# Patent

## Title
Deposition of low fluorine tungsten by sequential CVD process

## Abstract

Provided herein are methods of depositing bulk tungsten by sequential CVD pulses, such as by alternately pulsing tungsten hexafluoride and hydrogen gas in cycles of temporally separated pulses. Some methods include depositing a tungsten nucleation layer at low pressure followed by deposition of bulk tungsten by sequential CVD to form low stress tungsten films with low fluorine content. Methods described herein may also be performed in combination with non-sequential CVD deposition and fluorine-free tungsten deposition techniques.

## Background
BACKGROUND
Deposition of 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, contacts between metal layers and devices on the silicon substrate, and high aspect ratio features. In a conventional tungsten deposition process on a semiconductor substrate, the substrate is heated to the process temperature in a vacuum chamber, and a very thin portion of tungsten film which serves as a seed or nucleation layer is deposited. Thereafter, the remainder of the tungsten film (the bulk layer) is deposited on the nucleation layer by exposing the substrate to two reactants simultaneously. The bulk layer is generally deposited more rapidly than the nucleation layer. However, as devices shrink and more complex patterning schemes are utilized in the industry, deposition of thin tungsten films becomes a challenge.
SUMMARY
Provided herein are methods and apparatuses for depositing tungsten. One aspect involves a method of filling a feature including: (a) exposing a substrate in a chamber to alternating pulses of a reducing agent and a tungsten-containing precursor to deposit a tungsten nucleation layer on the substrate; and (b) exposing the substrate to alternating pulses of hydrogen and a tungsten-containing precursor to deposit a bulk tungsten layer over the tungsten nucleation layer, where the chamber pressure during (a) is no more than 10 Torr.
The method may further include: (c) exposing the substrate to a reducing agent and a tungsten-containing precursor simultaneously to deposit a second bulk tungsten layer. The method may also further include (d) performing (c) every 2 or more cycles of (b), where a cycle of (b) includes a pulse of hydrogen and a pulse of the tungsten-containing precursor.
In various embodiments, (b) is performed in cycles including a pulse of hydrogen and a pulse of the tungsten-containing precursor, and each cycle forms a submonolayer having a thickness of at least about 0.3 Å.
The tungsten-containing precursor in (a) may be different from the tungsten-containing precursor in (b). In some embodiments, the tungsten-containing precursor in (a) is fluorine-free.
The deposited tungsten may have a tensile stress less than about 1 GPa per 500 Å deposited.
Another aspect involves a method of depositing tungsten on a substrate including (a) depositing a tungsten layer on the substrate by (i) exposing the substrate to a reducing agent, and (ii) exposing the substrate to a fluorine-free tungsten-containing precursor; and (b) depositing a bulk tungsten layer in cycles including: (i) exposing the substrate to hydrogen (H2), (ii) exposing the substrate to a tungsten-containing precursor, and (iii) repeating (i)-(ii) in one or more cycles to deposit the bulk tungsten layer.
In some embodiments, the fluorine-free tungsten-containing precursor is selected from the group consisting of metal-organic tungsten-containing precursors, tungsten chlorides, and tungsten hexacarbonyl.
In various embodiments, the fluorine-free tungsten-containing precursor is tungsten hexachloride. In various embodiments, the fluorine-free tungsten-containing precursor is tungsten pentachloride.
The tungsten layer in (a) may be deposited to a thickness between about 2 Å and about 100 Å. Each cycle in (b) may form a submonolayer having a thickness of at least about 0.3 Å.
Another aspect involves a method of filling a feature including: (a) exposing the substrate to alternating pulses of hydrogen and a tungsten-containing precursor to deposit a bulk tungsten layer over the substrate; and (b) exposing the substrate to a tungsten-containing precursor and a reducing agent simultaneously to deposit a second bulk tungsten layer over the substrate.
In various embodiments, (a) and (b) are repeated sequentially.
The tungsten-containing precursor in (b) may be a fluorine-free tungsten-containing precursor selected from the group consisting of metal-organic tungsten-containing precursors, tungsten chlorides, and tungsten hexacarbonyl.
In some embodiments, the tungsten-containing precursor in (a) is different from the tungsten-containing precursor in (b).
Another aspect involves an apparatus for processing substrates including: (a) at least one process chamber including a pedestal configured to hold a substrate; (b) at least one outlet for coupling to a vacuum; (c) one or more process gas inlets coupled to one or more process gas sources; and (d) a controller for controlling operations in the apparatus, including machine-readable instructions for: (i) introducing a reducing agent and a tungsten-containing precursor in alternating pulses to the process chamber; and (ii) introducing hydrogen and a tungsten-containing precursor in alternating pulses to the process chamber, whereby the chamber pressure during (i) is no more than 10 Torr.
Another aspect involves an apparatus for processing substrates including: (a) at least one process chamber including a pedestal configured to hold a substrate; (b) at least one outlet for coupling to a vacuum; (c) one or more process gas inlets coupled to one or more process gas sources; and (d) a controller for controlling operations in the apparatus, including machine-readable instructions for: (i) introducing hydrogen and a tungsten-containing precursor in alternating pulses to the process chamber to deposit bulk tungsten layer; and (ii) introducing a tungsten-containing precursor and a reducing agent to the process chamber simultaneously to deposit a second bulk tungsten layer. The controller may further include machine-readable instructions for repeating (i) and (ii) sequentially.
These and other aspects are described further below with reference to the drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a schematic illustration of example films on a substrate.
FIGS. 1B-1H are schematic examples of various structures in which tungsten may be deposited in accordance with disclosed embodiments.
FIGS. 2A and 2B are process flow diagrams depicting operations for methods in accordance with disclosed embodiments.
FIG. 2C is a timing sequence diagram showing example cycles in a method in accordance with disclosed embodiments.
FIGS. 3A-3J are schematic diagrams of an example of a mechanism for depositing films in accordance with disclosed embodiments.
FIG. 3K is a process flow diagram depicting operations for a method in accordance with disclosed embodiments.
FIG. 4 is a schematic diagram of an example process tool for performing disclosed embodiments.
FIG. 5 is a schematic diagram of an example station for performing disclosed embodiments.
FIG. 6 depicts various timing sequence diagrams.
FIGS. 7-11B are plots of experimental results.



