# Patent

## Title
Tungsten films having low fluorine content

## Abstract

Aspects of the methods and apparatus described herein relate to deposition of tungsten nucleation layers and other tungsten-containing films. Various embodiments of the methods involve exposing a substrate to alternating pulses of a tungsten precursor and a reducing agent at low chamber pressure to thereby deposit a tungsten-containing layer on the surface of the substrate. According to various embodiments, chamber pressure may be maintained at or below 10 Torr. In some embodiments, chamber pressure may be maintained at or below 7 Torr, or even lower, such as at or below 5 Torr. The methods may be implemented with a fluorine-containing tungsten precursor, but result in very low or undetectable amounts of fluorine in the deposited layer.

## Background
BACKGROUND
Deposition of tungsten-containing materials using chemical vapor deposition (CVD) techniques is an integral part of many semiconductor fabrication processes. These materials may be used for horizontal interconnects, vias between adjacent metal layers, contacts between first metal layers and devices on the silicon substrate, and high aspect ratio features. In a conventional deposition process, a substrate is heated to a predetermined process temperature in a deposition chamber, and a thin layer of tungsten-containing material that serves as a seed or nucleation layer is deposited. Thereafter, the remainder of the tungsten-containing material (the bulk layer) is deposited on the nucleation layer. Conventionally, the tungsten-containing materials are formed by the reduction of tungsten hexafluoride (WF6).
SUMMARY
One aspect of the subject matter described herein relates to a method of depositing a low-fluorine tungsten-containing film on a substrate. The method involves exposing the substrate to alternating pulses of a fluorine-containing tungsten precursor and a reducing agent to thereby deposit the tungsten-containing film on the substrate, where a chamber pressure of a chamber housing the substrate during the fluorine-containing tungsten precursor pulses is less than 10 Torr. The fluorine concentration in the tungsten-containing film may be less than 1019 atoms/cm3. In some embodiments, the fluorine concentration in the tungsten film is less than 1018 atoms/cm3. According to various embodiments, the chamber pressure may be less than 7 Torr or less than 5 Torr. In some embodiments, the tungsten-containing film is a tungsten nucleation layer. In some embodiments, the tungsten-containing film is deposited on a first tungsten-containing film deposited via a fluorine-free process. In some embodiments, the tungsten-containing film is deposited on a barrier layer. Examples of reducing agents include silicon-containing, boron-containing, and germanium-containing reducing agents. In some embodiments, the fluorine-containing tungsten precursor pulses include hydrogen (H2). According to various embodiments, the tungsten-containing film may have low resistivity, for example, less than 130 μΩ/cm or less than 110 μΩ/cm. The method may further include depositing a tungsten bulk layer by chemical vapor deposition (CVD) on the tungsten-containing film.
Another aspect of the subject matter described herein relates to a method including depositing a first tungsten-containing film on a substrate by a fluorine-free process and depositing a second tungsten-containing film the first tungsten film by atomic layer deposition using a fluorine-containing precursor, where a chamber pressure of a chamber housing the substrate during deposition of the second tungsten-containing film is less than 10 Torr. In some embodiments, the first tungsten-containing film is deposited on a barrier layer. In some embodiments, the first tungsten-containing film is deposited on a silicon oxide. According to various embodiments, the chamber pressure may be less than 7 Torr or less than 5 Torr. According to various embodiments, the fluorine concentration in the second tungsten-containing film is less than 1019 atoms/cm3 or less than 1018 atoms/cm3.
Further aspects can be implemented in apparatus configured to implement any of the methods described herein. For example, another aspect of the subject matter described herein relates to an apparatus for processing substrates, including (a) at least one process chamber comprising 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, the controller including machine-readable instructions for introducing a reducing agent and a fluorine-containing tungsten precursor in alternating pulses to the process chamber, where the chamber pressure is less than 10 Torr.
These and other aspects are described further with reference to the Figures.



