US20030082301A1

US20030082301A1 - Enhanced copper growth with ultrathin barrier layer for high performance interconnects

Info

Publication number: US20030082301A1
Application number: US10/199,415
Authority: US
Inventors: Ling Chen; Hua Chung; Barry Chin; Hong Zhang
Original assignee: Applied Materials Inc
Current assignee: Applied Materials Inc
Priority date: 2001-10-26
Filing date: 2002-07-18
Publication date: 2003-05-01
Also published as: US20050173068A1; US20070003698A1; US20030079686A1; US20070026147A1; US20070099415A1; CN101174577A; US20080038463A1; US20100247767A1; US7780788B2; US8668776B2; US20030082307A1; KR20040058239A; US6916398B2; CN1774525B; CN100524692C; US8293328B2; US8318266B2; US20030124262A1; CN1774525A

Abstract

A method for depositing a refractory metal nitride barrier layer having a thickness of about 20 angstroms or less is provided. In one aspect, the refractory metal nitride layer is formed by introducing a pulse of a metal-containing compound followed by a pulse of a nitrogen-containing compound. The refractory metal nitride barrier layer provides adequate barrier properties and allows the grain growth of the first metal layer to continue across the barrier layer into the second metal layer thereby enhancing the electrical performance of the interconnect.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. Provisional Patent Application Serial No. 60/346,086, filed Oct. 26, 2001, which is incorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention relate to a method for manufacturing integrated circuit devices. More particularly, embodiments of the invention relate to forming thin barrier layers using cyclic or atomic layer deposition.

2. Description of the Related Art

Copper has recently become a choice metal for filling sub-micron high aspect ratio, interconnect features because copper and its alloys have lower resistivities than aluminum. However, copper and its alloys have a propensity to diffuse into surrounding materials such as silicon oxide, silicon, and other dielectric materials for example, causing an increase in the contact resistance of the circuit. Copper and its alloys also have a propensity to diffuse into surrounding elements such as transistor gates, capacitor dielectrics, transistor wells, transistor channels, electrical barrier regions, interconnects, among other known elements of integrated circuits.

Barrier layers are, therefore, deposited prior to copper metallization to prevent or impede the diffusion of copper atoms. Barrier layers typically consist of a refractory metal such as tungsten, titanium, tantalum, and nitrides thereof, which all have a greater resistivity than copper. Of this group, tantalum nitride is one of the most desirable elements for use as a barrier layer because it has one of the lowest resistivities of refractory metal nitrides and makes a good adhesion layer for copper metallization.

To deposit a barrier layer within a feature, the barrier layer must be deposited on the bottom of the feature as well as the sidewalls thereof. Therefore, the additional amount of the barrier layer on the bottom of the feature not only increases the overall resistance of the feature, but also forms an obstruction between higher and lower metal interconnects of a multi-layered interconnect structure.

It is especially difficult to deposit a suitable barrier layer in features having aspect ratios greater than about 3:1 using conventional deposition techniques. Usually, the barrier layer bridges the opening of the narrow features resulting in the formation of one or more voids or discontinuities within the feature. Since voids increase the resistance and reduce the electromigration resistance of the feature, features having voids make poor and unreliable electrical contacts.

There is a need, therefore, for an improved method for depositing a thin, conformal barrier layer in low aspect ratio features.