DETAILED DESCRIPTION
In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be 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.
Tungsten (W) fill of features is often used in semiconductor device fabrication to form electrical contacts. There are various challenges in tungsten fill as devices scale to smaller technology nodes and more complex patterning structures are used. One challenge is reducing the fluorine concentration or content in the deposited tungsten film. As compared to larger features, a smaller feature having the same fluorine concentration in the tungsten film as a larger feature affects the performance of the device more substantially. For example, the smaller the feature, the thinner the films are deposited. As a result, fluorine in the deposited tungsten film is more likely to diffuse through the thinner films, thereby potentially causing device failure.
One method of preventing fluorine diffusion includes depositing one or more barrier layers prior to depositing tungsten to prevent fluorine from diffusing from tungsten to other layers of the substrate such as an oxide layer. For example, FIG. 1A shows an example stack of layers deposited on a substrate. Substrate 190 includes a silicon layer 192, an oxide layer 194 (e.g., titanium oxide (TiOx), tetraethyl orthosilicate (TEOS) oxide, etc.), a barrier layer 196 (e.g., titanium nitride (TiN)), a tungsten nucleation layer 198, and a bulk tungsten layer 199. Barrier layer 196 is deposited to prevent fluorine diffusion from the bulk tungsten layer 199 and the tungsten nucleation layer 198 to the oxide layer. However, as devices shrink, barrier layers become thinner, and fluorine may still diffuse from the deposited tungsten layers. Although chemical vapor deposition of bulk tungsten performed at a higher temperature results in lower fluorine content, such films have poor step coverage.
Another challenge is reducing resistance in the deposited tungsten films. Thinner films tend to have higher resistance than thicker films. As features become smaller, the tungsten contact or line resistance increases due to scattering effects in the thinner tungsten films. Low resistivity tungsten films minimize power losses and overheating in integrated circuit designs. Tungsten nucleation layers typically have higher electrical resistivities than the overlying bulk layers. Barrier layers deposited in contacts, vias, and other features, may also have high resistivities. Further, thin barrier and tungsten nucleation films occupy a larger percentage of smaller features, increasing the overall resistance in the feature. Resistivity of a tungsten film depends on the thickness of the film deposited, such that resistivity increases as thickness decreases due to boundary effects.
Another challenge is reducing stress on deposited films. Thinner tungsten films tend to have increased tensile stress. Conventional techniques for depositing bulk tungsten films by chemical vapor deposition have a tensile stress greater than 2.5 GPa for a 200 Å film. High thermal tensile stress causes the substrate to curl, which makes subsequent processing difficult. For example, subsequent processes may include chemical mechanical planarization, deposition of materials, and/or clamping of the substrate to a substrate holder to perform processes in a chamber. However, these processes often rely on the substrate being flat, and a curled substrate results in nonuniform processing or inability to process the substrate. Although there are existing methods for reducing stress in films of other materials such as annealing, tungsten does not have the surface mobility to allow grains to be moved or altered once it is deposited due to its high melting point.
Provided herein are methods of depositing tungsten films having a low fluorine concentration using a sequential CVD process. The deposited films may also have low stress. Methods involve introducing hydrogen and a tungsten-containing precursor such as tungsten hexafluoride in cycles. Disclosed embodiments may be integrated with other tungsten deposition processes to deposit a low stress tungsten film having substantially lower fluorine content than films deposited by conventional CVD. For example, sequential CVD processes may be integrated with nucleation layer deposition at low pressure, fluorine-free tungsten layer deposition, and/or non-sequential CVD processes. Disclosed embodiments have a wide variety of applications. Methods may be used to deposit tungsten into features with high step coverage, and may also be used to deposit tungsten into 3D NAND and vertical NAND structures, including those with deep trenches.
Sequential CVD processes are distinguished from non-sequential CVD, pulsed CVD, atomic layer deposition (ALD), and nucleation layer deposition. Non-sequential CVD processes involve simultaneous exposure of two reactants, such that both reactants are flowed at the same time during deposition. For example, bulk tungsten may be deposited by exposing a substrate to hydrogen (H2) and tungsten hexafluoride (WF6) at the same time for a duration sufficient to fill features. Hydrogen and WF6 react during the exposure to deposit tungsten into the features. In pulsed CVD processes, one reactant is continuously flowed while the other reactant is pulsed, but the substrate is exposed to both reactants during deposition to deposit material during each pulse. For example, a substrate may be exposed to a continuous flow of H2 while WF6 is pulsed, and WF6 and H2 react during the pulse to deposit tungsten.
In contrast, sequential CVD processes implement separate exposures to each reactant such that the reactants are not flowed into the chamber at the same time during deposition. Rather, each reactant flow is introduced to a chamber housing the substrate in temporally separated pulses in sequence, repeated one or more times in cycles. Generally a cycle is the minimum set of operations used to perform a surface deposition reaction one time. The result of one cycle is the production of at least a partial film layer on a substrate surface. Cycles of sequential CVD are described in further detail below.
ALD and nucleation layer deposition also involve exposing the substrate to two reactants in temporally separated pulses in cycles. For example, in an ALD cycle, a first reactant is flowed into a chamber, the chamber is purged, a second reactant is flowed into the chamber, and the chamber is again purged. Such cycles are typically repeated to build film thickness. In conventional ALD and nucleation layer deposition cycles, the first reactant flow constitutes a first “dose” in a self-limiting reaction. For example, a substrate includes a limited number of active sites whereby a first reactant is adsorbed onto the active sites on the substrate and saturates the surface, and a second reactant reacts with the adsorbed layer to deposit material layer by layer in cycles.
However, in sequential CVD, reactants do not necessarily adsorb onto active sites on the substrate and in some embodiments, the reaction may not be self-limiting. For example, reactants used in sequential CVD may have a low adsorption rate. Moreover, reactants on the surface of the substrate may not necessarily react with a second reactant when the second reactant is introduced. Rather, in some embodiments of sequential CVD, some reactants on the substrate remain unreacted during the cycle, and are not reacted until a subsequent cycle. Some reactants may not react due to stoichiometric properties, steric hindrance, or other effects.
Methods described herein are performed on a substrate that may be housed in a chamber. The substrate may be a silicon wafer, e.g., a 200-mm wafer, 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. 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 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, or higher. One example of a feature is a hole or via in a semiconductor substrate or a layer on the substrate.
