TUNGSTEN WORDLINE FILL IN HIGH ASPECT RATIO 3D NAND ARCHITECTURE INCORPORATION BY REFERENCE 5 [0001] A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claim benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in its entirety and for all purposes. BACKGROUND 10 [0001] Deposition of materials including tungsten-containing materials is an integral part of many semiconductor fabrication processes. These materials may be used for horizontal interconnects, vias between adjacent metal layers, and contacts between metal layers and devices. As devices shrink and more complex patterning schemes are utilized in the industry, deposition of tungsten films becomes a challenge. The continued decrease in feature size and 15 film thickness bring various challenges including high resistivity for thinner films and difficulty in obtaining void-free fill in features. Deposition in complex high aspect ratio structures such as 3D NAND structures is particularly challenging. [0002] The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent 20 it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure. SUMMARY [0003] One aspect of the disclosure relates to a semiconductor processing apparatus that 25 includes a first showerhead; a dual inlet chamber having a first inlet, a second inlet, an outlet fluidly connected to the first showerhead; a first gas zone; and a second gas zone. The first gas zone includes a first process gas manifold, the first process gas manifold has: one or more first process gas charge volumes, a first divert valve fluidically connected to the one or more first process gas charge volumes, and a first injection process gas valve fluidically connected to the 30 first divert process gas valve, where the first process gas manifold is configured to be fluidically connected to one or more first process gas sources via the one or more first process gas charge volumes; and the first process gas manifold, via the first injection process gas valve, is fluidically connected to the first inlet of the dual inlet chamber. The second gas zone includes LAMRP644WO/10321-1WO 1

a second process gas manifold, the second process gas manifold has: one or more second process gas charge volumes, a second divert valve fluidically connected to the one or more second process gas charge volumes, and a second injection process gas valve fluidically connected to the second divert process gas valve, where the second process gas manifold is 5 configured to be fluidically connected to one or more second process gas sources via the one or more second process gas charge volumes; and the second process gas manifold, via the second injection process gas valve, is fluidically connected to the second inlet of the dual inlet chamber, where the first gas zone is separate from the second gas zone upstream of the dual inlet chamber. 10 [0004] In some implementations of the semiconductor processing apparatus, the semiconductor processing apparatus may include a divert manifold fluidically connected to the first process gas manifold via the first divert process gas valve and the second process gas manifold via the second divert process gas valve. [0005] In some implementations of the semiconductor processing apparatus, the 15 semiconductor processing apparatus may include a multi-station chamber having a first station with the first showerhead and one or more additional stations each having a showerhead. [0006] In some implementations of the semiconductor processing apparatus, at least one station of the multi-station chamber is fluidically connected to no more than one gas zone. [0007] In some implementations of the semiconductor processing apparatus, the dual inlet20 chamber includes an annulus surrounding a main line connected to the outlet. [0008] In some implementations of the semiconductor processing apparatus, the second inlet is at the side of the annulus. [0009] Another aspect of the disclosure relates to a method including: providing a 3-D structure of a partially manufactured semiconductor substrate to a chamber having a chamber25 pressure of no more than 100 Torr, the 3-D structure including sidewalls, a plurality of openings in the sidewalls leading to a plurality of features having a plurality of interior regions fluidically accessible through the openings to a chamber; depositing a first layer of tungsten within the 3-D structure such that the first layer lines the plurality of features of the 3-D structure; and treating the first layer non-conformally such that that the treatment is 30 preferentially applied at portions of the first layer near the plurality of openings relative to the plurality of interior regions; and depositing a second layer of tungsten within the 3-D structure on the first layer such that the second layer at least partially fills the plurality of interior regions of the 3-D structure; where treating the first layer non-conformally includes charging a gas LAMRP644WO/10321-1WO 2

including nitrogen trifluoride (NF ₃ ) to a first charge pressure of least 10 Torr and flowing the gas to the chamber. [0010] In some embodiments, the treatment inhibits tungsten deposition. [0011] In some embodiments, depositing a layer of tungsten includes an atomic layer 5 deposition using tungsten hexafluoride (WF ₆ ) and hydrogen (H ₂ ). [0012] In some embodiments, depositing a layer of tungsten includes delivering pulses of a tungsten precursor and hydrogen to the chamber via a showerhead. [0013] In some embodiments, depositing tungsten includes delivering a tungsten precursor and hydrogen to a showerhead via a dual inlet chamber. 10 [0014] In some embodiments, the tungsten precursor and hydrogen are injected at a first inlet of the dual inlet chamber. [0015] In some embodiments, the gas including NF ₃ is injected at a second inlet of the dual inlet chamber. [0016] In some embodiments, an inert gas is injected in the first inlet of the dual inlet15 chamber while the NF ₃ is injected at the second inlet of the dual inlet chamber. [0017] In some embodiments, the tungsten precursor and hydrogen gas are supplied through a first gas manifold and the NF ₃ is supplied through a second gas manifold. [0018] In some embodiments, the method further includes depositing a nucleation layer within the 3-D structure such that nucleation layer lines the plurality of features of the 3-D20 structure. [0019] In some embodiments, depositing the nucleation layer takes place at a first station in the chamber and the deposition of the first layer of tungsten, the treatment, and the deposition of the second layer of tungsten takes place in a second station in the chamber. [0020] These and other aspects of the disclosure are described below with reference to the25 drawings. BRIEF DESCRIPTION OF DRAWINGS [0021] Figures 1A–1E present different views and aspects of an example 3-D NAND structure. 30 [0022] Figure 2 is a process flow diagram illustrating certain operations in methods of treating and filling a feature with tungsten. LAMRP644WO/10321-1WO 3

[0023] Figure 3 is a schematic representation of a wordline feature at various stages of treatment and fill with tungsten. [0024] Figure 4 is another schematic representation of a wordline feature at various stages of treatment and fill with tungsten. 5 [0025] Figure 5 is a process flow diagram illustrating certain operations in methods of treatment of a feature surface. [0026] Figure 6 shows a schematic representation of apparatus that may be used to perform the methods described herein. [0027] Figure 7 shows an example dual inlet chamber and example showerhead. 10 [0028] Figure 8 shows a top view of an example inhibition gas manifold and process gas manifold. [0029] Figure 9 is a process flow diagram illustrating certain operations in methods for tungsten deposition. [0030] Figure 10 shows a schematic of an example process system that may be used to15 perform the methods described herein. DETAILED DESCRIPTION [0031] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be 20 practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments. 25 [0032] Provided herein are methods of filling features with tungsten (W). The methods described herein can be used to fill vertical features, such as in tungsten vias, and horizontal features, such as 3D NAND wordlines. [0033] The methods described herein are performed on a substrate that may be housed in a chamber. The substrate may be a silicon or other semiconductor wafer, e.g., a 200-mm wafer, 30 a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi-conducting material deposited thereon. The methods are not limit to semiconductor substrates and may be performed to fill any feature with LAMRP644WO/10321-1WO 4

tungsten. [0034] Substrates may have features such as via or contact holes, which may be characterized by one or more of narrow and/or re-entrant openings, constrictions within the feature, and high aspect ratios. A feature may be formed in one or more of the above described layers. For 5 example, the feature may be formed at least partially in a dielectric layer. In some embodiments, a feature may have an aspect ratio of at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, at least about 25:1, or higher. One example of a feature is a hole or via in a semiconductor substrate or a layer on the substrate. [0035] In some embodiments, the methods are used for wordline fill in 3-D NAND10 structures. Figure 1A presents a cross-sectional side-view of a 3-D NAND structure 110 (formed on a silicon substrate 102) having VNAND stacks (left 125 and right 126), central vertical structure 130, and a plurality of stacked horizontal features 120 with openings 122 on opposite sidewalls 140 of central vertical structure 130. Note that Figure 1A displays two stacks of the exhibited 3-D NAND structure 110, which together form the trench-like central 15 vertical structure 130. There may be more than two such stacks arranged in sequence and running spatially parallel to one another with the gap between each adjacent pair of stacks forming a central vertical structure 130, like that illustrated in Figure 1A. The horizontal features 120 are 3-D memory wordline features that are fluidically accessible from the central vertical structure 130 through the openings 122. The horizontal features 120 present in both 20 the 3-D NAND stacks 125 and 126 shown in Figure 1A (i.e., the left 3-D NAND stack 125 and the right 3-D NAND stack 126) are also accessible from the other sides of the stacks (far left and far right, respectively) through similar vertical structures formed by additional 3-D NAND stacks (to the far left and far right, but not shown). In other words, each 3-D NAND stack 125, 126 contains a stack of wordline features that are fluidically accessible from both sides of the 25 3-D NAND stack through a central vertical structure 130. In the particular example schematically illustrated in Figure 1A, each 3-D NAND stack contains 6 pairs of stacked wordlines, however, in other embodiments, a 3-D NAND memory layout may contain any number of vertically stacked pairs of wordlines. [0036] The wordline features in a 3-D NAND stack may be formed by depositing an 30 alternating stack of silicon oxide and silicon nitride layers, and then selectively removing the nitride layers leaving a stack of oxides layers having gaps between them. These gaps are the wordline features. Any number of wordlines may be vertically stacked in such a 3-D NAND structure so long as there is a technique for forming them available, as well as a technique available to successfully accomplish (substantially) void-free fills of the vertical features. LAMRP644WO/10321-1WO 5

