# Patent

## Title
Cyclical deposition of refractory metal silicon nitride

## Abstract

Embodiments of the invention relate to an apparatus and method of cyclical layer deposition utilizing three or more precursors. In one embodiment, the method includes providing at least one cycle of precursors to form a ternary material layer. Providing at least one cycle of precursors includes introducing a pulse of a first precursor, introducing a pulse of a second precursor, and introducing a pulse of a third precursor, wherein the pulses of two of the three precursors are introduced simultaneously or sequentially. In another embodiment, the method includes introducing a pulse of a first precursor, introducing a pulse of a second precursor, repeating the introduction of the first and the second precursors at least one time to form a binary material layer on the substrate surface, and introducing a pulse of a third precursor to form the ternary material layer.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims benefit of U.S. provisional patent application Ser. No. 60/337,646, entitled, “Deposition of Tantalum Silicon Nitride Using Atomic Layer Deposition for Copper Metallization”, which was filed Dec. 4, 2001 and is incorporated herein by reference.


BACKGROUND OF THE INVENTION
1. Field of the Invention
Embodiments of the invention generally relate to deposition of a semi-conductive layer onto a substrate. More specifically, the invention relates to a method of depositing a refractory metal layer using a cyclical deposition technique.
2. Description of the Related Art
The requirements of sub-quarter micron semiconductor devices with their VSLI or USLI integration necessitate using various layers, e.g., conductive layers and insulating layers. Typically, conductive layers are interconnected through features such as horizontal lines and vertical contact holes, vias, trenches, or openings in the insulating layer by a damascene or dual damascene process. With higher integration and increased device speed, the size of these features demands to be small, such as less than 0.25 micron of aperture, while the aspect ratio of the features, i.e., their height divided by width, needs to be greater than 5:1, and even greater than 10:1.
In the fabrication of semiconductor devices, such as dynamic random access memories (DRAMs), static random access memories (SRAMs), microprocessors, etc., insulating layers or barrier layers are used to separate conductive layers and prevent the diffusion of one material into an adjacent material. For example, diffusion barriers are needed to prevent copper diffusion, especially when an underlying low dielectric-constant dielectric layer is used. Low dielectric-constant materials are often soft and porous, and adhere poorly to adjacent materials. Therefore, a good barrier/adhesion layer is required for processing a low resistivity conductive layer, such as a copper layer, compatible with low dielectric-constant materials.
Diffusion barriers are also used to prevent undesirable reactions between conductive layers, such as spiking when aluminum contacts silicon surfaces, for example, and the formation of highly resistive alloy when aluminum comes into direct contact with tungsten. Further, diffusion resistant materials are used as adhesion or encapsulation materials or gate electrode liners for the high dielectric-constant dielectric layer in DRAM application.
Barrier/adhesion layers containing refractory metal materials are commonly used for VLSI and ULSI devices. Refractory metal materials with good adhesion properties to conductive layers, such as those containing titanium (Ti), tantalum (Ta), tungsten (W), titanium nitride (TiN), tantalum nitride (TaN), tungsten nitride (WN), etc., have been used in integrated circuit manufacturing to form liner/barrier layers.
Furthermore, a ternary refractory metal material such as refractory metal silicon nitride, e.g. tantalum silicon nitride (TaSiN) and titanium silicon nitride (TiSiN), forms a superior barrier layer/adhesion layer over a binary refractory metal material such as tantalum nitride, titanium nitride, or tungsten nitride. The incorporation of silicon into a tantalum nitride layer by metalorganic chemical vapor deposition (MOCVD) to form a tantalum silicon nitride layer has been shown to provide as a better diffusion and/or insulation barrier for copper interconnects than tantalum nitride barriers. Also, the incorporation of silicon into a titanium nitride layer to form a titanium silicon nitride layer helps to prevent fluorine diffusion for the subsequent tungsten application tungsten fluoride (WF6) as precursor. However, such deposition methods are performed at higher temperatures which may not be desirable for some applications, and have trouble controlling the composition of the barrier/adhesion layer, such as the ratio of the materials incorporated.
In addition, traditional deposition processes, such as physical vapor deposition (PVD) and chemical vapor deposition (CVD), have difficulty in filling high aspect ratio features and often result in poor step coverage, poor conformality, and byproduct formation. The complicated topography of devices with high aspect ratios requires precise control over film properties such as composition, thickness, morphology, and electrical characteristics. For example, conventional fabrication of titanium nitride adhesion layers used as tungsten liners often results in high and unpredictably variable contact resistance of the finished tungsten contact following fabrication. Typically, titanium nitride is deposited by decomposing a metalorganic compound of titanium using conventional CVD or PVD processes and may contain carbon and oxygen impurities, resulting in an increase in resistivity of the adhesion layer. In addition, the carbon and oxygen impurities in the titanium nitride layer may react with the byproducts of a subsequently deposited tungsten plug CVD process after the reduction of tungsten fluoride (WF6) or tungsten chloride (WCl6) compounds by silane, resulting in the localized formation of nucleated insulating structures.
Cyclical deposition techniques such as atomic layer deposition (ALD) and rapid sequential chemical vapor deposition provide a better degree of control over substrate surface reactions and is suitable for the deposition of material layers over features having high aspect ratios to provide good step coverage. One example of forming a binary material layer using a cyclical deposition technique comprises the sequential introduction of pulses of a first precursor/reactant and a second precursor/reactant. For instance, one cycle may comprise a pulse of the first precursor, followed by a pulse of a purge gas and/or a pump evacuation, followed by a pulse of a second precursor, and followed by a pulse of a purge gas and/or a pump evacuation. Sequential introduction of separate pulses of different precursors results in the alternating self-limiting surface adsorption or chemisorption of the precursors on the substrate surface and forms a monolayer or less of the binary material for each cycle. In this way, thin films are grown as a monolayer or less at a time to form a deposited layer or film, e.g., a tantalum nitride layer using a tantalum-containing precursor and ammonia gas as precursors.
Although the deposition rate is slower in cyclical deposition processes than conventional CVD and PVD processes, deposition can be conducted in a simplified chamber/reactor where process conditions such as gas flow and deposition temperature are not as critical. Further, cyclical deposition processes can be performed at lower temperatures and can use a wider range of precursors. A satisfactory apparatus and method for cyclical deposition techniques have not been established to form conformal layers of ternary materials utilizing three precursors.
There is a need, therefore, for a repeatable and controlled method of depositing a ternary metal silicon nitride layer.
SUMMARY OF THE INVENTION
Embodiments of the invention relate to an apparatus and method of cyclical layer deposition utilizing three or more precursors. In one embodiment, the method includes introducing a pulse of a nitrogen-containing precursor and providing at least one cycle of precursors to form a ternary material layer. The nitrogen-containing precursor is introduced first to prevent diffusion of a refractory metal-containing precursor and a silicon-containing precursor into an underlying layer. Providing at least one cycle of precursors further includes introducing a pulse of the refractory metal-containing precursor, introducing a pulse of the nitrogen-containing precursor, and introducing a pulse of the silicon-containing precursor. In one aspect of this embodiment, the nitrogen-containing precursor and the silicon-containing precursor are sequentially introduced. In another aspect, they are introduced at the same time.
In another embodiment, the method includes introducing a pulse of a first precursor, introducing a pulse of a second precursor, repeating the introduction of the first and the second precursors at least one time to form a binary material layer on the substrate surface, and introducing a pulse of a third precursor to form the ternary material layer. In one aspect of this embodiment, a method of forming a refractory metal silicon nitride layer on a substrate surface includes providing at least one cycle of precursors to form a refractory metal nitride layer before introducing a pulse of a silicon-containing precursors to form the refractory metal silicon nitride layer.
An optional plasma treatment step may be performed at various stages, e.g., either during and/or after formation of the ternary material layer. Also provided are methods of forming tantalum silicon nitride and titanium silicon nitride barrier/adhesion layers on a substrate, and a method of forming a copper film or a tungsten plug having an underlying refractory metal silicon nitride layer.



BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the features of the invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof, which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
FIG. 1A is a schematic flow chart of a ternary layer cyclical deposition process involving sequential delivery of three precursors and an optional plasma treatment step.
FIG. 1B is a schematic flow chart of a ternary layer cyclical deposition process in accordance with one embodiment where two precursors are introduced simultaneously prior to a third precursor is introduced.
FIG. 1C is a schematic flow chart of a ternary layer cyclical deposition process in accordance with another embodiment where two precursors are introduced simultaneously after a first and a second precursors are introduced.
FIG. 1D is a schematic flow chart of a ternary layer cyclical deposition process in accordance with one embodiment where two precursors are introduced to perform cyclical deposition of a binary layer before a third precursor is introduced to a ternary layer.
FIG. 2A depicts a schematic view of a deposition chamber to perform cyclical deposition of a metal silicon nitride layer.
FIG. 2B depicts a schematic view of the top portion of an expanding channel of a deposition chamber.
FIG. 3 depicts a schematic cross sectional view of an interconnect structure having a refractory metal silicon nitride barrier layer deposited thereon.
FIG. 4 is a comparison of results performed by flow sequences similar to the flow sequence 100 of FIG. 1A in accordance with embodiments of the invention.
FIGS. 5A–5C are results performed by a flow sequence similar to the flow sequence 400 of FIG. 1D in accordance with embodiments of the invention.
FIG. 6 is a TEM image of a via structure formed by a deposition method described herein.



DETAILED DESCRIPTION OF THE INVENTION
A method of forming a ternary material layer on a substrate surface using a cyclical deposition technique is provided. The method includes delivery of at least three precursors to a substrate in which delivery of two of the at least three precursors is performed simultaneously or sequentially. For example, first and second precursors are introduced simultaneously before a third precursor is introduced. Alternatively, a first precursor is introduced, then a second precursor is sequentially introduced before introducing a third precursor. Accordingly, the composition of the ternary material layer is adjusted to the requirements of different applications using different deposition flow sequences as described below.
The term “cyclical deposition” as used herein refers to a sequential flow of two or more reactants to form a thin layer over a structure and includes processing techniques such as atomic layer deposition and rapid sequential chemical vapor deposition. The term “temary material” as used herein is defined as a material having a composition including three elements. The term “adsorption” and “adsorb” as used herein are meant to include chemisorption, physisorption, or any other phenomenon allowing atoms/molecules to bond, react, or adhere to an exposed surface. The term “substrate structure” refers to any work-piece upon which film processing Is performed and may be used to denote a substrate, such as a semiconductor substrate or a glass substrate, as well as other material layers formed on the substrate, such as a dielectric layer or other layers.
Ternary Material Formation
In one embodiment, formation of a ternary material layer on a substrate surface is performed according to the flow sequences described in FIGS. 1A–1D. FIG. 1A depicts a flow sequence 100 involving three precursors using a cyclical deposition technique. Generally, a substrate is loaded to a process chamber and chamber conditions are adjusted at step 110. The chamber conditions correspond to a flow sequence, which is chosen for various underlying substrate materials and subsequent metallization schemes, such that the desired composition of the ternary layer is obtained. Typical chamber conditions include a temperature between about 175° C. and about 380° C., such as between about 250° C. and about 300° C., and a pressure of between about 0.5 Torr and about 50 Torr, such as between about 1 Torr and about 5 Torr.
At step 120, a purge gas is introduced as a continuous flow into the chamber. Examples of purge gases include, but are not limited to, helium (He), argon (Ar), nitrogen (N2), and hydrogen (H2).
At step 130, a first precursor is adsorbed on the structure/substrate surface by introducing a pulse of a first precursor into the processing chamber to form a monolayer or less of the first precursor which may not saturate the whole substrate surface. In one embodiment, a precursor that adsorbs on a substrate surface without diffusion into an underlying layer of the substrate is deposited as the first precursor. For example, a nitrogen-containing precursor is preferably chosen as the first precursor, such that diffusion,of the deposited material can be avoided.
At step 140, a second precursor is adsorbed on the structure/substrate surface by introducing a pulse of the second precursor into the processing chamber. At step 150, a third precursor is sequentially adsorbed on the substrate surface by introducing a pulse of a third precursor into the chamber. The three precursors may be optionally provided with the aid of a carrier gas. Examples of carrier gases include, but are not limited to, helium (He), argon (Ar), nitrogen (N2), and hydrogen (H2), and other gases. The purge gas and the carrier gas may include different gas flows or may include the same gas flow. If the purge gas and the carrier gas include different gas flows, the purge gas and the carrier gas preferably include the same type of gas. An evacuation of various gases is typically accompanied using a vacuum pump.
Typically, each of the three precursors is delivered at a flow rate of between about 5 sccm and about 5000 sccm, such as between about 50 sccm and about 300 sccm. In addition, each introduction is performed for a short period of pulsing time, such as a pulse in seconds at each step, and stopped for another period of time, usually in seconds such as about 30 seconds or less, to remove any un-reactive precursor or byproduct formation from the chamber after each step by the purge gas introduced at step 120.
The duration of each pulse of the three precursors is variable and the duration between each pulse is also variable. The variation depends on the different materials used, the flow sequence used, the volume capacity of the deposition chamber, the vacuum system coupled to the chamber, among other processing conditions. Typical duration between each pulse for each precursor is between about 50 milli-seconds and about 30 seconds, such as between about 100 milli-seconds and about 5 seconds.
Alternatively, the purge gas introduced as a continuous flow at step 120 may be provided as a pulse after the introduction of each precursor at steps 130, 140, and 150. The purge gas introduced and/or the vacuum pump evacuation introduced, whether continuously or as a pulse, can help to reduce the likelihood of gas phase reactions of the precursors due to excess amounts of the precursors remaining in the chamber and remove any remaining precursor, reactant, and by-product from the chamber.
The three precursors typically include atoms of an element with one or more reactive species. It is believed that the adsorption processes used to adsorb a precursor at each step is self-limiting in that one monolayer or less of the precursor may be adsorbed onto the substrate surface during a given pulse because the substrate surface has a finite number of reactive sites for adsorbing the precursor. Once the finite number of reactive sites is occupied by the precursor, further adsorption of any precursor will be blocked. Any of the precursor not adsorbed is flown out of the chamber as a result of the vacuum system, carrier gas flow, and/or purge gas flow.
Not wishing to be bound by theory, the second precursor introduced at step 140 may react with the reactive species of the first precursor to form a monolayer or less of a binary material. The sequential introduction ot the third precursor at step 150 may react with the reactive species of the first precursor, the second precursor, or the binary material to form a monolayer or lass of a ternary material. Each monolayer may be an atomic layer and may be about 5 Angatroms or less, such as about 1 Angstrom or less, depending on the materials to be deposited. The Introduction of the three precursors is repeated at least once to form thin monolayers of a ternary material layer and the thickness of the ternary material layer Is Incrementally increased at each cycle.
After each deposition cycle, the total thickness of the ternary material is determined at step 160. As such, steps 130 through 150 are repeated when a desired thickness of the layer has not been achieved. However, the process is stopped as indicated by step 180 when the desired thickness of the ternary material layer is achieved. Typically, a ternary material layer having a thickness of about 100 Angstroms or less is deposited.
Optionally, a plasma treatment step may be performed at step 170. The plasma treatment is believed to treat the surface of the deposited layer such that the deposited material is conformally more compact and the resistivity of the deposited material is reduced. In some cases, the thickness of the deposited layer is reduced by the plasma treatment. The gases used for plasma treatment is generated from a source gas including hydrogen, nitrogen, argon, helium, or a combination thereof, that is coupled to the processing chamber. The plasma treatment is performed at a temperature of less than about 380° C. and a pressure of less than about 10 Torr.
FIG. 1B depicts a flow sequence 200 of a cyclical deposition process in accordance with one embodiment of the invention where two precursors are introduced simultaneously. It is believed that the concurrent delivery of a first precursor and a second precursor and the sequential delivery of a third precursor provides a ternary material layer including thin monolayers containing each element of the first precursor, the second precursor, and the third precursor at their atomic level.
The flow sequence 200 includes loading a substrate at step 210, exposing the substrate to a purge gas flow at step 220, and an optional step 230 to deliver a first precursor, followed by the concurrent delivery of the first and a second precursor at step 240. Next, a third precursor is delivered at step 250 to format least a monolayer of a ternary material layer.
Steps 240 and 250 are repeated/cycled at least once to form a ternary material layer and the thickness of the ternary material layer is incrementally increased. After each deposition cycle, the total thickness of the ternary material layer is determined at step 260. As such, steps 240 through 250 are repeated if a desired thickness of the layer has not been achieved. An optional plasma treatment step similar to step 170 of the flow sequence 100 is provided at step 270. At step 280, the deposition process is stopped at a desired thickness of the ternary layer.
FIG. 1C depicts a flow sequence 300 in accordance with another embodiment of the invention in which two precursors are introduced at the same time. The flow sequence 300 includes an optional step 330 to deliver the first precursor and the sequential delivery of a second precursor at step 340. For example, a first precursor is preferably chosen and introduced at step 330 to avoid diffusion of any material to be deposited into the underlying substrate structure/surface. The flow sequence 300 further includes simultaneous delivery of a first and a third precursors at step 350.
Steps 340 and 350 are then repeated/cycled at least once to form a ternary material layer and the thickness of the ternary material layer is incrementally increased. After each deposition cycle, the total thickness of the ternary material layer is determined at step 360, and steps 340 through 350 are repeated when a desired thickness of the layer has not been achieved. Step 370 provides an optional plasma treatment step. The process is stopped at step 380 after a desired thickness of the ternary layer is achieved.
Not wishing to be bound by theory, it is believed that the simultaneous introduction of two precursors as described above with reference to FIGS. 1B and 1C creates a competition between the two precursors to adsorb onto the substrate surface and react with another precursor, which is believed to provide a conformally deposited ternary material layer.
Diffusion into a porous underlying low dielectric-constant dielectric layer is a problem with some precursors. Therefore, the delivery of the first precursor is included to provide adsorption of the first precursor without diffusing into the substrate such that diffusion of the second and/or the third precursors into the underlying layer is avoided. In one embodiment, a first precursor is a precursor that shows lesser tendency as compared to a second and a third precursor to diffuse into the substrate. For example, a nitrogen-containing precursor will not diffuse into the dielectric layer whereas a silicon-containing precursor and a refractory metal-containing precursor cause diffusion problem as the first precursor. This is especially important for depositing a ternary material layer to serve as a barrier layer for copper metallization when a porous underlying low-k dielectric layer is present. As a results, pre-cyclical deposition steps 230 and 330 are performed prior to the cyclical deposition of steps 240 and 250 in the flow sequence 200 and steps 340 and 350 in the flow sequence 300.
FIG. 1D depicts a flow sequence 400 of a cyclical deposition process in accordance with another embodiment of the invention where two precursors are cyclically introduced to form a binary material layer before a third precursor is introduced. The flow sequence 400 provides a cyclical deposition of a first and a second precursor introduced at steps 430 and 440 to form a predetermined thickness of a binary material layer at step 450. At step 470, a pulse of a third precursor is then introduced to form a thin ternary material layer on the substrate surface.
At step 480, an optional plasma treatment step is introduced into the flow sequence 400 before ending the deposition process at step 490. Alternatively, the plasma treatment step may be performed prior to the pulse of the third precursor being introduced into the chamber, as shown at step 460. In this instance, the processing chamber is purged prior to the pulse of the third precursor delivered into the chamber with the subsequent formation of the ternary material layer onto the substrate.
Sequential delivery of the three precursors as demonstrated in FIGS. 1A–1D is provided to adjust the composition of the ternary material layer according to the requirements of different applications. This is achieved, for example, by adjusting the duration for each pulse of the three precursors, the flow rate for delivery of the three precursors, the deposition pressure for each pulse of the three precursors, the different flow sequences described herein, and other factors.
Refractory Metal Silicon Nitride Formation
Exemplary methods of forming a ternary material layer such as a refractory metal silicon nitride layer are described below. The methods involve cyclically depositing a refractory metal-containing precursor, a nitrogen-containing precursor, and a silicon-containing precursor on a substrate surface, such as a surface of an underlying dielectric layer or gate dielectric electrode. Various exemplary flow sequences as described below can be used to adjust the composition, silicon incorporation level, thickness, density, and step coverage of the refractory metal silicon nitride layer.
For example, a refractory metal silicon nitride layer formed by the flow sequences described herein has a composition (RXSiYNZ, where R is the refractory metal) of about 0.6 or less (x value) of refractory metal materials and total of about. 0.4 or less (y plus z value) of silicon and nitrogen, such as between about 0.4 and about 0.6 (x value) of refractory metal materials, between about 0.0001 and about 0.4 (y value) of silicon, and between about 0.0001 and about 0.4 (z value) of nitrogen.
One example includes a tantalum silicon nitride layer formed by the flow sequence 100 having about 55% of tantalum, about 15% of silicon, and about 30% of nitrogen. An exemplary titanium silicon nitride layer formed by the flow sequence 200 includes about 60% of tantalum, about 10% of silicon, and about 30% of nitrogen.
Tables 1–3 provide exemplary flow sequences A–H to demonstrate the use of three precursors, a nitrogen-containing precursor, a refractory metal-containing precursor, and a silicon-containing precursor to sequentially and cyclically form a refractory metal silicon nitride layer in accordance with embodiments of the invention.
Exemplary flow sequences A–D using the flow sequence 100 to form a refractory metal silicon nitride layer are summarized in Table 1. In the exemplary flow sequences A–D, the monolayer formed by cyclical deposition of each precursor may be increased incrementally until a thickness of about 100 Angstroms or less of a refractory metal silicon nitride layer is formed. The refractory metal silicon nitride layer is a tantalum silicon nitride layer or a titanium silicon nitride layer, depending on the refractory metal-containing precursor used.







