized during the atomic layer deposition.

2. The method of claim 1 wherein the reactive gas comprises Cl2.

3. The method of claim 1 wherein the reactive gas comprises O2.

4. The method of claim 1 wherein the reactive gas comprises H2.

5. The method of claim 1 wherein the deposited residue comprises oxygen atoms.

6. A method of operating an atomic layer deposition apparatus, comprising the steps of:
placing a substrate into said chamber;
introducing at least a first precursor gas into said chamber to form a first deposition on said substrate by atomic layer deposition;
introducing at least a second precursor gas into said chamber to react with said first deposition; and
purging said chamber with a third gas which is reactive with deposited residue left upon surfaces within said chamber from at least one of said first and second precursor gases, the third gas differing from all precursor gases utilized during the operating, whereby at least a portion of said deposited residue is removed from said chamber by said purging.

7. The method of claim 6 wherein the third gas comprises Cl2.

8. The method of claim 6 wherein the third gas comprises O2.

9. The method of claim 6 wherein the third gas comprises H2.

10. The method of claim 6 wherein the deposited residue comprises oxygen atoms.

11. The method of claim 6 further comprising the steps of:
after said purging step, reintroducing at least said first precursor gas into said chamber to form a third deposition on said substrate; and
subsequently reintroducing at least said second precursor gas into said chamber to react with said third deposition.

12. The method of claim 11 further comprising after the reintroduction of said second precursor gas, the step of again purging said chamber with said third gas.

13. The method of claim 11 wherein said first deposition and said third deposition are substantially the same.