Thus, for example, a 3-D NAND stack may include between 2 and 256 horizontal wordline features, or between 8 and 128 horizontal wordline features, or between 16 and 64 horizontal wordline features, and so forth (the listed ranges understood to include the recited end points). [0037] Figure 1B presents a cross-sectional top-down view of the same 3-D NAND structure 5 110 shown in side-view in Figure 1A with the cross-section taken through the horizontal section 160 as indicated by the dashed horizontal line in Figure 1A. The cross-section of Figure 1B illustrates several rows of pillars 155, which run vertically from the base of semiconductor substrate 102 to the top of 3-D NAND stack 110. In some embodiments, these pillars 155 are formed from a polysilicon material. Polysilicon pillars may serve as gate electrodes for stacked 10 memory cells formed within the pillars. The top-view of Figure 1B illustrates that the pillars 155 form constrictions in the openings 122 to wordline features 120 - i.e. fluidic accessibility of wordline features 120 from the central vertical structure 130 via openings 122 (as indicated by the arrows in Figure 1G) is inhibited by pillars 155. This reduction in fluidic accessibility increases the difficulty of uniformly filling wordline features 120 with material. The structure15 of wordline features 120 and the challenge of uniformly filling them with tungsten material due to the presence of pillars 155 is further illustrated in Figures 1C, 1D, and 1E. [0038] Figure 1C exhibits a vertical cut through a 3-D NAND structure similar to that shown in Figure 1A, but here focused on a single pair of wordline features 120. Figure 1C also schematically illustrates a void 175 in the filled wordline features 120. Figure 1D also 20 schematically illustrates void 175, but in this figure illustrated via a horizontal cut through pillars 155, similar to the horizontal cut exhibited in Figure 1G. Figure 1E illustrates the accumulation of tungsten material around the constriction-forming pillars 155, the accumulation resulting in the pinch-off of openings 122, so that no additional tungsten material can be deposited in the region of voids 175. Apparent from Figures 1C and 1D is that void- 25 free tungsten fill relies on migration of sufficient quantities of deposition precursor down through vertical structure 130, through openings 122, past the constricting pillars 155, and into the furthest reaches of wordline features 120, prior to the accumulated deposition of tungsten around pillars 155 causing a pinch-off of the openings 122 and preventing further precursor migration into wordline features 120. Similarly, Figure 1E exhibits a single wordline feature 30 120 viewed cross-sectionally from above and illustrates how a generally conformal deposition of tungsten material begins to pinch-off the interior of wordline feature 120 because the significant width of pillars 155 acts to partially block, and/or narrow, and/or constrict what would otherwise be an open path through wordline feature 120. (It should be noted that the example in Figure 1E can be understood as a 2-D rendering of the 3-D features of the structure LAMRP644WO/10321-1WO 6

of the pillar constrictions shown in Figure 1D, thus illustrating constrictions that would be seen in a plan view rather than in a cross-sectional view.) [0039] Filling three-dimensional structures may use longer and/or more concentrated exposure to precursors to allow the innermost and bottommost areas to be filled. 5 [0040] Examples of feature fill for horizontally-oriented and vertically-oriented features are described below. It should be noted that in at least most cases, the examples are applicable to both horizontally-oriented and vertically-oriented features. Moreover, it should also be noted that in the description below, the term “vertical” may be used to refer to a direction generally orthogonal to the plane of the substrate and the term “lateral” to refer to a direction generally10 parallel to the plane of the substrate. [0041] Figure 2 is a process diagram illustrating operations in filling a structure with tungsten according to various embodiments. First, a tungsten (W) film is deposited in the structure in an operation 202. This operation may be referred to as Dep1. In many embodiments, operation 202 is a generally conformal deposition that lines the exposed surfaces of the structures. For 15 example, in a 3D NAND structure such as that shown in Figure 1A, the W film lines the wordline features 120. According to various embodiments, the W film is deposited using an ALD process to achieve good conformality. Further description of W ALD processes are given below. After operation 202, the features are not closed off with W, but sufficiently open to allow further reactant gases to enter the features in a subsequent deposition. 20 [0042] Next, in an operation 204, the deposited tungsten film is non-conformally treated by nitrogen trifluoride (NF ₃ ). Non-conformal treatment in this context refers to the treatment being preferentially applied at and near the opening or openings of the feature than in the feature interior. For 3D NAND structures, the treatment may be conformal in the vertical direction such that the bottom wordline feature is treated to approximately the same extent as 25 the top wordline feature, while non-conformal in that the interior of the wordline features are not exposed to the treatment or to a significantly lesser extent than the feature openings. [0043] In some embodiments, the NF ₃ treatment both inhibits tungsten nucleation and etches deposited tungsten. Nucleation inhibition inhibits subsequent tungsten nucleation at the treated surfaces. It can involve one or more of: deposition of an inhibition film, reaction of treatment 30 species with the W film to form a compound film, and adsorption of inhibition species. During the subsequent deposition operation, there is a nucleation delay on the inhibited portions of the underlying film relative to the non- or lesser-inhibited portions. Etch removes deposited film at the treated surfaces. This can involve reacting an etchant species with the tungsten film to LAMRP644WO/10321-1WO 7

form a gaseous byproduct that is then removed. [0044] Other gases such as ammonia (NH ₃ ) may be used for thermal inhibition processes. However, using NF ₃ offers advantages over other treatments. One advantage is that NF ₃ both inhibits tungsten nucleation and etches deposited tungsten from the treated surfaces. Nitrogen 5 acts as an inhibition species and fluorine act as an etchant. To perform a purely inhibition treatment, operation 204 can involve exposing the W film to a nitrogen-containing chemistry that does not contain fluorine or other halogens. To perform a purely etch treatment, operation 204 can involve exposing the W film to a halogen-containing chemistry that does not contain nitrogen. Treating the W film with a nitrogen-containing and halogen-containing 10 chemistry, inhibits W nucleation and etches the W film. Moreover, as discussed further below, NF ₃ allows the inhibition and deposition operations to be performed in the same station with a single plenum showerhead. [0045] In some embodiments, a treatment gas is pressurized to level significantly higher than the chamber pressure prior to introduction to chamber. This facilitates the gas reaching 15 the bottommost portion of the vertical structure. In the example of NF ₃ gas, the NF ₃ gas may be pressurized in a charge volume to a pressure between 10 Torr and 1000 Torr. In some embodiments, the pressure is between 400 Torr and 500 Torr. Charge volumes are discussed further below. [0046] As discussed further below, operation 204 may be a continuous flow or pulsed20 process. In the latter case, different gases may be pulsed in sequence to tune the treatment. [0047] After operation 204, a second deposition is performed in operation 206. The second deposition may be performed by an ALD or CVD process. For deposition into 3D NAND structures, an ALD process may be used to allow for good step coverage throughout the structure. Gases more easily reach feature interiors due to the effects of the treatment. After 25 an etch process, film deposited near the feature entrance is removed, allowing more space for gases to reach the interior of the feature and preventing pinch-off. In some embodiments, enough W film may be removed such that an underlying surface is wholly or partially exposed, increasing nucleation delay at these areas. After an inhibition process, nucleation delay is increased, allowing an inside-out fill process. Operation 206, which may be referred to as a 30 Dep2 process, may complete fill of the structures in some embodiments. In other embodiments, one more additional treatment/deposition operations may be performed. [0048] To tailor lateral non-conformality in the wordlines, pressure and treatment gas flow rate may be adjusted. Higher chamber pressure and lower treatment gas flow rate (and/or LAMRP644WO/10321-1WO 8