FIGS. 1B-1H are schematic examples of various structures in which tungsten may be deposited in accordance with disclosed embodiments. FIG. 1B shows an example of a cross-sectional depiction of a vertical feature 101 to be filled with tungsten. The feature can include a feature hole 105 in a substrate 103. The hole 105 or other feature may have a dimension near the opening, e.g., an opening diameter or line width of between about 10 nm to 500 nm, for example between about 25 nm and about 300 nm. The feature hole 105 can be referred to as an unfilled feature or simply a feature. The feature 101, and any feature, may be characterized in part by an axis 118 that extends through the length of the feature, with vertically-oriented features having vertical axes and horizontally-oriented features having horizontal axes.
In some embodiments, features are trenches in a 3D NAND structure. For example, a substrate may include a wordline structure having at least 60 lines, with between 18 to 48 layers, with trenches at least 200 Å deep. Another example is a trench in a substrate or layer. Features may be of any depth. In various embodiments, the feature may have an under-layer, such as a barrier layer or adhesion layer. Non-limiting examples of under-layers include dielectric layers and conducting layers, e.g., silicon oxides, silicon nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers.
FIG. 1C shows an example of a feature 101 that has a re-entrant profile. A re-entrant profile is a profile that narrows from a bottom, closed end, or interior of the feature to the feature opening. According to various implementations, the profile may narrow gradually and/or include an overhang at the feature opening. FIG. 1C shows an example of the latter, with an under-layer 113 lining the sidewall or interior surfaces of the feature hole 105. The under-layer 113 can be for example, a diffusion barrier layer, an adhesion layer, a nucleation layer, a combination of thereof, or any other applicable material. Non-limiting examples of under-layers can include dielectric layers and conducting layers, e.g., silicon oxides, silicon nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers. In particular implementations an under-layer can be one or more of Ti, TiN, WN, TiAl, and W. The under-layer 113 forms an overhang 115 such that the under-layer 113 is thicker near the opening of the feature 101 than inside the feature 101.
In some implementations, features having one or more constrictions within the feature may be filled. FIG. 1D shows examples of views of various filled features having constrictions. Each of the examples (a), (b) and (c) in FIG. 1D includes a constriction 109 at a midpoint within the feature. The constriction 109 can be, for example, between about 15 nm-20 nm wide. Constrictions can cause pinch off during deposition of tungsten in the feature using conventional techniques, with deposited tungsten blocking further deposition past the constriction before that portion of the feature is filled, resulting in voids in the feature. Example (b) further includes a liner/barrier overhang 115 at the feature opening. Such an overhang could also be a potential pinch-off point. Example (c) includes a constriction 112 further away from the field region than the overhang 115 in example (b).
Horizontal features, such as in 3-D memory structures, can also be filled. FIG. 1E shows an example of a horizontal feature 150 that includes a constriction 151. For example, horizontal feature 150 may be a word line in a VNAND structure.
In some implementations, the constrictions can be due to the presence of pillars in a VNAND or other structure. FIG. 1F, for example, shows a plan view of pillars 125 in a VNAND or vertically integrated memory (VIM) structure 148, with FIG. 1G showing a simplified schematic of a cross-sectional depiction of the pillars 125. Arrows in FIG. 1F represent deposition material; as pillars 125 are disposed between an area 127 and a gas inlet or other deposition source, adjacent pillars can result in constrictions 151 that present challenges in void free fill of an area 127.
The structure 148 can be formed, for example, by depositing a stack of alternating interlayer dielectric layers 129 and sacrificial layers (not shown) on a substrate 100 and selectively etching the sacrificial layers. The interlayer dielectric layers may be, for example, silicon oxide and/or silicon nitride layers, with the sacrificial layers a material selectively etchable with an etchant. This may be followed by etching and deposition processes to form pillars 125, which can include channel regions of the completed memory device.
The main surface of substrate 100 can extend in the x and y directions, with pillars 125 oriented in the z-direction. In the example of FIGS. 1F and 1G, pillars 125 are arranged in an offset fashion, such that pillars 125 that are immediately adjacent in the x-direction are offset with each other in the y-direction and vice versa. According to various implementations, the pillars (and corresponding constrictions formed by adjacent pillars) may be arranged in any number of manners. Moreover, the pillars 125 may be any shape including circular, square, etc. Pillars 125 can include an annular semi-conducting material, or circular (or square) semi-conducting material. A gate dielectric may surround the semi-conducting material. The area between each interlayer dielectric layer 129 can be filled with tungsten; thus structure 148 has a plurality of stacked horizontally-oriented features that extend in the x and/or y directions to be filled.
FIG. 1H provides another example of a view of horizontal feature, for example, of a VNAND or other structure including pillar constrictions 151. The example in FIG. 1H is open-ended, with material to be deposited able to enter horizontally from two sides as indicated by the arrows. (It should be noted that example in FIG. 1H can be seen as a 2-D rendering 3-D features of the structure, with the FIG. 1H being a cross-sectional depiction of an area to be filled and pillar constrictions shown in the figure representing constrictions that would be seen in a plan rather than cross-sectional view.) In some implementations, 3-D structures can be characterized with the area to be filled extending along two or three dimensions (e.g., in the x and y or x, y and z-directions in the example of FIG. 1G), and can present more challenges for fill than filling holes or trenches that extend along one or two dimensions. For example, controlling fill of a 3-D structure can be challenging as deposition gasses may enter a feature from multiple dimensions.
Examples of feature fill for horizontally-oriented and vertically-oriented features are described below. It should be noted that in most cases, the examples applicable to both horizontally-oriented or vertically-oriented features. Moreover, it should also be noted that in the description below, the term “lateral” may be used to refer to a direction generally orthogonal to the feature axis and the term “vertical” to refer to a direction generally along the feature axis.
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, feature fill using one or more techniques described herein may be used to fill features with other materials including other tungsten-containing materials (e.g., tungsten nitride (WN) and tungsten carbide (WC)), titanium-containing materials (e.g., titanium (Ti), titanium nitride (TiN), titanium silicide (TiSi), titanium carbide (TiC) and titanium aluminide (TiAl)), tantalum-containing materials (e.g., tantalum (Ta), and tantalum nitride (TaN)), and nickel-containing materials (e.g., nickel (Ni) and nickel silicide (NiSi). Further, the methods and apparatus disclosed herein are not limited to feature fill, but can be used to deposit tungsten on any appropriate surface including forming blanket films on planar surfaces.
FIG. 2A provides a process flow diagram for a method performed in accordance with disclosed embodiments. Operations 202-210 of FIG. 2A are performed to deposit a tungsten nucleation layer by ALD. In various embodiments described herein, operations 202-210 are performed at lower pressure than operation 280. For example, operations 202-210 may be performed at a low pressure less than about 10 Torr. In some examples, operations 202-210 are performed at a pressure of about 10 Torr, or a pressure of about 3 Torr. Without being bound by a particular theory, it is believed that performing operations 202-210 at a low pressure reduces fluorine concentration in the deposited tungsten film due to a lower partial pressure of a fluorine-containing precursor in the chamber when the film is deposited, such that less fluorine is incorporated into the film. Examples of processes for depositing a tungsten nucleation layer at low pressure to achieve low fluorine concentration in deposited tungsten are further described in U.S. patent application Ser. No. 14/723,275 filed on May 27, 2015.