BRIEF DESCRIPTION OF DRAWINGS
FIGS. 1A-1G are schematic examples of various structures in which a low fluorine layer may be deposited using a fluorine-containing precursor according to the processes described herein.
FIG. 2 is a process flow diagram illustrating certain operations in an example of a method of depositing a tungsten nucleation layer.
FIG. 3 is a plot showing fluorine (F) concentration profiles for tungsten (W)/titanium nitride TiN/undoped silicon glass (USG) stacks comparing F concentration for various W deposition methods.
FIG. 4 is a plot showing F concentration profiles for W/TiN/thermal oxide stacks with thin TiN layers comparing F concentration for various W deposition methods.
FIG. 5 is a plot showing F concentration profiles for W/TiN/thermal oxide stacks comparing F concentration for various W deposition methods.
FIG. 6 shows resistivity measurements for a 40 Torr ALD process (with H2 in the background) and a 3 Torr ALD process with no H2.
FIG. 7 is a process flow diagram illustrating certain operations in an example of a method of depositing tungsten.
FIG. 8 is a schematic diagram of an example process tool for performing disclosed embodiments.
FIG. 9 is a schematic diagram of an example station for performing disclosed embodiments.



DETAILED DESCRIPTION
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention 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 present invention. While the invention will be described in conjunction with the specific implementations, it will be understood that it is not intended to limit the invention to the implementations.
Described herein are methods of tungsten deposition and related systems and apparatus. Examples of applications include logic and memory contact fill, DRAM buried wordline fill, vertically integrated memory gate/wordline fill, and 3-D integration with through-silicon vias (TSVs). In some embodiments, the methods may be used for tungsten feature fill. Such features can include vertical features, such as vias, and horizontal features, such as vertical NAND (VNAND) wordlines. The methods may be used for conformal or bottom-up/inside-out fill.
Aspects of the methods and apparatus described herein relate to deposition of tungsten-containing layers such as tungsten nucleation layers. Various embodiments of the methods involve exposing a substrate to alternating pulses of a tungsten precursor and a reducing agent at low chamber pressure to thereby deposit a tungsten nucleation layer on the surface of the substrate. According to various embodiments, chamber pressure may be maintained at or below 10 Torr. In some embodiments, chamber pressure may be maintained at or below 7 Torr, or even lower, such as at or below 5 Torr. The methods may be implemented with a fluorine-containing tungsten precursor, but result in very low or undetectable amounts of fluorine in the deposited nucleation layer.
FIGS. 1A-1G are schematic examples of various structures in which a low fluorine layer may be deposited using a fluorine-containing precursor according to the processes described herein. In some embodiments, the structures include features to be filled with tungsten or a tungsten-containing material. In some embodiments, a feature can be characterized by one or more of: a narrow opening, a re-entrant opening, constrictions within the feature, and a high aspect ratio. FIG. 1A 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 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. The feature may be formed in one or more of these layers. For example, the feature may be formed at least partially in a dielectric layer. In some implementations, the feature hole 105 may have an aspect ratio of at least about 2:1, at least about 4:1, at least about 6:1 or higher. The feature hole 105 may also 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 to 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.
FIG. 1B 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. 1B 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. 1C shows examples of views of various filled features having constrictions. Each of the examples (a), (b) and (c) in FIG. 1C 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. 1D 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. 1E, for example, shows a plan view of pillars 125 in a VNAND or vertically integrated memory (VIM) structure 148, with FIG. 1F showing a simplified schematic of a cross-sectional depiction of the pillars 125. Arrows in FIG. 1E 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 154 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. 1E and 1F, 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. 1G provides another example of a view horizontal feature, for example, of a VNAND or other structure including pillar constrictions 151. The example in FIG. 1G 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. 1G can be seen as a 2-D rendering 3-D features of the structure, with the FIG. 1G 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. 1F), 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 direct generally along the feature axis.
