Multiple precursor cyclical deposition system

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] Embodiments of the present invention generally relate to an apparatus and method of deposition utilizing multiple precursors. More particularly, embodiments of the present invention relate to an apparatus and method of cyclical deposition utilizing multiple precursors in which delivery of at least two of the precursors to a substrate structure at least partially overlap.

[0003] 2. Description of the Related Art

[0004] Reliably producing sub-micron and smaller features is one of the key technologies for the next generation of very large scale integration (VLSI) and ultra large scale integration (ULSI) of semiconductor devices. However, as the fringes of circuit technology are pressed, the shrinking dimensions of interconnects in VLSI and ULSI technology have placed additional demands on the processing capabilities. The multilevel interconnects that lie at the heart of this technology require precise processing of high aspect ratio features, such as vias and other interconnects. Reliable formation of these interconnects is very important to VLSI and ULSI success and to the continued effort to increase circuit density and quality of individual substrates.

[0005] As circuit densities increase, the widths of vias, contacts, and other features, as well as the dielectric materials between them, decrease to sub-micron dimensions (e.g., less than 0.20 micrometers or less), whereas the thickness of the dielectric layers remains substantially constant, with the result that the aspect ratios for the features, i.e., their height divided by width, increase. Many traditional deposition processes have difficulty filling sub-micron structures where the aspect ratio exceeds 4:1. Therefore, there is a great amount of ongoing effort being directed at the formation of substantially void-free and seam-free sub-micron features having high aspect ratios.

[0006] Atomic layer deposition is one deposition technique being explored for the deposition of material layers over features having high aspect ratios. One example of atomic layer deposition of a binary material layer comprises the sequential introduction of pulses of a first precursor and a second precursor. For instance, one cycle for the sequential introduction of a first precursor and a second precursor may comprise a pulse of the first precursor, followed by a pulse of a purge gas and/or a pump evacuation, followed by a pulse of a second precursor, and followed by a pulse of a purge gas and/or a pump evacuation. Sequential introduction of separate pulses of the first precursor and the second precursor results in the alternating self-limiting chemisorption of monolayers of the precursors on the surface of the substrate and forms a monolayer of the binary material for each cycle. The cycle may be repeated to a desired thickness of the binary material. A pulse of a purge gas and/or a pump evacuation between the pulses of the first precursor and the pulses of the second precursor serves to reduce the likelihood of gas phase reactions of the precursors due to excess amounts of the precursor remaining in the chamber. Therefore, there is a need for an improved apparatus and method of atomic layer deposition utilizing three or more precursors.

SUMMARY OF THE INVENTION

[0007] Embodiments of the present invention relate to an apparatus and method of cyclical deposition utilizing three or more precursors in which delivery of at least two of the precursors to a substrate structure at least partially overlap. One embodiment of depositing a ternary material layer over a substrate structure comprises providing at least one cycle of gases to deposit a ternary material layer. One cycle comprises introducing a pulse of a first precursor, introducing a pulse of a second precursor, and introducing a pulse of a third precursor in which the pulse of the second precursor and the pulse of the third precursor at least partially overlap. In one aspect, the ternary material layer includes, but is not limited to, tungsten boron silicon (WB_xSi_y), titanium silicon nitride (TiSi_xN_y), tantalum silicon nitride (TaSi_xN_y), silicon oxynitride (SiO_xN_y), and hafnium silicon oxide (HfSi_xO_y). In one aspect, the composition of the ternary material layer may be tuned by changing the flow ratio of the second precursor to the third precursor between cycles.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] So that the manner in which the above recited features, advantages and objects 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.

[0009] 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.

[0010]FIG. 1 is a partial cross-sectional perspective view of one embodiment of a processing system adapted to perform cyclical deposition.

[0011]FIG. 1A is a partial cross-sectional view of one embodiment of a lid assembly of the processing system of FIG. 1.

[0012]FIG. 2 is a schematic cross-sectional view of another embodiment of a processing system adapted to perform cyclical deposition.

[0013] FIGS. <b>3</b>A-C are simplified cross-sectional views illustrating one embodiment of exposing a substrate structure to three precursors in which delivery of two of the three precursors at least partially overlap.

[0014] FIGS. <b>4</b>A-<b>4</b>D and <b>4</b>F are graphs of exemplary processes of sequential delivery of pulses of a first precursor, a second precursor, and a third precursor, in which the pulses of the second precursor and the third precursor at least partially overlap.