TABLE 1







Exemplary flow sequences in accordance


with embodiments of the flow sequence 100.











Precursors
Example A
Example B
Example C
Example D





1st precursor
a nitrogen-
a nitrogen-
a refractory
a refractory



containing
containing
metal-
metal-



precursor
precursor
containing
containing





precursor
precursor


2nd precursor
a refractory
a silicon-
a silicon-
a nitrogen-



metal-
containing
containing
containing



containing
precursor
precursor
precursor



precursor


3rd precursor
a silicon-
a refractory
a nitrogen-
a silicon-



containing
metal-
containing
containing



precursor
containing
precursor
precursor




precursor









In one aspect, the nitrogen-containing precursor is chosen as the first precursor to be introduced into the chamber because the other two precursors, the refractory metal-containing precursor and the silicon-containing precursor, have a higher propensity to diffuse into an underlying layer, such as a dielectric layer, especially a porous low-dielectric constant dielectric layer.
In another aspect, exemplary flow sequences A–B are performed by the flow sequence 100 such that the order of the introduction of the silicon-containing precursor and the refractory metal-containing precursor is provided to adjust the composition in the thus formed refractory metal silicon nitride layer. For example, it has been observed that a refractory metal silicon nitride layer formed by the exemplary flow sequence B results in higher silicon incorporation than another refractory metal silicon nitride layer formed by the exemplary flow sequence A.
In the exemplary flow sequences C and D, a refractory metal-containing precursor is delivered into a processing chamber prior to the sequential delivery of the other two precursors as compared to the exemplary flow sequences A and B where a nitrogen-containing precursor is delivered into a processing chamber first. In one embodiment, it is intended that the order of the two precursors, a nitrogen-containing and a silicon-containing precursor, may be reversed to form a tantalum silicon nitride layer such that the composition of the thus formed refractory metal silicon nitride layer can be adjusted.







TABLE 2







Exemplary flow sequences in accordance with


embodiments of the flow sequence 200 and 300.











Precursors
Example E
Example F







1st precursor
a nitrogen-
a nitrogen-




containing
containing




precursor
precursor



2nd precursor
a silicon-
a refractory




containing
metal-




precursor
containing





precursor



3rd precursor
a refractory
a silicon-




metal-
containing




containing
precursor




precursor










Exemplary flow sequence E using the flow sequence 200 and exemplary flow sequence F using the flow sequence 300 to form a refractory metal silicon nitride layer are summarized in Table 2. In the exemplary flow sequences E and F, a nitrogen-containing precursor is the first precursor delivered into the processing chamber to prevent diffusion of the other two precursors into the substrate, and the nitrogen-containing precursor and a silicon-containing precursor are introduced simultaneously.
Not wishing to be bound by theory, it is believed that when the silicon-containing precursor is introduced together with the nitrogen-containing precursor at steps 240 and 350 of the flow sequences 200 and 300, respectively, they compete with each other to adsorb onto the substrate surface and react with the refractory metal-containing precursor, prior to the adsorption of the refractory metal-containing precursor at step 250 of the flow sequences 200 or after the adsorption of the refractory metal-containing precursor at step 340 of the flow sequences 300. Such competition and cycling of steps 240 and 250 in the flow sequence 200 and competition and cycling of steps 340 and 350 in the flow sequence 300 enhance the formation of a true refractory metal silicon nitride layer, such as a tantalum silicon nitride layer or a titanium silicon nitride layer. Accordingly, the composition of the tantalum silicon nitride layer or the titanium silicon nitride layer can be adjusted to the need of different metallization schemes.
Exemplary flow sequences G and H using the flow sequence 400 to form a refractory metal silicon nitride layer are summarized in Table 3. In the exemplary flow sequences G and H, a nitrogen-containing precursor and a refractory metal-containing precursor are introduced as the first or the second precursors to perform cyclical deposition of a refractory metal nitride layer before a third silicon-containing precursor is introduced. The refractory metal nitride layer formed may be a tantalum nitride layer (TaN) or a titanium nitride layer (TiN).







