US20060035025A1 - Activated species generator for rapid cycle deposition processes - Google Patents

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 as300 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 aplasma generator200 according to one embodiment of the present invention in fluid communication with anexemplary processing chamber100.
• FIG. 2 shows a partial schematic view of anexemplary plasma generator200 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 aplasma generator200 according to one embodiment. As shown, theplasma generator200 is in fluid communication with aprocessing chamber100. Theplasma generator200 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 theprocessing chamber100 to form a film on a substrate surface therein.
• Theplasma generator200 is a continuous, steady-state system, having a fixed internal volume. Theplasma generator200 is configured such that an amount of activated compound that exits theplasma generator200 via a pulse to theprocessing chamber100 is replenished with a corresponding amount of non-activated compound. Accordingly, theplasma generator200 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.
• Theplasma generator200 acts as a reservoir because a gas volume contained therein is substantially greater than a pulse volume of compound that is introduced into theprocessing chamber100 during deposition. For example, theplasma generator200 may contain up to20 times the pulse volume required for deposition although any size or volume is envisioned. Theplasma generator200 should be sized so that when a pulse of activated compound exits theplasma generator200, the energy of the compounds within theplasma generator200 is not affected. As a result, at least a portion of the activated compound remaining in theplasma generator200 is maintained in a plasma state. Additionally, theplasma generator200 should be sized so that a desired number of activated species are available for delivery to a given deposition process. As a result, theplasma generator200 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 theplasma generator200 are repeatedly available for pulsing into theprocessing chamber100 according to process recipe requirements without extinguishing or diluting the plasma within theplasma generator200.
• Oneexemplary plasma generator200 is a remote plasma source disposed in close proximity to theprocessing chamber100. Theplasma generator200 may be located adjacent, underneath, either directly on or adjacent theprocessing chamber100. Preferably, theplasma generator200 is disposed directly on an upper/top surface of thechamber100, as shown inFIG. 1. However, theplasma generator200 may be formed integrally with theprocessing chamber100, as opposed to extending externally outward from theprocessing chamber100 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.
• Theplasma generator200 should be disposed a minimum distance from theprocessing chamber100. Product throughput and the efficiency of the system are greatly improved by reducing the distance between theplasma generator200 and theprocessing chamber100. 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.
• Theplasma generator200 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, theplasma generator200 will be described below in terms of an inductive coil plasma (ICP) generator with reference toFIG. 2.
• FIG. 2 shows a partial schematic view of anexemplary plasma generator200 utilizing an ICP generator. As shown, theplasma generator200 includes at minimum, aninlet205, anoutlet210, acirculation pump215,inductive coils220, and ahollow conduit225. Theinlet205 is in fluid communication with one or more chemical sources222 (three are shown for illustrative purposes). Theoutlet210 is in fluid communication with a gas delivery system disposed within theprocessing chamber100.
• Thehollow conduit225 is a tubular member defining an activation or internal volume250 therein. Thecirculation pump215 is disposed in fluid communication within thehollow conduit225, and may be any pump compatible with the process gases. It is believed that the activation volume250 is directly proportional to the number of activated species generated within theplasma generator200. In other words, the larger the volume of the activation volume250, the greater the number of activated species contained therein. Theinductive coils220 are disposed about thehollow conduit225 and utilize RF energy to excite the gas within thehollow conduit225 forming a plasma of reactive compounds therein.
• Thechemical sources222 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, theplasma generator200 may utilize a vaporizer/bubbler230 in fluid communication therewith to guarantee delivery of a gas to theinlet205. As mentioned above, thechemical sources222 and the activation volume250 may be pressure regulated so that a corresponding amount of compound that leaves thehollow conduit225 is replenished from the chemical services222. This maintains a steady-state operation throughout theplasma generator200.
• Considering theprocessing chamber100 in further detail, theprocessing chamber100 includes achamber body114, alid assembly120 for gas delivery, and a thermally controlledsubstrate support member146, as shown inFIG. 1. The thermally controlledsubstrate support member146 includes awafer support pedestal148 connected to asupport shaft148A. The thermally controlledsubstrate support member146 may be moved vertically within thechamber body114 so that a distance between thesupport pedestal148 and thelid assembly120 may be controlled.
• Thesupport pedestal148 includes an embeddedthermocouple150A that may be used to monitor the temperature thereof. For example, a signal from thethermocouple150A may be used in a feedback loop to control power applied to aheater element152A by apower source152. Theheater element152A may be a resistive heater element or other thermal transfer device disposed within or in contact with thepedestal148 utilized to control the temperature thereof. Optionally, thesupport pedestal148 may be heated using a heat transfer fluid (not shown).
• Thesupport pedestal148 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 pedestal148 may be a vacuum chuck. Using a vacuum chuck, thesupport pedestal148 may include a plurality of vacuum holes (not shown) that are placed in fluid communication with a vacuum source routed through thesupport shaft148A.
• Thechamber body114 includes aliner assembly154 formed from any suitable material such as aluminum, ceramic and the like. Thechamber body114 and theliner assembly154 define achamber channel158 there between. A purge gas is introduced into thechannel158 to minimize unwanted deposition on the chamber walls and to control the rate of heat transfer between the chamber walls and theliner assembly154.
