US20060035025A1

US20060035025A1 - Activated species generator for rapid cycle deposition processes

Info

Publication number: US20060035025A1
Application number: US11/146,295
Authority: US
Inventors: Donald Verplancken; Ashok Sinha
Original assignee: Applied Materials Inc
Current assignee: Applied Materials Inc
Priority date: 2002-10-11
Filing date: 2005-06-06
Publication date: 2006-02-16
Also published as: US20040071897A1; US6905737B2

Abstract

A method for providing activated species for a cyclical deposition process is provided herein. In one aspect, the method includes delivering a gas to be activated into a plasma generator, activating the gas to create a volume of reactive species, delivering a fraction of the reactive species into a processing region to react within a substrate therein, and maintaining at least a portion of the gas remaining in the plasma generator in an activated state after delivering the fraction of the gas into the process region. The plasma generator may include a high density plasma (HDP) generator, a microwave generator, a radio-frequency (RF) generator, an inductive-coupled plasma (ICP) generator, a capacitively coupled generator, or combinations thereof.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent application Ser. No. 10/269,335, filed Oct. 11, 2002, which is herein incorporated by reference.

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 present invention relate to a method of providing activated precursors gases to a rapid cycle deposition process.
2. Description of the Related Art
Atomic layer deposition (ALD) is based on the exchange of chemical molecules or atoms between alternating reactants to deposit monolayers of material on a substrate surface. The monolayers maybe sequentially deposited one over the other to form a film composed of a plurality of individual layers to provide a desired film thickness. Typically, the alternating reactant is introduced into a processing chamber having a substrate in which a film is to be deposited is disposed therein, separately from a different reactant. A purge gas and pump system are used between pulses of alternately introduced reactants to prevent any overlap or co-reaction between the reactants other than on the substrate. Each separate deposition step theoretically goes to saturation and self terminates, depositing at least a single molecular or atomic monolayer of material. Accordingly, the deposition is the outcome of a chemical or physical reaction between each of the alternating reactants and the substrate surface.
Compared to bulk deposition processes, such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) for example, ALD is a slow process. Slower rates of deposition are not helpful toward achieving competitive performance and productivity. Since ALD reactions follow the kinetics of molecular-surface interaction, one solution to increase the deposition rate is to increase the kinetics of the molecular-surface interactions. The kinetics of molecular-surface interactions depends on the individual reaction rate between reactants and the substrate surface on which the materials are deposited. Therefore, the kinetics of molecular-surface interactions can be increased by increasing the reactivity of the individual reactants.
A common approach to increasing gas reactivity is to decompose the gas, generating ions/radicals that are highly reactive, especially at lower temperatures. This form of gas decomposition can be accomplished using various techniques, of which plasma technology is well known. Plasma technology generates high energy electrons that partially decompose and/or ionize the reactant gases and can be powered using various sources, such as microwave and radio frequency (RF), for example.
However, cyclical deposition processes utilizing plasma generation to activate reactant gases suffer many drawbacks. A major drawback is the ability to sustain a plasma of reactive gases within a processing chamber during the deposition process. Cyclical deposition processes, such as ALD, require rapid, repetitive pulses of reactants sometimes as fast as 300 milliseconds (msec) or less. Often, when the reactive gases are pulsed into a processing chamber, the plasma in the chamber is depleted or extinguished and must be re-established prior to a subsequent cycle. In a quest to increase product throughput, time does not allow for the repeated regeneration or re-ignition of a plasma between each step of the deposition process.
There is a need, therefore, for a cyclical deposition process capable of repeatably and reliably delivering activated gases to a processing chamber.

