Patent Publication Number: US-10319583-B2

Title: Selective deposition of silicon nitride films for spacer applications

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority to U.S. Provisional Application No. 62/307,537, filed Mar. 13, 2016, the entire disclosure of which is hereby incorporated by reference herein. 
    
    
     TECHNICAL FIELD 
     The present disclosure relates generally to methods of depositing thin films. In particular, the disclosure relates to processes for the selective deposition of silicon nitride films by spatial ALD. 
     BACKGROUND 
     Silicon nitride thin films as a dielectric layer have been widely used in semiconductor fabrication processes. For example, SiN films are used in multi-patterning processes as spacer materials to achieve smaller device dimensions without employing the most expensive EUV lithography technology. Additionally, SiN can be used as a gate spacer material to isolate gate structure and contact areas to minimize potential leakage current. 
     Traditional silicon nitride spacer fabrication processes include conformal SiN film deposition on 3D structures (e.g., fins) followed by directional plasma dry etching to remove the top and bottom layer while keeping the sidewall film as a spacer. However, it has been found that the dry etch process could insidiously damage the sidewall surface and change the film properties; eventually affective device performance and yield. 
     Therefore, there is a need in the art for processes of depositing a selective spacer films. 
     SUMMARY 
     One or more embodiments of the disclosure are directed to processing methods. A substrate surface having at least one feature thereon is provided. The at least one feature comprises a top, a bottom and a sidewall. A film is formed on the at least one feature so that the film is formed on the top, bottom and sidewall. The film is treated with a plasma to change a property of the film on the top and bottom of the feature so that the top and bottom of the feature have higher wet etch rates than the film on the sidewall. 
     Additional embodiments of the disclosure are directed to processing methods comprising positioning a substrate surface in a processing chamber. The substrate surface has at least one feature thereon. The at least one feature has a top, bottom and sidewalls. The substrate surface is exposed to a deposition environment comprising at least one deposition cycle. The deposition cycle comprises sequential exposure to a silicon precursor and a nitrogen containing reactant to form a silicon nitride film on the top, bottom and sidewalls of the at least one feature. The silicon nitride film is exposed to a treatment environment to modify the silicon nitride film deposited on the top and bottom of the at least one feature so that the film on the top and bottom have a higher wet etch rate than the film on the sidewalls. The treatment environment comprises a plasma having a high ion concentration. 
     Further embodiments of the disclosure are directed to processing methods comprising placing a substrate having a substrate surface with a feature into a processing chamber comprising a plurality of process regions. Each process region is separated from adjacent process regions by a gas curtain. The feature comprises a top, a bottom and a sidewall. At least a portion of the substrate surface is exposed to a first process condition in a first process region of the processing chamber. The first process condition comprises a silicon precursor. The substrate surface is laterally moved through a gas curtain to a second process region of the processing chamber. The substrate surface is exposed to a second process condition in the second process region of the processing chamber. The second process condition comprises a nitrogen precursor. The substrate surface is laterally moved through a gas curtain to a third process region of the processing chamber. The substrate surface is exposed to a third process condition in the third process region of the processing chamber. The third process condition comprises a nitrogen reactant to form a silicon nitride film on the top, bottom and sidewalls of the feature. Exposure to the first process condition, the second process condition and the third condition is repeated to form a silicon nitride film with a predetermined thickness. The substrate surface is moved to a fourth process region of the processing chamber. The fourth process region comprises a treatment environment comprising a high ion concentration plasma that selectively decreases the wet etch rate of the silicon nitride film on the top and bottom of the feature. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments. 
         FIG. 1  shows a cross-sectional view of a batch processing chamber in accordance with one or more embodiment of the disclosure; 
         FIG. 2  shows a partial perspective view of a batch processing chamber in accordance with one or more embodiment of the disclosure; 
         FIG. 3  shows a schematic view of a batch processing chamber in accordance with one or more embodiment of the disclosure; 
         FIG. 4  shows a schematic view of a portion of a wedge shaped gas distribution assembly for use in a batch processing chamber in accordance with one or more embodiment of the disclosure; 
         FIG. 5  shows a schematic view of a batch processing chamber in accordance with one or more embodiment of the disclosure; and 
         FIGS. 6A through 6E  show a processing method in accordance with one or more embodiment of the disclosure; and 
         FIG. 7  shows a schematic view of a cross-section of a plasma assembly with a slot in accordance with one or more embodiment of the disclosure. 
     
    
    
     DETAILED DESCRIPTION 
     Before describing several exemplary embodiments of the disclosure, it is to be understood that the disclosure is not limited to the details of construction or process steps set forth in the following description. The disclosure is capable of other embodiments and of being practiced or being carried out in various ways. 
     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, amorphous silicon, 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 under-layer formed on the substrate as disclosed in more detail below, and the term “substrate surface” is intended to include such under-layer as the context indicates. Thus 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. 