In operation 202, the substrate is exposed to a tungsten-containing precursor such as WF6. For purposes of the description herein, although WF6 is used as an example of a tungsten-containing precursor, it should be understood that other tungsten-containing precursors may be suitable for performing disclosed embodiments. For example, a metal-organic tungsten-containing precursor may be used. Organo-metallic precursors and precursors that are free of fluorine, such as MDNOW (methylcyclopentadienyl-dicarbonylnitrosyl-tungsten) and EDNOW (ethylcyclopentadienyl-dicarbonylnitrosyl-tungsten) may also be used. The tungsten-containing precursor may include a combination of these compounds. In some embodiments, a carrier gas, such as nitrogen (N2), argon (Ar), helium (He), or other inert gases, may be flowed during operation 202.
Operation 202 may be performed for any suitable duration and at any suitable temperature. In some examples, operation 202 may be performed for a duration between about 0.25 seconds and about 30 seconds, about 0.25 seconds to about 5 seconds, or about 0.5 seconds to about 3 seconds. This operation may be performed in some embodiments for a duration sufficient to saturate the active sites on the surface of the substrate.
In operation 204, the chamber is optionally purged to remove excess WF6 that did not adsorb to the surface of the substrate. A purge may be conducted by flowing an inert gas at a fixed pressure thereby reducing the pressure of the chamber and re-pressurizing the chamber before initiating another gas exposure.
In operation 206, the substrate is exposed to a reducing agent to deposit a tungsten nucleation layer. The reducing agent may be a borane, silane, or germane. Example boranes include borane (BH3), diborane (B2H6), triborane, alkyl boranes, aminoboranes, carboranes, and haloborane. Example silanes include silane (SiH4), disilane (Si2H6), trisilane (Si3H8), alkyl silanes, aminosilanes, carbosilanes, and halosilane. Germanes include GenHn+4, GenHn+6, GenHn+8, and GenHm, where n is an integer from 1 to 10, and n is a different integer than m. Other germanes may also be used, e.g., alkyl germanes, aminogermanes, carbogermanes, and halogermanes. In general, halogermanes may not have significant reducing potential but there may be process conditions and tungsten-containing precursors suitable for film formation using halogermanes.
Operation 206 may be performed for any suitable duration. In some examples, Example durations include between about 0.25 seconds and about 30 seconds, about 0.25 seconds to about 5 seconds, or about 0.5 seconds to about 3 seconds. In some embodiments, this operation may be sufficient to react with the adsorbed layer of WF6 on the surface of the substrate. Operation 206 may be performed for a duration outside of these example ranges. In some embodiments, a carrier gas may be used, such as, for example, argon (Ar), helium (He), or nitrogen (N2).
After operation 206, there may be an optional purge step to purge excess reducing agent still in gas phase that did not react with WF6 on the surface of the feature. A purge may be conducted by flowing an inert gas at a fixed pressure thereby reducing the pressure of the chamber and re-pressurizing the chamber before initiating another gas exposure.
In operation 210, it is determined whether the tungsten nucleation layer has been deposited to an adequate thickness. If not, operations 202-208 are repeated until a desired thickness of a tungsten nucleation layer is deposited on the surface of the feature. Each repetition of operations 202-208 may be referred to as an ALD “cycle.” In some embodiments, the order of operations 202 and 206 may be reversed, such that reducing agent is introduced first.
After the tungsten nucleation layer is deposited to an adequate thickness, in operation 280, bulk tungsten is deposited by sequential CVD. In various embodiments, operation 280 may be performed at a pressure greater than the pressure during operations 202-210. For example, operation 280 may be performed at a pressure greater than or equal to about 10 Torr, for example about 10 Torr, or about 40 Torr.
FIG. 2B provides a process flow diagram for operations that may be performed during operation 280. Note that operations of FIG. 2B may be performed without performing operations of FIG. 2A. FIG. 2C provides a timing sequence diagram depicting examples cycles of sequential CVD in a process 200. FIGS. 3A-3J are schematic illustrations of an example mechanism for cycles of sequential CVD.
In FIG. 2B, in operation 282, the substrate is exposed to a reducing agent, such as H2. This operation may be referred to as a “pulse” or a “dose,” which may be used interchangeably herein. In embodiments described herein, H2 is provided as an example reducing agent, but it will be understood that other reducing agents, including silanes, boranes, germanes, phosphines, hydrogen-containing gases, and combinations thereof, may be used. Unlike non-sequential CVD, H2 is pulsed without flowing another reactant. In some embodiments, a carrier gas may be flowed. The carrier gas may be any of those described above with respect to operation 206 in FIG. 2A. Operation 282 may be performed for any suitable duration. In some examples, Example durations include between about 0.25 seconds and about 30 seconds, about 0.25 seconds to about 5 seconds, or about 0.5 seconds to about 3 seconds.
FIG. 2C shows H2 dose 220A in deposition cycle 211A which may correspond with operation 282 of FIG. 2B. During a H2 dose 220A, a carrier gas is flowed, the reducing agent is pulsed, and WF6 flow is turned off.
FIG. 3A depicts an example mechanism where H2 is introduced to the substrate 300, which has a tungsten nucleation layer 301 deposited thereon. Hydrogen is introduced in gas phase (311a and 311b) and some H2 (313a and 313b) is on the surface of the tungsten nucleation layer 301, but may not necessarily adsorb onto the surface. For example, H2 may not necessarily chemisorb onto the nucleation layer 301, but in some embodiments, may physisorb onto the surface of the nucleation layer 301.
Returning to FIG. 2B, in operation 284, the chamber is purged. This purge operation may remove excess H2 that remained in gas phase. A purge is conducted by flowing an inert gas at a fixed pressure thereby reducing the pressure of the chamber and re-pressurizing the chamber before initiating another gas exposure. The chamber may be purged for any suitable duration, for example, for a duration between about 0.1 seconds and about 3 seconds. Operation 284 of FIG. 2B may correspond to purge phase 240A of FIG. 2C. As shown in FIG. 2C, during purge phase 240A, the carrier gas is flowed but H2 flow and WF6 flow are turned off. FIG. 3B shows an example illustration whereby H2 previously in gas phase (311a and 311b in FIG. 3A) are purged from the chamber, and H2 previously on the surface (313a and 313b) remain on the surface of the tungsten nucleation layer 301.
Returning to FIG. 2B, in operation 286, the substrate is exposed to a tungsten-containing precursor (e.g., WF6) to form a sub-monolayer of film on the substrate. In various embodiments, WF6 is flowed to the chamber during this operation for a duration between about 0.1 seconds and about 3 seconds, or about 0.5 seconds. In some embodiments, WF6 may be diverted to fill the gas line and line change before dosing. In some embodiments, WF6 is flowed to the chamber but does not fully react with all H2 molecules on the surface of the substrate. Operation 286 may correspond to WF6 dose 260A in FIG. 2C. As shown in FIG. 2C, during the WF6 dose 260A, the carrier gas is flowed, the H2 flow is turned off, and the WF6 flow is turned on.