SUMMARY OF THE INVENTION

The present invention generally provides a method for delivering activated species to a cyclical deposition process. In one aspect, the method includes delivering a gas to be activated into a plasma generator, activating the gas to create a volume of reactive species, delivering a fraction of the reactive species into a processing region to react within a substrate therein, and maintaining at least a portion of the gas remaining in the plasma generator in an activated state after delivering the fraction of the gas into the process region.
A method for depositing films on a substrate surface is also provided. In one aspect, the method includes delivering a gas to be activated into a plasma generator and activating the gas to create a volume of one or more reactive species. The method also includes sequentially pulsing a fraction of the one or more reactive species and a second reactive compound into a processing region to deposit a film on the substrate surface, while maintaining at least a portion of at least one of said first and second gases in an activated state between pulses. In another aspect, the method includes delivering a first gas to be activated into a first plasma generator, activating at least a portion of the first gas to create a volume of one or more first reactive species, providing a second gas to be activated into a second plasma generator, and activating at least a portion of the second gas to create a volume of one or more second reactive species. The method further includes sequentially pulsing the first activated gas and the second activated gas to a processing region to deposit a film on the substrate surface, while maintaining at least a portion of at least one of said first and second gases in an activated state between pulses.
In any of the embodiments above, the plasma generator may include a high density plasma (HDP) generator, a microwave generator, radio-frequency (RF) generator, an inductive-coupled plasma (ICP) generator, a capacitively coupled generator, or any combination thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the present invention, and other features contemplated and claimed herein, 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. 1 shows a partial cross section view of an exemplary processing system having a plasma generator 200 according to one embodiment of the present invention in fluid communication with an exemplary processing chamber 100.
FIG. 2 shows a partial schematic view of an exemplary plasma generator 200 utilizing an inductive coil plasma (ICP) technology.
FIG. 3 illustrates a process flow sequence for cyclically depositing a tantalum nitride (TaN) film using according to embodiments of a processing system described herein.