Distribution of a material within a feature may be characterized by its step coverage. For the purposes of this description, “step coverage” is defined as a ratio of two thicknesses, i.e., the thickness of the material inside the feature divided by the thickness of the material near the opening. For purposes of this description, the term “inside the feature” represents a middle portion of the feature located about the middle point of the feature along the feature's axis, e.g., an area between about 25% and 75% of the distance or, in certain embodiments, between about 40% and 60% of the distance along the feature's depth measured from the feature's opening, or an end portion of the feature located between about 75% and 95% of the distance along the feature's axis as measured from the opening. The term “near the opening of the feature” or “near the feature's opening” represents a top portion of the feature located within 25% or, more specifically, within 10% of the opening's edge or other element representative of the opening's edge. Step coverage of over 100% can be achieved, for example, by filling a feature wider in the middle or near the bottom of the feature than at the feature opening.
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 alumide (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.
In some embodiments, the methods described herein involve deposition of a tungsten nucleation layer prior to deposition of a bulk layer. A nucleation layer is typically a thin conformal layer that facilitates subsequent deposition of bulk tungsten-containing material thereon. According to various embodiments, a nucleation layer may be deposited prior to any fill of the feature and/or at subsequent points during fill of the feature with tungsten or a tungsten-containing material.
In certain implementations, the nucleation layer is deposited using a pulsed nucleation layer (PNL) technique. In a PNL technique, pulses of a reducing agent, optional purge gases, and tungsten-containing precursor are sequentially injected into and purged from the reaction chamber. The process is repeated in a cyclical fashion until the desired thickness is achieved. PNL broadly embodies any cyclical process of sequentially adding reactants for reaction on a semiconductor substrate, including atomic layer deposition (ALD) techniques. PNL techniques for depositing tungsten nucleation layers are described in U.S. Pat. Nos. 6,635,965; 7,005,372; 7,141,494; 7,589,017, 7,772,114, 7,955,972 and 8,058,170, and U.S. Patent Publication No. 2010-0267235, all of which are incorporated by reference herein in their entireties. Nucleation layer thickness can depend on the nucleation layer deposition method as well as the desired quality of bulk deposition. In general, nucleation layer thickness is sufficient to support high quality, uniform bulk deposition. Examples may range from 5 Å-100 Å.
Fluorine (F) in deposited tungsten films and tungsten precursors may react during further integration operations to form highly reactive hydrofluoric acid (HF). HF can eat into oxide in oxide stacks, for example, or otherwise negatively affect integration. Conventional methods of depositing tungsten nucleation layers that use fluorinated precursors, such as tungsten hexafluoride (WF6), result in some amount of fluorine in the nucleation layers. FIG. 2 is a process flow diagram illustrating certain operations in an example of a method of depositing a tungsten nucleation layer. The method described with reference to FIG. 2 results in a tungsten nucleation layer having low fluorine content.
The method described below with reference to FIG. 2 involves exposing a substrate to alternating pulses of a reducing agent and fluorine-containing tungsten precursor. According to various embodiments, exposure to these alternating pulses may involve temporal switching or spatial switching. Temporal switching may be performed if the substrate remains stationary in a particular environment such as a chamber. Spatial switching may involve moving the substrate to a different environment. While the below description chiefly refers to temporal switching (and so assumes that the substrate remains in a particular chamber environment throughout the deposition), it is understood that the method can also be implemented by spatial switching.