FIG. 3C shows an example schematic for operation 286 of FIG. 2B. In FIG. 3C, the substrate is exposed to WF6, some of which is in gas phase (331a and 331b) and some of which is at or near the surface of the substrate (323a and 323b).
During operation 286 of FIG. 2B, some WF6 may react with H2 that remained on the surface from the prior dose. As shown in FIG. 3D, WF6 may react with H2 to temporarily form intermediate 343b, whereby in FIG. 3E, intermediate 343b fully reacts to leave tungsten 390 on the surface of the substrate 300 on the nucleation layer 301, and HF in gas phase (351a and 351b, for example).
During operation 286 of FIG. 2B, some WF6 may not fully react with H2 that remained on the surface from the prior dose. As shown in FIG. 3D, WF6 may partially react with H2 to form intermediate 343a, whereby in FIG. 3E, intermediate 343a remains partially reacted on the surface of the substrate 300 on the nucleation layer 301. The reaction mechanism involving WF6 and H2 may be slower than a reaction between a borane or a silane or a germane with WF6 for deposition of a tungsten nucleation layer due to activation energy barriers and steric effects. For example, without being bound by a particular theory, the stoichiometry of WF6 may use at least three H2 molecules to react with one molecule of WF6. It is possible that WF6 partially reacts with molecules of H2 but rather than forming tungsten, an intermediate is formed. For example, this may occur if there is not enough H2 in its vicinity to react with WF6 based on stoichiometric principles (e.g., three H2 molecules are used to react with one molecule of WF6) thereby leaving an intermediate 343a on the surface of the substrate.
During operation 286 of FIG. 2B, some WF6 may not react with H2 at all and may instead be physisorbed onto the surface of the substrate where no H2 physisorbed or remained on the substrate surface. In some embodiments, WF6 may remain on the substrate surface but may not be physisorbed or chemisorbed to the surface.
Operation 286 of FIG. 2B may thereby form a sub-monolayer of tungsten in many embodiments. For example, a sub-monolayer having a thickness of about 0.3 Å may be deposited after performing operations 282-286.
In operation 288 of FIG. 2B, the chamber is purged to remove reacted byproducts and WF6 in gas phase from the chamber. In some embodiments, a purge duration that is too short in operation 288 may increase non-sequential CVD reaction characteristics such that a higher stress film will be deposited. In some embodiments, the purge duration is between about 0.1 seconds and about 2 seconds and may prevent removing all of the WF6 from the substrate surface due to the low adsorption rate of WF6 to a surface of tungsten. In some embodiments, purge duration is between about 0.1 seconds and about 15 seconds, such as about 7 seconds. For example, for fabrication of a 3D NAND structure, the chamber may be purged for about 7 seconds during operation 288. The purge duration depends on the substrate and stress.
Operation 288 of FIG. 2B may correspond to purge phase 270A of FIG. 2C. As shown in FIG. 2C, purge phase 270A concludes deposition cycle 211A. FIG. 3F provides an example schematic of the substrate when the chamber is purged. Note that compound 343c may be an intermediate formed but not completely reacted, while some tungsten 390 may be formed on the substrate. Each cycle thereby forms a sub-monolayer of tungsten on the substrate.
In some embodiments, operations 286 and 282 may be reversed such that operation 286 is performed before 282. In some embodiments, operation 282 may be performed before operation 286.
In operation 290 of FIG. 2B, it is determined whether bulk tungsten has been deposited to an adequate thickness. If not, operations 282-288 are repeated until a desired thickness is deposited. In some embodiments, operations 282-288 are repeated until a feature is filled. In FIG. 2C, it is determined that bulk tungsten has not been deposited to an adequate thickness, so operations 282-288 of FIG. 2B are repeated in deposition cycle 211B, such that an H2 dose 220B is performed, followed by a purge phase 240B. A WF6 dose 260B is performed, followed by another purge phase 270B.
As an example, FIG. 3G shows operation 282 in the repeated cycle, whereby H2 311c in gas phase is introduced to the substrate with the deposited tungsten 390 and the partially reacted intermediate 343d thereon. Note that the H2 introduced may now fully react with the intermediate 343d on the substrate such that, as shown in FIG. 3H, the reacted compound 343d leaves behind deposited tungsten 390b and 390c, and byproducts HF 351c and 351d are formed in gas phase. Some H2 311c may remain in gas phase, while some H2 313c may remain on the tungsten layer 390a. In FIG. 3I, the chamber is purged (thereby corresponding with operation 284 of FIG. 2B, or operation 240B of FIG. 2C), leaving behind deposited tungsten 390a, 390b, and 390c, and some H2 313c. In FIG. 3J, WF6 is again introduced in a dose such that molecules 331c and 323c may then adsorb and/or react with H2 and the substrate. FIG. 3J may correspond to operation 286 of FIG. 2B or 260B of FIG. 2C. After the WF6 dose, the chamber may again be purged and cycles may be repeated again until the desired thickness of tungsten is deposited.
Tungsten films deposited using disclosed embodiments have low fluorine concentrations, such as about two orders of magnitude less fluorine concentration than tungsten deposited by non-sequential CVD. Deposition conditions, such as temperature, pulse times, and other parameters, may vary depending on hardware or process modifications. Overall tensile stress of films may be less than about 1 GPa.
FIG. 3K provides a process flow diagram for a method performed in accordance with disclosed embodiments. In operation 280, bulk tungsten is deposited by sequential CVD. The process conditions and chemistries may be any of those described above with respect to FIGS. 2B and 3A-3J. In operation 299, bulk tungsten is deposited by non-sequential CVD. During non-sequential CVD, a substrate is exposed to a tungsten-containing precursor and a reducing agent simultaneously to deposit bulk. Example tungsten-containing precursors include fluorine-containing precursors (e.g., WF6), chlorine-containing precursors (e.g., WClx), and tungsten hexacarbonyl (W(CO)6). Example reducing agents include hydrogen. In some embodiments, non-sequential CVD is deposited by exposing the substrate to WF6 and H2. Operations 280 and 299 may be performed sequentially, or any of operation 280 may be performed one or more times before or after performing operation 299. In some embodiments, operations 280 and 299 are performed in pulses, such that operation 299 is performed every 2 or more cycles of performing operation 280. Bulk tungsten may thus be deposited using a combination of sequential CVD and non-sequential CVD.
Disclosed embodiments may have various applications in tungsten deposition processes. For example, in some embodiments, a feature may be filled by depositing a tungsten nucleation layer by ALD cycles of alternating pulses of a reducing agent (e.g., a borane, a silane, or a germane) and WF6, followed by bulk tungsten deposition by sequential CVD as described above with respect to FIG. 2B.
In another example, in some embodiments, a tungsten nucleation layer may be deposited using ALD cycles of a reducing agent and WF6, followed by bulk tungsten deposition using a combination of CVD of fluorine-free tungsten using a reducing agent and a fluorine-free tungsten-containing precursor (e.g., a metal-organic tungsten precursor), and sequential CVD as described above with respect to FIG. 2B. Fluorine-free tungsten precursors may also include tungsten carbonyl (W(CO)6), and tungsten chlorides (WClx) such as tungsten pentachloride (WCl5) and tungsten hexachloride (WCl6).
In another example, a tungsten nucleation layer may be deposited on a feature by ALD cycles of alternating pulses of a reducing agent and WF6, and tungsten bulk may be deposited by alternating between sequential CVD as described above with respect to FIG. 2B and non-sequential CVD. For example, bulk tungsten may be deposited using a number of cycles of sequential CVD between pre-determined durations of non-sequential CVD. In a specific example, bulk tungsten may be deposited using about 5 cycles of sequential CVD, followed by 5 seconds of non-sequential CVD, followed by 5 cycles of sequential CVD, and another 5 seconds of non-sequential CVD.