SUMMARY OF THE INVENTION

A method for depositing a conformal refractory metal nitride layer having a thickness of about 20 angstroms or less is provided. The refractory metal nitride layer is formed by introducing a pulse of a metal-containing compound followed by a pulse of a nitrogen-containing compound. The refractory metal nitride layer may further be formed by introducing a pulse of a silicon-containing compound. The refractory metal nitride layer provides excellent barrier properties and permits the continuous, uninterrupted growth of a higher level conductive metal layer on a lower level conductive metal layer. In one aspect, the conductive metal layers each contain copper or copper alloys, and the refractory metal nitride layer contains tantalum nitride. In another aspect, the refractory metal layer contains titanium silicon nitride.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the present 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. [0011]
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. [0012]
FIG. 1 illustrates a schematic, partial cross section of an [0013] exemplary processing chamber 200 for use in a method of forming a barrier layer according to each of the embodiments of the present invention.
FIGS. [0014] 2A-2E illustrate steps for forming a metal interconnect in accordance with embodiments of a cycled deposition technique described herein.
FIG. 3 is a TEM image of a metal interconnect having a barrier layer deposited in accordance with embodiments of a cyclical deposition technique described herein. [0015]
FIG. 4 is a TEM image showing a continuous copper grain growth across a barrier layer deposited in accordance with embodiments of a cyclical deposition technique described herein.[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Embodiments of the present invention generally provide a method of forming a barrier layer through which conductive metal can be grown. In one embodiment, a cyclical deposition process is used to form a refractory metal nitride layer having a thickness less than about 20 angstroms. In one aspect of this embodiment, the refractory metal nitride layer is a tantalum nitride (TaN) layer that is preferably about 10 angstroms thick. In another aspect of this embodiment, the refractory metal nitride layer is a ternary material, such as titanium silicon nitride, for example. [0017]
The barrier layers deposited according to the cyclical deposition techniques described herein provide excellent barrier properties and permit the continuous growth of conductive metal layers thereon. The barrier layers are particularly useful between higher and lower level conductive metal interconnects. The barrier layers significantly enhance the metal interconnect electrical performance by lowering the overall electrical resistance of the feature and also providing good device reliability. [0018]
The barrier layers deposited according to the cyclical deposition methods described herein show evidence of an epitaxial growth phenomenon. In other words, the barrier layers take on the same or substantially the same crystallographic characteristics as the underlying layer. As a result, a substantially single crystal is grown such that there is no void formation at an interface between the barrier layer and the underlying layer. Likewise, subsequent metal layers deposited over the barrier layers exhibit the same or substantially the same epitaxial growth characteristics that continue the formation of the single crystal. Accordingly, no void formation is produced at this interface. The resulting structure resembling a single crystal eliminates voids formation, thereby substantially increasing device reliability. The single crystal structure also reduces the overall resistance of the interconnect feature while still providing excellent barrier properties. Furthermore, it is believed that the single crystalline growth reduces the susceptibility of electromigration and stress migration due to the conformal and uniform crystalline orientation across the interconnect material interfaces. [0019]
A TaN barrier layer having a thickness of about 20 angstroms or less, about 10 angstroms in at least one embodiment, is deposited by providing one or more pulses of a tantalum-containing compound at a flow rate between about 100 sccm and about 1,000 sccm for a time period of about 1.0 second or less and one or more pulses of a nitrogen-containing compound at a, flow rate between about 100 sccm and about 1,000 sccm for a time period of about 1.0 second or less to a reaction zone having a substrate disposed therein. Exemplary tantalum-containing compounds include pentaethyl methylamino-tantalum (PEMAT), pentadiethylamino-tantalum (PDEAT), pentadimethylamino-tantalum (PDMAT) and any derivatives of PEMAT, PDEAT, and PDMAT. Exemplary tantalum-containing compounds also include t-butylimino tris(diethylamino) tantalum (TBTDET), t-butylimino tris(dimethylamino) tantalum (TBTDMT), bis(cyclopentadienyl) tantalum trihydride, bis (methylcyclopentadienyl) tantalum trihydride, and tantalum halides, TaX[0020] ₅, where X is fluorine (F), bromine (Br) or chlorine (Cl), and/or derivatives thereof. Exemplary nitrogen-containing compounds include nitrogen gas, ammonia, hydrazine, methylhydrazine, dimethlyhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, and derivatives thereof.
It is to be understood that these compounds or any other compound not listed above may be a solid, liquid, or gas at room temperature. For example, PDMAT is a solid at room temperature and TBTDET is a liquid at room temperature. Accordingly, the non-gas phase precursors are subjected to a sublimation or vaporization step, which are both well known in the art, prior to introduction into the processing chamber. A carrier gas, such as argon, helium, nitrogen, hydrogen, or a mixture thereof, may also be used to help deliver the compound into the processing chamber, as is commonly known in the art. [0021]
Each pulse is performed sequentially, and is accompanied by a separate flow of non-reactive gas at a rate between about 200 sccm and about 1,000 sccm. The separate flow of non-reactive gas may be pulsed between each pulse of the reactive compounds or the separate flow of non-reactive gas may be introduced continuously throughout the deposition process. The separate flow of non-reactive gas, whether pulsed or continuous, serves to remove any excess reactants from the reaction zone to prevent unwanted gas phase reactions of the reactive compounds, and also serves to remove any reaction by-products from the processing chamber, similar to a purge gas. In addition to these services, the continuous separate flow of non-reactive gas helps deliver the pulses of reactive compounds to the substrate surface similar to a carrier gas. The term “non-reactive gas” as used herein refers to a single gas or a mixture of gases that does not participate in the metal layer formation. Exemplary non-reactive gases include argon, helium, nitrogen, hydrogen, and combinations thereof. [0022]