concentration) promotes treatment at the openings of the wordline features over treatment within the interiors of the wordline features. Thus, in some embodiments, chamber pressure may lower from operation 202 to 204. Example chamber pressures range from 3 Torr to 40 Torr. 5 [0049] According to various embodiments, operations 202, 204, and 206 may be performed in the same processing chamber or in different processing chambers. If performed in the same chamber, they may be performed in a single-station or multi-station chamber. In a multi-station chamber, various operations may be performed at various stations. For example, operation 202 may be performed in a first station and operation 204 in a second station. In another example, 10 operation 202 and operation 206 may be performed in a first station and operation 204 in a second station. In some embodiments, while various operations are performed in separate stations within a single chamber, only a single operation, i.e., operation 202, depositing W film in a structure, may be performed at a time. In another embodiment, when multiple substrates are being processed, various operations may occur concurrently. For example, a first substrate 15 is at station one for operation 202 and a second substrate is at station two for operation 204 in the same multi-station chamber. Both operation 202 and operation 204 may proceed concurrently in the same multi-station chamber. In some embodiments, chamber pressure may be low to prevent any cross-contamination or safety issues. In one example, in operation 202, a nucleation layer may be deposited using a boron-containing reducing agent (e.g., B ₂ H ₆ ) in 20 station one on a first substrate. A second substrate may be undergoing operation 204 in a second station. Both the nucleation layer deposition of B ₂ H ₆ in station one and the deposition of NF ₃ in station two can occur concurrently in the same multi-station chamber. To achieve this, the chamber pressure is set to a lower pressure, such as a pressure below 25 Torr. [0050] Figure 3 and Figure 4 illustrate examples of inhibition and etching effects, 25 respectively, of a treatment of a 3D NAND structure with tungsten. Figure 3 depicts inhibition effects of a nitrogen treatment and Figure 4 depicts etching effects of a halogen species, e.g., fluorine species. As discussed above, the NF ₃ treatment inhibitions tungsten nucleation as depicted in Figure 3 and etches tungsten film as depicted in Figure 4. The inhibition and etch effects of the NF ₃ treatment may both occur as a result of operation 204, but for clarity, are30 shown separately in different figures. [0051] Figure 3 illustrates an example of a process performed to fill a 3D NAND structure with tungsten that includes an inhibition operation. In Figure 3, a cross-sectional view of a single wordline of a 3D NAND structure is shown. (As in the example of Figure 1E, wordline features in Figure 3 show pillar constrictions that would be seen in a plan view rather than a LAMRP644WO/10321-1WO 9

cross-sectional view to illustrate the constrictions.) [0052] At 370, the wordline feature is shown after a Dep1 process. An under-layer 306 is shown; this may be for example a titanium nitride (TiN), tungsten nitride (WN), or tungsten carbonitride (WCN) barrier layer. A conformal W film 305 lines the feature surfaces including 5 the surfaces of the under-layer 306. In some embodiments, the conformal W film 305 is deposited directly on a dielectric surface such as an aluminum oxide or silicon oxide surface. The W layer 305 may be a nucleation layer, a nucleation and a bulk layer, or a bulk layer. [0053] Next, the feature is exposed to an inhibition chemistry to inhibit portions 365 at 371. In this example, the portions 365 through pillar constrictions 351 are inhibited while the 10 surfaces of the interior at 352 are not inhibited. Thus, in the example of Figure 3, the inhibition treatment is laterally non-conformal. However, the treatment may be uniform in a vertical direction such that each wordline is inhibited at approximately the same areas. [0054] Next, a process is performed to selectively deposit W accordance with the inhibition profile: bulk W 308 is preferentially deposited on the non-inhibited portions of the W layer15 305, such that hard-to-fill regions behind constrictions are filled, at 372. [0055] In this example, the bulk deposition continues, filling the remainder of the feature with bulk W 308 at 373. Figure 4 illustrates an example of a process performed to fill a 3D NAND structure with tungsten that includes an etch. In the example of Figure 4, an under- layer 406 is shown; this may be for example a barrier layer. As in the example of Figure 3, a 20 conformal W film 405 lines the feature surfaces. In some embodiments, the conformal W film 405 is deposited directly on a dielectric surface such as an aluminum oxide or silicon oxide surface. W layer 405 may be a nucleation layer, a nucleation and a bulk layer, or a bulk layer. [0056] This is followed by a non-conformal etch (with high selectivity to protect the under- layer 406 if present) at 471. For example, a non-conformal etch having high W:TiN selectivity 25 may be performed for TiN under-layers. As a result of the non-conformal etch, the conformal W layer 405 is left intact in the interior 452 of the feature, while thinned or completely removed at the feature openings 422. As in Figure 3, the etch may be uniform in a vertical direction such that each wordline is etched at the same areas. [0057] Next, bulk W 408 is deposited on the remaining portions of the W layer 405, such 30 that hard-to-fill regions behind constrictions are filled, at 472. In this example, the bulk deposition continues, filling the remainder of the feature with bulk W 408 at 473. In some embodiments, a dep-etch-dep operation can be repeated to fill the feature. According to various implementations, each subsequent deposition operation may or may not include deposition of LAMRP644WO/10321-1WO 10

a nucleation layer. In some implementations, the treatment may also include an inhibition effect. [0058] As discussed above, the treatment of NF ₃ inhibits nucleation and etches tungsten film. The inhibition in Figure 3 and etch in Figure 4, while shown separately, may both occur when 5 the tungsten film is treated with NF ₃ . [0059] In some embodiments, Dep1 is used to deposit a nucleation layer and Dep2 to deposit a bulk layer. In some embodiments, Dep1 and Dep2 each are used to deposit bulk W layers, Dep1 to deposit a conformal bulk layer and Dep 2 to fill the feature in the examples of Figures 3 and 4. 10 [0060] In some embodiments, the conformal W layer may be characterized as low resistivity and, in some embodiments, low stress and/or low fluorine. Because the wordline features are unfilled (with the exception of the nucleation layer if deposited), a relatively fast deposition technique may be used. In some embodiments, this involves alternating pulses of a W- containing precursor, such as tungsten hexafluoride (WF ₆ ), and hydrogen (H ₂ ) or other 15 reducing agent to deposit the first tungsten layer in an ALD process. Purge operations may separate the pulses. Relatively short pulse times may be used for deposition to increase throughput. [0061] The second bulk layer deposited in the Dep2 operation may be deposited using a second set of conditions than the first layer bulk layer. Like the first bulk layer, the second 20 bulk layer may be a low resistivity layer, and in some embodiments, a low stress and/or low fluorine layer. In some embodiments, operation 206 involves increased pulse times and increased purge times relative to operation 202. In particular embodiments, W-containing precursor pulse times may be increased. Increasing pulse and/or purge times can facilitate reactants diffusing into the wordlines. In some embodiments, the temperature may also be 25 changed from operation 202 to operation 206; for example, higher temperature may be used to speed reaction time. In some embodiments, a lower temperature may be used to allow the reactants to diffuse into the wordline features before reaction. In some embodiments, the second set of conditions may include a change in flowrates. For example, the flow rate of the W-containing precursor and/or reducing agent may be increased. 30 [0062] In some embodiments, a third bulk W layer may be deposited at different conditions. This layer may be characterized as an overburden layer that is removed in a subsequent step and can be deposited on sidewalls such as sidewalls 140 in the 3D NAND structure of Figure 1A. This layer may be characterized as low roughness. Higher resistivity and/or fluorine LAMRP644WO/10321-1WO 11