     As used in this specification and the appended claims, the terms “precursor”, “reactant”, “reactive gas” and the like are used interchangeably to refer to any gaseous species that can react with the substrate surface. 
     Some embodiments of the disclosure are directed to processes that use a reaction chamber with multiple gas inlet channels that can be used for introduction of different chemicals or plasma gases. Spatially, these channels are separated by inert purging gases and/or vacuum pumping holes to create a gas curtain that minimizes or eliminates mixing of gases from different channels to avoid unwanted gas phase reactions. Wafers moving through these different spatially separated channels get sequential and multiple surface exposures to different chemical or plasma environment so that layer by layer film growth in spatial ALD mode or surface etching process occur. In some embodiments, the processing chamber has modular architectures on gas distribution components and each modular component has independent parameter control (e.g., RF or gas flow) to provide flexibility to control, for example, gas flow and/or RF exposure. 
     Some embodiments of the disclosure use spatial architectures and comprise a first chemistry dosing on a substrate surface followed by a second chemical exposure to react with the dosed chemistry to form a film, followed by a third additional post treatment process. In use, embodiments of the disclosure have an ALD layer that can be exposed to in-situ post treatment. In some embodiments, the treatment is done once. In some embodiments, the treatment may be employed every cycle. The minimum amount of treatment might be in the range of every 1 to 100 deposition cycles or more. 
     Some embodiments of the disclosure are directed to selective SiN deposition methods that allow for different film properties based on the deposition location on a 3D structure. For example, a film deposited on the top and bottom of a structure can be treated to have different film properties than a film deposited on the sidewall of the structure. Some embodiments of the disclosure advantageously provide methods of forming a film in which wet etching can selectively remove portions of the film (e.g., the top and bottom) while leaving other portions of the film (e.g., the sidewall) as a spacer. Some embodiments of the disclosure are advantageously performed in a single processing chamber. 
     While the various embodiments of the disclosure are described with respect to the deposition of silicon nitride films, those skilled in the art will understand that the disclosure is not so limited. Other films can be deposited, treated and etched to leave a spacer. 
     In some embodiments, the silicon nitride selective deposition includes two processes in a single processing chamber: SiN film deposition and plasma treatment. A batch processing chamber can be used to process a spatial atomic layer deposition (ALD) sequence: silicon precursor exposure; nitrogen precursor exposure (thermal or plasma); RF plasma treatment with, for example, N 2 , NH 3 , H 2  or O 2  gases (which can be mixed with inert gases such as Ar or He). The silicon and nitrogen precursors forming a conformal SiN film and the plasma treatment modifying the film on the top and bottom of the feature. In some embodiments, the RF plasma treatment uses a hardware configured to have a directional treatment effect on the film. The plasma treatment process could form either N—H or Si—O bonds on the film surface and penetrate into the film a depth based on the treatment time and RF power. This has been found to produce higher wet etch rates on the top and bottom of the feature. The deposition layer thickness and plasma treatment level can be adjusted to increase the wet etch rate selectivity. Selective deposition in some embodiments is performed at wafer temperatures in the range of about 200° C. to about 550° C. One or more embodiments advantageously provide films in which a directional dry etch method is optional, such as physical bombardment, because the as deposited film shows different film properties at the top/bottom than the sidewalls of the features and a conformal dry etching can selectively remove the top/bottom of the film. 
     Referring to  FIGS. 6A through 6E , one or more embodiments of the disclosure are directed to processing methods to deposit a spacer film on a substrate surface  300  having a feature  310  thereon. The feature  310  can be any three-dimensional structure that a film can be deposited on. The feature  310  shown in the Figures is a mandrel; however, those skilled in the art will understand that this is merely representative of one possible structure. Suitable features  310  include, but are not limited to, ridges, trenches and vias. 
     The feature  310  includes a top  320 , a bottom  330  and a sidewall  340 . In the embodiment shown, the feature  310  has two sidewalls  340  on either side of the feature  310 . The feature  310  has a height defined by the top  320  and bottom  330  and a width defined by the distance between the sidewalls  340 . 
     The substrate surface  300  is provided with the at least one feature  310  thereon. As used in this specification and the appended claims, the term “provided” used in this manner means that the substrate surface  300  is placed or positioned in an environment for processing. 
     As shown in  FIG. 6B , a film  350  is formed on the substrate surface  300  so that the film forms on the at least one feature  310 . The film  350  forms on the top  320 , bottom  330  and sidewalls  340  of the feature  310 . In some embodiments, the film  350  forms conformally on the feature  310 . As used herein, the term “conformal”, or “conformally”, refers to a layer that adheres to and uniformly covers exposed surfaces with a thickness having a variation of less than 1% relative to the average thickness of the film. For example, a 1,000 Å thick film would have less than a 10 Å variation in thickness. This thickness and variation includes edges, corners, sides, and the bottom of recesses. For example, a conformal layer deposited by ALD in various embodiments of the disclosure would provide coverage over the deposited region of essentially uniform thickness on complex surfaces. 