DETAILED DESCRIPTION

The present invention provides a plasma generator having a close proximity to a processing chamber to provide one or more activated compounds for use in a radical-assisted, rapid cycle deposition process. The term “compound” is intended to include one or more precursors, reductants, reactants, and catalysts, or a combination thereof. The term “compound” is also intended to include a grouping of compounds, such as when two or more compounds are introduced in a processing system at the same time. For example, a grouping of compounds may include one or more catalysts and one or more precursors. The term “activated” as used herein refers to any one or more ions, electrons and/or radicals generated by catalysis, ionization, decomposition, dissociation, thermal degradation, or any combination thereof.
“Rapid cycle deposition” as used herein refers to the repetitive pulsing/dosing of two or more compounds to deposit a conformal layer on a substrate surface whereby each pulse/dose of compound has a duration less than about 300 milliseconds. The two or more compounds may be alternately or simultaneously pulsed into a reaction zone of a processing chamber having a substrate surface in which a film is to be deposited is disposed therein. When the two or more compounds are alternately pulsed, the compounds may be separated by a time delay/pause to allow each compound to adhere and/or react on the substrate surface. For example, 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 or tantalum silicon nitride for example, a third compound (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.
The term “pulse” or “dose” as used herein is intended to refer to a quantity of a particular compound that is intermittently or non-continuously introduced into the processing chamber. The quantity of a particular compound within each pulse may vary over time, depending on the duration of the pulse. However, a continuous flow of a particular compound is also contemplated by the present invention as described herein and thus, is not outside the scope thereof.
The term “substrate surface” as used herein is intended to refer to any workpiece or surface upon which film processing is performed. For example, the term “substrate surface” may be used to describe any semiconductor substrate, such as a silicon wafer or other substrate on which integrated circuits and other electronic devices are formed, including flat panel displays. The term “substrate surface” is also used to describe any material formed on a substrate, including conductive, semiconductive and insulative layers.
FIG. 1 shows a partial cross section view of an exemplary processing system having a plasma generator 200 according to one embodiment. As shown, the plasma generator 200 is in fluid communication with a processing chamber 100. The plasma generator 200 at least partially dissociates compounds into atomic or ionic species and provides at least a portion, if not all, of these activated species/compounds to the processing chamber 100 to form a film on a substrate surface therein.
The plasma generator 200 is a continuous, steady-state system, having a fixed internal volume. The plasma generator 200 is configured such that an amount of activated compound that exits the plasma generator 200 via a pulse to the processing chamber 100 is replenished with a corresponding amount of non-activated compound. Accordingly, the plasma generator 200 is able to operate at a steady-state with respect to gas volume and contains both activated and non-activated compounds at any given time.
The plasma generator 200 acts as a reservoir because a gas volume contained therein is substantially greater than a pulse volume of compound that is introduced into the processing chamber 100 during deposition. For example, the plasma generator 200 may contain up to 20 times the pulse volume required for deposition although any size or volume is envisioned. The plasma generator 200 should be sized so that when a pulse of activated compound exits the plasma generator 200, the energy of the compounds within the plasma generator 200 is not affected. As a result, at least a portion of the activated compound remaining in the plasma generator 200 is maintained in a plasma state. Additionally, the plasma generator 200 should be sized so that a desired number of activated species are available for delivery to a given deposition process. As a result, the plasma generator 200 does not require a separate ignition step to generate or sustain the plasma therein between each pulse, and product throughput is substantially increased. Instead, activated compounds remaining in the plasma generator 200 are repeatedly available for pulsing into the processing chamber 100 according to process recipe requirements without extinguishing or diluting the plasma within the plasma generator 200.
One exemplary plasma generator 200 is a remote plasma source disposed in close proximity to the processing chamber 100. The plasma generator 200 may be located adjacent, underneath, either directly on or adjacent the processing chamber 100. Preferably, the plasma generator 200 is disposed directly on an upper/top surface of the chamber 100, as shown in FIG. 1. However, the plasma generator 200 may be formed integrally with the processing chamber 100, as opposed to extending externally outward from the processing chamber 100 as separate components. An integrally formed plasma generator is shown and described in U.S. patent application Ser. No. 10/066,131, filed on Jan. 30, 2002, entitled “Method and Apparatus for Substrate Processing,” and published as US 20030141820, which is incorporated by reference herein.
The plasma generator 200 should be disposed a minimum distance from the processing chamber 100. Product throughput and the efficiency of the system are greatly improved by reducing the distance between the plasma generator 200 and the processing chamber 100. As such, a separate time-consuming ignition step is eliminated from the deposition process. Less energy is also required to generate and sustain the formation of reactive compounds. Most importantly, however, the reactive compounds experience a minimum level of energy loss during delivery to the substrate surface, thereby increasing the reaction kinetics of the deposition and providing a reliable and repeatable process.
The plasma generator 200 may be, for example, a high density plasma (HDP) generator, a microwave generator, radio-frequency (RF) generator, an inductive-coupled plasma (ICP) generator, a capacitively coupled generator, or any combination thereof. For ease and clarity of description, however, the plasma generator 200 will be described below in terms of an inductive coil plasma (ICP) generator with reference to FIG. 2.