concentration can be tolerated as the tungsten is to be removed. The third set of conditions can involve any one of: faster timing if ALD is used with shorter pulse times than during deposition of the second bulk W layer, using CVD instead of ALD, and introducing nitrogen (N ₂ ) during or between the flow of one or more reactant gases. 5 [0063] In the examples above, NF ₃ is used as the treatment gas. In other embodiments, another gas may be used, such as another nitrogen and halogen-containing gas or gas mixture. In some embodiments, there may be a surface morphology treatment that is performed after NF ₃ or other inhibition and/or etch treatment. This is discussed further with respect to Figure 5. 10 [0064] In Figure 5, in an operation 502, the surface is exposed to a halogen- and/or nitrogen- containing chemistry. In operation 502, nitrogen is an inhibition chemistry; other inhibition chemistries may be used in addition to or instead of nitrogen as appropriate. Fluorine- and chlorine- containing chemistries are used for etching. Operation 502 may be a continuous flow or a pulsed operation and may be a plasma or thermal, non-plasma operation. Other activation15 energies may also be applied. [0065] Example nitrogen-containing gases for inhibition include NF ₃ , NH ₃ , nitrogen (N ₂ ), and hydrazine (N ₂ H ₄ ). [0066] Example halogen-containing gases for etching include NF ₃ , F ₂ , hydrogen fluoride (HF), chlorine (Cl ₂ ), chlorine trifluoride (CF ₃ ), and other Cl-containing or F-containing gases. 20 Without a reducing agent to react with, these will etch the film. [0067] Next in an operation 504, there may be a purge with a non-halogen gas. An inert gas such as argon (Ar) or helium (He) may be used. N ₂ may also be used. The purge is a non- plasma process that can remove surface chlorine or fluorine species. In some embodiments (e.g., in which the substrate is not exposed to chlorine or fluorine species in operation 502)25 operation 504 may be omitted. [0068] Next, in an operation 506, the surface may be exposed to a surface morphology treatment gas. It has been found that inhibition treatments can result in a “rough” surface that can adversely affect the quality of the film deposited in Dep2. The surface morphology treatment gas may be a pulsed or continuous flow of a tungsten precursor, a reducing agent30 (e.g., H ₂ ), or both. [0069] In some embodiments, operations 502–506 are repeated one or more times. For example, each of the operations can be performed as a pulse in a multi-cycle sequence of pulses. LAMRP644WO/10321-1WO 12

In alternate embodiments, operation 502 may be performed as multiple cycles of pulses with one or both of operations 504 and 506 performed only at the completion of the multiple cycles. The order of operations 504 and 506 may be reversed in some embodiments. [0070] The methods described involve reacting a tungsten-containing precursor (also referred 5 to as a tungsten precursor) with a reducing agent to form an elemental tungsten film. [0071] Various tungsten-containing gases including, but not limited to tungsten hexafluoride (WF ₆ ), tungsten hexachloride (WCl ₆ ), and tungsten hexacarbonyl (W(CO) ₆ ) can be used as the tungsten-containing precursor. In certain implementations, the tungsten-containing precursor is a halogen-containing compound, such as WF6. In certain implementations, the reducing 10 agent is hydrogen gas, though other reducing agents may be used including silane (SiH4), disilane (Si2H6) hydrazine (N2H4), diborane (B2H6) and germane (GeH4). In many implementations, hydrogen gas is used as the reducing agent in the deposition of a bulk tungsten film. In some other implementations, a tungsten precursor that can decompose to form a bulk tungsten layer can be used without a reducing agent. 15 [0072] Deposition may proceed according to various implementations until a certain feature profile is achieved and/or a certain amount of tungsten is deposited. In some implementations, the deposition time and other relevant parameters may be determined by modeling and/or trial and error. For example, for an initial deposition for an inside out fill process in which tungsten can be conformally deposited in a feature until pinch-off, it may be straightforward to 20 determine based on the feature dimensions the tungsten thickness and corresponding deposition time that will achieve pinch-off. In some implementations, a process chamber may be equipped with various sensors to perform in-situ metrology measurements for end-point detection of a deposition operation. Examples of in-situ metrology include optical microscopy and X-Ray Fluorescence (XRF) for determining thickness of deposited films. 25 [0073] It should be understood that the tungsten films described herein may include some amount of other compounds, dopants and/or impurities such as nitrogen, carbon, oxygen, boron, phosphorous, sulfur, silicon, germanium and the like, depending on the particular precursors and processes used. The tungsten content in the film may range from 20% to 100% (atomic) tungsten. In many implementations, the films are tungsten-rich, having at least 50% 30 (atomic) tungsten, or even at least about 60%, 75%, 90%, or 99% (atomic) tungsten. In some implementations, the films may be a mixture of metallic or elemental tungsten (W) and other tungsten-containing compounds such as tungsten carbide (WC), tungsten nitride (WN), etc. CVD and ALD deposition of these materials can include using any appropriate precursors. For LAMRP644WO/10321-1WO 13

example, CVD and ALD deposition of tungsten nitride can include using halogen-containing and halogen-free tungsten-containing and nitrogen-containing compounds as described further below. [0074] As described above, the NF ₃ treatment has lateral non-conformality but top-to-bottom 5 uniformity. [0075] In some embodiments, charge volumes may be used to deliver gas to achieve lateral non-conformality but have top-to-bottom uniformity. Using charge volumes can enable delivering treatment gases to the bottom of high aspect ratio structures, such as to the bottom wordline of 3D NAND structures. The pressurized gas flows from the charge volume through10 a showerhead and reaches the substrate. [0076] An example apparatus is shown schematically in Figure 6, in which the gas sources are connected to charge volumes. In some embodiments, one or more gas sources may be connected to multiple charge volumes. The apparatus includes a gas manifold system, which provides line charges to the various gas distribution lines. The manifolds provide the treatment 15 gases and purge gas to the deposition chamber through valved charged volumes. The various valves are opened or closed to provide a line charge, i.e., to pressurize the distribution lines. [0077] FIG. 6 depicts a schematic showing how process gases may be provided to a wafer processing chamber (not shown) via a showerhead 602. Shown in the schematic are two gas zones fluidically connected to the showerhead 602 through a dual inlet chamber 604. In the 20 example described below, the first gas zone 606 includes deposition and purge gases. The second gas zone 608 includes a pressure gas and an inhibition gas that is chemically incompatible with the deposition gases. In other embodiments, the gas zones may be used to separately supply chemically incompatible gases to the showerhead 602. [0078] In the described example, the deposition gases include a metal precursor gas such as 25 tungsten hexafluoride (WF ₆ ) and hydrogen (H ₂ ). Examples of metal precursor gases are provided below. The purge gas may be argon (Ar) or other chemically inert gas. The inhibition gas may be nitrogen trifluoride (NF ₃ ), which can be used to inhibit nucleation on the deposited metal. H ₂ and NF ₃ are chemically incompatible as they can react explosively. Other examples of inhibition gases as well as other gases that may be supplied in the second gas zone are30 provided below. [0079] The showerhead 602 distributes gases to the chamber (not shown). Fluidically interposed between the showerhead 602 and the two gas zones is a dual inlet chamber 604. The dual inlet chamber 604 is fluidically connected to the first gas zone 606 and the second LAMRP644WO/10321-1WO 14

gas zone 608. The dual inlet chamber 604 has a first inlet 626 and a second inlet 628. Each gas zone connects to one of the two inlets of the dual inlet chamber 604. In the example shown in FIG. 6, the first gas zone 606 connects to the first inlet 626 and the second gas zone 608 connects to the second inlet 628 of the dual inlet chamber 604. 5 [0080] In some embodiments, the dual inlet chamber 604 may be used to flow gases separately from each gas zone to the showerhead. The individual gases from each gas zone may mix in the dual inlet chamber 604. The dual inlet chamber 604 may be used to mix gases from the first gas zone 606 and the second gas zone 608 prior to the gas mixture flowing to the chamber via the showerhead 602. However, this may be avoided in situations in which the gas flows10 include chemically incompatible gases. [0081] In some embodiments, the dual inlet chamber 604 includes an annulus. Further details of the dual inlet chamber 604 are provided below. [0082] In the example of Figure 6, the second gas zone 608 includes an inhibition gas source 616E and an inhibition gas manifold 612. The inhibition gas manifold 612 is fluidically 15 interposed between the inhibition gas source 616E and the dual inlet chamber 604. The inhibition gas source 616E supplies the inhibition gas to the inhibition gas manifold 612. [0083] The inhibition gas manifold 612 includes an injection valve 618E, a divert gas valve 620E, and a charge volume 614E. The three components, the injection valve 618E, the divert gas valve 620E, and the charge volume 614E, are fluidically connected to each other via a main 20 inhibition gas line 632 with the divert gas valve being fluidically interposed between the injection valve and the charge volume. The injection valve 618E is fluidically connected to the dual inlet chamber 604 and fluidically interposed between the dual inlet chamber and the divert gas valve 620E. The injection valve 618E may be used to control the flow of inhibition gas from the inhibition gas manifold 612 into the dual inlet chamber 604. The divert gas valve 25 620E is fluidically connected to a divert manifold 622 and directs the flow of inhibition gas from the charge volume 614E to the injection valve 618E or to the divert manifold 622. The divert manifold 622 may be used to relieve pressure from the inhibition gas manifold 612, to clear the inhibition gas manifold 612 of gas, or to stabilize the flow of inhibition gases. When inhibition gas is being flowed into the showerhead, the divert manifold 622 may be used to 30 relieve pressurize gas, ensuring the gas flows from the inhibition gas manifold 612 is stabilized before reaching the showerhead 602. The divert manifold 622 can be used to discharge any gas remaining in the inhibition gas manifold 612, including inhibition gas still in the charge volume 614E. In some cases, it may desirable to clear the inhibition gas manifold 612 of all LAMRP644WO/10321-1WO 15