TABLE 3







Exemplary flow sequences in accordance with


embodiments of the flow sequence 400.











Precursors
Example G
Example H







1st precursor
a nitrogen-
a refractory




containing
metal-




precursor
containing





precursor



2nd precursor
a refractory
a nitrogen-




metal-
containing




containing
precursor




precursor



3rd precursor
a silicon-
a silicon-




containing
containing




precursor
precursor










Further, the silicon-containing precursor is provided to incorporate a low-level of silicon into the surface of the deposited tantalum nitride (TaN) or titanium nitride (TiN) layer. The resulting substrate surface includes a thin monolayer of about 10 angstroms or less of tantalum silicon nitride (TaSiN) or titanium silicon nitride (TiSiN) to serve as a barrier layer or an adhesion layer for subsequent metallization applications. In addition, the thus deposited layer as a whole deposited by the flow sequences 400 serves as, for example, a better barrier layer for copper metallization or a better adhesion layer for tungsten metallization than the deposited tantalum nitride (TaN) or titanium nitride (TiN) layer alone.
It is believed that tantalum silicon nitride (TaSiN) or titanium silicon nitride (TiSiN) adheres well to subsequent conductive metal material, such as copper, tungsten, and others, and prevents the diffusion of the subsequent conductive metal material into the underlying substrate material, better than tantalum nitride (TaN) or titanium nitride (TiN).
The sequential introduction of reactants or precursors in examples A–H may be repeated to deposit a plurality of thin layers to form a conformal refractory metal silicon nitride layer to a desired thickness. The flow rate for introducing the refractory metal-containing precursor is generally between about 10 sccm and about 1000 sccm, such as between about 50 sccm and about 250 sccm with or without a carrier gas. The flow rate for introducing the nitrogen-containing precursor is typically between about 100 sccm and about 5000 sccm, such as between about 250 sccm and about 1000 sccm, and the flow rate for introducing the silicon-containing precursor is between about 5 sccm and about 500 sccm, such as between about 50 sccm and about 150 sccm
Deposition Precursors
For the formation of a refractory metal silicon nitride barrier/adhesion layer using a cyclical deposition technique, a refractory metal monolayer is formed using metalorganic or inorganic halide refractory metal-containing precursors. A silicon monolayer is formed using silicon-containing precursor, and a nitrogen monolayer is formed using nitrogen-containing precursors.
Precursors are selected based on vapor pressure, chemical property, subsequent metallization schemes, and availability. Precursors in a cyclical deposition application should be highly reactive with each other, require short pulsing times, and enhance the purity of a film. Table 4 is a list of exemplary precursors that may be used for depositing a refractory metal silicon nitride layer using a cyclical deposition technique described above.
For example, metalorganic precursors such as tantalum-containing PDMAT or PEMAT, or titanium-containing TDMAT or TEMAT, are useful for the cyclical deposition or atomic layer deposition of a refractory metal-containing barrier layer for subsequent applications, such as to serve as a copper barrier or tungsten liner. In one embodiment, it is contemplated that any metal-organic refractory metal-containing precursor suitable for deposition of tantalum, tantalum nitride, tantalum silicon nitride, titanium, titanium nitride, or titanium silicon nitride may be used.







TABLE 4





Exemplary deposition precursors.

















Titanium-containing


Tantalum-containing precursors
precursors





t-butylimino tris(diethylamino)
tetrakis (dimethylamino)


tantalum (TBTDET): (NEt2)3TaN-But
titanium (TDMAT)


pentakis (ethylmethylamino)
tetrakis (ethylmethylamino)


tantalum (PEMAT): Ta(NMeEt)5
titanium (TEMAT)


pentakis (dimethylamino)
tetrakis (diethylamino)


tantalum (PDMAT): Ta(NMe2)5
titanium (TDEAT)


pentakis (diethylamino)
titanium tetrachloride: TiCl4


tantalum PDEAT: Ta(NEt2)5


t-butylimino tris(ethylmethylamino)
titanium iodide: TiI4


tantalum(TBTMET): (NEt2Me)3TaN-But


t-butylimino tris(dimethyl amino)
titanium bromide: TiBr4


tantalum (TBTDMT): (NMe2)3TaN-But


bis(cyclopentadienyl)
other titanium halides


tantalum trihydride: (Cp)2TaH3


bis(methylcyclopentadienyl)


