Process gas lamps during semiconductor processing

Abstract

Provided herein are systems and methods for semiconductor processing including a feature fill process. The method includes providing a substrate having a feature to be filled with metal in a chamber, and flowing a metal precursor and a reducing agent into the chamber to deposit metal in the feature in a chemical vapor deposition (CVD) process, the CVD process including a ramp-down phase in which a flow rate of the metal precursor into the chamber is ramped down from a first flow rate to a second flow rate, or a ramp-up phase in which a flow rate of the metal precursor into the chamber is ramped up from a first flow rate to a second flow rate.

Description

[Technical field]

[0001] Incorporation by Reference The PCT Application Form is being filed contemporaneously herewith as a part of this application. Each application to which this specification claims the benefit of priority as identified in the contemporaneously filed PCT Application Form is hereby incorporated by reference in its entirety and for all purposes. [Background technology]

[0002] Feature fill processes can be used to fill features on semiconductor substrates with metal or dielectric materials. Chemical vapor deposition (CVD) processes can include reacting two process gases to deposit a solid thin film within the feature. Advanced fill processes can be used to fill device features with aggressive geometries. For example, a deposition-inhibition-deposition (DID) process can include a first deposition followed by an inhibition process to inhibit deposition at the feature opening and a subsequent deposition to fill the feature.

[0003] The background and contextual discussion contained herein is provided solely to generally present the context of the present disclosure. Most of this disclosure presents the work of the inventors, and is not meant to imply that such work is admitted to be prior art merely because it was mentioned in the background section or presented as context elsewhere in this specification. Summary of the Invention

[0004] Provided herein are systems and methods for semiconductor processing including feature fill processes that include ramping process gas flow rates during process steps.

[0005] One aspect of the present disclosure relates to a method for filling a feature with a metal, the method including providing a substrate having a feature to be filled with the metal in a chamber, and flowing a metal precursor and a reducing agent into the chamber to deposit the metal in the feature in a chemical vapor deposition (CVD) process, the CVD process including a ramp-down stage in which a flow rate of the metal precursor into the chamber is ramped down from a first flow rate to a second flow rate.

[0006] In some embodiments, the CVD process includes a second stage after the ramp-down stage where the metal precursor flow rate is constant.

[0007] In some embodiments, the CVD process includes a second stage, prior to the ramp-down stage, where the metal precursor flow rate is constant.

[0008] In some embodiments, the reductant flow rate is constant during the ramp-down phase.

[0009] In some embodiments, the reductant flow rate is ramped during the ramp-down phase.

[0010] In some embodiments, the method further comprises performing an inhibition treatment prior to the CVD step to inhibit metal deposition.

[0011] In some embodiments, metal deposition is preferentially suppressed near the feature opening.

[0012] In some embodiments, the feature includes a waist and a stage prior to the ramp-down stage is used to fill a portion of the feature below the waist.

[0013] In some embodiments, the ramp-down phase is used to fill the waist of the feature.

[0014] In some embodiments, the feature is a first feature having a first size, the substrate has a second feature having a second size, the second size being larger than the first size, and a ramp-down phase is used to complete filling of the first feature.

[0015] In some embodiments, the method further includes ramping up the flow of the metal precursor from the second flow rate to a third flow rate after the first feature is completely filled.

[0016] Another aspect of the disclosure relates to a method of filling a feature with a metal, the method including: a feature to be filled with the metal in a chamber; and flowing a metal precursor and a reducing agent into the chamber to deposit the metal in the feature in a chemical vapor deposition (CVD) process. The CVD process includes a ramp-up stage in which a flow rate of the metal precursor into the chamber is ramped up from a first flow rate to a second flow rate.

[0017] In some embodiments, the substrate has a second feature smaller than the feature, and further includes filling the second feature. The ramp-up phase may occur after the second feature is completely filled and before the feature is completely filled.

[0018] In some embodiments, the CVD process includes a second stage after the ramp-up stage where the metal precursor flow rate is constant.

[0019] In some embodiments, the CVD process includes a second stage, prior to the ramp-up stage, where the metal precursor flow rate is constant.

[0020] In some embodiments, the reductant flow rate is constant during the ramp-up phase.

[0021] In some embodiments, the reductant flow rate is ramped during the ramp-up phase.

[0022] In some embodiments, the method further comprises performing an inhibition treatment prior to the CVD step to inhibit metal deposition.

[0023] Also described are apparatus for carrying out the methods described herein.

[0024] These and other aspects of the disclosure are discussed further below with reference to the drawings. [Brief description of the drawings]

[0025] [Figure 1A] FIG. 2 illustrates an example of a gas manifold that may be used in the implementations described herein.

[0026] [Figure 1B] FIG. 2 illustrates an example of ramping of a reactant gas through stages.

[0027] [Figure 2A] 1A-1C illustrate examples of features that may be filled with metal according to various implementations. [Figure 2B] 1A-1C illustrate examples of features that may be filled with metal according to various implementations. [Figure 2C] 1A-1C illustrate examples of features that may be filled with metal according to various implementations. [Figure 2D] 1A-1C illustrate examples of features that may be filled with metal according to various implementations. [Figure 2E] 1A-1C illustrate examples of features that may be filled with metal according to various implementations. [Figure 2F] 1A-1C illustrate examples of features that may be filled with metal according to various implementations. [Figure 2G] 1A-1C illustrate examples of features that may be filled with metal according to various implementations. [Figure 2H] 1A-1C illustrate examples of features that may be filled with metal according to various implementations.