In another embodiment, a ternary barrier layer having a thickness less than about 20 angstroms, preferably about 10 angstroms in at least one embodiment, is deposited by providing one or more pulses of a refractory metal-containing compound at a flow rate between about 10 sccm and about 1,000 sccm, one or more pulses of a nitrogen-containing compound at a flow rate between about 100 sccm and about 5,000 sccm, and one or more pulses of a silicon-containing compound at a flow rate between about 5 sccm and about 500 sccm. Each pulse lasts about 1.0 second or less, and can be adjusted to provide a desirable composition, silicon incorporation level, thickness, density, and step coverage of the refractory metal silicon nitride layer. A “ternary barrier layer” as used herein refers to a material having a composition that includes three major elements, such as titanium, nitrogen and silicon, for example. [0023]
Exemplary titanium-containing compounds include tetrakis (dimethylamino) titanium (TDMAT), tetrakis (ethylmethylamino) titanium (TEMAT), tetrakis (diethylamino) titanium (TDEAT), titanium tetrachloride (TiCl[0024] ₄), titanium iodide (Til₄), titanium bromide (TiBr₄), and other titanium halides. Exemplary silicon-containing compounds include silane, disilane, methylsilane, dimethylsilane, chlorosilane, dichlorosilane, and trichlorosilane. Exemplary nitrogen-containing compounds include nitrogen gas, ammonia, hydrazine, methylhydrazine, dimethlyhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, and derivatives thereof.
As mentioned above, these compounds or any other compound not listed above may be a solid, liquid, or gas at room temperature. The non-gas phase precursors must be subjected to a sublimation or vaporization step, which are both well known in the art, prior to introduction into the processing chamber. A carrier gas, such as argon, helium, nitrogen, hydrogen, or a mixture thereof, may also be used to help deliver the compound into the processing chamber, as is commonly known in the art. [0025]
Similar to the process described above, each pulse of compound is performed sequentially, and is accompanied by a separate flow of non-reactive gas. The separate flow of non-reactive gas may be pulsed between each pulse of reactive compound or the separate flow of non-reactive gas may be introduced continuously throughout the deposition process. Exemplary non-reactive gases include argon, helium, nitrogen, hydrogen, and combinations thereof. [0026]
A “compound” is intended to include one or more precursors, reductants, reactants, and catalysts. Each compound may be a single compound or a mixture/combination of two or more compounds. [0027]
A “thin layer” as used herein refers to a layer of material deposited on a substrate surface having a thickness of about 20 angstroms or less, such as about 10 angstroms. A “feature” as used herein refers to a via, contact, line, or any other interconnect facet, e.g., vertical or horizontal interconnect, having an aspect ratio (height to width ratio) of about 4:1 or greater. A “substrate surface”, as used herein, refers to any substrate surface upon which film processing is performed. For example, a substrate surface may include silicon, silicon oxide, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal alloys, and other conductive materials, depending on the application. A substrate surface may also include dielectric materials such as silicon dioxide and carbon doped silicon oxides. [0028]
“Cyclical deposition” as used herein refers to the sequential introduction of two or more compounds to deposit a thin layer on a substrate surface. The two or more compounds are sequentially introduced into a reaction zone of a processing chamber. Each compound is separated by a time delay/pause to allow each compound to adhere and/or react on the substrate surface. In one aspect, a first compound or compound A is dosed/pulsed into the reaction zone followed by a first time delay/pause. Next, a second compound or compound B is dosed/pulsed into the reaction zone followed by a second time delay. When a ternary material is desired, such as titanium silicon nitride, for example, a third compound (C), is dosed/pulsed into the reaction zone followed by a third time delay. These sequential tandems of a pulse of reactive compound followed by a time delay may be repeated indefinitely until a desired film or film thickness is formed on the substrate surface. [0029]
A “pulse/dose” as used herein is intended to refer to a quantity of a particular compound that is intermittently or non-continuously introduced into a reaction zone of a processing chamber. The quantity of a particular compound within each pulse may vary over time, depending on the duration of the pulse. A particular compound may include a single compound or a mixture/combination of two or more compounds. [0030]
A “reaction zone” is intended to include any volume that is in fluid communication with a substrate surface being processed. The reaction zone may include any volume within a processing chamber that is between a gas source and the substrate surface. For example, the reaction zone includes any volume downstream of a dosing valve in which a substrate is disposed. [0031]
The durations for each pulse/dose are variable and may be adjusted to accommodate, for example, the volume capacity of the processing chamber as well as the capabilities of a vacuum system coupled thereto. Additionally, the dose time of a compound may vary according to the flow rate of the compound, the pressure of the compound, the temperature of the compound, the type of dosing valve, the type of control system employed, as well as the ability of the compound to adsorb onto the substrate surface. Dose times may also vary based upon the type of layer being formed and the geometry of the device being formed. [0032]
Typically, the duration for each pulse/dose or “dose time” is typically about 1.0 second or less. However, a dose time can range from microseconds to milliseconds to seconds, and even to minutes. In general, a dose time should be long enough to provide a volume of compound sufficient to adsorb/chemisorb onto substantially the entire surface of the substrate and form a layer of the compound thereon. [0033]
FIG. 1 illustrates a schematic, partial cross section of an [0034] exemplary processing chamber 200 for use in a method of forming a barrier layer according to each of the embodiments of the present invention. Such a processing chamber 200 is available from Applied Materials, Inc. located in Santa Clara, Calif., and a brief description thereof follows. A more detailed description may be found in commonly assigned U.S. patent application Ser. No. 10/032,284, entitled “Gas Delivery Apparatus and Method For Atomic Layer Deposition”, filed on Dec. 21, 2001, which is incorporated herein by reference.
The [0035] processing chamber 200 may be integrated into an integrated processing platform, such as an Endura™ platform also available from Applied Materials, Inc. Details of the Endura™ platform are described in commonly assigned U.S. patent application Ser. No. 09/451,628, entitled “Integrated Modular Processing Platform”, filed on Nov. 30, 1999, which is incorporated by reference herein.