At block 202, the process involves pulsing a reducing agent in a chamber housing a wafer or other substrate. The reducing agent is a compound that can reduce (and/or forming a decomposition product that can reduce) a tungsten precursor to form tungsten (W). The reducing agent may be a stronger reducing agent than hydrogen (H2), with examples including silicon-containing reducing agents such as silanes, boron-containing reducing agents such as boranes, and germanium-reducing agents such as germanes. Specific examples include silane (SiH4), disilane (Si2H6), borane (BH3), diborane (B2H6), germane (GeH4) and digermane (Ge2H6). Other reducing agents such as hydrazines may be employed. In some embodiments, the reducing agent or a decomposition product thereof may be adsorbed or other otherwise deposited onto the substrate surface and available to react. At block 204, excess reducing agent that is not deposited on the substrate surface is purged from the chamber. A purge operation may not be performed in some embodiments.
At block 206, a fluorine-containing tungsten precursor such as WF6 is pulsed in the chamber housing the substrate, the chamber being at a low chamber pressure during the pulse. Low pressure is less than 10 Torr. In some implementations, the pressure is less than 7 Torr, less than 5 Torr, or 3 Torr or less.
In the example of FIG. 2, the substrate remains in a single chamber during the process. As such, the chamber may be at low pressure during any of the operations of FIG. 2. In some embodiments, the chamber pressure is substantially constant during the process. One having ordinary skill in the art will understand that a substantially constant chamber pressure includes a chamber pressure that has minor fluctuations due to the introduction of different gas flows, etc. In some embodiments, however, chamber pressure can be higher in block 202 than in block 206. The fluorine-containing tungsten precursor reacts with the reducing agent or decomposition product to form a layer or sub-layer of a tungsten film. As described further below, by performing block 206 at low pressure, the amount of fluorine incorporated into the film is significantly reduced. Blocks 202-206 may be optionally repeated one or more times to build up a desired thickness of tungsten. Block 208. Various modifications may be made to the process depicted in FIG. 2. In some embodiments, for example, block 206 may be performed prior to block 202 such that the fluorine-containing tungsten precursor may be pulsed prior to the reducing agent pulse. As such, the fluorine-containing precursor or a decomposition product thereof may be adsorbed onto the substrate available to react with the incoming pulse of reducing agent.
FIG. 3 is a plot showing fluorine (F) concentration profiles for tungsten (W)/titanium nitride TiN/undoped silicon glass (USG) stacks, with profiles shown for a stack having a W layer deposited at 3 Torr, 10 Torr and 40 Torr by ALD, respectively. Tungsten hexafluoride and diborane were used as the tungsten precursor and reducing agent, respectively. Each profile is characterized by a relatively flat portion up to a depth of about 275 Å, followed by a rise in F concentration at the W/TiN interface, and a decrease as the depth increases into the TiN/USG interface and USG layer. The rise shown in the W layer is an artifact of the measurement process, and likely reflects F content in the TiN layer. As such, the F content in the W layer is best indicated by the flat portion of the profile.
Notably, while the 10 Torr film (line 304) has significantly lower fluorine content than the 40 Torr film (line 306), the ALD film deposited at less than 10 Torr (line 302) has over 100× fluorine content reduction as compared to films deposited at 10 Torr (line 304) and 40 Torr (line 306). The flat portion of line 302 is at 1017 atoms/cm3, below the detection level of the tool used to measure fluorine, indicating that the fluorine level may be lower than 1017 atoms/cm3. This measurement level also corresponds to tungsten deposited using a fluorine-free precursor, indicating that the low pressure (<10 Torr) process may be used to deposit an essentially fluorine-free tungsten nucleation layer using a fluorine-containing precursor.
The low pressure process also reduces the amount of fluorine in an underlying dielectric layer in some embodiments. FIG. 4 is a plot showing fluorine F concentration profiles for tungsten W/TiN/thermal oxide with the W deposited by ALD on thin (30 Å) TiN barrier layers. Profiles of three 300 Å W nucleation/30 Å TiN/1000 Å thermal oxide stacks are shown, with the 300 Å W tungsten nucleation layers deposited at 3 Torr, 10 Torr and 40 Torr, respectively. Here, the F concentration in the 3 Torr W layer is below the F detection level (as in FIG. 3). Further, the lower pressure process results in lower F concentration in the thermal oxide layer.
As indicated above, the low pressure ALD deposition of a tungsten nucleation layer using a fluorine-containing tungsten precursor results in fluorine content comparable to films deposited using fluorine-free precursors or by physical vapor deposition (PVD) of a solid tungsten target. FIG. 5 is a plot showing F concentration profiles for W/TiN/thermal oxide stacks. Profiles are shown for the following W deposition methods: ALD at 40 Torr using WF6 (line 506), ALD at 10 Torr using WF6 (line 504), ALD at 3 Torr using WF6 (line 502), ALD at 40 Torr using a fluorine-free tungsten (FFW) precursor (line 505), and PVD (line 503).