In another example, a feature may be filled by first depositing a tungsten nucleation layer by ALD cycles of alternating pulses of a reducing agent and WF6, then partially filling the feature using sequential CVD, and filling the rest of the feature by non-sequential CVD.
In another example, a feature may be filled by depositing a tungsten nucleation layer by ALD cycles of alternating pulses of a reducing agent and WF6, followed by partial deposition of bulk tungsten by sequential CVD, and complete bulk fill by CVD of fluorine-free tungsten (such as using a metal-organic tungsten precursor). For example, a number of cycles of sequential CVD may be performed to partially fill a feature with bulk tungsten, followed by CVD using simultaneous exposure to MDNOW and H2 to fill the rest of the feature. Note in some embodiments, a feature may be filled without depositing a nucleation layer, but a nucleation layer may help reduce growth delay of bulk tungsten.
It will be understood that various combinations of the applications described herein may be used to deposit tungsten and methods are not limited to the examples provided herein. For example, chlorine-containing tungsten precursors (WClx) such as tungsten pentachloride (WCl5) and tungsten hexachloride (WCl6) may be used instead of or in combination with WF6 in embodiments described herein.
Apparatus
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, Calif., or any of a variety of other commercially available processing systems. In some embodiments, sequential chemical vapor deposition (CVD) 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 (H2) and tungsten hexafluoride (WF6) may be alternately introduced to the surface of the semiconductor substrate, at the first station, using an individual gas supply system that creates a localized atmosphere at the substrate surface. Another station may be used for fluorine-free tungsten deposition, or non-sequential CVD. Another station may be used to deposit the tungsten nucleation layer at low pressure. Two or more stations may be used to deposit tungsten in a parallel processing. Alternatively a wafer may be indexed to have the sequential CVD operations performed over two or more stations sequentially.
FIG. 4 is a block diagram of a processing system suitable for conducting tungsten thin film deposition processes in accordance with embodiments. The system 400 includes a transfer module 403. The transfer module 403 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 403 is a multi-station reactor 409 capable of performing atomic layer deposition (ALD), and sequential CVD according to embodiments. Multi-station reactor 409 may also be used to perform fluorine-free tungsten deposition and/or non-sequential CVD in some embodiments. Reactor 409 may include multiple stations 411, 413, 415, and 417 that may sequentially perform operations in accordance with disclosed embodiments. For example, reactor 409 could be configured such that station 411 performs nucleation layer deposition by ALD, station 413 performs sequential CVD, station 415 performs fluorine-free tungsten deposition, and station 417 performs non-sequential CVD. Stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate. An example of a deposition station 500 is depicted in FIG. 5, including substrate support 502 and showerhead 503. A heater may be provided in pedestal portion 501.
Also mounted on the transfer module 403 may be one or more single or multi-station modules 407 capable of performing plasma or chemical (non-plasma) pre-cleans. The module may also be used for various treatments to, for example, prepare a substrate for a deposition process. The system 400 also includes one or more wafer source modules 401, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 419 may first remove wafers from the source modules 401 to loadlocks 421. A wafer transfer device (generally a robot arm unit) in the transfer module 403 moves the wafers from loadlocks 421 to and among the modules mounted on the transfer module 403.
In various embodiments, a system controller 429 is employed to control process conditions during deposition. The controller 429 will typically include one or more memory 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.
The controller 429 may control all of the activities of the deposition apparatus. The system controller 429 executes system control software, including 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. Other computer programs stored on memory devices associated with the controller 429 may be employed in some embodiments.
Typically there will be a user interface associated with the controller 429. The user 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.
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 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 purpose processor. System control software may be coded in any suitable computer readable programming language.
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 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.
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 utilizing the user interface.
Signals for monitoring the process may be provided by analog and/or digital input connections of the system controller 429. The signals for controlling the process are output on the analog and digital output connections of the deposition apparatus 400.
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 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.
In some implementations, a controller 429 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing 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 or systems. The controller 429, 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 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.
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 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 operational 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.
The controller 429, 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 429 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 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 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 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 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.
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 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.
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 manufacturing factory.
The controller 429 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 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 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.
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 with data from these sensors to maintain desired process conditions.
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 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) 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 microwave plasma resist stripper.
EXPERIMENTAL
Experiment 1
An experiment was conducted for four processes for depositing bulk tungsten at 395° C. at a pressure of 40 Torr. In each process, bulk tungsten was deposited on a tungsten nucleation layer deposited using atomic layer deposition (ALD) alternating cycles of diborane (B2H6) and tungsten hexafluoride (WF6). FIG. 6 provides example pulsing schemes for each of these four processes. In Process 1, H2 and WF6 are simultaneously and continuously flowed into the chamber, such as during traditional chemical vapor deposition (CVD). In Process 2, H2 is continuously flowed while WF6 is pulsed (e.g., pulsed CVD). In Process 3, WF6 is continuously flowed while H2 is pulsed (e.g., pulsed CVD). In Process 4, H2 and WF6 are alternately pulsed using a method such as that described above with respect to FIG. 2B (e.g., sequential CVD). The thickness of the tungsten nucleation layer, the stress, nonuniformity, and resistivity of films deposited using each of these four processes were measured and compiled in Table 1 below.