gases prior to the flow of additional inhibition gas into the inhibition gas manifold. The charge volume 614E is fluidically interposed between the inhibition gas source 616E and the divert gas valve 620E. The charge volume 614E stores and pressurizes the inhibition gas from the inhibition gas source 616E. When either the divert gas valve 620E is closed or when the divert 5 gas valve directs the flow of gas to the injection valve 618E and the injection valve is closed, gas may be flowed from the inhibition gas source 616E to the charge volume 614E where the gas is stored and pressurized. [0084] In one example, the second gas zone 608-- includes NF ₃ . When the NF ₃ gas is not being used in the process, the injection valve 618E is closed to prevent NF ₃ gas from being flowed 10 into the dual inlet chamber 604. The inhibition gas source 616E flows NF ₃ gas into main inhibition gas line 632 and into the charge volume 614E. Since the injection valve 618 is closed, the NF ₃ gas will fill the charge volume 614E and will become pressurized. The pressurized NF ₃ gas increases the mass flow rate of the gas when the gas is released by opening the injection valve 618. When the process uses the flow of NF ₃ to the substrate, the injection 15 valve 618E is opened. The pressurized NF ₃ gas flows into the dual inlet chamber 604 and into the showerhead 602. [0085] While the inhibition gas pressure is building in the charge volume 614E, the showerhead 602 may flow process gas from the first gas zone 606 into the chamber. The first gas zone 606 has a process gas manifold 610 and at least one gas source 616. In the 20 embodiment shown, there are four different gas sources 616. In some embodiments, there may be a single gas source 616. In other embodiments, there may be multiple gas sources. As indicated above, examples of gases supplied from the gas sources are Ar, H ₂ , and WF ₆ . In the embodiment shown, there are four individual gas sources 616. Each process gas source 616A, 616B, 616C, and 616D supplies a gas to a separate line within the process gas manifold 610. 25 In some embodiments, the gas type for each gas source 616 may be unique for each line, e.g., the gas in 616A is different than the gas in 616B, the gas in 616A and 616B are different than the gas in 616C, etc. In other embodiments, the same gas may be used as the gas for two or more gas sources, e.g., the gas in process gas source 616A may be the same gas as in the gas source 616B. 30 [0086] The first gas zone 606 has the process gas manifold 610. In the embodiment shown, the process gas manifold 610 has an injection valve 618A, a divert gas valve 620A, and charge volumes 614 with corresponding charge volume valves 624. The injection valve 618A fluidically connects the gas from the process gas manifold 610 to the dual inlet chamber 604. The divert gas valve 620A is fluidically interposed between the injection valve 618A and the LAMRP644WO/10321-1WO 16

charge volume valves 624. The injection valve 618A, the divert gas valves 620A, and charge volume valves 624 are fluidically connected via a main process gas line 630. Similar to the divert gas valve 620E in the inhibition gas manifold 612, the divert gas valve 620A in the process gas manifold 610 can divert gas within the main process gas line 630 and/or from the 5 charge volumes 614 to the divert manifold 622. [0087] Process gas from the process gas sources 616 are flowed into the corresponding charge volumes 614. When a charge volume valve 624 is closed, the process gas from a corresponding gas source 616 may fill the corresponding charge volume 614. As the process gas from the process gas sources 616 fills the charge volume 614, the gas may become pressurized. The 10 charge volumes 614 store the pressurize gas until the gas is released into the main process gas line 630 by opening the corresponding charge volume valve 624. [0088] In one example, WF ₆ gas is provided by the process gas source 616A. When WF ₆ is not used for wafer processing, the charge volume valve 624A is closed. The process gas source 616A flows WF ₆ into the charge volume 614A. The WF ₆ gas fills the charge volume 614A 15 and becomes pressurized. When the WF ₆ gas is pressurized to a desired pressure in the charge volume 614A, the process gas source 616A ceases flow of WF ₆ gas into the charge volume. Once wafer processing in the chamber uses WF ₆ gas, the charge volume valves 624B, 624C, and 624D for the other gases close, preventing the gas in the other charge volumes 614 from flowing into the main process gas line 630. Similarly, the injection valve 618E from the 20 inhibition gas manifold 612 is closed to prevent inhibition gas from entering the dual inlet chamber 604. The charge volume valve 624A for the WF ₆ gas is opened and the WF ₆ gas stored within the charge volume 614 flows into the main process gas line 630. The WF ₆ gas flows through the divert gas valve 620A and through the injection valve 618A into the dual inlet chamber 604. From the dual inlet chamber 604, the gas flows into the showerhead 602 25 before being injected into the chamber for wafer processing. [0089] In the process described in Figure 2, the deposition of W film in the structure may use H ₂ as a reducing agent and the non-conformal treatment 204 may use NF ₃ to inhibit and etch. However, when H ₂ and NF ₃ gases mix together, they may react explosively. Thus, preventing inadvertent mixtures of the two gases is critical. In this example, the gas source 616B in the30 first gas zone 606 provides H ₂ gas to the process gas manifold 610 and the gas source 616E in the second gas zone 608 provides NF ₃ gas to the inhibition gas manifold 612. As described above, for the non-conformal treatment of the deposited tungsten film, NF ₃ gas is flowed into the chamber. After a purge, deposition gases such as WF ₆ and H ₂ gas is flowed into the chamber. NF ₃ gas is flowed through the inhibition gas manifold 612 through the dual inlet LAMRP644WO/10321-1WO 17

chamber 604 through the showerhead 602 to the chamber (not shown). Prior to NF ₃ gas being flowed into the chamber, the charge volume valve 624B for the H ₂ gas is closed and an inert gas is flowed throughout the lines to clear any remaining H ₂ gas from the line. Subsequently, NF ₃ gas is flowed through the inhibition gas manifold 612 through the dual inlet chamber 604 5 into the showerhead 602. Inert gas may be supplied by a gas source, such as the gas source 616C, in the first gas zone 606, or may be supplied by another gas source (not shown) fluidically connected to the first inlet 626 of the dual inlet chamber 604. Concurrent to the NF ₃ gas being flowed, the inert gas in the first gas zone 606 flows through the process gas manifold 610 into the dual inlet chamber 604 via the first inlet 626. This prevents the NF ₃ gas in the dual 10 inlet chamber 604 from flowing out through the first inlet 626 and forces the NF ₃ gas into the showerhead 602. The inert gas flowing from the process gas manifold 610 prevents NF ₃ gas from flowing into the process gas manifold 610 and creates a barrier between the NF ₃ gas and the H ₂ gas. Alternatively, when the inert gas from an outside source (not shown) is used, the injection valve 618 is closed, preventing any gas from flowing into or out of the process gas 15 manifold 610. The outside gas source flows the inert gas into the first inlet 626 of the dual inlet chamber 604, thus preventing any NF ₃ gas from the second gas zone 608 from flowing out of the first inlet 626 and into the first gas zone 606 where the H ₂ gas is. Thus, in both cases, the NF ₃ gas and the H ₂ gas have at least two barriers between them, the closed valve and the inert gas, preventing any potential mixture between the two gases. 20 [0090] After the NF ₃ gas is flowed, a purge is performed. The purge may clear any remaining NF ₃ gas in the showerhead 602, the dual inlet chamber 604, and the lines. One the flow path for the H ₂ gas is purged and cleared of NF ₃ gas, H ₂ gas can be flowed into the process chamber. An inert gas coming from the second gas zone 608 is flowed to the dual inlet chamber 604 and used to prevent H ₂ gas from flowing back up stream towards the NF ₃ gas. In addition, the 25 injection valve 618E may be closed to prevent NF ₃ gas from flowing into the dual inlet chamber 604 and mixing with the H ₂ gas. [0091] In multi-station chambers, each station has a corresponding showerhead 602. Depending on the tool configuration, each station may also have a corresponding process gas manifold 610 and inhibition gas manifold 612. In some embodiments, some stations in the 30 multi-station chamber have only a process gas manifold 610 while other stations have both the process gas manifold 610 and the inhibition gas manifold 612. In this embodiment, the stations with both the process gas manifold 610 and the inhibition gas manifold 612 will have a corresponding dual inlet chamber 604. For example, a multi-station chamber with four stations have station one and station four supplied with corresponding process gas manifolds. Stations LAMRP644WO/10321-1WO 18