FIG. 5 shows that the F percentage in the bulk of the W ALD film is greatest for the 40 Torr ALD process, followed by the 10 Torr ALD process. F content in the 10 Torr ALD film is approximately equal to that in the FFW film. The F content is lowest in the 3 Torr ALD and PVD films. Notably, there is less F measured in the 3 Torr WF6 film than a FFW film.
At the TiN/oxide interface, the F content is highest for the 40 Torr ALD film, followed by (in order) the 10 Torr ALD film, the 3 Torr ALD film, and the FFW and PVD films.
The non-linear correlation of fluorine content to chamber pressure seen in FIGS. 3-5 was unexpected, in part because fluorine in WF6-based ALD deposited films is generally fairly unresponsive to variations in other process parameters such as temperature. Raising the substrate temperature can reduce fluorine content to some extent, but not enough to approach that of a FFW film. Further, an increase in temperature results in a decrease in step coverage. By contrast, the low pressure processes disclosed herein can result in excellent step coverage (e.g., at least 90%). It should also be noted that CVD deposition using fluorine-based tungsten precursors does not respond to chamber pressure in the manner shown in FIGS. 3-5. Without being bound by a particular theory, it is believed that low chamber pressure during an ALD process may allow fluorine (F2) or other F-containing byproducts of the reaction to diffuse out of the W film or leave the surface of the W film as it is deposited.
In the process of FIG. 2, a carrier gas may be used to deliver the reactants to the chamber. If used, the carrier gas typically has a much higher flow rate than the reactants such that the chamber pressure may be approximated by the partial pressure of the carrier gas. The carrier gas may also function as the purge gas between reactant pulses, or a separate purge gas may be used. An inert component such as argon, xenon, krypton, nitrogen, or helium may be used as a carrier gas.
According to various implementations, hydrogen may or may not be run in the background in addition to or instead of another carrier gas. In some embodiments, hydrogen is not run in the background, such that the nucleation layer deposition is a hydrogen (H2)-free process. Adding H2 can improve fluorine reduction, possibly due to the generation of HF.
In addition to preventing the deleterious effects of fluorine contamination, the low pressure process can result in reduced resistivity. FIG. 6 shows resistivity measurements for a 40 Torr ALD process (with H2 in the background) and a 3 Torr ALD process with no H2. WF6 was used as the tungsten containing precursor and B2H6 as the reducing agent. Resistivity is significantly lower for the low pressure process, which may be due to the reduced amount of F impurity in the film. It should be noted that the films deposited in generating the data in FIG. 6 were amorphous, with the resistivity of the 3 Torr film very low for an amorphous film.
It is noted that the 3 Torr ALD depositions used to generate the data in FIGS. 3-6 were performed on different tools than the 10 Torr and 40 Torr ALD depositions due to limitations in the tool used to deposit at 10 Torr and 40 Torr.
In some embodiments, a first tungsten layer may be deposited by a fluorine-free process prior to depositing a tungsten layer by ALD at low pressure using a fluorine-containing tungsten precursor. Such processes may be useful, for example, to reduce fluorine content in an underlying layer or at an interface between layers. FIG. 7 is a process flow diagram illustrating certain operations in an example of a method of depositing tungsten. The method includes depositing a first tungsten layer in a non-fluorine process (702). The first tungsten layer may be deposited, for example, on a barrier or adhesion layer, such as a titanium (Ti), TiN, Ti/TiN, tungsten nitride (WN), or other layer. In some implementations the first tungsten may be deposited directly on a dielectric layer, such as a silicon oxide layer.
Examples of non-fluorine processes include ALD and CVD processes that use no fluorine-containing precursors. Examples of fluorine-free tungsten precursors that may be used include tungsten hexacarbonyl (W(CO)6), tungsten chlorides such as tungsten hexachloride (WCl6) and tungsten pentachloride (WCl5), and organotungsten precursors such as W2(NMe2)6, W(OEt)6, W(OnPr)6, (tBuN═)2W(NMe2)2, (tBuN═)2W(NEtMe)2, W(Cp)2H2, W(NEt2)2(NEt)2, W(iPrCp)2H2, (tBuN═)2W(HNMe)2, W(EtCp)2H2 and derivatives thereof. Further examples include ethylcyclopentadienyl-dicarbonylnitrosyl-tungsten (EDNOW), methylcyclopentadienyl-dicarbonylnitrosyl-tungsten (MDNOW), and ethylcyclopentadienyl)tricarbonylhydridotungsten (ETHW), available from Praxair, as well as tungsten bis(alkylimino)bis(alkylamino) compounds having the following structure:




where each R may be independently selected from methyl, ethyl, propyl, butyl and tert-butyl groups. These groups may be substituted or unsubstituted, though are typically unsubstituted. For example, the tungsten-containing precursor is bis(tert-butylimino) bis(dimethylamino) tungsten (W[N(C4H9)]2[N(CH3)2]2.

The first tungsten layer may be deposited to a thickness sufficient to prevent fluorine from a fluorine-containing tungsten process in a subsequent deposition from reaching an underlying material. Example thicknesses may range from 10 Å to 100 Å, though thicknesses outside these ranges may be implemented.
The method continues by depositing a second tungsten layer by low pressure ALD using a fluorine-containing precursor. Block 704. The second tungsten layer may be a tungsten nucleation layer deposited directly on the first tungsten layer. Block 704 may involve a process as described above with respect to FIG. 2.
Deposition rate for block 704 may be significantly higher than for block 702. As such, block 702 may result in a fluorine-free layer that protects an underlying layer from fluorine with block 704 resulting in a faster deposition with very low fluorine content.
In some embodiments, deposition of a tungsten nucleation layer may be followed by one or more treatment operations prior to tungsten bulk deposition. Treating a deposited tungsten nucleation layer to lower resistivity is described for example in U.S. Pat. Nos. 7,772,114 and 8,058,170 and U.S. Patent Publication No. 2010-0267235, incorporated by reference herein.
Low pressure ALD deposition of a tungsten layer may be followed by tungsten bulk deposition. Tungsten bulk deposition can occur by a CVD process in which a reducing agent and a tungsten-containing precursor are flowed into a deposition chamber to deposit a bulk fill layer in the feature. An inert carrier gas may be used to deliver one or more of the reactant streams, which may or may not be pre-mixed. Unlike PNL or ALD processes, the CVD operation generally involves flowing the reactants continuously together until the desired amount is deposited. In certain implementations, the CVD operation may take place in multiple stages, with multiple periods of continuous and simultaneous flow of reactants separated by periods of one or more reactant flows diverted.
Various tungsten-containing gases including, but not limited to, WF6, WCl6, WCl5, W(CO)6 or the organotungsten precursors listed above can be used as the tungsten-containing precursor. In certain implementations, the tungsten-containing precursor is a halogen-containing compound, such as WF6. In certain implementations, the reducing agent is hydrogen gas, though other reducing agents may be used including silane (SiH4), disilane (Si2H6) hydrazine (N2H4), diborane (B2H6) and germane (GeH4). In many implementations, hydrogen gas is used as the reducing agent in the CVD process. In some other implementations, a tungsten precursor that can decompose to form a bulk tungsten layer can be used. Bulk deposition may also occur using other types of processes including ALD processes. Still further, bulk deposition may occur using a sequential CVD process. Descriptions of such processes are given in concurrently-filed U.S. patent application Ser. No. 14/723,270. Examples of temperatures may range from 200° C. to 500° C. According to various implementations, any of the CVD W operations described herein can employ a low temperature CVD W fill, e.g., at about 250° C. to 350° C. or about 300° C.
Deposition may proceed according to various implementations until a certain feature profile is achieved and/or a certain amount of tungsten is deposited. In some implementations, the deposition time and other relevant parameters may be determined by modeling and/or trial and error. For example, for an initial deposition for an inside out fill process in which tungsten can be conformally deposited in a feature until pinch-off, it may be straightforward to determine based on the feature dimensions the tungsten thickness and corresponding deposition time that will achieve pinch-off. In some implementations, a process chamber may be equipped with various sensors to perform in-situ metrology measurements for end-point detection of a deposition operation. Examples of in-situ metrology include optical microscopy and X-Ray Fluorescence (XRF) for determining thickness of deposited films.
It should be understood that the any of the tungsten films described herein may include some amount of other compounds, dopants and/or impurities such as nitrogen, carbon, oxygen, boron, phosphorous, sulfur, silicon, germanium and the like, depending on the particular precursors and processes used. The tungsten content in the film may range from 20% to 100% (atomic) tungsten. In many implementations, the films are tungsten-rich, having at least 50% (atomic) tungsten, or even at least about 60%, 75%, 90%, or 99% (atomic) tungsten. In some implementations, the films may be a mixture of metallic or elemental tungsten (W) and other tungsten-containing compounds such as tungsten carbide (WC), tungsten nitride (WN), etc.