• Thechamber body114 also includes apumping channel162 disposed along the sidewalls thereof. The pumpingchannel162 includes a plurality ofapertures162A and is coupled to apump system118 via aconduit117. Athrottle valve118A is coupled between the pumpingchannel162 and thepump system118. The pumpingchannel162, thethrottle valve118A, and thepump system118 control the amount of gas flow from theprocessing chamber100. The size, number, and position of theapertures162A in communication with thechamber100 are configured to achieve uniform flow of gases exiting thelid assembly120 over thesupport pedestal148 having a substrate disposed thereon.
• Thelid assembly120 includes alid plate120A having agas manifold134 mounted thereon. Thelid plate120A provides a fluid tight seal with an upper fraction of thechamber body114 when in a closed position. Thegas manifold134 includes one or more valves132 (two are shown,132A,132B). The valves132 may be type of valve capable of precisely and repeatedly delivering short pulses of compounds into thechamber100. In some cases, the on/off cycles or pulses of the valves132 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 valves132 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.
• Theprocessing chamber100 further includes areaction zone159 that is formed within thechamber body114 when thelid assembly120 is in a closed position. Generally, thereaction zone159 includes the volume within theprocessing chamber100 that is in fluid communication with awafer133 disposed therein. Thereaction zone159, therefore, includes the volume downstream of each valve132 within thelid assembly120, and the volume between thesupport pedestal148 and the lower surface of thelid plate120. More particularly, thereaction zone159 includes the volume between the outlet of the valves132 and an upper surface of thewafer133.
• Acontroller170, such as a programmable logic computer (PLC), regulates the operations of the various components of theprocessing chamber100. Thecontroller170 typically includes aprocessor172 in data communication with memory, such asrandom access memory174 and ahard disk drive176. Thecontroller170 is in communication with at least thepump system118, thepower source152, and the valves132. Anexemplary controller170 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 valves132 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.
• Theprocessing chamber100 described above is available from Applied Materials, Inc. located in Santa Clara, Calif. A more detailed description of theprocessing chamber100 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. Theprocessing chamber100 may be integrated into a processing platform, such as an ENDURA® platform also available from Applied Materials, Inc.
• Theplasma generator200 andprocessing chamber100 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 oneprocess flow sequence300 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 theprocessing chamber100 to stabilize the pressure and temperature therein, as shown instep302. 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 valve132. 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.
• Instep303, 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 theplasma generator200. 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. Theplasma generator200 remains in an “on” mode, and maintains the gas therein in the plasma state over repeated cycles.
• Instep304, a fraction of the activated PDMAT is then pulsed to thereaction zone159 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 theplasma generator200, 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 theplasma generator200. By eliminating the extra ignition step, product throughput and product repeatability is substantially increased.
• Instep306, a pulse of ammonia is provided to thereaction zone159 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, activatedspecies generator200 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.
• Steps304 and306 are then repeated until a desired thickness of the TaN film is formed on the substrate surface, as shown instep308. Thereafter, the process is stopped atstep310 when the desired thickness for the film is achieved.
• Referring again tosteps304 and306, 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 theprocessing chamber100. In other words, at least a portion of a pulse of PDMAT may still be in thereaction zone159 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 (35)

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 ofclaim 1, wherein the metal precursor comprises a metal selected from the group consisting of tungsten, tantalum and titanium.

3. The method ofclaim 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 ofclaim 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 ofclaim 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 ofclaim 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 ofclaim 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 ofclaim 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 ofclaim 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 ofclaim 9, wherein the second precursor gas comprises a metal.

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

13. The method ofclaim 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 ofclaim 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 ofclaim 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 ofclaim 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 ofclaim 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:

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

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 ofclaim 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 ofclaim 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 ofclaim 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;

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

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

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

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

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

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

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

33. The apparatus ofclaim 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 ofclaim 31, wherein the process chamber comprises a ceramic liner assembly.

35. The apparatus ofclaim 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.

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