[0028] [Figure 3A] FIG. 1 illustrates an example of a multi-stage deposition process. [Figure 3B] FIG. 1 illustrates an example of a multi-stage deposition process.

[0029] [Figure 4] FIG. 1 is a flow diagram illustrating steps in a method for filling a feature.

[0030] [Diagram 5] 5A-5C show examples of features during various steps in FIG. 4.

[0031] [Figure 6] FIG. 1 illustrates an example of ramping flow during an atomic layer deposition (ALD) process.

[0032] [Figure 7] FIG. 1 illustrates an example of an apparatus that can be used to implement the methods described herein.

[0033] [Figure 8] FIG. 1 illustrates an example of a process station that can be used to perform the methods described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] Provided herein are systems and methods for semiconductor processing including feature fill processes. The methods include ramping process gas flow rates during process steps. Example processes include chemical vapor deposition (CVD) processes, treatment processes, and etch processes.

[0035] In a particular example, filling the feature with metal can include flowing a metal precursor and a reducing agent into a process chamber for a CVD reaction. The metal precursor flow rate is ramped down during at least a portion of the deposition. In some embodiments, ramping the metal precursor flow rate results in a low stress thin film and good filling characteristics. In another example, the reactant flow rate is ramped down as the deposition process begins to deposit a thin film near the top of the feature to reduce the amount of thin film deposited as a stressful layer. These and other embodiments are discussed further below.

[0036] An apparatus used to carry out the methods described herein may include a gas manifold system as shown in FIG. 1A. Manifold 104 has an input 101 from a source of a first reactant gas (e.g., a metal-containing precursor gas). Manifold 111 has an input 109 from a source of a second reactant gas (e.g., hydrogen (H2) or other reducing gas). There may or may not be an input from a carrier gas to manifold 104 and / or manifold 111. Manifold 121 has an input 117 from a source of an inert gas. Manifolds 104, 111, and 121 provide process and / or carrier or purge gases to the deposition chamber through valved delivery lines 105, 113, and 125, respectively. Various valves may be opened or closed to provide line feeds, i.e., to pressurize the delivery lines. For example, to pressurize delivery line 105, valve 106 is closed to vacuum and valve 108 is closed. After an appropriate time increment, valve 108 is opened and gas is delivered to the chamber. A similar process can be used to deliver gas from manifolds 111 and 121. Figure 1A also shows a vacuum pump where valves 106, 117, and 123, respectively, can be opened to purge the system.

[0037] The supply of gases through the various distribution lines is controlled by a controller, such as a mass flow controller (MFC) controlled by a microprocessor, digital signal processor, or the like, that is programmed with flow rates, duration of flow, and process sequencing.

[0038] Valve and MFC commands are sent to an embedded digital input / output controller (IOC) in a discrete packet of information containing instructions for all time-critical commands for all or part of the deposition sequence. Lam Research's ALTUS system provides at least one IOC sequence. The IOCs may be physically located at various locations within the equipment, for example, within the process modules or on a standalone power rack installed some distance away from the process modules. Within each module, there may be multiple IOCs (e.g., three per module). In terms of the actual instructions contained in the sequence, all commands for controlling the valves and setting the flows (for all process and inert gases) to the MFCs may be contained in a single IOC sequence. This ensures that the timing of all equipment is tightly controlled, both in absolute terms and relative to each other. There may be multiple IOC sequences operating at any given time.

[0039] The flow rates can be ramped up or down. According to various embodiments, the ramp step duration can be as little as 300 microseconds or arbitrarily long. A particular process, such as a CVD deposition or inhibition process, can have one or more stages. During each stage, the flow rate of each gas is ramped up, ramped down, or constant. According to various embodiments, each stage can be at least 3 seconds in duration, and arbitrarily long.

[0040] FIG. 1B shows an example of ramping of reactant gases over a stage. The stage can be the only stage of a single stage process, or one stage of a multi-stage process. At 151, a first reactant gas is shown ramping down, and a second reactant gas has a constant flow rate. Similarly, at 153, the first reactant gas is ramped up, and a second reactant gas has a constant flow rate. In some embodiments, both reactant gases may ramp during a stage, as shown at 155 and 157. According to various embodiments, the direction of the ramps may be the same (as at 157) or different (as at 155). Furthermore, the rate of ramping may be the same or different.

[0041] According to various embodiments, the inert gas (e.g., diluent gas) may be independently ramped or held constant during a stage. This may be done in addition to or instead of ramping one or more reactant gases, as shown in FIG. 1B.

[0042] In some embodiments, a method for filling a feature with a material is provided. For example, the method may be used to fill a feature with a metal. Examples of features that may be filled with a metal are provided below with reference to Figures 2A-2H.

[0043] The methods described herein are performed on a substrate that may be contained within the chamber. The substrate may be a silicon or other semiconductor wafer, e.g., a 200 mm wafer, a 300 mm wafer, or a 450 mm wafer, including a wafer having one or more layers of material, such as a dielectric, conductive, or semiconductive material deposited thereon. The methods are not limited to semiconductor substrates and may be performed to fill any feature with a metal-containing material or other material.

[0044] The substrate may have features such as vias or contact holes that may be characterized by one or more of a narrow and / or recessed opening, a waist, and a high aspect ratio within the feature. The features may be formed in one or more of the layers mentioned above. For example, the features may be formed at least partially within a dielectric layer. In some embodiments, the features 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 in a layer on the substrate.