[0015]FIG. 4E is a graph of one exemplary process of sequentially delivering a first precursor, a second precursor, and a third precursor in which there is no purge gas which separates the flow of the second precursor and the third precursor.

[0016]FIG. 5 is a schematic cross-sectional view of one example of tuning the composition of a ternary material layer.

[0017]FIG. 6 is a flow chart illustrating one embodiment of a process utilizing a continuous flow of a purge gas to deposit a ternary material layer with a tuned composition.

[0018]FIG. 7 is a flow chart illustrating one embodiment of a process utilizing pulses of a purge gas to deposit a ternary material layer with a tuned composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0019] Process Chamber Adapted for Cyclical Deposition

[0020]FIGS. 1, 1A, and <b>2</b> are drawings of exemplary embodiments of a processing system that may be used to perform cyclical deposition. The term “cyclical deposition” as used herein refers to the sequential introduction of reactants to deposit a thin layer over a structure and includes processing techniques such as atomic layer deposition and rapid sequential chemical vapor deposition. The sequential introduction of reactants may be repeated to deposit a plurality of thin layers to form a layer to a desired thickness. Not wishing to be bound by theory, it is believed that the mode of deposition of cyclical deposition provides conformal coverage over substrate structures.

[0021]FIG. 1 is a partial cross-sectional perspective view of one embodiment of a processing system <b>100</b>. The processing system <b>100</b> comprises a lid assembly <b>120</b> includes a lid plate <b>122</b>, a manifold block <b>150</b>, one or more valves (one valve <b>155</b>A is shown in FIG. 1), one or more reservoirs <b>170</b>, and a distribution plate <b>130</b>. The lid assembly <b>120</b> has one or more isolated zones/flow paths to deliver one or more process gases to a workpiece/substrate surface disposed in the processing system <b>100</b>. The isolated zones/flow paths prevent exposure or contact of the precursor gases within the lid assembly. The term “process gas” is intended to include one or more reactive gas, precursor gas, purge gas, carrier gas, as wells as a mixture or mixtures thereof.

[0022] The chamber body <b>105</b> includes a pumping plate <b>109</b>, a liner <b>107</b>, a support pedestal <b>111</b>, and a slit valve disposed therein. The slit valve is formed within a side wall of the chamber body <b>105</b> and allows transfer of a workpiece to and from the interior of the chamber body <b>105</b>. The support pedestal <b>111</b> is disposed within the chamber body <b>105</b> and includes a lifting mechanism to position a workpiece, such as a semiconductor wafer for example, therein. The workpeice may be heated, such as by a heated support pedestal <b>111</b> or by radiant heat emitted from a secondary source, depending on the requisite process conditions. A purge channel <b>108</b> is formed within the liner <b>107</b> and is in fluid communication with a pump system to helps evacuate fluids from the chamber body <b>105</b>. The pumping plate <b>109</b> has a plurality of apertures <b>109</b>A formed there-through and defines an upper surface of the purge channel <b>108</b> controlling the flow of fluid between the chamber body <b>105</b> and the pumping system.

[0023]FIG. 1A is a partial cross-sectional view of the lid assembly <b>120</b> of the process system <b>100</b> of FIG. 1. As shown, the lid assembly includes two valves <b>155</b>A,B. The valves <b>155</b>A,B are preferably high speed actuating valves. The valves <b>155</b>A,B may precisely and repeatedly deliver short pulses of process gases into the chamber body <b>105</b>. The valves <b>155</b>A,B 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). The on/off cycles or pulses of the valves <b>155</b> may be less than about 100 msec. In one aspect, the valves <b>155</b>A,B are three-way valves tied to both a precursor gas source and a continuous purge gas source. Each valve <b>155</b>A,B meters a precursor gas while a purge gas continuously flows through the valve <b>155</b>A,B.