tantalum trihydride: (CpMe)2TaH3











Nitrogen-containing precursors
Silicon-containing precursors





ammonia: NH3
silane: SiH4


hydrazine: NH2NH2
disilane: Si2H6


Methylhydrazine: (CH3)(H)NNH2
Methylsilane: CH3SiH3


Dimethylhydrazine: (CH3)2NNH2
Dimethylsilane: (CH3)2SiH2


t-butylhydrazine: (CH3)3C(H)NNH2
Chlorosilane: (SiH3Cl),


Phenylhydrazine: C6H5N2H3
Dichlorosilane: (SiH2Cl2),


Azoisobutane: 2,2′-(CH3)6C2N2
Trichlorosilane: (SiHCl3),


Ethylazide: (C2H5N3),









In another embodiment, it is contemplated that inorganic precursors such as tantalum halides or titanium halides are useful as refractory metal-containing precursors for subsequent application, such as tungsten metallization.
The nitrogen-containing precursor is selected for its ability to reduce a refractory metal-containing precursor, thus forming a refractory metal nitride film. Some refractory metal-containing precursors have a double bond, such as TBTDET, and could require a stronger reducing agent than ammonia gas, e.g., hydrazine, methylhydrazine, dimethylhydrazine and t-butylhydrazine, in order not to slow down the deposition rate of the refractory metal silicon nitride layer.
Silane or substituted silanes are highly reactive compounds at low temperatures, such as the chamber temperature used herein for a cyclical deposition technique, and provide an excellent source of silicon to incorporate into the layer.
Deposition Chambers
FIG. 2A depicts a schematic cross-sectional view of a processing system 50 that can be used in accordance with embodiments described herein. Details of the processing system 50 are described in U.S. patent application Ser. No. 10/032,284, entitled “Gas Delivery Apparatus and Method for Atomic Layer Deposition”, filed on Dec. 21, 2001, and is incorporated by reference herein. In addition, cyclical deposition utilizing three or more precursors may be performed in other chambers as well, such as a TxZ chamber and a SPRINT PLUS chamber, both available from Applied Materials, Inc., located in Santa Clara, Calif.
The processing system 50 generally includes a process chamber 500, a gas delivery apparatus 530, a control unit 580, along with other hardware components such as a number of power supplies (not shown) and vacuum pumps. One vacuum pump 578 is shown in FIG. 2A. The vacuum pump 578 evacuates gases from the chamber 500 and helps maintain chamber pressure within a desired pressure range. The salient features of process chamber 500 are briefly described below.
The chamber 500 comprises a substrate support 512, which may be heated, such as by a resistive heater or a radiant heat source, to heat a substrate 510 disposed thereon prior to or during deposition. The substrate temperature can be maintained or controlled at a desired temperature range suitable for a deposition process, for example, between about 20° C. to about 500° C. A temperature window for precursors disclosed herein is less than about 380° C. In general, a temperature window for substrate temperature is that range of temperatures that induces adsorption of the precursors onto the substrate, generally below the thermal decomposition temperature for a particular precursor. A temperature sensor, such as a thermocouple, is typically embedded in the substrate support 512 to monitor the substrate temperature. In addition, a purge ring 522 may be disposed on the substrate support 512 to define a purge channel 524, which provides a purge gas to a peripheral portion of the substrate 510 to prevent deposition thereon.
The chamber 500 also includes a chamber lid 532 connecting with a gas delivery apparatus 530 at an upper portion of the chamber 500 to provide a gas, such as a process gas, a reactant/precursor gas, and/or a purge gas, to the chamber 500. The chamber lid 532 includes an expanding channel 534, extending from a central portion to a peripheral portion of the chamber lid 532 and having an increasing inner diameter to define a processing zone or a reaction zone 564 and to substantially cover the substrate surface. Particularly, the lower portion of the expanding channel 534, near the bottom of the reaction zone 564 and around the substrate surface, is dramatically expanded to cover the substrate surface and the lower portion of the expanding channel 534 may include one or more surfaces, such as a tapered surface, straight surface, concave surface, convex surface, and combinations thereof.
More particularly, the lower portion of the expanding channel 534 may be tapered and downwardly sloping in the shape of a cone to help reduce variations in the velocity of a reactant gas traveling through the lower portion to the substrate surface and provide uniform exposure of the reactant gas. Such an increase in diameter of the expanding channel 534 or tapered expansion of the lower portion of the expanding channel 534 around the substrate 510 results in a decreased gas flow when a process gas or purge gas travels through the expanding channel 534. As a result, an improved velocity profile of a gas flowing through the expanding channel 534 across the substrate surface, i.e., from the center of the substrate to the edge of the substrate, is achieved.
In general, the above design applies to an expanding channel 534 adapted to provide a total gas flow of between about 5 sccm and about 3,000 sccm. The reduction of the velocity of the gas flow helps reduce the likelihood that a gas flow will blow off reactants or precursors adsorbed on the surface of the substrate 510.
The chamber lid 532 further includes a choke structure 562 adjacent the periphery of the substrate 510 to restrict any gas flowing therethrough and to isolate the reaction zone 564 near the top portion of the chamber 500, away from the rest of the chamber portions such that a reactant gas or purge gas needs only adequately fill the reaction zone 564 to ensure sufficient exposure of the substrate 510 to the reactant gas or purge gas. Since the reaction zone 564 includes a smaller volume compared to the inner volume of a conventional CVD chamber, less gas is required to fill the volume of the reaction zone 564.
Overall, the expanding channel 534 and the choke structure 562 of the chamber lid 532 are designed to help distribute the process gas or purge gas more uniformly and provide a more evenly controlled gas pressure adjacent the substrate 510 within the reaction zone 264. Typically, the chamber pressure is about 100 Torr or less. The chamber lid 532 may further include cooling elements and/or heating elements depending on the particular gas being delivered therethrough to prevent gas decomposition, deposition, or condensation on the chamber lid 532.
The gas delivery apparatus 530 is connected with the expanding channel 534 via gas inlets 536A, 536B located adjacent the upper portion of the expanding channel 534. Typically, the gas delivery apparatus 530 includes a number of purge gas sources 540 and carrier gas sources (not shown), a number of reactant/precursor gas sources 538, 539 and other gas sources, a number of reactant gas valves 542A, 542B and purge gas valves 552A, 552B, a number of valve seat assemblies 544A, 544B and purge gas valve seat assemblies 546A, 546B, a number of reactant gas lines 543A, 543B and purge gas lines 545A, 545B, and a number of gas conduits 550A, 550B, for flowing gases through the gas inlets 536A and 536B, into the expanding channel 534.
FIG. 2B depicts a cross-sectional view of the top portion of the expanding channel 534 demonstrating the arrangements of the gas inlets 536A and 536B. As shown in FIG. 2B, each gas conduit 550A, 550B and gas inlet 536A, 536B may be positioned at an angle a from center lines 502A, 502B of the gas conduit 550A, 550B and from a radius line 504 of the center of the expanding channel 534. Entry of a gas through the gas conduit 550A, 550B preferably positioned at an angle a (i.e., when α>0°) causes the gas to flow in a circular direction as shown by arrows 506A, 506B. By providing gas at an angle α as opposed to directly straight-on to the walls of the expanding channel (i.e. when α=0°), a more laminar flow in the same circular direction (i.e., clockwise or counter-clockwise) through the expanding channel 534 rather than a turbulent flow is provided. In one embodiment of the invention, the distance between the gas inlets (536A, 536B, and others) and the substrate 510 is made far enough that the circular flow dissipates to a downwardly flow.
Referring back to FIG. 2A, each gas conduit 550A, 550B and gas inlet 536A, 536B may be positioned horizontally as shown in FIG. 5A or may be angled downwardly or upwardly at an angle to provide a gas flow. In addition, the diameter of the gas conduits 550A, 550B may be increasing from the reactant gas lines 543A, 543B of the reactant gas valves 542A, 542B to the gas inlet 536A, 536B to help reduce the velocity of the gas flow prior to its entry into the expanding channel 534.
Process precursors, typically in a liquid or solid phase at room temperature, are stored in reactant gas sources 538, 539, and other additional gas sources. Prior to delivery to the chamber 500, the process precursors are heated to between about 30° C. and about 120° C. to convert into a vapor-gas phase by a device coupled to the gas sources, such as a bubbler or an ampoule. Alternatively, some precursors are vaporized directly into gas phase by another device, such as a direct liquid injector (DLI), coupled to the gas sources.
Reactant gases and/or purge gases are delivered from various gas sources through gas lines into various gas valves to provide a combined gas flow and/or separate gas flows. For example, reactant gas valves 542A, 542B and purge gas valves 552A, 552B are coupled to programmable logic controllers 548A and 548B to control the opening and actuation of the diaphragms of the valve seat assemblies 544A, 544B, 546A, 546B.
In one embodiment of the invention and with reference to gas valves 542A and 552A, a combined gas flow includes a continuous flow of a purge gas from the purge gas source 540 through purge gas line 545A and pulses of a reactant gas from the reactant gas source 538 through reactant gas line 543A. The combined gas flow is thus adjusted by controlling the diaphragm of the purge gas valve seat assembly 546A to leave the purge gas line 545A open and the diaphragm of the reactant gas valve seat assembly 544A to open and close the reactant gas line 543A for a period of reactant gas pulsing time determined by the flow sequences as described supra.
In another embodiment and with reference to gas valves 542A and 552A, separate gas flows includes pulses of a purge gas from the purge gas source 540 through purge gas line 545A and pulses of a reactant gas from the reactant gas source 538 through reactant gas line 543A. The separate gas flows are thus adjusted by controlling the diaphragms of the purge gas valve seat assembly 546A and of the reactant gas valve seat assembly 544A to open and close the purge gas line 545A and reactant gas line 543A for a period of pulsing time determined by the flow sequences as described supra.
A control unit 580, such as a programmed personal computer, work station computer, or the like, may be coupled to the chamber 500, the gas delivery apparatus 530, and other components of the chamber 500, to control processing conditions, such as the heating and monitoring of the substrate support 512, chamber pressure, and delivery of various gas flows, during different stages of a substrate processing flow sequence. Additionally, the control unit 580 monitors and regulates other activities used in substrate processing such as substrate transport.
For example, the control unit 580, coupled to logic controllers, 548A and 548B, is configured to control various process gas flows and purge gas flow from the gas sources 538, 539, 540 through the gas valves 542A, 542B, 552A, 552B. Furthermore, the control unit 580 may comprise a central processing unit (CPU) 582, a support circuitry 584, and a memory unit 586 containing associated control software 583. The associated control software is executed after the substrate 510 is positioned on the substrate support 512. The software routines, when executed, transform a general-purpose computer into a specific process computer that controls the chamber operation so that a chamber process is performed. Alternatively, the software routines may be performed in hardware, as an application specific integrated circuit or other type of hardware implementation, or a combination of software or hardware.
Optionally, a remote plasma source (not shown) may be coupled to the chamber 500 to clean deposits and reactive precursors formed on interior surfaces. The remote plasma source may include a plasma gas supply, a plasma gas flow controller, a plasma chamber, and a plasma chamber inlet. The gas flow controller may be coupled to the control unit 580 to control the flow of a plasma gas from the plasma gas supply to the plasma chamber. An ignited plasma is typically generated by applying an electric field to the plasma gas in the plasma chamber and creating a plasma of reactive species, using a radio-frequency (RF) power source, for example.
In operation, the tantalum containing precursor, the nitrogen-containing precursor and the silicon-containing precursor stored within various reactant gas sources are pulsed into the expanding channel 534 of the chamber 500 through gas inlets 536A and 536B. For example, the tantalum containing-precursor may be stored at the reactant gas source 538 and delivered through gas inlet 536A, and the nitrogen-containing precursor and the silicon-containing precursor may be stored at different gas sources, such as gas sources 539 and others, but may share the same gas inlet 536B, since the nitrogen-containing precursor and the silicon-containing precursor will not react with each other at gas phase under the delivery conditions described herein.
In one embodiment of the invention, another one or more gas inlets may be located along the length of the expanding channel 534, preferably near the upper portion, to provide additional gases, such as a third precursor gas, into the chamber 500. In this aspect, the nitrogen-containing precursor and the silicon-containing precursor may be delivered into the chamber 500 through different gas inlets.
The gas flows of each purge gas and reactant gas, whether combined or separated, flow through the expanding channel 534 as a circular pattern and provide a sweeping action across the inner surface of the expanding channel 534. The circular pattern dissipates to a downwardly flow toward the surface of the substrate 210. The velocity of the gas flow reduces as it travels through the expanding channel 234. The gas flow then travels across the surface of the substrate 210 and across the bottom surface 260 of the chamber lid 232. The bottom surface 260 of the chamber lid 232, which is downwardly sloping, helps reduce the variation of the velocity of the gas flow across the surface of the substrate 210. The gas flow then travels by the choke 262 and into the pumping zone 266 of the chamber 200. Excess gas, by-products, etc. flow into the pumping channel 279 where they are exhausted from the chamber 200 by a vacuum system 278. In one aspect, the gas flow proceeds through the expanding channel 234 and between the surface of the substrate 210 and the bottom surface 260 of the chamber lid 232 in a laminar manner which aids in uniform exposure of a reactant gas to the surface of the substrate 210 and efficient purging of inner surfaces of the chamber lid 232.
In addition, one or two ignited plasmas, generated by a remote plasma chamber, may be introduced into the chamber 500 to treat the surface of the deposited layer. In FIGS. 1A–1D, the plasma treatment step is performed after a binary or ternary layer has been formed on the substrate.
Deposition of a Barrier Layer
Typically, formation of a refractory metal silicon nitride layer such as a tantalum silicon nitride (TaxSiyNz) layer or a titanium silicon nitride (TixSiyNz) layer serves as a barrier/adhesion layer for subsequent metallization. For example, a metal refractory silicon layer may be used as a copper barrier or tungsten liner during a damascene metallization procedure, such as for lining dual damascene trenches and vias.
FIG. 3 depicts a schematic cross sectional view of a substrate structure 600 having a refractory metal silicon nitride barrier layer 620 deposited thereon in accordance with aspects of the invention. As shown, the substrate structure 600 includes an underlying dielectric layer 610 that has been patterned to form a recess 630, such as a via, a line, or a contact hole. These features are formed in dielectric materials by conventional photolithographic and etching techniques. In some cases, such recess has been patterned to contact another underlying conductive metal material 602. Alternatively, a substrate 610 without a dielectric layer formed thereon may be used to deposit a barrier/adhesion layer 620.
Materials that may be suitable for the dielectric layer 610 include, but are not limited to silicon dioxide, phosphorus-silicate-glass (PSG), boron silicate glass (BSG), boron doped phosphorus-silicate-glass (BPSG), fluoro-silicon glass (FSG), porous polymers (e.g. polymides), carbon-containing silicon oxides (e.g. Black DiamondTM, available from Applied Materials, Inc. of Santa Clara, Calif.), doped monocrystalline silicon, gallium-arsenide, silicon dioxide derived from tetraethyl orthosilicate (TEOS) or silane by plasma enhanced chemical vapor deposition (PECVD).
A tantalum silicon nitride or titanium silicon nitride barrier/adhesion layer 620 is deposited conformally and evenly, particularly on the sidewall 602S, bottom 602B, and top 602T of the dielectric layer 610, to provide good step coverage. In subsequent metallization steps, a metal layer 650, filled with copper or tungsten, for example, may be formed over the refractory metal silicon nitride barrier/adhesion layer through various deposition techniques such as electroplating, CVD, PVD, etc. among others.
EXAMPLE A
FIG. 4 is a comparison of the results of two flow sequences similar to the flow sequence 100 in FIG. 1A where three precursors are sequentially introduced into the flow sequence to form a tantalum silicon nitride layer. The difference between these two flow sequences was the order of the second and the third precursors. The precursors in these two flow sequences were ammonia used as the first precursor, and silane and pentakis (ethylmethylamino) tantalum (PEMAT) used as the second and the third precursors or vice versa. The two flow sequences were performed at about 215° C. chamber temperature. As a test, delivery of the ammonia was at a flow rate of about 500 sccm and a deposition pressure of about 10 Torr for a pulse of about 10 second. Delivery of the PEMAT was at a flow rate of about 200 sccm for a pulse of about 10 second, with an argon carrier gas of a deposition pressure of about 5 Torr. Delivery of the silane was at a flow rate of about 50 sccm for a pulse of about 10 second, with an argon carrier gas of a deposition pressure of about 2 Torr at a flow rate of about 500 sccm.
The deposition rates for the two flow sequences as measured by Angstroms per cycle are shown as a function of silane exposure time in seconds per cycle. The results in FIG. 4 show that silicon incorporation for each pulse is saturated after about 5 to about 10 second of exposure time and each pulse of the silane precursor is provided to increase the thickness of the thus formed tantalum silicon nitride layer to about 1.2 Angstrom or less for each deposition cycle.
Significantly, the flow sequence of using ammonia, PEMAT, and silane as the first, second, and third precursors, respectively, results in about 13% of silicon incorporation into the final tantalum silicon nitride layer, which is higher than about 7% of silicon incorporation for the flow sequence of using ammonia, silane, and PEMAT as the first, second, and third precursors, respectively.
EXAMPLE B
The results performed by a flow sequence similar to the flow sequence 400 in FIG. 1D form a titanium nitride layer prior to the formation of a titanium silicon nitride layer are summarized below. The precursors used were ammonia as the first precursor, tetrakis (diethylamino) titanium (TDMAT) as the second precursor, and silane as the third precursor.
In FIG. 5A, the flow sequence is performed at various temperatures between about 150° C. and about 350° C. Decomposition of the titanium nitride layer as measured by X-ray fluorescence (XRF) counts in kilocounts per second (kcps) is shown as a function of the temperature of the heater for heating up the chamber. The results suggest that deposition is better at a temperature of about 250° C. or less because decomposition of the TDMAT precursor as indicated by the X-ray fluorescence (XRF) counts starts at a temperature of about 250° C. or more. The decomposition is not as severe when a longer duration of a pulse of a purge gas is delivered to the chamber after the delivery of each of the first two precursors, TDMAT and ammonia.
In FIGS. 5B–5C, the flow sequence was performed at a heater temperature of about 200° C. and TDMAT decomposition was measured by the X-ray fluorescence (XRF) counts as a function of the exposure time for each pulse of TDMAT. The measurements for the exposure time from about 2 seconds to about 30 seconds are shown in FIG. 5B for TDMAT and ammonia and the measurements for the exposure time form about 50 seconds to about 600 seconds are shown in FIG. 5C. Delivery of the ammonia was at a flow rate of about 500 sccm. Delivery of the TDMAT was at a flow rate of about 2 milligrams per minute, with a helium carrier gas at a flow rate of about 500 sccm. Delivery of the silane was at a flow rate of about 50 sccm for a pulse of about 10 second. The results suggest that minor TDMAT decomposition is still observed at the temperature as low as 200 if overexposure of the TDMAT occurs. In addition, in FIG. 5A, the ammonia is very stable and no decomposition occurs even under overexposure.
The deposition rates as measured by Angstroms per cycle are shown in FIGS. 5B and 5C as a function of TDMAT exposure time in seconds per cycle. The results in FIGS. 5B and 5C show that silicon incorporation for each pulse is saturated after about 5 to about 10 second of exposure time and each pulse of the silane precursor is provided to increase the thickness of the thus formed tantalum silicon nitride layer to about 1.2 Angstrom or less for each deposition cycle.
FIG. 6 is a TEM image of a via structure formed by a cyclical deposition method according to the flow sequence 400 without performing the plasma treatment step (step 460) to form a tantalum silicon nitride (TaSiN) layer of about 15 Angstrom. The TEM image of the overall via structure shows good step coverage. The tantalum silicon nitride layer is conformally and evenly deposited, particularly along the sidewall, bottom, and top of the via structure.
While foregoing is directed to various embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