     In some embodiments, the film  350  comprises SiN. The formation of the SiN can be performed by any suitable method including, but not limited to, atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD) and plasma-enhanced chemical vapor deposition (PECVD). In some embodiments, the film  350  is SiN formed by and ALD process in which the substrate surface  300  is sequentially exposed to a silicon precursor and a nitrogen reactant. As used in this regard, a “silicon precursor” reacts with the surface of the substrate so that silicon molecules remain on the substrate surface. As used in this regard, a “nitrogen reactant” reacts with the silicon molecules on the substrate surface. 
     In some embodiments, the SiN film is formed on the substrate surface  300  with exposure to a nitrogen precursor between the exposure to the silicon precursor and the nitrogen reactant. As used in this regard, a “nitrogen precursor” reacts with the substrate surface and minimally reacts with the silicon species already on the substrate surface. Stated differently, the nitrogen precursor comprises a species that does not react with silicon precursor molecules on the substrate surface. The exposure to the nitrogen precursor can occur before, during or after exposure to the silicon precursor as both the nitrogen precursor species and the silicon precursor species are reactive with the substrate surface and are minimally reactive with each other. 
     Suitable silicon precursors include, but are not limited to, silane, disilane, dichlorisilane (DCS), bis(diethylamino)silane (BDEAS), tetrakis(dimethylamino)silane (TDMAS) and/or bis(tertiary-butylamino)silane (BTBAS). In some embodiments, the silicon precursor comprises dichlorosilane. In one or more embodiments, the silicon precursor consists essentially of dichlorosilane meaning that there is less than 1% on an atomic basis of silicon species other than dichlorosilane. 
     Suitable nitrogen precursors include, but are not limited to, molecular nitrogen and ammonia. The process conditions employed during nitrogen precursor exposure can affect the reactivity of the nitrogen species with the silicon species on the surface. In some embodiments, the process conditions are configured such that the nitrogen precursor reacts substantially only with the substrate surface. As used in this regard, the term “substantially only” means that the nitrogen precursor reacts with less than about 10% of the surface silicon species. 
     The nitrogen reactant is a species that forms the silicon nitride film on the substrate surface. In some embodiments, the nitrogen reactant provides the nitrogen atoms for the formation of the nitride film (e.g., SiN). In one or more embodiments, the nitrogen reactant does not include a nitrogen-containing species and forms the nitride film by facilitating a reaction between surface species. Suitable nitrogen reactants include, but are not limited to, nitrogen plasma, ammonia plasma, a plasma comprising a mixture of two or more of hydrogen, nitrogen, ammonia, helium, argon or oxygen. In some embodiments, the nitrogen reactant comprises a plasma of argon and ammonia, or a plasma of argon and nitrogen, or a plasma of argon and oxygen, or a plasma of helium and ammonia. In some embodiments, the nitrogen reactant comprises a plasma without nitrogen that reacts with the nitrogen species on the surface. In some embodiments, the nitrogen reactant comprises a plasma of hydrogen and argon, or a plasma of hydrogen and nitrogen, or a plasma of hydrogen and helium, or a plasma of hydrogen and ammonia, or a plasma of hydrogen and oxygen. 
     As shown in  FIG. 6C , after formation of the film  350  (e.g., silicon nitride), the film  350  is treated with a plasma  360  having a high ion concentration. The plasma  360  can be a directional plasma. As used in this specification and the appended claims, the term “directional plasma” means that the energetic species present in the plasma (ions and radicals) move in a specified direction. For example, in  FIG. 6C , the plasma  360  is illustrated moving downward so that the energetic species are able to contact the film  350  on the top surface  320  and bottom surface  330  but have minimal contact with the film  350  on the sidewalls  340 . 
     A plasma with a high ion concentration has a concentration greater than or equal to about 10 10 /cm 3 . In one or more embodiments, the plasma with the high ion concentration has a concentration greater than or equal to about 10 9 /cm 3 , 10 11 /cm 3 , 10 12 /cm 3 , 10 13 /cm 3  or 10 14 /cm 3 . 
     A directional plasma can be formed as a remote plasma in which the plasma species are excited remotely from the substrate surface and flow toward the substrate surface. The substrate and substrate support may not be part of the electrical path used to generate the plasma. A directional plasma may also be formed as a direct plasma in which the substrate or substrate support serve as an electrode in the plasma formation. A direct plasma is generally a diffuse plasma and can be made directional by applying a bias to the substrate so that the ions are attracted to and move toward the substrate. 
     As shown in  FIG. 6D , treating the film  350  with the plasma having a high ion concentration modifies a property of the film  350  at the top  320  and bottom  330 . In some embodiments, the property of the film  350  that is changed to form the modified top film  352  and modified bottom film  353  affects the wet etch rate in dilute HF (1%) so that the modified top film  352  and modified bottom film  353  can be etched from the feature  310  without substantially affecting the sidewall film  354 . In some embodiments, the treatment damages the film  350  on the top and bottom of the feature  310  so that the film can be selectively etched relative to the sidewall. 