TABLE 1







Resistivity and Stress












Nucleation Layer






Thickness
Stress
Nonuniformity
Resistivity


Process
(Å)
(Mpa)
(%)
(μohm-cm)














1
507
2251
10.89
13.32


2
533
2207
4.31
12.79


3
517
2275
41.56
13.20


4
673
1634
21.77
10.81









As shown in Table 1, both the stress and the resistivity of the tungsten film deposited using Process 4 are significantly lower than the films deposited using any of Processes 1-3.
Experiment 2
An experiment was conducted for processes for depositing bulk tungsten on two substrates, both substrates including a titanium nitride (TiN) barrier layer and a tungsten nucleation layer deposited by ALD alternating cycles of B2H6 and WF6. One substrate involved deposition of bulk tungsten using non-sequential CVD, involving exposing the substrate to WF6 and H2 simultaneously at 300° C. Another substrate involved deposition of bulk tungsten using sequential CVD as described above with respect to FIG. 2B, involving alternating pulses of WF6 and H2 at a chamber pressure of 10 Torr. The fluorine concentration was measured for both substrates. The conditions for this experiment are shown in Table 2. The results are plotted in FIG. 7.







TABLE 2







Experiment 2 Conditions










700
701



Non-sequential CVD
Sequential CVD















Barrier Layer
TiN
TiN



Nucleation Layer
ALD
ALD




B2H6/WF6
B2H6/WF6





10 Torr



Bulk Tungsten
CVD
Sequential CVD



Layer
WF6 and H2
WF6/H2




300° C.
10 Torr










Line 700 shows the fluorine concentration for the substrate with tungsten deposited by non-sequential CVD. Line 701 shows the fluorine concentration for the substrate with tungsten deposited by sequential CVD. The W/TiN interface line at about 350 Å represents the interface between the tungsten nucleation layer and the TiN barrier layer. The TiN/Oxide interface dotted line at about 475 Å represents the interface between the TiN barrier layer and the oxide. Note that the fluorine concentration on the y-axis of the plot is by orders of magnitude, and the sequential CVD fluorine concentration 701 is substantially lower than the non-sequential CVD fluorine concentration 700—up to two orders of magnitude lower in fluorine concentration at some substrate depths.
Experiment 3
An experiment was conducted for processes for depositing bulk tungsten on substrates at different pressures. Three substrates each included a TiN barrier layer. One substrate involved deposition of a tungsten nucleation layer deposited by ALD alternating cycles of B2H6 and WF6 at 10 Torr followed by CVD of bulk tungsten by exposing the substrate to WF6 and H2 at 300° C. Another substrate involved deposition of a tungsten nucleation layer deposited by ALD alternating cycles of B2H6 and WF6 at 10 Torr followed by sequential CVD of bulk tungsten by alternating pulses of WF6 and H2 at 10 Torr. A third substrate involved ALD of a tungsten nucleation layer deposited by alternating cycles of B2H6 and WF6 at 3 Torr followed by sequential CVD of bulk tungsten using alternating pulses of WF6 and H2 at 10 Torr. The fluorine concentration was measured for all three substrates. The conditions for this experiment are shown in Table 3. The results are plotted in FIG. 8.







TABLE 3







Experiment 3 Conditions











800
801
803



Non-sequential
Sequential CVD
Sequential CVD



CVD
at High P
at Low P














Barrier Layer
TiN
TiN
TiN


Nucleation Layer
ALD
ALD
ALD



B2H6/WF6
B2H6/WF6
B2H6/WF6




10 Torr
 3 Torr


Bulk Tungsten
CVD
Sequential CVD
Sequential CVD


Layer
WF6 and H2
WF6/H2
WF6/H2



300° C.
10 Torr
10 Torr









Line 800 represents the fluorine concentration for the first substrate where bulk tungsten was deposited by non-sequential CVD. Dashed line 801 represents the fluorine concentration for the second substrate where the nucleation layer was deposited at 10 Torr, followed by bulk tungsten deposited by sequential CVD. Dotted line 803 represents the fluorine concentration for the third substrate where the nucleation layer was deposited at 3 Torr, followed by bulk tungsten deposited by sequential CVD. The results show that low pressure nucleation layer followed by sequential CVD (803) exhibited lower fluorine concentration than the second substrate (801), even at the W/TiN interface and even in the TiN layer (between 350 Å and 475 Å). This suggests there may be reduced fluorine diffusion into the TiN layer and the oxide due to the reduced amount of fluorine concentration in the tungsten film.
Experiment 4
An experiment was conducted for processes for depositing bulk tungsten on substrates using different combinations of tungsten deposition. Three substrates were compared. One substrate included 1 kÅ of thermal oxide, 30 Å TiN, 18 Å tungsten nucleation layer deposited at 3 Torr using ALD alternating pulses of WF6 and B2H6, and bulk tungsten deposited at 10 Torr using sequential CVD pulses of WF6 and H2. The fluorine concentration of this substrate is depicted by dashed line 912 in FIG. 9. Another substrate included 1 kÅ of thermal oxide, 30 Å TiN, 10 Å of fluorine-free tungsten, 12 Å tungsten nucleation layer deposited at 3 Torr using ALD alternating pulses of WF6 and B2H6, and bulk tungsten deposited by sequential CVD at 10 Torr using pulses of WF6 and H2. The fluorine concentration of this second substrate is depicted by line 911 in FIG. 9. A third substrate included 5 kÅ of TEOS-deposited oxide, 30 Å of fluorine-free tungsten, 12 Å tungsten nucleation layer deposited at 3 Torr using ALD alternating pulses of WF6 and B2H6, and bulk tungsten deposited by sequential CVD at 10 Torr using WF6 and H2. The fluorine concentration of this substrate is depicted by dotted line 913 in FIG. 9. The layers as deposited on each substrate for this experiment are summarized in Table 4.