## Claims

1. A method for depositing a refractory metal silicon nitride layer on a surface of an underlying layer, comprising:
introducing a pulse of a nitrogen-containing precursor, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a refractory metal-containing precursor and a silicon-containing precursor into the underlying layer; and
exposing the surface to a cyclic deposition process in a process chamber by providing at least one cycle of precursors to form the refractory metal silicon nitride layer, the at least one cycle comprising:
introducing a pulse of the refractory metal containing precursor into the process chamber;
pulsing a purge gas into the process chamber;
introducing a pulse of the nitrogen-containing precursor into the process chamber;

pulsing the purge gas into the process chamber;
introducing a pulse of the silicon-containing precursor into the process chamber; and
pulsing the purge gas into the process chamber.

2. The method of claim 1, further comprising constantly flowing a gas selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

3. The method of claim 2, wherein the purge gas is selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

4. The method of claim 3, further comprising treating with a plasma generated from one or more gases selected from the group consisting of hydrogen, helium, nitrogen, argon, and combinations thereof, after the refractory metal silicon nitride layer is formed.

5. The method of claim 1, wherein tho material of the refractory metal silicon nitride layer comprises a material selected from the group consisting of tantalum silicon nitride (TaxSiyNz) and titanium silicon nitride (TixSiyNz).

6. The method of claim 5, wherein TaxSiyNz comprises tantalum to silicon to nitrogen in a ratio in which x is about 0.6 or less, y plus z is about 0.4 or less, y is between about 0.001 to about 0.4, and z is between about 0.001 and about 0.4.