The [0036] chamber 200 includes a chamber body 202 having a slit valve 208 formed in a sidewall 204 thereof and a substrate support 212 disposed therein. The substrate support 212 is mounted to a lift motor 214 to raise and lower the substrate support 212 and a substrate 210 disposed thereon. The substrate support 212 may also include a vacuum chuck, an electrostatic chuck, or a clamp ring for securing the substrate 212 to the substrate support 212 during processing. Further, the substrate support 212 may be heated using an embedded heating element, such as a resistive heater, or may be heated using radiant heat, such as heating lamps disposed above the substrate support 212. A purge ring 222 may be disposed on the substrate support 212 to define a purge channel 224 that provides a purge gas to prevent deposition on a peripheral portion of the substrate 210.
A [0037] gas delivery apparatus 230 is disposed at an upper portion of the chamber body 202 to provide a gas, such as a process gas and/or a purge gas, to the chamber 200. A vacuum system 278 is in communication with a pumping channel 279 to evacuate gases from the chamber 200 and to help maintain a desired pressure or a desired pressure range inside a pumping zone 266 of the chamber 200.
The [0038] gas delivery apparatus 230 includes a chamber lid 232 having an expanding channel 234 formed within a central portion thereof. The chamber lid 232 also includes a bottom surface 260 extending from the expanding channel 234 to a peripheral portion of the chamber lid 232. The bottom surface 260 is sized and shaped to substantially cover the substrate 210 disposed on the substrate support 212. The expanding channel 234 has an inner diameter that gradually increases from an upper portion 237 to a lower portion 235 adjacent the bottom surface 260 of the chamber lid 232. The velocity of a gas flowing therethrough decreases as the gas flows through the expanding channel 234 due to the expansion of the gas. The decreased gas velocity reduces the likelihood of blowing off reactants adsorbed on the surface of the substrate 210.
The [0039] gas delivery apparatus 230 also includes at least two high speed actuating valves 242 having one or more ports. At least one valve 242 is dedicated to each reactive compound. For example, a first valve is dedicated to a refractory metal-containing compound, such as tantalum and titanium, and a second valve is dedicated to a nitrogen-containing compound. When a ternary material is desired, a third valve is dedicated to an additional compound, such as a silicon-containing compound if a silicide is desired.
The valves [0040] 242 may generally be any type of valve capable of reliably, repeatedly, and precisely metering the desired precursors at the desired rate of introduction. In some cases, dosing may be as fast as 1-2 milliseconds (msec). As one example, the valves 242 may be electronically controlled (EC) valves, which are commercially available from Fujikin of Japan as part number FR-21-6.35 UGF-APD. The valves 242 precisely and repeatedly deliver short pulses of the reactive compounds into the chamber body 202. The on/off cycles or pulses of the valves 242 are less than about 100 msec. The valves 242 can be directly controlled by a system computer, such as a mainframe for example, or controlled by a chamber/application specific controller, such as a programmable logic computer (PLC) which is described in more detail in the co-pending U.S. patent application Ser. No. 09/800,881, entitled “Valve Control System For ALD Chamber”, filed on Mar. 7, 2001, which is incorporated by reference herein.
An exemplary process for forming a TaN barrier layer on a 200 mm wafer using a cyclical deposition process of alternate/sequential pulses of PDMAT and ammonia is described below. The process may be performed within a processing chamber, such as the [0041] processing chamber 200 described in FIG. 1. PDMAT is a preferred tantalum-containing compound for a number of reasons. PDMAT is relatively stable, and has a vapor pressure which makes it easy to deliver. PDMAT may also be produced with a low halide content, such as less than 100 ppm, and may even be produced with a halide content of less than 30 ppm or even less than 5 ppm. Not wishing to be bound by theory, it is believed that an organo-metallic precursor with a low halide content is beneficial because halides (such as chlorine) incorporated in the barrier layer may attack the copper layer deposited thereover.
To deposit the TaN layer, an inert/purge gas such as argon is first introduced into the [0042] processing chamber 200 to stabilize the pressure and temperature therein. This separate flow of gas flows continuously during the deposition process such that only the separate flow of gas flows between pulses of each compound. After the chamber pressure and temperature have been stabilized between about 200° C. and about 300° C. at about 1 Torr to about 5 Torr, a first pulse of PDMAT is provided from the gas source 238 at a flow rate between about between about 100 sccm and about 400 sccm, with a pulse time of about 0.6 seconds or less. A pulse of ammonia is then provided from the gas source 239 at a flow rate between about 200 sccm and about 600 sccm, with a pulse time of about 0.6 seconds or less.
A pause between pulses of PDMAT and ammonia is about 1.0 second or less, about 0.5 seconds or less, or about 0.1 seconds or less. A pause after the pulse of ammonia is also about 1.0 second or less, about 0.5 seconds or less, or about 0.1 seconds or less. Argon gas flowing between about 100 sccm and about 1,000 sccm, such as between about 100 sccm and about 400 sccm, is continuously provided from the [0043] gas source 240 through each valve 242. In one aspect, at least a portion of a pulse of PDMAT may still be in the chamber when at a least a portion of a pulse of ammonia enters so that some co-reaction or gas phase co-reaction takes place. In another aspect, the duration of the purge gas and/or pump evacuation is designed to prevent the pulses of PDMAT and ammonia from mixing together in the reaction zone.
The heater temperature is maintained between about 100° C. and about 300° C. at a chamber pressure between about 1.0 and about 5.0 Torr. Each cycle consisting of a pulse of PDMAT, pause, pulse of ammonia, and pause provides a tantalum nitride layer having a thickness between about 0.3 Å and about 1.0 Å per cycle. The alternating sequence may be repeated until the desired thickness is achieved, which is less than about 20 Å, such as about 10 Å. Accordingly, the deposition method requires between 10 and 70 cycles, more typically between 20 and 30 cycles. [0044]
A similar deposition method is used to deposit a barrier layer consisting of titanium silicon nitride. Each cycle consists of a pulse of a titanium-containing compound, a pause, a pulse of a silicon-containing compound, a pause, a pulse of a nitrogen-containing compound, and a pause. In one aspect, each cycle consists of a pulse of TDMAT, a first pause, a pulse of silane, a second pause, a pulse of ammonia, and a third pause. [0045]