three and station four have both corresponding process gas manifolds 610 and corresponding inhibition gas manifolds 612. In this example, station three and station four will each have a corresponding dual inlet chamber 604 fluidically interposed between the corresponding showerhead 602 and corresponding process gas manifolds 610 and corresponding inhibition 5 gas manifolds 612. Depending on the tool configuration, each of the process gas manifolds 610 may be supplied with the same gases or may be supplied with different gases. Similarly, depending on the tool configuration, each of the inhibition gas manifolds 612 may be supplied with the same inhibition gas or different inhibition gas. [0092] FIG. 7 shows an example of an arrangement of a dual inlet chamber 704 and 10 showerhead 702. The dual inlet chamber 704 has a first inlet 726, a second inlet 728, and an outlet 734. The showerhead 702 and the dual inlet chamber 704 are fluidically connected to each other via an outlet gas line 740. The dual inlet chamber 704 may be placed as close as possible to the showerhead 702. For example, the dual inlet chamber 704 may be placed immediately outside the processing chamber (not shown). By placing the dual inlet chamber 15 704 close to the showerhead 702, gas in the dual inlet chamber may reach the showerhead 702 quickly to decrease wafer processing time and the pressurized gas remains pressurized, thus allowing gas to flow completely down the 3D NAND structure. [0093] In the example shown, the first inlet 726 fluidically connects a first inlet gas line 736 to the dual inlet chamber 704 and the second inlet 728 fluidically connects a second inlet gas line 20 738 to the dual inlet chamber. In some embodiments, the first inlet gas line 736 may be fluidically connected to the first gas zone (not shown) and the second inlet gas line 738 may be fluidically connected to the second gas zone (not shown) as discussed in FIG. 6. [0094] The dual inlet chamber 704 may have a single gas or multiple gases flowed through the dual inlet chamber and out through the outlet 734. In some embodiments, the first inlet 726 25 may have a gas flowed into the dual inlet chamber 704 and the second inlet 728 has a second gas flowed into the dual inlet chamber. The dual inlet chamber 704 may allow the two gases to mix and form a gas mixture of the two gases. The newly formed gas mixture may be flowed out of the dual inlet chamber 704 through the outlet 734 and into the showerhead 702 for dispersion into the processing chamber (not shown). 30 [0095] FIG. 7 shows a dual inlet chamber 704 including an annulus 750. The dual inlet chamber 704 allows for uniform gas distribution from both the first inlet 726 and the second inlet 728 to the outlet 734. Gas entering from the first inlet 726 travels through main line 752 directly to the outlet 734 and into the showerhead 702. Gas entering from the side of the dual LAMRP644WO/10321-1WO 19

inlet chamber 704, through the second inlet 728 enters through a side of the annulus 750. The annulus 750 evenly distributes the delivery of gas from the second inlet 728, the side of the annulus, to the main line 752. Thus, the annulus allows for uniform distribution of gases from both the first inlet 726 and the second inlet 728 to the outlet 734 and into the showerhead 702. 5 [0096] Below the dual inlet chamber 704 is the showerhead 702. The showerhead distributes the gas from the dual inlet chamber 704 into the chamber (not shown). The showerhead may be a single plenum or a dual plenum showerhead. The treatment process using NF ₃ in process 204 is advantageous over other treatment using other gases, such as ammonia (NH ₃ ), because it allows for a single plenum showerhead. NH ₃ gas difficult to purge and may leave residue10 (after a purge) in the hardware. The residue may react with other process gases such as WF ₆ , SiH ₄ , and B ₂ H ₆ . Thus, when a gas like NH ₃ is used for the treatment process, a dual plenum showerhead prevents cross contamination of the NH ₃ gas residue left in the showerhead and the other process gases. However, NF ₃ gas allows a single plenum showerhead to be used. While NF ₃ may be reactive with other process gases, a purge operation is able to clear the NF ₃ 15 gas and NF ₃ residue from the showerhead. Thus, a single plenum may be used as long as the gases are purged from the showerhead 702 before the use of the next gas. [0097] FIG. 8 shows examples of a process gas manifold 810 and an inhibition gas manifold 812. As in the example of FIG. 6, in one example, the process gas manifold 810 is the gas manifold in the first gas zone (not shown) and the inhibition gas manifold 812 is the gas 20 manifold in the second gas zone (not shown). In the example shown, the process gas manifold 810 has four charge volumes 814, four charge volume valves 824, a divert gas valve 820A, and an injection gas valve 818A. The six valves, the four charge volume valves 824, the divert gas valve 820A, and the injection gas valve 818A are fluidically connected in series, as shown in the schematic depicted in FIG.6. As discussed above in FIG.6, the number of charge volumes 25 814 in the process gas manifold 810 may vary. In some embodiments, there may be a single charge volume 814. In other embodiments, there may be multiple charge volumes 814. In the example shown in FIG. 8, there are four charge volumes 814. The charge volumes 814 are parallel to each other and are each fluidically connected to the injection gas valve 818 by their corresponding charge volume valve 824. Each charge volume 814 has a charge volume port 30 842 that connects to an outside gas source (not shown). The charge volume 814 stores and pressurizes gas from the outside gas source. This allows control of the mass flow of the gas when the gas is released from the charge volume 814. Depending on the application, each charge volume 814 may vary in size. The size of each charge volume 814 depends on different factors, for example, the type of gas being charged in the volume, the volume of gas used for LAMRP644WO/10321-1WO 20

the application, and the pressure used for the application. In some embodiments, each charge volume 814 on the process gas manifold 810 may have the same size. In other embodiments, the size of each charge volume 814 will vary. For example, in a particular process gas manifold 810, three of the four charge volumes have a volume of 0.3 liters and the fourth charge volume 5 has a volume of 0.1 liters. In another example, a process gas manifold 810 has four charge volumes 814, with each charge volume having a volume of 0.3 liters. In some embodiments, the apparatus can be reconfigured to use charge volumes of different sizes depending on the particular process. [0098] Each of the charge volumes 814 is fluidically connected to the injection gas valve 818A 10 via a corresponding charge volume valve 824. The corresponding charge volume valve 824 is fluidically interposed between the injection gas valve 818A and their corresponding charge volume 814. When a charge volume valve 824 is closed, the gas flow from the corresponding charge volume 814 stops and is prevented from reaching the injection gas valve 818A. Gas flows into the charge volume 814 and pressurizes. When the charge volume valve 824 is put 15 in the open position, the gas in the charge volume is released and flows through the process gas manifold 810. [0099] Fluidically interposed between the charge volume valves 824 and the injection gas valve 818A is the divert gas valve 820A. The divert gas valve 820A has a divert gas valve port 844A to connect to a divert gas manifold (not shown). The divert gas valve 820A directs the 20 flow of gas from a charge volume 814 to either the injection gas valve 818A or the divert gas valve port 844A. In some embodiments, the divert gas valve 820A may be three-way valve that can stop the flow of gas. [0100] The injection gas valve 818A has an injection gas valve outlet 846A that fluidically connects the process gas manifold 810 with a dual inlet chamber (not shown). The injection 25 gas valve 818A controls the flow of gas out of the process gas manifold 810. When the injection gas valve 818A is closed, flow out of the process gas manifold 810 stops. When the injection gas valve is opened, the gas from the process gas manifold flows out to the injection gas valve outlet 846A. [0101] The inhibition gas manifold 812 has an injection gas valve 818E, a divert gas valve 30 820E, and a charge volume 814E fluidically connected to each other. The divert gas valve 820E is fluidically interposed between the injection gas valve 818E and the charge volume 814E. The charge volume 814E has a charge volume port 842E to connect to a gas source (not shown). The gas source provides the gas to the inhibition gas manifold 812 through the charge LAMRP644WO/10321-1WO 21