[0024] Valve <b>155</b>A receives a first process gas from an inlet precursor gas channel <b>153</b>A and an inlet purge gas channels <b>124</b>A and delivers the first process gas through an outlet process gas channel <b>154</b>A formed through the manifold block <b>150</b> and the lid plate <b>122</b>. The outlet gas channel <b>154</b>A feeds into the chamber body <b>105</b> through centrally located openings <b>131</b>A, <b>131</b>B formed in the distribution plate <b>130</b>. An inner diameter of the gas channel <b>154</b>A gradually increases within the lid plate <b>122</b> to decrease the velocity of the first process gas. A dispersion plate <b>132</b> is also disposed adjacent the openings <b>131</b>A, <b>131</b>B to prevent the first process gas from impinging directly on the workpiece surface by slowing and re-directing the velocity profile of the flowing gases. Without this re-direction, the force asserted on the workpiece by the first process gas may prevent deposition because the kinetic energy of the impinging first process gas can sweep away reactive molecules already disposed on the workpiece surface.

[0025] Valve <b>155</b>B receives a second process gas from an inlet precursor gas channel <b>153</b>B and an inlet purge gas channels <b>124</b>B and delivers the second process gas through an outlet process gas channel <b>154</b>B formed through the manifold block <b>150</b> and the lid plate <b>122</b>. The outlet gas channel <b>154</b>B feeds into the chamber body <b>105</b> via a cavity <b>156</b> in the distribution plate <b>130</b> and through apertures <b>133</b> formed in the distribution plate <b>130</b>.

[0026] The lid assembly further comprises a third valve similar to valve <b>155</b>B which receives a third process gases from an inlet precursor gas channel and from an inlet purge channel and deliver the third process gas through an outlet process gas channel formed through the manifold block <b>150</b> and the lid plate <b>122</b>. The outlet gas channel feeds into the chamber body <b>105</b> via the cavity <b>156</b> in the distribution plate <b>130</b> and through the apertures <b>133</b> formed in the distribution plate <b>130</b>. In one aspect, cavity <b>156</b> may comprise a plurality of channels separating the second process gas and the third process gas.

[0027] Referring to FIG. 1, one or more fluid delivery conduits <b>126</b> (only one delivery conduit <b>126</b> is shown) are preferably disposed about a perimeter of the chamber body <b>105</b> to carry the one or more process gases from their respective source to the lid assembly <b>120</b>. Each fluid delivery conduit <b>126</b> is connectable to a fluid source at a first end thereof and has an opening/port <b>192</b>A at a second end thereof. The opening <b>192</b>A is connectable to a respective receiving port <b>192</b>B disposed on a lower surface of the lid plate <b>122</b>. The receiving port <b>192</b>B is formed on a first end of a fluid channel <b>123</b> that is formed within the lid plate <b>122</b>. A fluid may flow from the fluid delivery conduit <b>126</b>, through the ports <b>192</b>A and <b>192</b>B, to the fluid channel <b>123</b>. This connection facilitates the delivery of a fluid from its source, through the lid plate assembly <b>120</b>, and ultimately within the chamber body <b>105</b>.

[0028] The one or more reservoirs <b>170</b> may be in fluid communication between a fluid source and the valves <b>155</b>. The reservoirs <b>170</b> provide bulk fluid delivery to the respective valves <b>155</b> to insure a required fluid volume is always available to the valves <b>155</b>. Preferably, the lid assembly <b>120</b> includes at least one reservoir <b>170</b> for each process gas. Each reservoir <b>170</b> contains between about 2 times the required volume and about 20 times the required volume of a fluid delivery cycle provided by the valves <b>155</b>.

[0029] In operation, a workpiece, such as a semiconductor wafer for example, is inserted into the chamber body <b>105</b> through the slit valve and disposed on the support pedestal <b>111</b>. The support pedestal <b>111</b> is lifted to a processing position within the chamber body <b>105</b>. Each precursor gas flows from its source through its fluid delivery conduit <b>126</b> into its designated fluid channel <b>123</b>, into its designated reservoir <b>170</b>, through the manifold block <b>150</b>, through its designated valve <b>155</b>, back through the manifold block <b>150</b>, through the lid plate <b>122</b>, and through the distribution plate <b>130</b>. A purge gas, such as argon, helium, hydrogen, nitrogen, or mixtures thereof, for example, is allowed to flow and continuously flows during the deposition process. The purge gas flows through its fluid delivery conduit <b>126</b> to its designated fluid channel <b>123</b>, through the manifold block <b>150</b>, through its designated valve <b>155</b>, back through the manifold block <b>150</b>, through the lid plate <b>122</b>, through the distribution plate <b>130</b>, and into the chamber body <b>105</b>. A separate purge gas channel may be provided for each of the valves <b>155</b> because the flow rate of the purge gas is dependent on the differing flow rates of the precursor gases.