To initiate the cyclical deposition of a Ti[0046] _xSi_yN layer, argon is introduced into the processing chamber 200 to stabilize the chamber pressure between about 1 Torr and about 5 Torr and the chamber temperature between about 200° C. and about 300° C. This separate flow of argon flows continuously during the deposition process such that only the argon flows between pulses of each compound. The separate flow of argon flows between about 100 sccm and about 1,000 sccm, such as between about 100 sccm and about 400 sccm.
After the chamber pressure and temperature have been stabilized at about 250° C. and 5 Torr, a pulse of TDMAT is provided at a flow rate between about between about 10 sccm and about 1,000 sccm, with a pulse time of about 0.6 seconds or less. A pulse of silane is then provided at a flow rate between about 5 sccm and about 500 sccm, with a pulse time of about 1 second or less. A pulse of ammonia is then provided at a flow rate between about 100 sccm and about 5,000 sccm, with a pulse time of about 0.6 seconds or less. [0047]
A pause between pulses of TDMAT and silane is about 1.0 second or less, about 0.5 seconds or less, or about 0.1 seconds or less. A pause between pulses of silane and ammonia is about 1.0 second or less, about 0.5 seconds or less, or about 0.1 seconds or less. A pause after the pulse of ammonia is also about 1.0 second or less, about 0.5 seconds or less, or about 0.1 seconds or less. In one aspect, a pulse of TDMAT may still be in the chamber when a pulse of silane enters, and a pulse of silane may still be in the chamber when a pulse of ammonia enters. [0048]
The heater temperature is maintained between about 100° C. and about 300° C. at a chamber pressure between about 1.0 and about 5.0 Torr. Each cycle consisting of a pulse of TDMAT, pause, pulse of silane, pause, pulse of ammonia, and pause provides a titanium silicon nitride layer having a thickness between about 0.3 Å and about 1.0 Å per cycle. The alternating sequence may be repeated until the desired thickness is achieved, which is less than about 20 Å, such as about 10 Å. Accordingly, the deposition method requires between 10 and 70 cycles. [0049]
FIGS. [0050] 2A-2D are cross sectional views of a wafer at different stages of a multi-layer metal interconnect fabrication sequence incorporating a thin barrier layer deposited using a cyclical deposition process described herein. FIG. 2A shows a lower level metal interconnect 110 having a dielectric layer 112 formed thereon. The dielectric layer 112 may be any dielectric material including a low k dielectric material, whether presently known or yet to be discovered. For example, the dielectric layer 112 may be a silicon oxide or a carbon doped silicon oxide, for example. The dielectric layer 112 has been etched to form a feature 114 therein using conventional and well-known techniques. The feature 114 may be a plug, via, contact, line, wire, or any other interconnect facet. The feature 114 has vertical sidewalls 116 and a bottom 118, typically having an aspect ratio of 4:1 or greater, such as 6:1. The bottom 118 exposes at least a portion of the lower level metal interconnect 110.
Referring to FIG. 2B, a [0051] barrier layer 130 is deposited using the techniques described above on the bottom 118 as well as the side walls 116 of the feature 114. The barrier layer 130 has a thickness less than about 20 Å, preferably about 10 Å. The barrier layer may be a binary material or a ternary material as discussed above.
Optionally, the patterned or etched [0052] substrate dielectric layer 112 may be cleaned to remove native oxides or other contaminants from the surface thereof prior to depositing the barrier layer 130. For example, reactive gases may be excited into a plasma within a remote plasma source chamber and delivered to the processing chamber 200. An exemplary remote plasma chamber is a Reactive Pre-clean II chamber available from Applied Materials, Inc., located in Santa Clara, Calif. Alternatively, the processing chamber 200 may be modified to deliver the pre-cleaning gas plasma through existing gas inlets.
In one aspect, the reactive pre-clean process forms radicals from a plasma of one or more reactive gases such as argon, helium, hydrogen, nitrogen, fluorine-containing compounds, and combinations thereof. For example, a reactive gas may include a mixture of tetrafluorocarbon (CF[0053] ₄) and oxygen (O₂), or a mixture of helium (He) and nitrogen trifluoride (NF₃).
The plasma is typically generated by applying a power of about 500 to 2,000 watts RF at a frequency of about 200 KHz to 114 MHz. The flow of reactive gases ranges between about 100 and about 1,000 sccm and the plasma treatment lasts for about 10 to about 150 seconds. Preferably, the plasma is generated in one or more treatment cycles and purged between cycles. For example, four treatment cycles lasting 35 seconds each is effective. [0054]
In another aspect, the patterned or etched [0055] dielectric layer 112 may be pre-cleaned first using an argon plasma and then a hydrogen plasma. A processing gas having greater than about 50% argon by number of atoms is introduced at a pressure of about 0.8 mtorr. A plasma is struck to subject the dielectric layer 112 to an argon sputter cleaning environment. The argon plasma is preferably generated by applying between about 50 watts and about 500 watts of RF power. The argon plasma is maintained for between about 10 seconds and about 300 seconds to provide sufficient cleaning time for the deposits that are not readily removed by a reactive hydrogen plasma. Following the argon plasma, the chamber pressure is increased to about 140 mTorr, and a processing gas consisting essentially of hydrogen and helium is introduced into the processing region. Preferably, the processing gas comprises about 5% hydrogen and about 95% helium. The hydrogen plasma is generated by applying between about 50 watts and about 500 watts power. The hydrogen plasma is maintained for about 10 seconds to about 300 seconds.
Referring to FIGS. 2C and 2D, a metal, metal alloy, or a combination thereof is deposited over the [0056] barrier layer 130 to at least partially fill the feature 114. In one aspect, a metal seed layer 140 of a copper-containing material is first deposited having a thickness of about 1,000 Å to about 2,000 Å. Next, a copper metal layer 142 is deposited over the seed layer 140 to fill the feature 114.
In one aspect, the copper-containing [0057] seed layer 140 is deposited using high density plasma physical vapor deposition (HDP-PVD) to enable good conformal coverage. One example of a HDP-PVD chamber is the Ionized Metal Plasma (IMP) Vectra™ chamber, available from Applied Materials, Inc. of Santa Clara, Calif. The IMP chamber may also be integrated into an Endura™ platform, also available from Applied Materials, Inc. Of course, other techniques, such as physical vapor deposition, chemical vapor deposition, electroless plating, and electroplating, may be used.