     In some embodiments, the wet etch rate of the modified top film  352  and modified bottom film  353  is greater than or equal to about 15 Å/min. In some embodiments, the wet etch rate of the modified top film  352  and modified bottom film  353  is greater than or equal to about 20 Å/min or 25 Å/min. In some embodiments, the wet etch rate of the modified top film  352  and modified bottom film  353  is greater than 2 times the wet etch rate of the sidewall film  354 , or greater than 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 times. 
     The plasma used in the treatment can be any suitable plasma (e.g., direct or remote) which is capable of modifying the film properties. In some embodiments, the treatment comprises one or more of hydrogen, argon, nitrogen, ammonia, oxygen or helium. 
     The amount of time used for treatment may affect the amount of damage caused to the film on the top and bottom of the feature. The plasma species and power may affect the depth of the damage caused to the film. A treatment process that causes deeper damage to the film can be repeated less often than a treatment process that causes shallower damage to the film. For example, a He/NH 3  plasma may cause deeper damage than an Ar/NH 3  plasma so that the film deposited can be thicker before treating with the He/NH 3  plasma. 
     The formation and treatment of the film  350  can be repeated until a film with a predetermined total thickness has been formed. Each step in the film formation process can be sequentially repeated to form a film for treatment. The film can then be treated and the process repeated. In some embodiments, treating the film  350  with the plasma  360  occurs after a film having a thickness in the range of about 1 Å to about 50 Å is deposited. Stated differently, the film  350  is treated after about 1 Å to about 50 Å has been deposited. 
     In some embodiments of the method, the film  350  is etched. The modified top film  352  and modified bottom film  353  are selectively etched relative to the sidewall film  354 . As used in this regard, selectively etching means that the amount, rate, or degree of etching on the top and bottom is greater than the etching on the sidewall. In some embodiments, the film is etched with dilute HF to selectively remove the film from the top and bottom of the feature.  FIG. 6E  shows the result of an etch process. While the drawing shows square corners for the top and bottom of the feature  310  and the sidewall film  354 , those skilled in the art will understand that this is merely illustrative and that the edges and corners are not perfectly straight or square. 
     Some embodiments of the disclosure are directed to processes of depositing a spacer material using a batch processing chamber, also referred to as a spatial processing chamber.  FIG. 1  shows a cross-section of a processing chamber  100  including a gas distribution assembly  120 , also referred to as injectors or an injector assembly, and a susceptor assembly  140 . The gas distribution assembly  120  is any type of gas delivery device used in a processing chamber. The gas distribution assembly  120  includes a front surface  121  which faces the susceptor assembly  140 . The front surface  121  can have any number or variety of openings to deliver a flow of gases toward the susceptor assembly  140 . The gas distribution assembly  120  also includes an outer edge  124  which in the embodiments shown, is substantially round. 
     The specific type of gas distribution assembly  120  used can vary depending on the particular process being used. Embodiments of the disclosure can be used with any type of processing system where the gap between the susceptor and the gas distribution assembly is controlled. While various types of gas distribution assemblies can be employed (e.g., showerheads), embodiments of the disclosure may be particularly useful with spatial gas distribution assemblies which have a plurality of substantially parallel gas channels. As used in this specification and the appended claims, the term “substantially parallel” means that the elongate axis of the gas channels extend in the same general direction. There can be slight imperfections in the parallelism of the gas channels. In a binary reaction, the plurality of substantially parallel gas channels can include at least one first reactive gas A channel, at least one second reactive gas B channel, at least one purge gas P channel and/or at least one vacuum V channel. The gases flowing from the first reactive gas A channel(s), the second reactive gas B channel(s) and the purge gas P channel(s) are directed toward the top surface of the wafer. Some of the gas flow moves horizontally across the surface of the wafer and out of the process region through the purge gas P channel(s). A substrate moving from one end of the gas distribution assembly to the other end will be exposed to each of the process gases in turn, forming a layer on the substrate surface. 
     In some embodiments, the gas distribution assembly  120  is a rigid stationary body made of a single injector unit. In one or more embodiments, the gas distribution assembly  120  is made up of a plurality of individual sectors (e.g., injector units  122 ), as shown in  FIG. 2 . Either a single piece body or a multi-sector body can be used with the various embodiments of the disclosure described. 
     A susceptor assembly  140  is positioned beneath the gas distribution assembly  120 . The susceptor assembly  140  includes a top surface  141  and at least one recess  142  in the top surface  141 . The susceptor assembly  140  also has a bottom surface  143  and an edge  144 . The recess  142  can be any suitable shape and size depending on the shape and size of the substrates  60  being processed. In the embodiment shown in  FIG. 1 , the recess  142  has a flat bottom to support the bottom of the wafer; however, the bottom of the recess can vary. In some embodiments, the recess has step regions around the outer peripheral edge of the recess which are sized to support the outer peripheral edge of the wafer. The amount of the outer peripheral edge of the wafer that is supported by the steps can vary depending on, for example, the thickness of the wafer and the presence of features already present on the back side of the wafer. 