[0045] FIG. 2A shows a schematic example of a DRAM architecture including a metal buried wordline (bWL) 208 in a silicon substrate 202. The metal bWL is formed in a trench etched into the silicon substrate 202. Lining the trench is a conformal barrier layer 206 and an insulating layer 204 disposed between the conformal barrier layer 206 and the silicon substrate 202. In the example of FIG. 2A, the insulating layer 204 may be a gate oxide layer formed from a high-k dielectric material, such as a silicon oxide or silicon nitride material. In some embodiments disclosed herein, the conformal barrier layer is a TiN or tungsten-containing layer. In some embodiments, one or both of the layers 204 and 206 are absent.

[0046] The bWL structure shown in Figure 2A is an example of an architecture that includes a conductive metal fill layer. During bWL fabrication, a conductive metal film is deposited in features that may be defined by etched recesses in silicon substrate 202, conformally lined by layers 206 and 204, if present.

[0047] 2B-2H are further schematic examples of various structures into which a metal fill layer may be deposited according to disclosed embodiments. FIG. 2B is an example of a cross-sectional view of a vertical feature 201 to be filled with metal. The feature may include a feature hole 205 in a substrate. The hole 205 or other feature may have an opening diameter or line width with dimensions close to the opening, e.g., between about 10 nm and 500 nm, e.g., between about 25 nm and about 300 nm. The feature hole 205 may be referred to as an unfilled feature or simply a feature. The feature 201, and any feature, may be characterized in part by an axis 218 that extends through the length of the feature, with vertically oriented features having a vertical axis and horizontally oriented features having a horizontal axis.

[0048] In some embodiments, the features are wordline features of a 3D NAND structure. For example, a substrate may include a wordline structure having any number of wordlines (e.g., 50-150) with vertical channels at least 200 Å deep. Another example is a trench in a substrate or layer. The features may be of any depth. In various embodiments, the features may have an underlayer, such as a barrier layer or an adhesion layer. Non-limiting examples of underlayers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0049] FIG. 2C illustrates an example of a feature 201 having an inwardly concave profile. An inwardly concave profile is a profile that narrows from the bottom, closed end, or interior of the feature to the feature opening. According to various implementations, the profile can be gradually narrowed and / or include an overhang at the feature opening. FIG. 2C illustrates an example of the latter, where an underlayer 213 lines the sidewalls or interior surface of the feature hole 105. The underlayer 213 can be, for example, a diffusion barrier layer, an adhesion layer, a nucleation layer, a combination thereof, or any other applicable material. Non-limiting examples of underlayers can include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers. In certain implementations, the underlayer can be one or more of titanium, titanium nitride, tungsten nitride, titanium aluminide, tungsten, and molybdenum. In some embodiments, the underlayer is different from or does not include the metal of the metal conductive layer. In some embodiments, the underlayer does not include tungsten. In some embodiments, the underlayer does not include molybdenum. The underlayer 213 forms an overhang 215 such that the underlayer 213 is thicker near the opening of the feature 201 compared to the interior of the feature 201.

[0050] In some implementations, features may be filled with one or more constrictions within the feature. FIG. 2D shows example diagrams of various filled features with constrictions. Examples (a), (b), and (c) in FIG. 2D each include a constriction 209 at a midpoint within the feature. The constriction 209 may be, for example, about 15 nm to 20 nm wide. The constriction may cause pinch-off during deposition of tungsten, molybdenum, or other conductive material within the feature using conventional techniques, where the deposited metal blocks further deposition beyond the constriction before that portion of the feature is filled, resulting in a void within the feature. Example (b) further includes a liner / barrier overhang 215 at the feature opening. Such an overhang may also be a potential pinch-off point. Example (c) includes a constriction 212 farther from the field region than the overhang 215 in example (b).

[0051] In some embodiments, deposition into a feature that includes a constriction may begin with a high flow rate of the metal-containing precursor for a short period of time to ensure that the metal-containing precursor can reach and fill the bottom-most portion of the feature (beyond the constriction). An example of a high flow rate is 1200 sccm. Then, when filling the narrow constriction, the flow of the metal-containing precursor is ramped down to a lower flow rate, for example, 1200 sccm to 200 sccm. After the narrow portion of the feature is filled, the metal-containing precursor may be held constant at a low flow rate to allow for a lower stress thin film near the top of the feature without compromising the fill performance. In some embodiments, such a ramped deposition may be the second deposition of a deposition-inhibition-deposition (DID) sequence. Horizontal features may also be filled, such as 3D memory structures. For example, the horizontal features may be wordline features in a 3D NAND (also called vertical NAND or VNAND) structure. In some implementations, the constriction may be due to the presence of pillars in a 3D NAND or other structure. FIG. 2E shows a cross-sectional side view of a 3D NAND structure 210 (formed on a silicon substrate 202) having a VNAND stack (left side 225 and right side 226), a central vertical structure 230, and multiple stacked horizontal features 220 with openings 222 on opposite sidewalls 240 of the central vertical structure 230. FIG. 2F shows two "stacks" of the 3D NAND structure 210 shown, which together form a "trench-like" central vertical structure 230, although it is noted that in certain embodiments there can be more than two "stacks" arranged in sequence and extending spatially parallel to one another, with the gap between each adjacent pair of "stacks" forming the central vertical structure 230, as explicitly shown in FIG. 2F. In this embodiment, the horizontal features 120 are 3D memory wordline features, fluidically accessible from the central vertical structure 230 through the openings 222.Although not explicitly shown in the figures, the horizontal features 220 present in both 3D NAND stacks 225 and 226 shown in FIG. 2E (i.e., the left-hand 3D NAND stack 225 and the right-hand 3D NAND stack 226) are also accessible from the other side (left-most and right-most, respectively) of the stack through similar vertical structures formed by additional 3D NAND stacks (left-most and right-most, not shown). In other words, each 3D NAND stack 225, 226 includes a stack of wordline features that are fluidly accessible from both sides of the 3D NAND stack through a central vertical structure 1230. In the particular example shown diagrammatically in FIG. 2F, each 3D NAND stack includes six pairs of stacked wordlines, although in other embodiments, the 3D NAND memory layout may include any number of vertically stacked pairs of wordlines.