The IMP chamber includes a target, coil, and biased substrate support member. To form the [0058] copper seed layer 140, a power between about 0.5 kW and about 5 kW is applied to the target, and a power between about 0.5 kW and 3 kW is applied to the coil. A power between about 200 and about 500 W at a frequency of about 13.56 MHz is applied to bias the substrate. Argon is flowed into the chamber at a rate of about 35 sccm to about 85 sccm, and nitrogen may be added to the chamber at a rate of about 5 sccm to about 100 sccm. The substrate support member is heated to a temperature between about 50° C. and 250° C. as the pressure of the chamber is typically between about 5 mTorr to about 100 mTorr.
Referring to FIG. 2D, the [0059] copper metal layer 142 may be deposited over the copper seed layer 140 using CVD, PVD, electroless, or electroplating techniques. In one aspect, the copper layer 142 is formed using an electroplating cell, such as the Electra™ Cu ECP system, available from Applied Materials, Inc., of Santa Clara, Calif. The Electra™ Cu ECP system may also be integrated into an Endura™ platform also available from Applied Materials, Inc. A copper electrolyte solution and copper electroplating technique is described in commonly assigned U.S. Pat. No. 6,113,771, entitled “Electro-deposition Chemistry”, which is incorporated by reference herein. Typically, the electroplating bath has a copper concentration greater than about 0.7M, a copper sulfate concentration of about 0.85, and a pH of about 1.75. The electroplating bath may also contain various additives as is well known in the art. The temperature of the bath is between about 15° C. and about 25° C. The bias is between about −15 volts to about 15 volts. In one aspect, the positive bias ranges from about 0.1 volts to about 10 volts and the negatives bias ranges from about −0.1 to about −10 volts.
Optionally, an anneal treatment may be performed following copper deposition whereby the wafer is subjected to a temperature between about 100° C. and about 400° C. for about 10 minutes to about 1 hour, preferably about 30 minutes. A non-reactive gas such as helium, hydrogen, nitrogen, or a mixture thereof is introduced at a rate of 100 to about 10,000 sccm. The chamber pressure is maintained between about 2 Torr and about 10 Torr. The RF power is about 200 W to about 1,000 W at a frequency of about 13.56 MHz, and the preferable substrate spacing is between about 300 mils and about 800 mils. [0060]
Following deposition, the top portion of the resulting structure may be planarized following the copper metal deposition. A chemical mechanical polishing (CMP) apparatus may be used, such as the Mirra™ System available from Applied Materials, Santa Clara, Calif., for example. For example, portions of the [0061] copper 140 and the dielectric 112 are removed from the top of the structure leaving a fully planar surface. Optionally, the intermediate surfaces of the structure may be planarized between the deposition of the subsequent layers described above.
As stated above, the processing steps of the embodiments described herein may be performed in an integrated processing platform such as the Endura™ platform available from Applied Materials, Inc. of Santa Clara, Calif. To facilitate the control and automation of the overall system, the integrated processing system may include a [0062] controller 140 comprising a central processing unit (CPU) 142, memory 144, and support circuits 146. The CPU 142 may be one of any form of computer processors that are used in industrial settings for controlling various drives and pressures. The memory 144 is connected to the CPU 142, and may be one or more of a readily available memory such as random access memory (RAM), read only memory (ROM), floppy disk, hard disk, or any other form of digital storage, local or remote. Software instructions and data can be coded and stored within the memory 144 for instructing the CPU 142. The support circuits 146 are also connected to the CPU 142 for supporting the processor 142 in a conventional manner. The support circuits 146 may include cache, power supplies, clock circuits, input/output circuitry, subsystems, and the like.
FIG. 3 is a transmission electron microscope (TEM) image of a [0063] feature 300 having a titanium nitride barrier layer 310 deposited therein according to the deposition techniques described above. The feature 300 had an aspect ratio of 5:1 and was formed on a 200 mm wafer. The barrier layer 310 consisted of tantalum nitride and was deposited at 250° C. and 2 Torr. Each cycle lasted about 2 seconds and 30 cycles were performed. The tantalum nitride barrier layer 310 had a thickness of about 15 angstroms. As shown, the barrier layer 310 is conformal and shows good step coverage throughout the entire feature 300.
FIG. 4 is a TEM image showing a partial cross sectional view of a multilevel, [0064] interconnect structure 400. The multi-level, interconnect structure 400 included a lower level copper interconnect 405, a tantalum nitride barrier layer 410, and an upper level copper interconnect 420. As shown, the copper grain growth of the lower level copper interconnect 405 extended across the barrier layer 410 into the upper level copper interconnect 420. The barrier layer 410 consisted of tantalum nitride and was deposited at 250° C. and 2 Torr. Each cycle lasted about 2 seconds and 30 cycles were performed. The barrier layer 410 had a thickness of about 10 angstroms, which was sufficient to inhibit copper migration into the dielectric material, but not establish a growth pattern of its own.
It is believed that a refractory metal nitride layer having a thickness greater than about 20 angstroms will terminate the growth pattern of the lower level metal interconnect. A refractory metal nitride layer having a thickness of about 20 angstroms or more will establish a distinct growth pattern of its own, which would be initially adopted by the higher interconnect until the higher interconnect reaches a particular thickness and establishes its own pattern, thereby forming a different crystal structure. This phenomenon occurs because a growth pattern of a subsequently deposited layer typically resembles a growth pattern of an underlying layer during its initial stages of deposition, but the subsequent layer then takes on its own, inherent pattern once the subsequent layer reaches a particular thickness. [0065]
Tantalum nitride, for example, has a natural inclination to form an amorphous structure at about 20 angstroms or more. Below about 20 angstroms, TaN resembles the growth pattern of its underlying layer. Therefore, a subsequent copper interconnect layer was surprisingly grown across a barrier layer deposited according to the methods of the present invention exhibiting a similar growth pattern as the underlying copper interconnect. [0066]
The barrier layers [0067] 310, 410 shown and described with reference to FIGS. 3 and 4 were measured using a TEM instrument. It can be appreciated that a margin of error is present with this kind of measurement technique as well as any other measurement technique for determining a thickness of a deposited layer. Therefore, the thicknesses provided herein are approximate and quantified according to the best available known techniques and are not intended to limit the scope of the present invention.
While the foregoing is directed to embodiments of the present 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. [0068]