CVD, ALD and low pressure ALD deposition of these materials can include using any appropriate precursors. For example, CVD and ALD deposition of tungsten nitride can include using halogen-containing and halogen-free tungsten-containing and nitrogen-containing compounds as described further below. CVD and ALD deposition of titanium-containing layers can include using precursors containing titanium with examples including tetrakis(dimethylamino)titanium (TDMAT) and titanium chloride (TiCl4), and if appropriate, one or more co-reactants. CVD and ALD deposition of tantalum-containing layers can include using precursors such as pentakis-dimethylamino tantalum (PDMAT) and TaF5 and, if appropriate, one or more co-reactants. CVD and ALD deposition of cobalt-containing layers can include using precursors such as tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt, bis(cyclopentadienyl)cobalt, and dicobalt hexacarbonyl butylacetylene, and one or more co-reactants. CVD and ALD deposition of nickel-containing layers can include using precursors such as cyclopentadienylallylnickel (CpAllylNi) and MeCp2Ni. Examples of co-reactants can include N2, NH3, N2H4, N2H6, SiH4, Si3H6, B2H6, H2, and AlCl3. The methods described herein may be used for ALD of various films using fluorine-containing precursors.
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, low pressure ALD may be performed at a station that is one of two, five, or even more deposition stations positioned within a single deposition chamber. Thus, for example, diborane and tungsten hexafluoride may be alternately introduced to the surface of the semiconductor substrate, at the 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 CVD. Two or more stations may be used to deposit tungsten in a parallel processing. Alternatively a wafer may be indexed to have various operations performed over two or more stations sequentially.
FIG. 8 is a block diagram of a processing system suitable for conducting tungsten thin film deposition processes in accordance with embodiments. The system 800 includes a transfer module 803. The transfer module 803 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 803 is a multi-station reactor 809 capable of performing ALD and CVD according to embodiments. Multi-station reactor 809 may also be used to perform low pressure tungsten ALD and/or tungsten CVD in some embodiments. Multi-station reactor 809 may include multiple stations 811, 813, 815, and 817 that may sequentially perform operations in accordance with disclosed embodiments. For example, multi-station reactor 809 could be configured such that station 811 performs fluorine-free nucleation layer deposition by ALD, station 813 performs low pressure ALD, and stations 815 and 817 perform 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 900 is depicted in FIG. 9, including substrate support 902 and showerhead 903. A heater may be provided in pedestal portion 901. The pedestal 901 may include a chuck for clamping the wafer. In certain embodiments, an electrostatic or mechanical chuck may be used rather than a vacuum chuck to facilitate providing a low pressure environment. Gases may be exhausted out of deposition station 900 by an exhaust (not shown).
Also mounted on the transfer module 803 may be one or more single or multi-station modules 807 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 800 also includes one or more wafer source modules 801, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 819 may first remove wafers from the source modules 801 to loadlocks 821. A wafer transfer device (generally a robot arm unit) in the transfer module 803 moves the wafers from loadlocks 821 to and among the modules mounted on the transfer module 803.
In various embodiments, a system controller 829 is employed to control process conditions during deposition. The controller 829 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 829 may control all of the activities of the deposition apparatus. The system controller 829 executes system control software, including sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the controller 829 may be employed in some embodiments.
Typically there will be a user interface associated with the controller 829. 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 829. The signals for controlling the process are output on the analog and digital output connections of the system 800.
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 829 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 829, 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, 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 829, 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 829 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 comprising 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 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 829 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 comprises 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.