[0052] In some embodiments, the metal precursor flow rate can be increased during the filling of the innermost and bottommost of the composite 3D structure to be filled. The method can also be used to fill interconnect features to 3D word lines. FIG. 2F shows a partially fabricated 3D NAND device with such features. Alternating oxide layers 211 and metal word lines 240 on a substrate 200 are shown in a stepped structure. For ease of illustration, five metal word lines 240 are shown, but according to various implementations, the structure can include any number of word lines, such as 48 word lines, 256 word lines, 512 word lines, or 1024 word lines. In some implementations, the features to be filled are at least 10 microns deep, or at least 20 microns deep.

[0053] An oxide layer 224 is deposited over the stepped structures with features 237 etched into the oxide layer 224. These features 237 can be filled with metal using methods described herein to provide interconnections to wordlines 240.

[0054] The method may also be used to fill multiple adjacent features, such as DRAM bWL trenches. The filling process for DRAM bWL trenches may distort the trenches such that the final trench width and resistance are significantly non-uniform. This phenomenon is called line bending. FIG. 2G shows an unfilled 221, narrow asymmetric trench structure DRAM bWL exhibiting line bending after filling. As shown, multiple features are shown on a substrate. These features are spaced apart, and in some embodiments, adjacent features have a pitch between about 20 nm and about 60 nm, or between about 20 nm and 40 nm. The pitch is defined as the distance between the median axis of one feature and the median axis of an adjacent feature. Unfilled features may be approximately V-shaped with sloping sidewalls, as shown in the example of FIG. 2G, where the width of the feature narrows from the top of the feature to the bottom of the feature. The feature widens from the bottom of the feature to the top of the feature. A sequence of depositions using inhibition may be used to mitigate line bending. These include constraining the total depth of the feature.

[0055] In some embodiments, the method is used to fill structures with features of different sizes. FIG. 2H shows an example of such a structure, which includes a small feature 202 and larger features 204, 206, and 228 etched into a dielectric layer 229. In one example, the structure of FIG. 2H can be filled starting with a high tungsten-containing precursor (e.g., tungsten hexafluoride (WF6)) flow, then ramped down to a lower flow when feature 202 is nearly filled. At a low flow of WF6, the tungsten grain size is smaller, resulting in a smoother interface at the seam with less void space. After feature 202 is filled, the WF6 flow is then ramped up to fill feature 204, and ramped down before feature 204 is fully filled. A low flow of WF6 is used to complete the filling of feature 204. A similar ramp-up and subsequent ramp-down protocol can be used to fill features 206 and 228.

[0056] In some embodiments, the method includes depositing a first metal layer in the feature. The first metal layer can be a nucleation layer, a bulk layer, or a bulk layer deposited on a nucleation layer. It can be deposited by an ALD process to conformally line the feature. The first metal layer can be exposed to an inhibition treatment. In some embodiments, the inhibition treatment is applied preferentially near the top of the feature such that subsequent deposition at the bottom of the feature is not inhibited or is inhibited to a lesser extent than near the top. This results in bottom-up filling.

[0057] Examples of feature filling for horizontally and vertically oriented features are described below. It should be noted that, at least in most cases, the examples are applicable to both horizontally oriented (parallel to the plane of the substrate) or vertically oriented (orthogonal to the plane of the substrate) features.

[0058] In some embodiments, filling the feature with metal may include starting deposition at a high metal precursor flow rate and ramping down during deposition. In some embodiments, a single-stage CVD deposition may be used, such as 151 in FIG. 1B, where reactant 1 is a metal precursor such as tungsten hexafluoride (WF6) and reactant 2 is hydrogen gas (H2). In other embodiments, a uniform flow rate may be used before or after ramping. FIGS. 3A and 3B show examples of a two-stage and three-stage process, respectively. In FIG. 3A, in stage 1, the metal precursor starts at a high flow rate and is ramped down. In stage 2, it is at a constant low flow rate. In the example of FIG. 3A, the starting flow rate of stage 2 is the ending flow rate of stage 1. However, in other embodiments, these values ​​may be different. In FIG. 3B, stage 1 has a constant high flow rate for the metal precursor. Stage 2 ramps down and stage 3 is at a lower constant flow rate. Stage 3 may be omitted in some embodiments.

[0059] The examples of Figures 3A and 3B, and other single or multi-step sequences in which the metal precursor is ramped down during one step, can be used to fill features with good filling but lower stress. A high flow rate at the beginning of the filling process can promote good filling characteristics, while ramping down the flow rate can result in a film with lower stress. For features with large openings, very high flow rates can be used to increase deposition rate and throughput at the beginning of deposition. As the feature closes, the metal precursor flow rate can be ramped down to ensure a smoother surface for seamless filling.