FIG. 2 shows a partial schematic view of an exemplary plasma generator 200 utilizing an ICP generator. As shown, the plasma generator 200 includes at minimum, an inlet 205, an outlet 210, a circulation pump 215, inductive coils 220, and a hollow conduit 225. The inlet 205 is in fluid communication with one or more chemical sources 222 (three are shown for illustrative purposes). The outlet 210 is in fluid communication with a gas delivery system disposed within the processing chamber 100.
The hollow conduit 225 is a tubular member defining an activation or internal volume 250 therein. The circulation pump 215 is disposed in fluid communication within the hollow conduit 225, and may be any pump compatible with the process gases. It is believed that the activation volume 250 is directly proportional to the number of activated species generated within the plasma generator 200. In other words, the larger the volume of the activation volume 250, the greater the number of activated species contained therein. The inductive coils 220 are disposed about the hollow conduit 225 and utilize RF energy to excite the gas within the hollow conduit 225 forming a plasma of reactive compounds therein.
The chemical sources 222 store/contain the compounds used for deposition. The compounds may be stored in either solid, liquid, or gas phases. In the event that a gas/vapor phase is required, the plasma generator 200 may utilize a vaporizer/bubbler 230 in fluid communication therewith to guarantee delivery of a gas to the inlet 205. As mentioned above, the chemical sources 222 and the activation volume 250 may be pressure regulated so that a corresponding amount of compound that leaves the hollow conduit 225 is replenished from the chemical services 222. This maintains a steady-state operation throughout the plasma generator 200.
Considering the processing chamber 100 in further detail, the processing chamber 100 includes a chamber body 114, a lid assembly 120 for gas delivery, and a thermally controlled substrate support member 146, as shown in FIG. 1. The thermally controlled substrate support member 146 includes a wafer support pedestal 148 connected to a support shaft 148A. The thermally controlled substrate support member 146 may be moved vertically within the chamber body 114 so that a distance between the support pedestal 148 and the lid assembly 120 may be controlled.
The support pedestal 148 includes an embedded thermocouple 150A that may be used to monitor the temperature thereof. For example, a signal from the thermocouple 150A may be used in a feedback loop to control power applied to a heater element 152A by a power source 152. The heater element 152A may be a resistive heater element or other thermal transfer device disposed within or in contact with the pedestal 148 utilized to control the temperature thereof. Optionally, the support pedestal 148 may be heated using a heat transfer fluid (not shown).
The support pedestal 148 may be formed from any process-compatible material, including aluminum nitride and aluminum oxide (Al₂O₃or alumina) and may also be configured to hold a substrate thereon employing a vacuum, i.e., support pedestal 148 may be a vacuum chuck. Using a vacuum chuck, the support pedestal 148 may include a plurality of vacuum holes (not shown) that are placed in fluid communication with a vacuum source routed through the support shaft 148A.
The chamber body 114 includes a liner assembly 154 formed from any suitable material such as aluminum, ceramic and the like. The chamber body 114 and the liner assembly 154 define a chamber channel 158 there between. A purge gas is introduced into the channel 158 to minimize unwanted deposition on the chamber walls and to control the rate of heat transfer between the chamber walls and the liner assembly 154.
The chamber body 114 also includes a pumping channel 162 disposed along the sidewalls thereof. The pumping channel 162 includes a plurality of apertures 162A and is coupled to a pump system 118 via a conduit 117. A throttle valve 118A is coupled between the pumping channel 162 and the pump system 118. The pumping channel 162, the throttle valve 118A, and the pump system 118 control the amount of gas flow from the processing chamber 100. The size, number, and position of the apertures 162A in communication with the chamber 100 are configured to achieve uniform flow of gases exiting the lid assembly 120 over the support pedestal 148 having a substrate disposed thereon.
The lid assembly 120 includes a lid plate 120A having a gas manifold 134 mounted thereon. The lid plate 120A provides a fluid tight seal with an upper fraction of the chamber body 114 when in a closed position. The gas manifold 134 includes one or more valves 132 (two are shown, 132A, 132B). The valves 132 may be type of valve capable of precisely and repeatedly delivering short pulses of compounds into the chamber 100. In some cases, the on/off cycles or pulses of the valves 132 may be as fast as about 100 msec or less. Typically, the on/off cycles of the valves are between 100 msec and 1 second. Exemplary valves 132 capable of these rapid cycle times are electronically controlled (EC) valves commercially available from Fujikin of Japan as part number FR-21-6.35 UGF-APD. Other valves that operate at substantially the same speed and precision may also be used.
The processing chamber 100 further includes a reaction zone 159 that is formed within the chamber body 114 when the lid assembly 120 is in a closed position. Generally, the reaction zone 159 includes the volume within the processing chamber 100 that is in fluid communication with a wafer 133 disposed therein. The reaction zone 159, therefore, includes the volume downstream of each valve 132 within the lid assembly 120, and the volume between the support pedestal 148 and the lower surface of the lid plate 120. More particularly, the reaction zone 159 includes the volume between the outlet of the valves 132 and an upper surface of the wafer 133.
A controller 170, such as a programmable logic computer (PLC), regulates the operations of the various components of the processing chamber 100. The controller 170 typically includes a processor 172 in data communication with memory, such as random access memory 174 and a hard disk drive 176. The controller 170 is in communication with at least the pump system 118, the power source 152, and the valves 132. An exemplary controller 170 is described in more detail in the U.S. patent application Ser. No. 09/800,881, entitled “Valve Control System for ALD Chamber,” filed on Mar. 7, 2001, issued May 11, 2004, as U.S. Pat. No. 6,734,020, which is incorporated by reference herein.
The processing system described above may utilize executable software routines to initiate process recipes or sequences. The software routines, when executed, may be used to precisely control the activation of the electronic control valves 132 for the execution of process sequences according to the present invention. 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 and hardware.