     In some embodiments, as shown in  FIG. 1 , the recess  142  in the top surface  141  of the susceptor assembly  140  is sized so that a substrate  60  supported in the recess  142  has a top surface  61  substantially coplanar with the top surface  141  of the susceptor  140 . As used in this specification and the appended claims, the term “substantially coplanar” means that the top surface of the wafer and the top surface of the susceptor assembly are coplanar within ±0.2 mm. In some embodiments, the top surfaces are coplanar within ±0.15 mm, ±0.10 mm or ±0.05 mm. 
     The susceptor assembly  140  of  FIG. 1  includes a support post  160  which is capable of lifting, lowering and rotating the susceptor assembly  140 . The susceptor assembly may include a heater, or gas lines, or electrical components within the center of the support post  160 . The support post  160  may be the primary means of increasing or decreasing the gap between the susceptor assembly  140  and the gas distribution assembly  120 , moving the susceptor assembly  140  into proper position. The susceptor assembly  140  may also include fine tuning actuators  162  which can make micro-adjustments to susceptor assembly  140  to create a predetermined gap  170  between the susceptor assembly  140  and the gas distribution assembly  120 . 
     In some embodiments, the gap  170  distance is in the range of about 0.1 mm to about 5.0 mm, or in the range of about 0.1 mm to about 3.0 mm, or in the range of about 0.1 mm to about 2.0 mm, or in the range of about 0.2 mm to about 1.8 mm, or in the range of about 0.3 mm to about 1.7 mm, or in the range of about 0.4 mm to about 1.6 mm, or in the range of about 0.5 mm to about 1.5 mm, or in the range of about 0.6 mm to about 1.4 mm, or in the range of about 0.7 mm to about 1.3 mm, or in the range of about 0.8 mm to about 1.2 mm, or in the range of about 0.9 mm to about 1.1 mm, or about 1 mm. 
     The processing chamber  100  shown in the Figures is a carousel-type chamber in which the susceptor assembly  140  can hold a plurality of substrates  60 . As shown in  FIG. 2 , the gas distribution assembly  120  may include a plurality of separate injector units  122 , each injector unit  122  being capable of depositing a film on the wafer, as the wafer is moved beneath the injector unit. Two pie-shaped injector units  122  are shown positioned on approximately opposite sides of and above the susceptor assembly  140 . This number of injector units  122  is shown for illustrative purposes only. It will be understood that more or less injector units  122  can be included. In some embodiments, there are a sufficient number of pie-shaped injector units  122  to form a shape conforming to the shape of the susceptor assembly  140 . In some embodiments, each of the individual pie-shaped injector units  122  may be independently moved, removed and/or replaced without affecting any of the other injector units  122 . For example, one segment may be raised to permit a robot to access the region between the susceptor assembly  140  and gas distribution assembly  120  to load/unload substrates  60 . 
     Processing chambers having multiple gas injectors can be used to process multiple wafers simultaneously so that the wafers experience the same process flow. For example, as shown in  FIG. 3 , the processing chamber  100  has four gas injector assemblies and four substrates  60 . At the outset of processing, the substrates  60  can be positioned between the injector assemblies  30 . Rotating  17  the susceptor assembly  140  by 45° will result in each substrate  60  which is between gas distribution assemblies  120  to be moved to an gas distribution assembly  120  for film deposition, as illustrated by the dotted circle under the gas distribution assemblies  120 . An additional 45° rotation would move the substrates  60  away from the injector assemblies  30 . The number of substrates  60  and gas distribution assemblies  120  can be the same or different. In some embodiments, there are the same numbers of wafers being processed as there are gas distribution assemblies. In one or more embodiments, the number of wafers being processed are fraction of or an integer multiple of the number of gas distribution assemblies. For example, if there are four gas distribution assemblies, there are 4x wafers being processed, where x is an integer value greater than or equal to one. In an exemplary embodiment, the gas distribution assembly  120  includes eight process regions separated by gas curtains and the susceptor assembly  140  can hold six wafers. 
     The processing chamber  100  shown in  FIG. 3  is merely representative of one possible configuration and should not be taken as limiting the scope of the disclosure. Here, the processing chamber  100  includes a plurality of gas distribution assemblies  120 . In the embodiment shown, there are four gas distribution assemblies (also called injector assemblies  30 ) evenly spaced about the processing chamber  100 . The processing chamber  100  shown is octagonal; however, those skilled in the art will understand that this is one possible shape and should not be taken as limiting the scope of the disclosure. The gas distribution assemblies  120  shown are trapezoidal, but can be a single circular component or made up of a plurality of pie-shaped segments, like that shown in  FIG. 2 . 