TABLE 4







Experiment 4 Conditions











911
912
913














1st Layer
1 kÅ Thermal
1 kÅ Thermal
5 kÅ TEOS-



Oxide
Oxide
deposited Oxide


2nd Layer
30 Å TiN
30 Å TiN
30 Å Fluorine-





Free Tungsten


3rd Layer
10 Å Fluorine-
18 Å ALD
12 Å ALD



Free Tungsten
Nucleation Layer
Nucleation Layer




B2H6/WF6
B2H6/WF6




 3 Torr
 3 Torr


4th Layer
12 Å ALD
Bulk W by
Bulk W by



Nucleation Layer
Sequential CVD
Sequential CVD



B2H6/WF6
WF6/H2
WF6/H2



 3 Torr
10 Torr
10 Torr


5th Layer
Bulk W by



Sequential CVD



WF6/H2



10 Torr









As shown in FIG. 9, fluorine concentration for films deposited using a combination of fluorine-free tungsten, low pressure nucleation layer, and sequential CVD had less fluorine diffusion (see lines 911 and lines 913 beyond the W/TiN interface where depths are greater than 425 Å). Fluorine concentration near the nucleation layer was lowest between 300 Å and 425 Å for the film with more fluorine-free tungsten deposited on the substrate, while bulk tungsten for the film deposited using sequential CVD and low pressure nucleation without a fluorine-free tungsten layer had lower fluorine concentration between about 50 Å and 300 Å (see line 912). These results suggest that a combination of depositing fluorine-free tungsten and sequential CVD of tungsten may result in tungsten films achieving extremely low fluorine concentrations and reduced fluorine diffusion.
Experiment 5
An experiment was conducted for processes films deposited by sequential CVD in combination with low pressure versus high pressure nucleation layer deposition. One substrate included a tungsten nucleation layer deposited using ALD alternating cycles of WF6 and B2H6 at 10 Torr with bulk tungsten deposition by sequential CVD in accordance with FIG. 2B as described above using alternating pulses of WF6 and H2 at 10 Torr. The stress and resistivity of the film was measured at various thicknesses and is shown as line 1001 “low pressure nucleation” in FIGS. 10A and 10B. Another substrate included a tungsten nucleation layer deposited using ALD alternating cycles of WF6 and B2H6 at 40 Torr with bulk tungsten deposition by sequential CVD in accordance with FIG. 2B as described above using alternating pulses of WF6 and H2 at 10 Torr. The stress and resistivity of the film was measured at various thicknesses and is shown as line 1002 “high pressure nucleation” in FIGS. 10A and 10B. Conditions for the nucleation and bulk layer depositions are shown in Table 5.







TABLE 5







Experiment 5 Conditions










1001 Low Pressure
1002 High Pressure



Nucleation
Nucleation















Nucleation Layer
ALD
ALD




B2H6/WF6
B2H6/WF6




10 Torr
40 Torr



Bulk Tungsten
Sequential CVD
Sequential CVD



Layer
WF6/H2
WF6/H2




10 Torr
10 Torr











Temperature
300° C.










As shown in the results, the substrate with the nucleation layer deposited at low pressure had substantially lower stress than the substrate with the nucleation layer deposited at high pressure, while the resistivity remained approximately the same.
Experiment 6
An experiment was conducted for processes films deposited by sequential CVD in combination with low temperature versus high temperature nucleation layer deposition. One substrate included a tungsten nucleation layer deposited using ALD alternating cycles of WF6 and B2H6 at 10 Torr and 250° C. with bulk tungsten deposition by sequential CVD in accordance with FIG. 2B as described above using alternating pulses of WF6 and H2 at 10 Torr. The stress and resistivity of the film was measured at various thicknesses and is shown as line 1102 “low T nucleation” in FIGS. 11A and 11B. Another substrate included a tungsten nucleation layer deposited using ALD alternating cycles of WF6 and B2H6 at 10 Torr and 300° C. with bulk tungsten deposition by sequential CVD in accordance with FIG. 2B as described above using alternating pulses of WF6 and H2 at 10 Torr. The stress and resistivity of the film was measured at various thicknesses and is shown as line 1104 “high T nucleation” in FIGS. 11A and 11B. Conditions for the nucleation and bulk layer depositions are shown in Table 6.







TABLE 6







Experiment 6 Conditions












1102 Low Temp
1104 High Temp




Nucleation
Nucleation















Nucleation Layer
ALD
ALD




B2H6/WF6
B2H6/WF6












10
Torr
10
Torr



250°
C.
300°
C.











Bulk Tungsten
Sequential CVD
Sequential CVD



Layer
WF6/H2
WF6/H2












10
Torr
10
Torr










As shown in the results, the substrate with the nucleation layer deposited at low temperature had substantially lower stress than the substrate with the nucleation layer deposited at high temperature, while the resistivity of the film deposited at higher temperature was slightly lower than the resistivity of the film deposited at lower temperature. These results suggest that lower temperature deposition of the nucleation layer in combination with sequential CVD bulk deposition can significantly reduce the stress of the film.
CONCLUSION
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 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.

## Claims

1. A method of filling a feature comprising:
(a) exposing a substrate in a chamber to alternating pulses of a reducing agent and a first tungsten-containing precursor to deposit a tungsten nucleation layer on the substrate; and
(b) exposing the substrate to alternating pulses of hydrogen and a second tungsten-containing precursor to deposit a bulk tungsten layer over the tungsten nucleation layer,
wherein the chamber pressure during (a) is no more than 10 Torr.

2. The method of claim 1, further comprising, (c) exposing the substrate to another reducing agent and a third tungsten-containing precursor simultaneously to deposit a second bulk tungsten layer.

3. The method of claim 2, further comprising, (d) performing (c) every 2 or more cycles of (b), wherein a cycle of (b) comprises a pulse of hydrogen and a pulse of the second tungsten-containing precursor.

4. The method of claim 1, wherein (b) is performed in cycles comprising a pulse of hydrogen and a pulse of the second tungsten-containing precursor, and each cycle forms a submonolayer having a thickness of at least about 0.3 Å.

5. The method of claim 1, wherein the first tungsten-containing precursor in (a) is different from the second tungsten-containing precursor in (b).

6. The method of claim 5, wherein the tungsten-containing precursor in (a) is fluorine-free.

7. The method of claim 1, wherein the deposited tungsten has a tensile stress less than about 1 GPa per 500 Å deposited.

8. The method of claim 1, wherein exposing the substrate to the alternating pulses of the hydrogen and the second tungsten-containing precursor to deposit the bulk tungsten layer comprises a non-self-limiting reaction between the hydrogen and the second tungsten-containing precursor.

9. A method of filling a feature comprising:
(a) exposing the substrate to alternating pulses of hydrogen and a first tungsten-containing precursor to deposit a bulk tungsten layer over the substrate; and
(b) exposing the substrate to a second tungsten-containing precursor and a reducing agent simultaneously to deposit a second bulk tungsten layer over the substrate.

10. The method of claim 9, wherein (a) and (b) are repeated sequentially.

11. The method of claim 9, wherein the second tungsten-containing precursor in (b) is a fluorine-free tungsten-containing precursor selected from the group consisting of metal-organic tungsten-containing precursors, tungsten chlorides, and tungsten hexacarbonyl.

12. The method of claim 9, wherein the first tungsten-containing precursor in (a) is different from the second tungsten-containing precursor in (b).