The processing chamber 100 described above is available from Applied Materials, Inc. located in Santa Clara, Calif. A more detailed description of the processing chamber 100 may be found in commonly assigned U.S. patent application Ser. No. 10/016,300, entitled “Lid Assembly for a Processing System to Facilitate Sequential Deposition Techniques,” filed on Dec. 12, 2001, issued Apr. 12, 2005, as U.S. Pat. No. 6,878,206, which is incorporated herein by reference. The processing chamber 100 may be integrated into a processing platform, such as an ENDURA® platform also available from Applied Materials, Inc.
The plasma generator 200 and processing chamber 100 may be used to conformally deposit any type of dielectric or conductive film on a substrate surface. Dielectric layers include, for example, silicon oxide films, silicon carbon films, and carbon doped silicon oxide films. Conductive layers may include, for example, refractory metal films and refractory metal nitride films, in which the refractory metal is titanium, tantalum, or tungsten. The conductive layers may also include ternary layers, such as titanium silicon nitride or tantalum silicon nitride films. To further describe embodiments of the present invention, a processing sequence for forming a tantalum nitride (TaN) film using a rapid cycle deposition process will be described below.
FIG. 3 illustrates one process flow sequence 300 for depositing tantalum nitride (TaN) according to embodiments of the processing system described herein. The TaN barrier layer may be formed by alternately introducing one or more tantalum-containing compounds, such as Ta(NMe₂)₅(PDMAT) for example, and one or more nitrogen-containing compounds, such as ammonia for example, to the substrate surface. However, any tantalum-containing compound may be used, such as Ta(NEt₂)₅(PDEAT), Ta(NEtMe)₅(PEMAT), (Et₂N)₃Ta(NBu) (TBTDET), (MeEtN)₃Ta(NBu) (TBTMET), (Me₂N)₃Ta(NBu) (TBTDMT), tantalum chloride (TaCI₅), tantalum bromide (TaBr₅), tantalum iodide (TaI₅), tantalum hydrides, such as (Cp)₂TaH₃or (CpMe)₂TaH₃and combinations thereof. Likewise, any nitrogen-containing compound may be used, such as hydrazine (N₂H₄), monomethyl hydrazine (CH₃N₂H₃), dimethyl hydrazine (C₂H₆N₂H₂), t-butyl hydrazine (C₄H₉N₂H₃), phenyl hydrazine (C₆H₅N₂H₃), 2,2′-azotertbutane ((CH₃)₆C₂N₂), ethylazide (C₂H₅N₃), among others.
To initiate the cyclical deposition of the TaN layer, a carrier/purge gas such as argon is introduced into the processing chamber 100 to stabilize the pressure and temperature therein, as shown in step 302. Preferably, the chamber temperature is stabilized to between about 200° C. and about 300° C., and the pressure is stabilized to between about 1 Torr and about 5 Torr. The purge gas, such as helium (He), argon (Ar), nitrogen (N₂) and hydrogen (H₂), or combinations thereof, is then allowed to flow continuously during the deposition process such that only the purge gas flows between pulses of each compound. Typically, the purge gas continuously flows between about 100 sccm and about 1,000 sccm, such as between about 100 sccm and about 400 sccm, through each valve 132. Alternatively, once the pressure and temperature have been stabilized, the purge gas may be shut off and pulsed between pulses of compounds to assist the removal of the compounds from the chamber.
In step 303, at least a portion of the tantalum-containing source gas, PDMAT, is ignited into a plasma to form a volume of activated or excited species within the plasma generator 200. The PDMAT is activated using an RF power between about 200 watts and about 1,500 watts at a pressure at least slightly greater than the pressure within the process chamber. The plasma generator 200 remains in an “on” mode, and maintains the gas therein in the plasma state over repeated cycles.
In step 304, a fraction of the activated PDMAT is then pulsed to the reaction zone 159 at a rate between about 100 sccm and about 500 sccm, with a pulse time of about 0.3 seconds or less. Each fraction of PDMAT is less than the volume of activated PDMAT contained within the plasma generator 200, but is sufficient in volume to create at least a continuous monolayer on the substrate in the process chamber. As a result, activated PDMAT is readily available without a separate ignition step to either initiate or sustain the plasma within the plasma generator 200. By eliminating the extra ignition step, product throughput and product repeatability is substantially increased.
In step 306, a pulse of ammonia is provided to the reaction zone 159 at a rate between about 200 sccm and about 600 sccm, with a pulse time of about 0.6 seconds or less. In one aspect, at least a portion of the ammonia is also activated using a separate, but similar, activated species generator 200 to create a volume of excited species. In this aspect, the ammonia is activated using an RF power between about 200 watts and about 1,500 watts at a pressure at least slightly greater than the pressure within the process chamber.
Steps 304 and 306 are then repeated until a desired thickness of the TaN film is formed on the substrate surface, as shown in step 308. Thereafter, the process is stopped at step 310 when the desired thickness for the film is achieved.
Referring again to steps 304 and 306, a pause between pulses of PDMAT and ammonia is typically between about 1.0 second or less, preferably about 0.5 seconds or less, more preferably about 0.1 seconds or less. However, it may be desirable to operate without a pause between PDMAT and ammonia such that at least a portion of a pulse of PDMAT and at least a portion of a pulse of ammonia at least partially overlap within the processing chamber 100. In other words, at least a portion of a pulse of PDMAT may still be in the reaction zone 159 when at least a portion of a pulse of ammonia enters, allowing the reactive compounds to co-react much like in a CVD technique. Reducing time between pulses at least provides higher throughput.
Furthermore, the time interval for each pulse of PDMAT and ammonia is variable and depends on the volume capacity of the process chamber as well as the vacuum system coupled thereto. In general, the process conditions are advantageously selected so that each pulse provides a sufficient amount of compound so that at least a monolayer of the activated compound is conformally adsorbed on the substrate surface. Thereafter, excess compounds remaining in the chamber may be removed by the purge gas stream in combination with the vacuum system.
In the illustrated embodiment described above, the metal-containing compound and the nitrogen-containing compound were both ignited into a plasma of excited species. It should be understood that either the metal-containing compound or the nitrogen-containing compound or both could be ignited into a plasma to form a conformal, thin layer having desired physical and electrical properties. As is known in the art, plasma excited species are highly reactive at lower temperatures which increases product throughput, reduces cost of ownership and operation, and minimizes damage to the workpiece.
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.