     The embodiment shown in  FIG. 3  includes a load lock chamber  180 , or an auxiliary chamber like a buffer station. This chamber  180  is connected to a side of the processing chamber  100  to allow, for example the substrates (also referred to as substrates  60 ) to be loaded/unloaded from the chamber  100 . A wafer robot may be positioned in the chamber  180  to move the substrate onto the susceptor. 
     Rotation of the carousel (e.g., the susceptor assembly  140 ) can be continuous or intermittent (discontinuous). In continuous processing, the wafers are constantly rotating so that they are exposed to each of the injectors in turn. In discontinuous processing, the wafers can be moved to the injector region and stopped, and then to the region  84  between the injectors and stopped. For example, the carousel can rotate so that the wafers move from an inter-injector region across the injector (or stop adjacent the injector) and on to the next inter-injector region where the carousel can pause again. Pausing between the injectors may provide time for additional processing steps between each layer deposition (e.g., exposure to plasma). 
       FIG. 4  shows a sector or portion of a gas distribution assembly  220 , which may be referred to as an injector unit  122 . The injector units  122  can be used individually or in combination with other injector units. For example, as shown in  FIG. 5 , four of the injector units  122  of  FIG. 4  are combined to form a single gas distribution assembly  220 . (The lines separating the four injector units are not shown for clarity.) While the injector unit  122  of  FIG. 4  has both a first reactive gas port  125  and a second gas port  135  in addition to purge gas ports  155  and vacuum ports  145 , an injector unit  122  does not need all of these components. 
     Referring to both  FIGS. 4 and 5 , a gas distribution assembly  220  in accordance with one or more embodiment may comprise a plurality of sectors (or injector units  122 ) with each sector being identical or different. The gas distribution assembly  220  is positioned within the processing chamber and comprises a plurality of elongate gas ports  125 ,  135 ,  145  in a front surface  121  of the gas distribution assembly  220 . The plurality of elongate gas ports  125 ,  135 ,  145 ,  155  extend from an area adjacent the inner peripheral edge  123  toward an area adjacent the outer peripheral edge  124  of the gas distribution assembly  220 . The plurality of gas ports shown include a first reactive gas port  125 , a second gas port  135 , a vacuum port  145  which surrounds each of the first reactive gas ports and the second reactive gas ports and a purge gas port  155 . 
     With reference to the embodiments shown in  FIG. 4 or 5 , when stating that the ports extend from at least about an inner peripheral region to at least about an outer peripheral region, however, the ports can extend more than just radially from inner to outer regions. The ports can extend tangentially as vacuum port  145  surrounds reactive gas port  125  and reactive gas port  135 . In the embodiment shown in  FIGS. 4 and 5 , the wedge shaped reactive gas ports  125 ,  135  are surrounded on all edges, including adjacent the inner peripheral region and outer peripheral region, by a vacuum port  145 . 
     Referring to  FIG. 4 , as a substrate moves along path  127 , each portion of the substrate surface is exposed to the various reactive gases. To follow the path  127 , the substrate will be exposed to, or “see”, a purge gas port  155 , a vacuum port  145 , a first reactive gas port  125 , a vacuum port  145 , a purge gas port  155 , a vacuum port  145 , a second gas port  135  and a vacuum port  145 . Thus, at the end of the path  127  shown in  FIG. 4 , the substrate has been exposed to the first reactive gas  125  and the second reactive gas  135  to form a layer. The injector unit  122  shown makes a quarter circle but could be larger or smaller. The gas distribution assembly  220  shown in  FIG. 5  can be considered a combination of four of the injector units  122  of  FIG. 4  connected in series. 
     The injector unit  122  of  FIG. 4  shows a gas curtain  150  that separates the reactive gases. The term “gas curtain” is used to describe any combination of gas flows or vacuum that separate reactive gases from mixing. The gas curtain  150  shown in  FIG. 4  comprises the portion of the vacuum port  145  next to the first reactive gas port  125 , the purge gas port  155  in the middle and a portion of the vacuum port  145  next to the second gas port  135 . This combination of gas flow and vacuum can be used to prevent or minimize gas phase reactions of the first reactive gas and the second reactive gas. 
     Referring to  FIG. 5 , the combination of gas flows and vacuum from the gas distribution assembly  220  form a separation into a plurality of process regions  250 . The process regions are roughly defined around the individual gas ports  125 ,  135  with the gas curtain  150  between 250. The embodiment shown in  FIG. 5  makes up eight separate process regions  250  with eight separate gas curtains  150  between. A processing chamber can have at least two process region. In some embodiments, there are at least three, four, five, six, seven, eight, nine, 10, 11 or 12 process regions. 
     During processing a substrate may be exposed to more than one process region  250  at any given time. However, the portions that are exposed to the different process regions will have a gas curtain separating the two. For example, if the leading edge of a substrate enters a process region including the second gas port  135 , a middle portion of the substrate will be under a gas curtain  150  and the trailing edge of the substrate will be in a process region including the first reactive gas port  125 . 