Claims

1. A method for forming a refractory metal nitride layer, comprising:

alternately pulsing a metal-containing compound and a nitrogen-containing compound until a refractory metal nitride layer having a thickness that exhibits a crystalline like structure and is sufficient to inhibit atomic migration is deposited over at least a portion of a substrate surface.

2. The method of claim 1, wherein the refractory metal nitride layer comprises tantalum nitride.

3. The method of claim 1, wherein the pulsing occurs at a pressure between about 1 and about 5 Torr at a temperature between about 200° C. and about 300° C.

4. The method of claim 1, wherein each pulse is repeated until the refractory metal nitride layer has a thickness less than about 20 angstroms.

5. The method of claim 1, wherein each pulse is repeated until the refractory metal nitride layer has a thickness of about 10 angstroms.

6. The method of claim 1, wherein the refractory metal nitride layer has a thickness of about 10 angstroms.

7. The method of claim 1, wherein the alternately pulsing is repeated between about 10 and about 70 times to form the refractory metal nitride layer.

8. The method of claim 1, further comprising flowing a non-reactive gas continuously during each pulse of the metal-containing compound and each pulse of the nitrogen-containing compound.

9. The method of claim 8, wherein the non-reactive gas comprises argon, nitrogen, helium, or a combination thereof.

10. The method of claim 8, wherein the non-reactive gas has a flowrate of about 200 sccm to about 1,000 sccm.

11. The method of claim 1, wherein each pulse of the metal-containing compound has a flow rate of about 100 sccm to about 1,000 sccm.

12. The method of claim 1, wherein each pulse of the nitrogen-containing compound has a flow rate of about 100 sccm to about 1,000 sccm.

13. The method of claim 1, wherein each pulse of the metal-containing compound and the nitrogen-containing is separated by a time delay.

14. The method of claim 13, wherein each time delay is sufficient for a volume of the metal-containing compound or a volume of the nitrogen-containing compound to adsorb onto the substrate surface.

15 The method of claim 14, wherein the time delay is sufficient to remove any non-adsorbed molecules from the substrate surface.

16. The method of claim 1, wherein the nitrogen-containing compound is selected from a group consisting of nitrogen gas, ammonia, hydrazine, methylhydrazine, dimethlyhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, and derivatives thereof, and combinations thereof.