7. The method of claim 5, wherein TixSiyNz comprises titanium to silicon to nitrogen in a ratio in which x is about 0.6 or less, y plus z is about 0.4 or less, y is between about 0.001 to about 0.4, and z is between about 0.001 and about 0.4.

8. The method of claim 3, wherein the refractory metal-containing precursor is selected from the group consisting of pentakis (dimethylamino) tantalum (PDMAT), pentakis (ethylmethylamino) tantalum (PEMAT), pentakis (diethylamino) tantalum (PDEAT), t-butylimino tris(diethylamino) tantalum (TBTDET), t-butylimino tris(ethylmethylamino) tantalum (TBTMET), t-butylimino tris(dimethylamino) tantalum (TBTDMT), bis(cyclopentadienyl) tantalum trihydride, bis(methylcyclopentadienyl) tantalum trihydride, a titanium-containing precursor, and derivatives thereof.

9. The method of claim 8, wherein the titanium-containing precursor is selected from the group consisting of tetrakis (dimethylamino) titanium (TDMAT), tetrakis (ethylmethylamino) titanium (TEMAT), tetrakis (diethylamino) titanium (TDEAT), titanium tetrachloride (TiCl4), titanium iodide (TiI4, titanium bromide (TiBr4), and derivatives thereof.

10. The method of claim 9, wherein the silicon-containing precursor is selected from the group consisting of silane, disilane, methylsilane, dimethylsilane, chlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), and derivatives thereof.

11. The method of claim 10, wherein the nitrogen-containing precursor is selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhyd razine (C6H5N2H3), 2,2′-azoisobutane ((CH3)6C2N2), ethylazide (C2H5N3), and derivatives thereof.

12. A method for depositing a refractory metal silicon nitride layer on a surface of an underlying layer, comprising:
introducing a pulse of a nitrogen-containing precursor, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a refractory metal-containing precursor and a silicon-containing precursor into the underlying layer; and
providing at least one cycle of precursors to form the refractory metal silicon nitride layer in a process chamber, the at least one cycle comprising:
introducing a pulse of the refractory metal-containing precursor;
pulsing a purge gas into the process chamber;
simultaneously introducing a pulse of the nitrogen-containing precursor and the silicon-containing precursor to contact with and adsorb on the surface; and
pulsing the purge gas into the process chamber.

13. The method of claim 12, further comprising constantly flowing a gas selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

14. The method of claim 13, wherein the purge gas is selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

15. The method of claim 14, further comprising treating with a plasma generated from one or more gases selected from the group consisting of hydrogen, helium, nitrogen, argon, and combinations thereof, after the refractory metal silicon nitride layer is formed.

16. The method of claim 14, wherein the material of the refractory metal silicon nitride layer comprises a material selected from the group consisting of tantalum silicon nitride (TaxSiyNz) and titanium silicon nitride (TixSiyNz).

17. The method of claim 16, wherein TaxSiyNzcomprises tantalum to silicon to nitrogen in a ratio in which x is about 0.6 or less, y plus z is about 0.4 or less, y is between about 0.001 to about 0.4, and z is between about 0.001 and about 0.4.

18. The method of claim 16, wherein TixSiyNzcomprises titanium to silicon to nitrogen in a ratio in which x is about 0.6 or less, y plus z is about 0.4 or less, y is between about 0.001 to about 0.4, and z is between about 0.001 and about 0.4.

19. The method of claim 16, wherein the refractory metal-containing precursor is selected from the group consisting of pentakis (dimethylamino) tantalum (PDMAT), pentakis (ethylmethylamino) tantalum (PEMAT), pentakis (diethylamino) tantalum (PDEAT), t-butylimino tris(diethylamino) tantalum (TBTDET), t-butylimino tris(ethylmethylamino) tantalum (TBTMET), t-butylimino tris(dimethylamino) tantalum (TBTDMT), bis(cyclopentadienyl) tantalum trihydride, bis(methylcyclopentadienyl) tantalum trihydride, a titanium-containing precursor, and derivatives thereof.

20. The method of claim 19, wherein the titanium-containing precursor is selected from the group consisting of tetrakis (dimethylamino) titanium (TDMAT), tetrakis (ethylmethylamino) titanium (TEMAT), tetrakis (diethylamino) titanium (TDEAT), titanium tetrachloride (TiCl4), titanium iodide (TiI4), titanium bromide (TiBr4), and derivatives thereof.

21. The method of claim 20, wherein the silicon-containing precursor is selected from the group consisting of silane, disilane, methylsilane, dimethylsilane, chlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), and derivatives thereof.

22. The method of claim 21, wherein the nitrogen-containing precursor is selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethyihydrazine, t-butylhydrazine, phenylhyd razine (C6H5N2H3), 2,2′-azoisobutane ((CH3)6C2N2), ethylazide (C2H5N3), and derivatives thereof.

23. A method for depositing a refractory metal silicon nitride ternary material layer on a substrate surface, comprising:
exposing the substrate surface to a nitrogen precursor;
providing at least one cycle of precursors to form a binary material layer on the substrate surface, wherein the at least one cycle of precursors further comprises introducing a pulse of a first precursor, introducing a purge gas pulse, introducing a pulse of a second precursor, and introducing the purge gas pulse; and
introducing a pulse of a third precursor after the binary material layer is formed to form the refractory metal silicon nitride ternary material layer.

24. The method of claim 23, further comprising constantly flowing a gas selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

25. The method of claim 24, wherein the purge gas is selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

26. The method of claim 25, further comprising treating the substrate surface with a plasma generated from one or more gases selected from the group consisting of hydrogen, helium, nitrogen, argon, and combinations thereof, after the binary material layer is formed.

27. The method of claim 25, further comprising treating the substrate surface with a plasma generated from one or more gases selected from the group consisting of hydrogen, helium, nitrogen, argon, and combinations thereof, after the ternary material layer is formed.

28. The method of claim 25, wherein the ternary material layer comprises a material selected from the group consisting of tantalum silicon nitride and titanium silicon nitride.

29. A method for forming a refractory metal silicon nitride layer on a substrate surface, comprising:
providing at least one cycle of precursors to form a refractory metal nitride layer on the substrate surface, wherein the at least one cycle of precursors further comprises sequential introduction of pulses of a nitrogen-containing precursor, a purge gas, a refractory metal-containing precursor, and the purge gas; and
introducing a pulse of a silicon-containing precursor to contact with and adsorb on the refractory metal nitride layer.

30. The method of claim 29, further comprising constantly flowing a gas selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

31. The method of claim 30, wherein the purge gas is selected from the group consisting of argon, nitrogen, hydrogen, helium, and combinations thereof.

32. The method of claim 31, further comprising treating the substrate surface with a plasma generated from one or more gases selected from the group consisting of hydrogen, helium, nitrogen, argon, and combinations thereof, after the refractory metal nitride layer is formed.

33. The method of claim 31, further comprising treating the substrate surface with a plasma generated from one or more gases selected from the group consisting of hydrogen, helium, nitrogen, argon, and combinations thereof, after the refractory metal silicon nitride layer is formed.

34. The method of claim 31, wherein the refractory metal silicon nitride layer comprises a material selected from the group consisting of tantalum silicon nitride (TaxSiyNz) and titanium silicon nitride (TixSiyNz).

35. The method of claim 34, wherein TaxSiyNz comprises tantalum to silicon to nitrogen in a ratio in which x is about 0.6 or less, y plus z is about 0.4 or less, y is between about 0.001 to about 0.4, and z is between about 0.001 and about 0.4.

36. The method of claim 34, wherein TixSiyNz comprises titanium to silicon to nitrogen in a ratio in which x is about 0.6 or less, y plus z is about 0.4 or less, y is between about 0.001 to about 0.4, and z is between about 0.001 and about 0.4.

37. The method of claim 34, wherein the refractory metal-containing precursor is selected from the group consisting of pentakis (dimethylamino) tantalum (PDMAT), pentakis (ethylmethylamino) tantalum (PEMAT), pentakis (diethylamino) tantalum (PDEAT), t-butylimino tris(diethylamino) tantalum (TBTDET), t-butylimino tris(ethylmethylamino) tantalum (TBTM ET), t-butylimino tris(dimethylamino) tantalum (TBTDMT), bis(cyclopentadienyl) tantalum trihydride, bis(methylcyclopentadienyl) tantalum trihydride, a titanium-containing precursor, and derivatives thereof.

38. The method of claim 37, wherein the titanium-containing precursor is selected from the group consisting of tetrakis (dimethylamino) titanium (TDMAT), tetrakis (ethylmethylamino) titanium (TEMAT), tetrakis (diethylamino) titanium (TDEAT), titanium tetrachloride (TiCl4), titanium iodide (TiI4), titanium bromide (TiBr4), and derivatives thereof.