     A factory interface  280 , which can be, for example, a load lock chamber, is shown connected to the processing chamber  100 . A substrate  60  is shown superimposed over the gas distribution assembly  220  to provide a frame of reference. The substrate  60  may often sit on a susceptor assembly to be held near the front surface  121  of the gas distribution plate  120 . The substrate  60  is loaded via the factory interface  280  into the processing chamber  100  onto a substrate support or susceptor assembly (see  FIG. 3 ). The substrate  60  can be shown positioned within a process region because the substrate is located adjacent the first reactive gas port  125  and between two gas curtains  150   a ,  150   b . Rotating the substrate  60  along path  127  will move the substrate counter-clockwise around the processing chamber  100 . Thus, the substrate  60  will be exposed to the first process region  250   a  through the eighth process region  250   h , including all process regions between. 
     Embodiments of the disclosure are directed to processing methods comprising a processing chamber  100  with a plurality of process regions  250   a - 250   h  with each process region separated from an adjacent region by a gas curtain  150 . For example, the processing chamber shown in  FIG. 5 . The number of gas curtains and process regions within the processing chamber can be any suitable number depending on the arrangement of gas flows. The embodiment shown in  FIG. 5  has eight gas curtains  150  and eight process regions  250   a - 250   h.    
     A plurality of substrates  60  are positioned on a substrate support, for example, the susceptor assembly  140  shown  FIGS. 1 and 2 . The plurality of substrates  60  are rotated around the process regions for processing. Generally, the gas curtains  150  are engaged (gas flowing and vacuum on) throughout processing including periods when no reactive gas is flowing into the chamber. 
     Accordingly, one or more embodiments of the disclosure are directed to processing methods utilizing a batch processing chamber like that shown in  FIG. 5 . A substrate  60  is placed into the processing chamber which has a plurality of sections  250 , each section separated from adjacent section by a gas curtain  150 . 
     Some embodiments of the method comprise exposing a substrate surface having a feature thereon to a deposition environment to deposit a film. As used in this regard, a “deposition environment” comprises one or more process regions or process conditions that individually or sequentially deposit a film. 
     In an exemplary process, at least a portion of the substrate surface is exposed to a first process condition in a first section  250   a  of the processing chamber. The first process condition of some embodiments comprises a silicon precursor to form a silicon film. In one or more embodiments, the first process condition comprises dichlorosilane. 
     The substrate surface is laterally moved through a gas curtain  150  to a second section  250   b . The silicon layer is exposed to a second process condition in the second section  250   b . The second process condition of some embodiments comprises a nitrogen precursor to form a nitrogen film. In one or more embodiments, the second process condition comprises ammonia. 
     The substrate surface is laterally moved from the second process region to a third section  250   c . The third section  250   c  of some embodiments comprises a third process condition comprising a reactant to form a film on the top, bottom and sidewalls of the feature. The fourth section  250   d  may comprise an inert environment. In some embodiments, the third section  250   c  comprises an inert environment so that there is substantially no surface reaction and the fourth section  250   d  comprises the third process condition. In one or more embodiments, the third process condition comprises a N 2 /Ar plasma. 
     The exposure to the first process condition, the second process condition and the third process condition can be repeated to form a film with a predetermined thickness. For example, referring to  FIG. 5 , the first section  250   a  and fifth section  250   e  may comprise the first process condition; the second section  250   b  and sixth section  250   f  may comprise the second process condition; the third section  250   c  and seventh section  250   g  may comprise an inert environment; and the fourth section  250   d  and eighth section  250   h  may comprise the third process condition. In this arrangement, each rotation of the substrate forms two layers. Those skilled in the art will understand that the use of ordinals such as “first” and “second” to describe process regions do not imply a specific location within the processing chamber, or order of exposure within the processing chamber. 
     Once a layer of a predetermined thickness has been formed, the first process condition, second process condition and third process condition may be changed to inert environments. The inert environment in the third section  250   c , for example, can be changed to a treatment environment comprising a high ion concentration plasma that selectively decreases the wet etch rate of the silicon nitride film on the top and bottom of the feature. For example, the high ion concentration plasma may comprise He/NH 3 . After exposure to the treatment environment, the individual sections of the processing chamber can be changed back to the previous settings or the process can be stopped. 
     Referring to  FIG. 7 , some embodiments use a plasma assembly  380  with a slot  382 . The plasma forms in the plasma cavity  384  and flows through the slot  382  toward the substrate surface  300 . The view shown in  FIG. 7  is a cross-sectional view in which the slot  382  extends out of the page. The slot  382  through which the plasma formed in plasma cavity  384  flows has edges  386 . In some embodiments, the plasma has a high ion energy and concentration adjacent the edges  386  of the slot  382 . 