Claims

1. A method for forming a material with activated species during a cyclical deposition process, comprising:

activating a precursor gas to create reactive species within a plasma generator;

exposing a substrate to a metal precursor within a process region during a first time period;

exposing the substrate to a fraction of the reactive species to form a metal-containing compound during a second time period; and

maintaining at least a portion of the reactive species within the plasma generator in an activated state during the first and second time periods.

2. The method of claim 1, wherein the metal precursor comprises a metal selected from the group consisting of tungsten, tantalum and titanium.

3. The method of claim 2, wherein the metal precursor comprises a tantalum precursor selected from the group consisting of Ta(NMe₂)₅(PDMAT), Ta(NEt₂)₅(PDEAT), Ta(NEtMe)₅(PEMAT), (Et₂N)₃Ta(NBu) (TBTDET), (MeEtN)₃Ta(NBu) (TBTMET), (Me₂N)₃Ta(NBu) (TBTDMT), derivatives thereof and combinations thereof.

4. The method of claim 2, wherein the metal-containing compound comprises a material selected from the group consisting of tungsten, tantalum, titanium, tungsten nitride, tantalum nitride, titanium nitride, titanium silicon nitride, tantalum silicon nitride, alloys thereof, derivatives thereof and combinations thereof.

5. The method of claim 1, wherein first time period lasts for about 1 second or less and the second time period lasts for about 1 second or less.

6. The method of claim 5, wherein first time period lasts for about 0.5 seconds or less and the second time period lasts for about 0.5 seconds or less.

7. The method of claim 6, wherein first time period lasts for about 0.1 seconds or less and the second time period lasts for about 0.1 seconds or less.

8. The method of claim 5, wherein the plasma generator comprises a high density plasma generator, a microwave generator, radio-frequency generator, an inductive-coupled plasma generator, a capacitively coupled generator, derivatives thereof and combinations thereof.

9. A method for forming a material with activated species during a cyclical deposition process, comprising:

activating a first precursor gas to create a volume of reactive species within a plasma generator;

exposing a substrate to a second precursor gas within a process region during a first time period; and

exposing the substrate to a fraction of the reactive species to form a product compound during a second time period.

10. The method of claim 9, wherein at least a portion of the reactive species is maintained within the plasma generator in an activated state during the first and second time periods.

11. The method of claim 9, wherein the second precursor gas comprises a metal.

12. The method of claim 11, wherein the metal is selected from the group consisting of tungsten, tantalum and titanium.

13. The method of claim 12, wherein the product compound comprises a material selected from the group consisting of tungsten, tantalum, titanium, tungsten nitride, tantalum nitride, titanium nitride, titanium silicon nitride, tantalum silicon nitride, alloys thereof, derivatives thereof and combinations thereof.

14. The method of claim 9, wherein first time period lasts for about 1 second or less and the second time period lasts for about 1 second or less.