volume 814E. In the embodiment shown there is a single charge volume 814E and thus no charge volume valve is used. In some embodiments, there may be multiple charge volumes 814. In this case, each charge volume 814 would be in parallel to each other charge volume and each charge volume would have a corresponding charge volume valve to control the flow 5 from the respective charge volume. [0102] The inhibition gas manifold 812 has a divert gas valve 820E with a divert gas valve port 844E. The divert gas valve port 844E of the divert gas valve 820E fluidically connects to a divert gas manifold (not shown). Similar to the divert gas valve 820 in the process gas manifold 810, the divert gas valve directs the flow of gas from the charge volume 814E to 10 either the injection gas valve 818E or the divert gas valve port 844E. In some embodiments, the divert gas valve 820E may be a three-way valve that can stop the flow of gas. [0103] The injection gas valve 818E in the inhibition gas manifold 812 has an injection gas valve outlet 846E and an injection gas valve inlet 848. The injection gas valve outlet 846E fluidically connects the inhibition gas manifold 812 to the dual inlet chamber (not shown). The 15 injection gas valve inlet 848 connects another gas, such as an inert gas, to the inhibition gas manifold 812. For example, the injection gas valve inlet 848 may be connected to Ar and be used to flow inert gas into the chamber, preventing any other process gas from flowing to the inhibition gas manifold 812. The injection gas valve 818E controls the flow of gas out of the inhibition gas manifold 812. When the injection gas valve 818E is closed, flow out of the 20 inhibition gas manifold 812 stops, when the injection gas valve is opened, the flow of gas flows to the injection gas valve outlet 846E. Deposition of Tungsten films [0104] In some implementations, the methods described herein involve deposition of a tungsten nucleation layer prior to deposition of a bulk layer. In the examples described herein, 25 the nucleation layer may be deposited as the first conformal deposition or to as a seed layer for the first conformal deposition. A nucleation layer is a thin conformal layer that facilitates subsequent deposition of bulk tungsten-containing material thereon. According to various implementations, a nucleation layer may be deposited prior to any fill of the feature and/or at subsequent points during fill of the feature. In some implementations of the method described 30 herein, a nucleation layer is deposited only at the beginning of feature fill and is not necessary at subsequent depositions. As described above, in some embodiments, the conformal Dep1 deposition is a nucleation layer. It may also be a bulk layer deposited on a nucleation layer. [0105] In nucleation layer deposition, pulses of a reducing agent, optional purge gases, and LAMRP644WO/10321-1WO 22

tungsten-containing precursor may be sequentially injected into and purged from the reaction chamber in an ALD sequence. Nucleation layer thickness can depend on the nucleation layer deposition method as well as the desired quality of bulk deposition. In general, nucleation layer thickness is sufficient to support high quality, uniform bulk deposition. Examples may 5 range from 10Å-100Å. [0106] The methods described herein are not limited to a particular method of tungsten nucleation layer deposition and include deposition of bulk tungsten film on tungsten nucleation layers formed by any method including PNL, ALD, CVD, and physical vapor deposition (PVD). Moreover, in certain implementations, bulk tungsten may be deposited directly in a 10 feature without use of a nucleation layer. For example, in some implementations, the feature surface and/or an already-deposited under-layer supports bulk tungsten deposition. In some implementations, a bulk tungsten deposition process that does not use a nucleation layer may be performed. [0107] In various implementations, tungsten nucleation layer deposition can involve 15 exposure to a tungsten-containing precursor such as tungsten hexafluoride (WF ₆ ), tungsten hexachloride (WCl ₆ ), and tungsten hexacarbonyl (W(CO) ₆ ). In certain implementations, the tungsten-containing precursor is a halogen-containing compound, such as WF ₆ . Organo- metallic precursors, and precursors that are free of fluorine such as MDNOW (methylcyclopentadienyl-dicarbonylnitrosyl-tungsten) and EDNOW (ethylcyclopentadienyl-20 dicarbonylnitrosyl-tungsten) may also be used. [0108] Examples of reducing agents can include boron-containing reducing agents including diborane (B ₂ H ₆ ) and other boranes, silicon-containing reducing agents including silane (SiH ₄ ) and other silanes, hydrazines, and germanes. In some implementations, pulses of tungsten- containing precursors can be alternated with pulses of one or more reducing agents, e.g.,25 S/W/S/W/B/W, etc., W represents a tungsten-containing precursor, S represents a silicon- containing precursor, and B represents a boron-containing precursor. In some implementations, a separate reducing agent may not be used, e.g., a tungsten-containing precursor may undergo thermal or plasma-assisted decomposition. [0109] According to various implementations, hydrogen may or may not be run in the 30 background. Further, in some implementations, deposition of a tungsten nucleation layer may be followed by one or more treatment operations prior to tungsten bulk deposition. Treating a deposited tungsten nucleation layer to lower resistivity may include pulses of reducing agent LAMRP644WO/10321-1WO 23

and/or tungsten precursor. Bulk Deposition [0110] Bulk deposition may also involve an ALD process in which a tungsten precursor and a reducing agent are sequentially injected into and purged from a reaction chamber. Hydrogen 5 may be used as the reducing agent rather than a stronger reducing agent like diborane that is used in nucleation layer deposition. [0111] Tungsten bulk deposition can also occur by a CVD process in which a reducing agent and a tungsten-containing precursor are flowed into a deposition chamber to deposit a bulk fill layer in the feature. An inert carrier gas may be used to deliver one or more of the reactant 10 streams, which may or may not be pre-mixed. Unlike ALD processes, this operation generally involves flowing the reactants continuously until the desired amount is deposited. In certain implementations, the CVD operation may take place in multiple stages, with multiple periods of continuous and simultaneous flow of reactants separated by periods of one or more reactant flows diverted. 15 [0112] It should be understood that the tungsten films described herein may include some amount of other compounds, dopants and/or impurities such as nitrogen, carbon, oxygen, boron, phosphorous, sulfur, silicon, germanium and the like, depending on the particular precursors and processes used. The tungsten content in the film may range from 20% to 100% (atomic) tungsten. In many implementations, the films are tungsten-rich, having at least 50% 20 (atomic) tungsten, or even at least about 60%, 75%, 90%, or 99% (atomic) tungsten. [0113] Figure 9 shows an example of an ALD method of forming a W film. The method according to Figure 9 may be used, for example, in one or both of operations 202 and 206 of Figure 2. First, in an operation 905, the W precursor is pulsed. After the W precursor is pulsed, an optional purge 915 may occur. Argon or any inert gas may be used to purge the chamber 25 of any unadsorbed precursor. The substrate is exposed to a co-reactant 925, which may be a reducing agent to reduce the W precursor or other co-reactant to react with the W precursor to form elemental W. The reactant may be a hydrogen-containing reactant. In some embodiments, the hydrogen-containing reactant may be thermal (non-plasma) hydrogen (H ₂ ). For plasma-based process, a remote or in-situ plasma generated from H ₂ may be used. An 30 optional purge may be performed at 935, followed by repeating operations 905–935 until the film is fully grown. This may be a conformal film lining a feature, such as conformal W film 305 or 405 or a bulk layer that fills all or some of the feature such as bulk W 308 or 408. LAMRP644WO/10321-1WO 24