[0060] 4 and 5 show examples of deposition processes that include steps of performing a ramp phase. In FIG. 5, at 500, a feature 502 is shown in a pre-fill stage. The feature 502 can be formed in one or more layers on a semiconductor substrate and can optionally have one or more layers lining the sidewalls and / or bottom of the feature. Looking at FIG. 4, at step 401, a metal film is deposited in the feature. This step can be called Dep1. In many embodiments, step 401 is generally a conformal deposition that lines the exposed surfaces of the structure. For example, in a 3D NAND structure such as that shown in FIG. 2E, the metal film lines the wordline feature 220. According to various embodiments, the metal film is deposited using an atomic layer deposition (ALD) process to achieve good conformality. In alternative embodiments, a chemical vapor deposition (CVD) process can be used. Additionally, the process can also be performed using any suitable metal deposition, including physical vapor deposition (PVD) or plating processes. In some embodiments, after step 401, the feature is not closed, but is opened sufficiently to allow additional reactant gases to enter the feature in a subsequent deposition.

[0061] In an ALD process, the feature is exposed to alternating pulses of reactive gases. In an example of tungsten deposition, a tungsten-containing precursor such as tungsten hexafluoride (WF6), tungsten hexachloride (WCl6), tungsten pentachloride (WCl5), tungsten hexacarbonyl (W(CO)6), or a tungsten-containing organometallic compound may be used. In some embodiments, the pulse of the tungsten-containing precursor is pulsed with a reducing agent such as hydrogen (H2), diborane (B2H6), silane (SiH4), or germane (GeH4). In a CVD process, the wafer is exposed to reactive gases simultaneously. Deposition chemistries for other thin films are shown below. In FIG. 5, at 510, a feature 502 is shown forming a layer of material 504 that fills within the feature 502 after Dep1.

[0062] Next, in step 403 of FIG. 4, the deposited metal film is exposed to an inhibiting treatment. This can be a conformal or non-conformal treatment. Non-conformal treatment in this context refers to the treatment being applied preferentially to one or more openings of the feature or near the openings compared to the interior of the feature. For 3D NAND structures, the treatment can be conformal in the vertical direction such that the bottom wordline features are treated to roughly the same extent as the top wordline features, while the interior of the wordline features is non-conformal in that it is not exposed to the treatment or is treated to a significantly lesser extent compared to the feature openings. Conformal treatment refers to the entire feature being treated to roughly the same extent. Such treatment can be done, for example, to mitigate line bending of the feature as in FIG. 2G.

[0063] The inhibition treatment treats the feature surface to inhibit subsequent metal nucleation on the treated surface. This may include one or more of the following: deposition of an inhibition film, reaction of a chemical species with the Dep1 film to form a compound film (e.g., WN or Mo2N), and absorption of an inhibition chemical species. During the subsequent deposition step, there is a nucleation delay on the inhibited portion of the underlying film compared to the non-inhibited or less inhibited portion (if any). According to various embodiments, the treatment can be a non-plasma process or a plasma process. In the case of a non-plasma process, it can be activated purely thermally or by some other energy such as UV. In some embodiments, the inhibition step includes exposure to a metal precursor that can be co-flowed with an inhibition gas or delivered in alternating pulses with it.

[0064] The plasma can be a remote or in-situ plasma. In some embodiments, the plasma is generated from nitrogen (N2) gas, although other nitrogen-containing gases can be used. In some embodiments, the plasma is a radical-based plasma that does not have a significant number of ions. Such plasmas are typically generated remotely. In some embodiments, the nitrogen radicals can react with the underlying thin film to form metal nitrides. For thermal inhibition treatment, nitrogen- and hydrogen-containing compounds, such as ammonia (NH3), can be used. Hydrazine can also be used.

[0065] In some embodiments, the inhibition process further involves flowing a metal precursor. The metal precursors can be flowed together with the nitrogen-containing gas, or they can be flowed in alternating pulses. The metal precursor can be ramped up or down during the inhibition process. In some embodiments, the nitrogen-containing gas can be ramped up or down.

[0066] Returning to FIG. 5, at 520, the feature 502 is shown after an inhibition treatment. The inhibition treatment has the effect of inhibiting subsequent deposition on the treated surface 506. The inhibition may be characterized by an inhibition depth and an inhibition gradient. For non-conformal inhibition, the inhibition varies with feature depth. For example, inhibition may be greater at the feature opening compared to the bottom of the feature and extend only partially into the feature. In the example shown in FIG. 5, the inhibition depth is about half the full feature depth. In addition, the inhibition treatment may be stronger at the top of the feature, as shown diagrammatically by the dotted line that is deeper in the feature. As noted above, in other embodiments, inhibition may be uniform throughout the feature.

[0067] Returning to FIG. 4, after step 403, a second layer of metal is deposited in the feature in step 405. The second deposition can be called Dep2 and can be done by ALD or CVD process. For deposition into 3D NAND structures, an ALD process can be used to allow good step coverage throughout the structure. The Dep2 step is influenced by the preceding inhibition step. For example, if the feature opening is preferentially inhibited throughout the feature, deposition will occur preferentially within the feature. In another example, nitrogen on the surface of the deposited metal along the sidewall of the feature can prevent metal-metal (e.g., tungsten-tungsten bonding), thereby reducing line bending.