     According to one or more embodiments, the substrate is subjected to processing prior to and/or after forming the layer. This processing can be performed in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is moved from the first chamber to a separate, second chamber for further processing. The substrate can be moved directly from the first chamber to the separate processing chamber, or it can be moved from the first chamber to one or more transfer chambers, and then moved to the separate processing chamber. Accordingly, the processing apparatus may comprise multiple chambers in communication with a transfer station. An apparatus of this sort may be referred to as a “cluster tool” or “clustered system,” and the like. 
     Generally, a cluster tool is a modular system comprising multiple chambers which perform various functions including substrate center-finding and orientation, annealing, annealing, deposition and/or etching. According to one or more embodiments, a cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber may house a robot that can shuttle substrates between and among processing chambers and load lock chambers. The transfer chamber is typically maintained at a vacuum condition and provides an intermediate stage for shuttling substrates from one chamber to another and/or to a load lock chamber positioned at a front end of the cluster tool. Two well-known cluster tools which may be adapted for the present disclosure are the Centura® and the Endura®, both available from Applied Materials, Inc., of Santa Clara, Calif. However, the exact arrangement and combination of chambers may be altered for purposes of performing specific steps of a process as described herein. Other processing chambers which may be used include, but are not limited to, cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, chemical clean, thermal treatment such as RTP, plasma nitridation, anneal, orientation, hydroxylation and other substrate processes. By carrying out processes in a chamber on a cluster tool, surface contamination of the substrate with atmospheric impurities can be avoided without oxidation prior to depositing a subsequent film. 
     According to one or more embodiments, the substrate is continuously under vacuum or “load lock” conditions, and is not exposed to ambient air when being moved from one chamber to the next. The transfer chambers are thus under vacuum and are “pumped down” under vacuum pressure. Inert gases may be present in the processing chambers or the transfer chambers. In some embodiments, an inert gas is used as a purge gas to remove some or all of the reactants. According to one or more embodiments, a purge gas is injected at the exit of the deposition chamber to prevent reactants from moving from the deposition chamber to the transfer chamber and/or additional processing chamber. Thus, the flow of inert gas forms a curtain at the exit of the chamber. 
     The substrate can be processed in single substrate deposition chambers, where a single substrate is loaded, processed and unloaded before another substrate is processed. The substrate can also be processed in a continuous manner, similar to a conveyer system, in which multiple substrate are individually loaded into a first part of the chamber, move through the chamber and are unloaded from a second part of the chamber. The shape of the chamber and associated conveyer system can form a straight path or curved path. Additionally, the processing chamber may be a carousel in which multiple substrates are moved about a central axis and are exposed to deposition, etch, annealing, cleaning, etc. processes throughout the carousel path. 
     During processing, the substrate can be heated or cooled. Such heating or cooling can be accomplished by any suitable means including, but not limited to, changing the temperature of the substrate support and flowing heated or cooled gases to the substrate surface. In some embodiments, the substrate support includes a heater/cooler which can be controlled to change the substrate temperature conductively. In one or more embodiments, the gases (either reactive gases or inert gases) being employed are heated or cooled to locally change the substrate temperature. In some embodiments, a heater/cooler is positioned within the chamber adjacent the substrate surface to convectively change the substrate temperature. 
     The substrate can also be stationary or rotated during processing. A rotating substrate can be rotated continuously or in discreet steps. For example, a substrate may be rotated throughout the entire process, or the substrate can be rotated by a small amount between exposures to different reactive or purge gases. Rotating the substrate during processing (either continuously or in steps) may help produce a more uniform deposition or etch by minimizing the effect of, for example, local variability in gas flow geometries. 
     In atomic layer deposition type chambers, the substrate can be exposed to the first and second precursors either spatially or temporally separated processes. Temporal ALD is a traditional process in which the first precursor flows into the chamber to react with the surface. The first precursor is purged from the chamber before flowing the second precursor. In spatial ALD, both the first and second precursors are simultaneously flowed to the chamber but are separated spatially so that there is a region between the flows that prevents mixing of the precursors. In spatial ALD, the substrate is moved relative to the gas distribution plate, or vice-versa. 
     In embodiments, where one or more of the parts of the methods takes place in one chamber, the process may be a spatial ALD process. Although one or more of the chemistries described above may not be compatible (i.e., result in reaction other than on the substrate surface and/or deposit on the chamber), spatial separation ensures that the reagents are not exposed to each in the gas phase. For example, temporal ALD involves the purging the deposition chamber. However, in practice it is sometimes not possible to purge the excess reagent out of the chamber before flowing in additional regent. Therefore, any leftover reagent in the chamber may react. With spatial separation, excess reagent does not need to be purged, and cross-contamination is limited. Furthermore, a lot of time can be used to purge a chamber, and therefore throughput can be increased by eliminating the purge step. 
     Reference throughout this specification to “one embodiment,” “certain embodiments,” “one or more embodiments” or “an embodiment” means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of the phrases such as “in one or more embodiments,” “in certain embodiments,” “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. 
     Although the disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure include modifications and variations that are within the scope of the appended claims and their equivalents.