39. The method of claim 38, wherein the silicon-containing precursor is selected from the group consisting of silane, disilane, methylsilane, dimethylsilane, chlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), and derivatives thereof.

40. The method of claim 39, wherein the nitrogen-containing precursor is selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine (C6H5N2H3), 2,2′-azoisobutane ((CH3)6C2N2), ethylazide (C2H5N3), and derivatives thereof.

41. A method for forming a tantalum silicon nitride layer on a surface of an underlying layer inside a deposition chamber, comprising:
providing at least one cycle of precursors, the at least one cycle comprising:
introducing a pulse of a nitrogen-containing precursor into the chamber, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a tantalum-containing precursor and a silicon-containing precursor into the underlying layer;
introducing a pulse of the silicon-containing precursor to contact with and adsorb on the surface; and
introducing a pulse of the tantalum-containing precursor to contact with and adsorb on the surface, wherein the pulse of the silicon-containing precursor is introduced after the introduction of the pulse of the nitrogen-containing precursor and before the introduction of the pulse of the tantalum-containing precursor.

42. A method for forming a tantalum silicon nitride layer on a surface of an underlying layer inside a deposition chamber, comprising:
providing at least one cycle of precursors, the at least one cycle comprising:
introducing a pulse of a nitrogen-containing precursor into the chamber, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a tantalum-containing precursor and a silicon-containing precursor into the underlying layer;
introducing a pulse of the tantalum-containing precursor to contact with and adsorb on the surface;
introducing a pulse of the silicon-containing precursor to contact with and adsorb on the surface, wherein the pulse of the silicon-containing precursor is introduced after the introduction of the pulse of the tantalum-containing precursor.

43. A method for forming a tantalum silicon nitride layer on a surface of an underlying layer, comprising:
introducing a pulse of a nitrogen-containing precursor inside a deposition chamber, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a tantalum-containing precursor and a silicon-containing precursor into the underlying layer; and
providing at least one cycle of precursors to form the tantalum silicon nitride layer on the surface, the at least one cycle comprising:
introducing a pulse of the tantalum-containing precursor to contact with and adsorb on the surface;
introducing a purge gas into the deposition chamber;
simultaneously introducing a pulse of the nitrogen-containing precursor and a pulse of the silicon-containing precursor into the chamber; and
introducing the purge gas into the deposition chamber.

44. A method for forming a tantalum silicon nitride layer on a surface of an underlying layer, comprising:
providing at least one cycle of precursors to form a tantalum nitride layer on the surface, wherein the at least one cycle of precursors further comprises sequential introduction of pulses of a nitrogen-containing precursor, a purge gas, a tantalum-containing precursor and the purge gas to form the tantalum nitride layer; and
introducing a pulse of a silicon-containing precursor to contact with and adsorb on the tantalum nitride layer and to form the tantalum silicon nitride layer.

45. A method for forming a titanium silicon nitride layer on a surface of an underlying layer inside a deposition chamber, comprising:
providing at least one cycle of precursors, the at least one cycle comprising:
introducing a pulse of a nitrogen-containing precursor into the deposition chamber, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a titanium-containing precursor and a silicon-containing precursor into the underlying layer;
introducing a pulse of the silicon-containing precursor to contact with and adsorb on the surface; and
introducing a pulse of the titanium-containing precursor to contact with and adsorb on the surface, wherein the pulse of the silicon-containing precursor is introduced after the introduction of the pulse of the nitrogen-containing precursor and before the introduction of the pulse of the titanium-containing precursor.

46. A method for forming a titanium silicon nitride layer on a surface of an underlying layer inside a deposition chamber, comprising:
providing at least one cycle of precursors to form the titanium silicon nitride layer on the surface, the at least one cycle comprising:
introducing a pulse of a nitrogen-containing precursor into the deposition chamber, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a titanium-containing precursor and a silicon-containing precursor into the underlying layer;
introducing a pulse of the titanium-containing precursor to contact with and adsorb on the surface;
purging the deposition chamber with a purge gas;
introducing a pulse of the silicon-containing precursor to contact with and adsorb on the surface, wherein the pulse of the silicon-containing precursor is introduced after the introduction of the pulse of the titanium-containing precurser; and
purging the deposition chamber with the purge gas.

47. A method for forming a titanium silicon nitride layer on a surface of an underlying layer, comprising:
introducing a pulse of a nitrogen-containing precursor inside a deposition chamber, wherein the nitrogen-containing precursor is introduced first to prevent diffusion of a titanium-containing precursor and a silicon-containing precursor into the underlying layer; and
providing at least one cycle of precursors to form the titanium silicon nitride layer on the surface, the at least one cycle comprising:
introducing a pulse of the titanium-containing precursor to contact with and adsorb on the surface;
purging the deDosition chamber with a purge gas;
simultaneously introducing a pulse of the nitrogen-containing precursor and a pulse of the silicon-containing precursor into the deposition chamber; and
purging the deposition chamber with the purge gas.

48. A method for forming a titanium silicon nitride layer on a substrate surface, comprising:
providing at least one cycle of precursors to form a titanium nitride layer on the substrate surface, wherein the at least one cycle further comprises sequential introduction of pulses of a nitrogen-containing precursor, a purge gas, a titanium-containing precursor and the purge gas to form the titanium nitride layer; and
introducing a pulse of a silicon-containing precursor into the chamber to contact with and adsorb on the titanium nitride layer and to form the titanium silicon nitride layer.

49. A method for forming a metal film having an underlying refractory metal silicon nitride layer on a substrate surface inside a deposition chamber, comprising:
depositing the underlying refractory metal silicon nitride layer onto the substrate surface, comprising:
introducing a pulse of a nitrogen-containing precursor first to prevent diffusion of a refractory metal-containing precursor and a silicon-containing precursor;
providing at least one cycle of precursors to form the underlying refractory metal silicon nitride layer, the at least one cycle comprising:
introducing a pulse of the refractory metal-containing precursor;
introducing a purge gas pulse;
introducing a pulse of the nitrogen-containing precursor;
introducing the purge gas pulse;
introducing a pulse of the silicon-containing precursor; and
introducing the purge gas pulse; and

depositing a metal layer over the underlying refractory metal silicon nitride layer.

50. The method of claim 49, wherein tho material of the underlying refractory metal silicon nitride layer comprises a material is selected from the group consisting of tantalum silicon nitride and titanium silicon nitride.

51. The method of claim 50, wherein the metal layer comprises a metal selected from the group consisting of copper and tungsten.

52. A method for forming a metal film having an underlying refractory metal silicon nitride layer on a substrate surface inside a deposition chamber, comprising:
depositing the underlying refractory metal silicon nitride layer onto the substrate surface, comprising:
introducing a pulse of a nitrogen-containing precursor first to prevent diffusion of a refractory metal-containing precursor and a silicon-containing precursor; and
providing at least one cycle of precursors to form the underlying refractory metal silicon nitride layer, the at least one cycle comprising:
introducing a pulse of the refractory metal-containing precursor;
introducing a purge gas pulse:
simultaneously introducing a pulse of the nitrogen-containing precursor and the silicon-containing precursor to contact with and adsorb on the surface; and


depositing a metal layer over the underlying refractory metal silicon nitride layer.

53. The method of claim 52, wherein the material of the underlying refractory metal silicon nitride layer is comprises a material selected from the group consisting of tantalum silicon nitride and titanium silicon nitride.

54. The method of claim 53, wherein the metal layer comprises a metal selected from the group consisting of copper and tungsten.

55. A method for forming a metal film having an underlying refractory metal silicon nitride layer on a substrate surface inside a deposition chamber, comprising:
depositing the underlying refractory metal silicon nitride layer onto the substrate surface such that the underlying refractory metal silicon nitride layer acts as a barrier/adhesion layer for subsequent metallization, wherein depositing the underlying refractory metal silicon nitride layer further comprises:
providing at least one cycle of precursors to form a refractory metal nitride layer on the substrate surface, wherein the at least one cycle of precursors further comprises sequential introduction of pulses of a nitrogen-containing precursor, a purge gas, a refractory metal-containing precursor and the purge gas; and
introducing a pulse of a silicon-containing precursor to contact with and adsorb on the refractory metal nitride layer; and

depositing a metal layer over the underlying refractory metal silicon nitride layer.

56. The method of claim 55, wherein the underlying refractory metal silicon nitride layer is comprises a material selected from the group consisting of tantalum silicon nitride and titanium silicon nitride.

57. The method of claim 56, wherein the metal layer comprises a metal selected from the group consisting of copper and tungsten.