[0068] In the example of FIG. 5, deposition is inhibited near the feature opening so that during the Dep2 stage shown at 530, material deposits preferentially at the bottom of the feature while not depositing, or depositing to a lesser extent, at the feature opening. This may prevent the formation of voids and seams in the filled feature. Thus, during Dep2, material 504 may be filled in a manner that may be characterized as a bottom-up fill rather than a conformal Dep1 fill. As deposition continues, the inhibiting effect is removed. The incubation time, which is the time before a Dep2 thin film can grow on the treated surface, is called the Dep2 delay time.

[0069] In some embodiments, Dep2 includes a ramp process as shown in FIG. 3A, where stage 1 is approximately the Dep2 delay time.

[0070] 5, as Dep2 progresses, inhibition is overcome on all surfaces and the feature is completely filled with material 504, as shown at 540. This step may be stage 2 of the deposition process, as shown in FIG.

[0071] Although the DID process in Figure 5 shows the feature being preferentially suppressed at the top of the feature, in some embodiments the entire feature may be suppressed. Such a process may be useful, for example, to prevent line bending.

[0072] In the above description, ramping flow rates has been primarily discussed in the context of metal precursors during CVD or inhibition steps, where the metal precursor is continuously flowed during deposition or inhibition. The ramp process can also be used in other contexts, including ramping metal precursors during atomic layer deposition (ALD) sequences. FIG. 6 shows an example of two deposition cycles of an ALD process, including a reactant 1 pulse / purge / reactant 2 pulse / purge sequence in each cycle. (Purge gas flow is not shown). In the example, each pulse of reactant 1 flow rate is ramped.

[0073] The techniques described herein can also be used in applications involving dielectric thin film deposition, including dielectric gap filling. For example, the flow of a dielectric precursor can be ramped down as the fill reaches the top of a feature. In other embodiments, the flow can be ramped during other processes, including the flow of an etching gas.

[0074] A variety of metal precursors can be used to fill the features with metal. Metal precursors are metal-containing compounds that decompose or react to form a metal film. Examples of tungsten precursors include tungsten hexafluoride (WF6), tungsten pentachloride (WCl5), and tungsten hexachloride (WCl6), and tungsten hexacarbonyl (W(CO)6). Metalloorganic tungsten-containing precursors, such as MDNOW (methylcyclopentadienyl-dicarbonylnitrosyl-tungsten) and EDNOW (ethylcyclopentadienyl-dicarbonylnitrosyl-tungsten), can also be used.

[0075] To deposit molybdenum (Mo), Mo-containing precursors can be used, including molybdenum hexafluoride (MoF6), molybdenum pentachloride (MoCl5), molybdenum dioxide dichloride (MoO2Cl2), molybdenum oxide tetrachloride (MoOCl4), and molybdenum hexacarbonyl (Mo(CO)6).

[0076] To deposit ruthenium (Ru), Ru precursors can be used. Examples of ruthenium precursors that can be used for oxidation reactions include (ethylbenzyl)(1-ethyl-1,4-cyclohexadienyl)Ru(0), (1-isopropyl-4-methylbenzyl)(1,3-cyclohexadienyl)Ru(0), (2,3-dimethyl-1,3-butadienyl)Ru(0) tricarbonyl, (1,3-cyclohexadienyl)Ru(0) tricarbonyl, and (cyclopentadienyl)(ethyl)Ru(II) dicarbonyl. Examples of ruthenium precursors that react with non-oxidizing reactants are bis(5-methyl-2,4-hexanediketonato)Ru(II) dicarbonyl, and bis(ethylcyclopentadienyl)Ru(II).

[0077] To deposit cobalt (Co), cobalt-containing precursors can be used, including cyclopentadienylcobalt dicarbonyl (I), cobalt carbonyl, various cobalt amidinate precursors, cobalt diazadienyl complexes, cobalt amidinate / guanidinate precursors, and combinations thereof.

[0078] The metal-containing precursor can be reacted with a reducing agent as described above. In some embodiments, H2 is used as a reducing agent for bulk layer deposition to deposit high purity thin films.

[0079] In some implementations, the methods described herein include deposition of a nucleation layer prior to deposition of the bulk layer. Examples of reducing agents for nucleation layer deposition can include boron-containing reducing agents, including diborane (B2H6) and other boranes, silicon-containing reducing agents, including silane (SiH4) and other silanes, hydrazine, and germane.

[0080] experiment The features were filled with tungsten using a deposition-inhibition-deposition (DID) process. The DID process included conformal thin film deposition (Dep1), inhibition, and CVD deposition of a bulk thin film to fill the features (Dep2). Three flow regimes for Dep2 were compared: Process 1-Dep2 flow rate of Xsccm; Process 2-Dep2 flow rate of 3Xsccm, no ramp; and Process 3-Dep2 flow rate of 3Xsccm with ramp down. For each feature, the fill quality was observed and the stress at 1.2kA was measured. [Table 1]

[0081] The results show that ramp-down can balance stress and packing performance.

[0082] Device Any suitable chamber may be used to practice the disclosed embodiments. Exemplary deposition apparatus include various systems, such as the ALTUS® and ALTUS® Max available from Lam Research Corp. of Fremont, Calif., or any of a variety of other commercially available processing systems.

[0083] In some embodiments, the first deposition may be performed in a first station, which is one of two, five, or even more deposition stations located in a single deposition chamber. Thus, for example, diborane (B2H6) and tungsten hexachloride (WF6) may be introduced in alternating pulses to the surface of the semiconductor substrate in the first station, using a separate gas supply system that creates a local atmosphere at the substrate surface. Another station may be used for the suppression process, and a third and / or fourth station may be used for the subsequent bulk filling. In some embodiments, the suppression may be performed in a separate module.