15. The method of claim 14, wherein first time period lasts for about 0.5 seconds or less and the second time period lasts for about 0.5 seconds or less.

16. The method of claim 15, wherein first time period lasts for about 0.1 seconds or less and the second time period lasts for about 0.1 seconds or less.

17. The method of claim 14, wherein the plasma generator comprises a high density plasma generator, a microwave generator, radio-frequency generator, an inductive-coupled plasma generator, a capacitively coupled generator, derivatives thereof and combinations thereof.

18. A method for forming a material with activated species during a cyclical deposition process, comprising:

exposing a substrate to a tantalum precursor within a process region during a first time period; and

exposing the substrate to a fraction of the reactive species to form a tantalum-containing layer during a second time period.

19. The method of claim 18, wherein the tantalum precursor comprises a compound selected from the group consisting of Ta(NMe₂)₅(PDMAT), Ta(NEt₂)₅(PDEAT), Ta(NEtMe)₅(PEMAT), (Et₂N)₃Ta(NBu) (TBTDET), (MeEtN)₃Ta(NBu) (TBTMET), (Me₂N)₃Ta(NBu) (TBTDMT), derivatives thereof and combinations thereof.

20. The method of claim 18, wherein the precursor gas comprises a nitrogen-containing compound.

21. A method for forming a material with activated species during a cyclical deposition process, comprising:

positioning a substrate within a process region;

activating a precursor gas to create a volume of ionic species within a plasma generator;

exposing the substrate to a precursor compound to form a precursor layer thereon;

purging the process region with a purge gas;

flowing a fraction of the ionic species from the plasma generator to the process region;

exposing the precursor layer to the fraction of the ionic species to form a product compound thereon; and

purging the process region with the purge gas.

22. The method of claim 21, wherein at least a portion of the ionic species is maintained within the plasma generator in an activated state during the exposing and purging steps.

23. A method for forming a material with activated species during a cyclical deposition process, comprising:

positioning a substrate within a process region;

flowing a fraction of the ionic species from the plasma generator to the process region; and

forming a product compound by repeating a deposition cycle comprising exposing the substrate sequentially to a precursor compound, a purge gas, the fraction of the ionic species and the purge gas.

24. The method of claim 23, wherein at least a portion of the ionic species is maintained within the plasma generator in an activated state during the deposition cycle.

25. An apparatus for generating and delivering activated species during a cyclical deposition process, comprising:

a process chamber containing a process region between a substrate support pedestal and a lid assembly;

a plasma generator positioned to fluidly communicate with the process region, wherein the plasma generator comprises a high density plasma generator, a microwave generator, radio-frequency generator, an inductive-coupled plasma generator, a capacitively coupled generator, derivatives thereof and combinations thereof;

a volume of ionic species within the plasma generator; and

a fraction of the ionic species within the process region.

26. The apparatus of claim 25, further comprising a gas manifold attached to the lid assembly, wherein the gas manifold contains at least one valve capable of providing gas pulses of about 1 second or less.

27. The apparatus of claim 26, wherein the at least one valve is capable of providing gas pulses of about 0.5 seconds or less.

28. The apparatus of claim 27, wherein the at least one valve is capable of providing gas pulses of about 0.1 seconds or less.

29. The apparatus of claim 26, wherein the plasma generator is extending externally from the process chamber.

30. The apparatus of claim 26, wherein the plasma generator is formed integrally within the process chamber.

31. The apparatus of claim 26, further comprising at least one precursor source in fluid communication to the gas manifold.

32. The apparatus of claim 31, wherein a vaporizer is positioned between the at least one precursor source and the gas manifold.

33. The apparatus of claim 32, wherein the at least one precursor source contains a tantalum precursor selected from the group consisting of Ta(NMe₂)₅(PDMAT), Ta(NEt₂)₅(PDEAT), Ta(NEtMe)₅(PEMAT), (Et₂N)₃Ta(NBu) (TBTDET), (MeEtN)₃Ta(NBu) (TBTMET), (Me₂N)₃Ta(NBu) (TBTDMT), derivatives thereof and combinations thereof.

34. The apparatus of claim 31, wherein the process chamber comprises a ceramic liner assembly.

35. The apparatus of claim 26, wherein a vaporizer is positioned intermediate a first precursor source containing a tantalum precursor and a first valve and the plasma generator is intermediate a second precursor source containing ammonia and a second valve.