[0114] In some embodiments, operation 202 in Figure 2 includes deposition of W nucleation layer, either as the conformal layer, or as a part of the conformal layer on which bulk W is deposited. [0115] In some embodiments, a W nucleation layer is deposited using one or more of a 5 boron-containing reducing agent (e.g., B ₂ H ₆ ) or a silicon-containing reducing agent (e.g., SiH ₄ ) as a co-reactant. For example, one or more S/W cycles, where S/W refers to a pulse of silane followed by a pulse of a W-containing precursor, may be employed to deposit a W nucleation layer on which a bulk W layer is deposited. In another example, one or more B/W cycles, where B/W refers to a pulse of diborane followed by a pulse of a W-containing precursor, may 10 be employed to deposit a W nucleation layer on which a bulk W layer is deposited. B/W and S/W cycles may both be used to deposit a W nucleation layer, e.g., x(B/W) + y(S/W), with x and y being integers. Examples of B- and S-containing reducing agents are given below. For deposition of a W nucleation layers, in some embodiments, the W-containing precursor may be a non-oxygen containing precursor, e.g., WF ₆ or WCl ₅ . Oxygen in oxygen-containing 15 precursors may react with a silicon- or boron-containing reducing agent to form WSi _x O _y or WB _x O _y , which are impure, high resistivity films. Oxygen-containing precursors may be used with oxygen incorporation minimized. In some embodiments, H ₂ may be used as a reducing gas instead of a boron-containing or silicon-containing reducing gas. Example thicknesses for deposition of a W nucleation layer range from 5 Å to 30 Å. Films at the lower end of this range 20 may not be continuous; however, as long as they can help initiate continuous bulk W growth, the thickness may be sufficient. In some embodiments, the reducing agent pulses may be done at lower substrate temperatures than the W precursor pulses. For example, or B ₂ H ₆ or a SiH ₄ (or other boron- or silicon-containing reducing agent) pulse may be performed at a temperature below 300 ^o C, with the W pulse at temperatures greater than 300 ^o C. 25 [0116] While the description below focuses on tungsten feature fill, aspects of the disclosure may also be implemented in filling features with other materials. For example, the treatment sequence described in Figure 5 may be implemented with feature fill processes that use molybdenum, cobalt, or ruthenium-containing materials. APPARATUS 30 [0117] Any suitable chamber may be used to implement the disclosed embodiments. Example deposition apparatuses include various systems, e.g., ALTUS ^® and ALTUS ^® Max, available from Lam Research Corp., of Fremont, California, or any of a variety of other commercially available processing systems. LAMRP644WO/10321-1WO 25

[0118] In some embodiments, a first deposition may be performed at a first station that is one of two, five, or even more deposition stations positioned within a single deposition chamber. Thus, for example, hydrogen (H ₂ ) and tungsten hexafluoride (WF ₆ ) may be introduced in alternating pulses to the surface of the semiconductor substrate, at the first station, using an 5 individual gas supply system that creates a localized atmosphere at the substrate surface. Another station may be used for NF ₃ treatment, and a third and/or fourth for subsequent ALD bulk fill. [0119] Figure 10 is a schematic of a process system suitable for conducting deposition processes in accordance with embodiments. The system 1000 includes a transfer module 1003. 10 The transfer module 1003 provides a clean, pressurized environment to minimize risk of contamination of substrates being processed as they are moved between various reactor modules. Mounted on the transfer module 1003 is a multi-station reactor 1009 capable of performing ALD, treatment, and CVD according to various embodiments. Multi-station reactor 1009 may include multiple stations 1011, 1013, 1015, and 1017 that may sequentially 15 perform operations in accordance with disclosed embodiments. For example, multi-station reactor 1009 may be configured such that station 1011 performs a tungsten nucleation layer deposition using a tungsten precursor and a boron- or silicon-containing reducing agent, station 1013 performs an ALD tungsten bulk deposition of a conformal layer using H ₂ as reducing agent, station 1015 performs a NF ₃ treatment operation, and station 1017 may perform a bulk20 ALD fill after treatment using H ₂ ae reducing agent . [0120] Stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate. [0121] Returning to Figure 10, also mounted on the transfer module 1003 may be one or more single or multi-station modules 1007 capable of performing plasma or chemical (non- 25 plasma) pre-cleans, other deposition operations, or etch operations. The module may also be used for various treatments to, for example, prepare a substrate for a deposition process. The system 1000 also includes one or more wafer source modules 1000, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 1019 may first remove wafers from the source modules 1001 to loadlocks 1021. A 30 wafer transfer device (generally a robot arm unit) in the transfer module 1003 moves the wafers from loadlocks 1021 to and among the modules mounted on the transfer module 1003. [0122] In various embodiments, a system controller 1029 is employed to control process conditions during deposition. The controller 1029 will typically include one or more memory LAMRP644WO/10321-1WO 26

devices and one or more processors. A processor may include a CPU or computer, analog and/or digital input/output connections, stepper motor controller boards, etc. [0123] The controller 1029 may control all of the activities of the deposition apparatus. The system controller 1029 executes system control software, including sets of instructions for 5 controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the controller 1029 may be employed in some embodiments. [0124] Typically there will be a user interface associated with the controller 1029. The user 10 interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc. [0125] System control logic may be configured in any suitable way. In general, the logic can be designed or configured in hardware and/or software. The instructions for controlling the 15 drive circuitry may be hard coded or provided as software. The instructions may be provided by “programming.” Such programming is understood to include logic of any form, including hard coded logic in digital signal processors, application-specific integrated circuits, and other devices which have specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general- 20 purpose processor. System control software may be coded in any suitable computer readable programming language. [0126] The computer program code for controlling the germanium-containing reducing agent pulses, hydrogen flow, and tungsten-containing precursor pulses, and other processes in a process sequence can be written in any conventional computer readable programming 25 language: for example, assembly language, C, C++, Pascal, Fortran, or others. Compiled object code or script is executed by the processor to perform the tasks identified in the program. Also as indicated, the program code may be hard coded. [0127] The controller parameters relate to process conditions, such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate 30 temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe and may be entered utilizing the user interface. [0128] Signals for monitoring the process may be provided by analog and/or digital input connections of the system controller 1029. The signals for controlling the process are output LAMRP644WO/10321-1WO 27

on the analog and digital output connections of the deposition apparatus 1000. [0129] The system software may be designed or configured in many different ways. For example, various chamber component subroutines or control objects may be written to control operation of the chamber components necessary to carry out the deposition processes in 5 accordance with the disclosed embodiments. Examples of programs or sections of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code. [0130] In some implementations, a controller 1029 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing 10 equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and/or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system 15 or systems. The controller 1029, depending on the processing requirements and/or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery 20 settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and/or load locks connected to or interfaced with a specific system. [0131] Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and/or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The 25 integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational30 parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or dies of a wafer. LAMRP644WO/10321-1WO 28

[0132] The controller 1029, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller 1029 may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The 5 computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a 10 network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and/or settings, which are then communicated to the system from the remote computer. In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the 15 parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus as described above, the controller may be distributed, such as by including one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more 20 integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber. [0133] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or 25 module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a CVD chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and/or manufacturing of semiconductor wafers. 30 [0134] As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and/or load ports in a semiconductor LAMRP644WO/10321-1WO 29

manufacturing factory. [0135] The controller 1029 may include various programs. A substrate positioning program may include program code for controlling chamber components that are used to load the substrate onto a pedestal or chuck and to control the spacing between the substrate and other 5 parts of the chamber such as a gas inlet and/or target. A process gas control program may include code for controlling gas composition, flow rates, pulse times, and optionally for flowing gas into the chamber prior to deposition in order to stabilize the pressure in the chamber. A pressure control program may include code for controlling the pressure in the chamber by regulating, e.g., a throttle valve in the exhaust system of the chamber. A heater 10 control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas such as helium to the wafer chuck. [0136] Examples of chamber sensors that may be monitored during deposition include mass flow controllers, pressure sensors such as manometers, and thermocouples located in the 15 pedestal or chuck. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain desired process conditions. [0137] The foregoing describes implementation of disclosed embodiments in a single or multi-chamber semiconductor processing tool. The apparatus and process described herein may be used in conjunction with lithographic patterning tools or processes, for example, for 20 the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following steps, each step provided with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) 25 curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma- assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave30 plasma resist stripper. CONCLUSION [0138] Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be LAMRP644WO/10321-1WO 30

practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein. LAMRP644WO/10321-1WO 31