[0084] 7 is a schematic diagram of a process system suitable for performing a conductive deposition process according to embodiments. System 700 includes a transfer module 703. The transfer module 703 provides a clean, pressurized environment to minimize the risk of contamination of substrates to be processed as they are moved between various reactor modules. Mounted on the transfer module 703 is a multi-station reactor 709 capable of performing processes such as ALD, CVD, and inhibition according to various embodiments. The multi-station reactor 709 can include multiple stations 711, 713, 715, and 717 that can sequentially perform steps according to disclosed embodiments. For example, a multi-station reactor 709 may be configured such that station 711 performs W, Mo, Co, or Ru nucleation layer deposition using a metal precursor and a boron-containing or silicon-containing reducing agent, station 713 performs ALD W, Mo, Co, or Ru bulk deposition of a conformal layer using H2 as the reducing agent, station 715 performs an inhibition treatment step (with optional ramping), and station 717 performs CVD bulk deposition with ramping of the metal precursor to fill the features. The stations may include a heated pedestal or substrate support, one or more gas inlets or showerheads or distribution plates.

[0085] In some embodiments, suppression may be performed in another module, such as module 707, and the multi-station module may be used for deposition (or other processes, such as etching).

[0086] An example of a station is shown in Figure 8, which shows a station 800 configured for semiconductor processing. The station has a showerhead 821 and a substrate support 804. The showerhead is connected to one or more gas sources, such as those described above with reference to Figure 1A. In some embodiments, the station may be connected to a remote plasma generator 850. In alternative embodiments, one or more of the showerhead and substrate support may be powered by the station being connected to a plasma generator for in-situ plasma generation.

[0087] Returning to FIG. 7, also mounted on the transfer module 703 can be one or more single or multi-station modules 707 capable of performing plasma or chemical (non-plasma) pre-clean, plasma or non-plasma suppression steps, other deposition steps, or etching steps. Modules can also be used for various processing, such as preparing substrates for deposition processes. The system 700 also includes one or more wafer source modules 701 where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 719 first transfers the wafer from the source module 701 to the load lock 721. A wafer transfer device (typically a robot arm unit) in the transfer module 703 moves the wafer from the load lock 721 to or into the modules mounted on the transfer module 703.

[0088] In various embodiments, a system controller 729 is used to control process conditions during deposition. The controller 729 will typically include one or more memory devices and one or more processors. The processor may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0089] The controller 729 may control all operations of the deposition apparatus. The system controller 729 executes system control software that includes sets of instructions for 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. In some embodiments, other computer programs stored in a memory device associated with the controller 729 may be used.

[0090] Typically, there will be a user interface associated with the controller 729. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0091] The system control logic may be configured in any suitable manner. In general, the logic may be designed or configured in hardware and / or software. The instructions for controlling the drive circuitry may be hard-coded or provided as software. The instructions may be provided by "programming." Such programming is understood to include any form of logic, including hard-coded logic in digital signal processors, application specific integrated circuits, and other devices having specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general purpose processor. The system control software may be coded in any suitable computer readable programming language.

[0092] The computer program code for controlling the germanium-containing reducing agent pulses, hydrogen flows, and tungsten-containing precursor pulses, and other processes in the process sequence, can be written in any conventional computer-readable programming language, such as assembly language, C, C++, Pascal, Fortran, or others. The compiled object code or script is executed by the processor to perform the tasks identified in the program. Also, as noted, the program code can be hard-coded.

[0093] The controller parameters relate to process conditions, such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe and may be entered using a user interface.

[0094] Signals for monitoring the process may come by analog and / or digital input connections of the system controller 729. Signals for controlling the process are output on analog and digital output connections of the deposition apparatus 700.

[0095] The system software can be designed or configured in many ways. For example, various chamber component subroutines or control objects can be written to control the operation of chamber components necessary to carry out a deposition process in accordance with 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.

[0096] In some implementations, the controller 729 is part of a system, which may be part of the examples described above. Such a system may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after the processing of semiconductor wafers or substrates. The electronics may be referred to as a "controller," which may control various components or subparts of one or more systems. Depending on the processing requirements and / or type of system, the controller 729 may be programmed to control any of the processes disclosed herein, including delivery of process gases, process gas flow ramp recipes, 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 settings, positional and operational settings, wafer transfer into and out of tools and other transfer tools and / or load locks connected or interfaced to a particular system.

[0097] Generally speaking, a controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable end-point measurements, etc. 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 the program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer 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.

[0098] The controller 729 can be part of or coupled to a computer that is integrated into the system, coupled to the system, otherwise networked to the system, or a combination thereof, in some implementations. For example, the controller 729 can be in the "cloud," or all or part of a fab host computer system, which allows remote access of wafer processing. The computer can allow remote access to the system to monitor the current progress of a fabrication process, look at the history of past fabrication processes, look at trends or performance metrics from multiple fabrication processes, change parameters of a current process, set up processing steps following a current process, or start a new process. In some examples, a remote computer (e.g., a server) can provide a process recipe to the system over a network, which can include a local network or the Internet. The remote computer can include a user interface, which allows for entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the controller receives instructions in the form of data that specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters can be specific to the type of process to be performed and the type of tool with which the controller is configured to interface or control. Thus, as described above, the controller can be distributed, such as by including one or more separate controllers networked together and working toward 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 integrated circuits on the chamber that communicate with one or more remotely located integrated circuits (at the platform level or as part of a remote computer) that together control the process on the chamber.