17. The method of claim 1, wherein the metal-containing compound is selected from a group consisting of pentaethyl methylamino-tantalum (PEMAT), pentadiethylamino-tantalum (PDEAT), pentadimethylamino-tantalum (PDMAT), t-butylimino tris(diethylamino) tantalum (TBTDET), t-butylimino tris(dimethylamino) tantalum (TBTDMT), bis(cyclopentadienyl) tantalum trihydride, bis (methylcyclopentadienyl) tantalum trihydride, tantalum fluoride, tantalum bromide, tantalum chloride, derivatives thereof, and combinations thereof.

18. A method for forming a refractory metal nitride layer, comprising:

alternately pulsing a metal-containing compound, a silicon-containing compound, and a nitrogen-containing compound until a refractory metal silicon nitride layer having a thickness less than about 20 angstroms is deposited over at least a portion of a substrate surface.

19. The method of claim 18, wherein the refractory metal silicon nitride layer comprises titanium silicon nitride.

20. The method of claim 18, wherein the pulsing occurs at a pressure of about 2 Torr and a temperature of about 250° C.

21. The method of claim 18, wherein each pulse is repeated until the refractory metal silicon nitride layer has a maximum thickness that still exhibits a crystalline like structure.

22. The method of claim 18, wherein each pulse is repeated until the refractory metal nitride layer has a thickness of about 10 angstroms.

23. The method of claim 18, wherein the refractory metal silicon nitride layer has a thickness of about 10 angstroms.

24. The method of claim 18, wherein the alternately pulsing is repeated between about 10 and about 70 times to form the 20 angstrom refractory metal silicon nitride layer.

25. The method of claim 18, further comprising flowing a non-reactive gas continuously during each pulse of the metal-containing compound, each pulse of the silicon-containing compound, and each pulse of the nitrogen-containing compound.

26. The method of claim 25, wherein the non-reactive gas comprises argon.

27. The method of claim 25, wherein the non-reactive gas has a flowrate of about 100 sccm to about 1,000 sccm.

28. The method of claim 1, wherein each pulse of the metal-containing compound, each pulse of the silicon-containing compound, and each pulse of the nitrogen-containing is separated by a time delay.

29. The method of claim 28, wherein each time delay is sufficient for a volume of the metal-containing compound, a volume of the silicon-containing compound, or a volume of the nitrogen-containing compound to adsorb onto the substrate surface.

30 The method of claim 29, wherein the time delay is sufficient to remove any non-adsorbed molecules from the substrate surface.

31. The method of claim 18, wherein the nitrogen-containing compound is selected from a group consisting of nitrogen gas, ammonia, hydrazine, methylhydrazine, dimethlyhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, and derivatives thereof, and combinations thereof.

32. The method of claim 18, wherein the metal-containing compound is selected from a group consisting of tetrakis (dimethylamino) titanium (TDMAT), tetrakis (ethylmethylamino) titanium (TEMAT), tetrakis (diethylamino) titanium (TDEAT), titanium tetrachloride (TiCl₄), titanium iodide (Til₄), titanium bromide (TiBr₄), and combinations thereof.

33. The method of claim 18, wherein the silicon-containing compound is selected from a group consisting of silane, disilane, methylsilane, dimethylsilane, chlorosilane (SiH₃Cl), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiHCl₃), and combinations thereof.

34. A method for forming a metal interconnect on a substrate, comprising:

depositing a first metal layer on a substrate surface;

depositing a refractory metal nitride layer having a thickness less than about 20 angstroms over at least a portion of the first metal layer by alternately introducing one or more pulses of a metal-containing compound and one or more pulses of a nitrogen-containing compound; and

depositing a second metal layer over the refractory metal nitride layer.

35. The method of claim 34, wherein the refractory metal nitride layer comprises tantalum nitride.

36. The method of claim 34, wherein a grain growth of the first metal layer continues across the barrier layer into the second metal layer.

37. The method of claim 34, wherein each pulse is repeated until the refractory metal nitride layer has a maximum thickness that still exhibits a crystalline like structure.

38. The method of claim 34, wherein each pulse is repeated until the refractory metal nitride layer has a thickness of about 10 angstroms.

39. The method of claim 34, wherein the refractory metal nitride layer has a thickness of about 10 angstroms.

40. The method of claim 34, wherein the metal layers comprise copper, a copper alloy, or combinations thereof.

41. The method of claim 40, wherein depositing the metal layers comprises first depositing a copper seed layer and then an electrochemical plating copper layer.

42. The method of claim 34, further comprising chemical mechanical polishing the substrate surface after depositing each metal layer.

43. The method of claim 34, further comprising reactively cleaning the substrate surface prior to depositing the barrier layer.

44. The method of claim 34, further comprising flowing a carrier gas continuously during each pulse of the metal-containing compound and each pulse of the nitrogen-containing compound.

45. The method of claim 34, wherein each pulse is separated by a time delay.

46. The method of claim 45, wherein the time delay is sufficient to remove any non-adsorbed molecules from the substrate surface.

47. The method of claim 34, further comprising sequentially introducing a silane-containing compound to deposit a ternary metal containing barrier layer.

48. The method of claim 47, wherein the ternary metal containing barrier layer comprises titanium silicon nitride.