## Claims

1. A method comprising:
exposing a substrate to alternating pulses of a fluorine-containing tungsten precursor and a reducing agent to thereby deposit a tungsten-containing film on the substrate, wherein a chamber pressure of a chamber housing the substrate during the fluorine-containing tungsten precursor pulses is less than 10 Torr, and wherein the total fluorine concentration in the tungsten-containing film is less than 1018 atoms/cm3.

2. The method of claim 1, wherein the chamber pressure is less than 7 Torr.

3. The method of claim 1, wherein the chamber pressure is less than 5 Torr.

4. The method of claim 1, wherein the tungsten-containing film is a tungsten nucleation layer.

5. The method of claim 1, wherein the tungsten-containing film is deposited on a first tungsten-containing film deposited via a fluorine-free process.

6. The method of claim 1, wherein the tungsten-containing film is deposited on a barrier layer.

7. The method of claim 1, wherein the reducing agent is selected from silicon-containing, boron-containing, and germanium-containing reducing agents.

8. The method of claim 1, wherein the fluorine-containing tungsten precursor pulses include hydrogen (H2).

9. The method of claim 1, wherein the resistivity of the tungsten-containing film is less than 130 μΩ/cm.

10. The method of claim 1, wherein the resistivity of the tungsten-containing film is less than 110 μΩ/cm.

11. The method of claim 1, further comprising depositing a tungsten bulk layer by chemical vapor deposition (CVD) on the tungsten-containing film.

12. The method of claim 1, wherein deposition of the tungsten-containing film is a H2-free process.

13. A method comprising:
depositing a first tungsten-containing film on a substrate by a fluorine-free process; and
depositing a second tungsten-containing film on the first tungsten-containing film by atomic layer deposition using a fluorine-containing precursor, wherein a chamber pressure of a chamber housing the substrate during deposition of the second tungsten-containing film is less than 10 Torr and wherein the total fluorine concentration in the second tungsten-containing film is less than 1018 atoms/cm3.

14. The method of claim 13, wherein the first tungsten-containing film is deposited on a barrier layer.

15. The method of claim 13, wherein the first tungsten-containing film is deposited on a silicon oxide.

16. The method of claim 13, wherein the chamber pressure is less than 7 Torr.

17. The method of claim 13, wherein the chamber pressure is less than 5 Torr.

18. The method of claim 13, wherein the first tungsten-containing film is at least about 90% atomic tungsten.

19. The method of claim 13, wherein the first tungsten-containing film is at least about 99% atomic tungsten.

20. A method comprising:
exposing a substrate to alternating pulses of a fluorine-containing tungsten precursor and a reducing agent to thereby deposit a tungsten-containing film having a thickness on the substrate, wherein a chamber pressure of a chamber housing the substrate during the fluorine-containing tungsten precursor pulses is less than 10 Torr, and wherein a fluorine concentration profile of the tungsten-containing film is characterized by having a first profile portion where the fluorine concentration is less than 1018 atoms/cm3, wherein the first profile portion represents a majority of the thickness of the tungsten-containing film.