[0099] 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 module, a cleaning 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 system that may be associated with or used in the fabrication and / or production of semiconductor wafers.

[0100] As noted above, depending on the process step or steps to be performed by the tool, the controller may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, other controllers, or tools used in material transport carrying containers of wafers to or from the tool's locations and / or load ports within a semiconductor production factory.

[0101] The controller 729 may include a variety of programs. A substrate positioning program may include program code for controlling chamber components used to load the substrate onto a pedestal or chuck and to control the spacing between the substrate and other parts of the chamber, such as the gas inlets and / or the target. A process gas control program may include code for controlling gas composition, flow rates, ramp recipes, pulse times, and optionally the inflow of gas into the chamber prior to deposition to stabilize the pressure in the chamber. A pressure control program may include code for controlling the pressure in the chamber, for example, by adjusting a throttle valve in the exhaust system of the chamber. A heater control program may include code for controlling the current to a heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas, such as helium, to the wafer chuck.

[0102] Examples of chamber sensors that may be monitored during deposition include mass flow controllers, pressure sensors such as manometers, and thermocouples located in the pedestal or chuck. Appropriately programmed feedback and control algorithms may be used in conjunction with the data from these sensors to maintain desired process conditions.

[0103] The above describes implementation of the disclosed embodiments in single or multi-chamber semiconductor processing tools. The apparatus and processes described herein may be used in connection with lithographic patterning tools or processes for the fabrication or manufacture of, for example, semiconductor devices, displays, LEDs, solar panels, etc. Typically, although not necessarily, such tools / processes will be used or performed together within a common fabrication facility. Lithographic patterning of thin films typically involves some or all of the following steps, with several possible tools for each step: (1) application of photoresist to a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing the photoresist using a hot plate or furnace or a UV curing tool; (3) exposing the photoresist to visible or UV or X-ray light using a tool such as a wafer stepper; (4) developing the resist to selectively remove the resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into the underlying thin film or workpiece by using a dry or plasma-assisted etching tool; (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

[0104] conclusion Although the above embodiments have been described in some detail for the purpose of clarity of understanding, it will be apparent that some changes and modifications may be implemented within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the process, system, and apparatus of the present embodiments. Therefore, the present embodiments should be considered as illustrative and not restrictive, and the present embodiments are not limited to the details shown herein.

Claims

1. providing a substrate having features to be filled with a metal in a chamber; a chemical vapor deposition (CVD) process flowing a metal precursor and a reducing agent into the chamber to deposit a metal in the feature, the CVD process including a ramp-down phase in which a flow rate of the metal precursor into the chamber is ramped down from a first flow rate to a second flow rate; A method comprising:

2. 10. The method of claim 1, wherein the CVD process includes a second stage after the ramp-down stage in which the flow rate of the metal precursor is constant.

3. 10. The method of claim 1, wherein the CVD process includes a second stage prior to the ramp-down stage in which the flow rate of the metal precursor is constant.

4. 2. The method of claim 1, wherein the flow rate of the reducing agent is constant during the ramp-down phase.

5. 2. The method of claim 1, wherein the flow rate of the reducing agent is ramped during the ramp-down phase.

6. 10. The method of claim 1, further comprising performing an inhibition treatment prior to the CVD step to inhibit metal deposition.

7. 7. The method of claim 6, wherein metal deposition is preferentially inhibited near feature openings.

8. 10. The method of claim 1, wherein the feature comprises a waist and a step prior to the ramp-down step is used to fill a portion of the feature below the waist.

9. 9. The method of claim 8, wherein the ramp-down step is used to fill the waist of the feature.

10. 10. The method of claim 1, wherein the feature is a first feature having a first size, the substrate has a second feature having a second size, the second size being larger than the first size, and the ramp-down phase is used to complete filling of the first feature.

11. 11. The method of claim 10, further comprising ramping up the flow of the metal precursor from the second flow rate to a third flow rate after the first feature is completely filled.

12. 1. A method comprising: providing a substrate having features to be filled with a metal in a chamber; a chemical vapor deposition (CVD) process flowing a metal precursor and a reducing agent into the chamber to deposit a metal in the feature, the CVD process including a ramp-up phase in which a flow rate of the metal precursor into the chamber is ramped up from a first flow rate to a second flow rate; A method comprising:

13. 13. The method of claim 12, wherein the substrate has a second feature smaller than the feature, further comprising filling the second feature, and wherein the ramp-up step occurs after the second feature is completely filled and before the feature is completely filled.

14. 13. The method of claim 12, wherein the CVD process includes a second stage after the ramp-up stage in which the flow rate of the metal precursor is constant.

15. 13. The method of claim 12, wherein the flow rate of the reducing agent is constant during the ramp-up phase.

16. 13. The method of claim 12, wherein the flow rate of the reducing agent is ramped during the ramp-up phase.

17. 13. The method of claim 12, further comprising performing an inhibition treatment prior to the CVD step to inhibit metal deposition.

18. 1. An apparatus comprising: a process chamber having a pedestal support and a showerhead; one or more gas lines for conducting gases to the showerhead; a controller having instructions configured to perform the method of claim 1; An apparatus comprising:

19. 1. An apparatus comprising: a process chamber having a pedestal support and a showerhead; one or more gas lines for conducting gases to the showerhead; a controller having instructions configured to perform the method of claim 12; An apparatus comprising:

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