[0030] More particularly, a first purge gas and a first reactant gas flows through the slotted openings <b>131</b>A, <b>131</b>B (FIG. 1A) formed in the dispersion plate <b>130</b>; a second purge gas and a second reactant flows through the apertures <b>133</b> formed in the dispersion plate <b>130</b>; and a third purge gas and a third reactant flows through the apertures <b>133</b> formed in the dispersion plate <b>130</b>. As explained above, the flow path through the slotted openings <b>131</b>A, <b>131</b>B and the flow path through the apertures <b>133</b> are isolated from one another. The first purge gas and first precursor gas flowing through the slotted openings <b>131</b>A, <b>131</b>B are deflected by the dispersion plate <b>132</b>. The dispersion plate <b>132</b> converts the substantially downward, vertical flow profile of the gases into an at least partially horizontal flow profile. The processing system <b>100</b> as described in FIGS. 1 and 1A is more fully described in U.S. patent application (Ser. No. Unknown) entitled “Chamber Hardware Design For Titanium Nitride Atomic Layer Deposition” to Nguyen et al. filed on Dec. 21, 2001, which is incorporated by reference in its entirety to the extent not inconsistent with the present disclosure.

[0031]FIG. 2 is a schematic cross-sectional view of another embodiment of a processing system <b>210</b> that may be used to perform cyclical deposition. The processing system <b>210</b> includes a housing <b>214</b> defining a processing chamber <b>216</b> with a slit valve opening <b>244</b> and a vacuum lid assembly <b>220</b>. Slit valve opening <b>244</b> allows transfer of a wafer (not shown) between processing chamber <b>216</b> and the exterior of system <b>210</b>. Any conventional wafer transfer device may achieve the aforementioned transfer.

[0032] The vacuum lid assembly <b>220</b> includes a lid <b>221</b> and a process fluid injection assembly <b>230</b> to deliver reactive (i.e. precursor, reductant, oxidant), carrier, purge, cleaning and/or other fluids into the processing chamber <b>216</b>. The fluid injection assembly <b>230</b> includes a gas manifold <b>234</b> mounting a plurality of control valves <b>232</b> (one is shown in FIG. 2), and a baffle plate <b>236</b>. Programmable logic controllers may be coupled to the control valves <b>232</b> to provide sequencing control of the valves. Valves <b>232</b> provide rapid gas flows with valve open and close cycles of less than about one second, and in one embodiment, of less than about 0.1 second. In one embodiment, the valves <b>232</b> are surface mounted, electronically controlled valves, such as electronically controlled valves available from Fujikin of Japan as part number FR-21-6.35 UGF-APD. Other valves that operate at substantially the same speed may also be used.

[0033] The lid assembly <b>220</b> may further include one or more gas reservoirs (not shown) which are fluidically connected between one or more process gas sources (such as vaporized precursor sources) and the gas manifold <b>234</b>. The gas reservoirs may provide bulk gas delivery proximate to each of the valves <b>232</b>. The reservoirs are sized to insure that an adequate gas volume is available proximate to the valves <b>232</b> during each cycle of the valves <b>232</b> during processing to minimize time required for fluid delivery thereby shortening sequential deposition cycles. For example, the reservoirs may be about 5 times the volume required in each gas delivery cycle.

[0034] The vacuum lid assembly <b>220</b> may include one or more valves, such as four valves <b>232</b>. Three of the valves <b>232</b> are fluidly coupled to three separate reactant gas sources. One of the valves <b>232</b> is fluidly coupled to a purge gas source. Each valve <b>232</b> is fluidly coupled to a separate trio of gas channels <b>271</b><i>a</i>, <b>271</b><i>b</i>, <b>273</b> (one trio is shown in FIG. 2) of the gas manifold <b>234</b>. Gas channel <b>271</b><i>a </i>provides passage of gases through the gas manifold <b>234</b> to the valves <b>232</b>. Gas channel <b>271</b><i>b </i>delivers gases from the valves <b>232</b> through the gas manifold <b>234</b> and into a gas channel <b>273</b>. Channel <b>273</b> is fluidly coupled to a respective inlet passage <b>286</b> disposed through the lid <b>221</b>. Gases flowing through the inlet passages <b>286</b> flow into a plenum or region <b>288</b> defined between the lid <b>221</b> and the baffle plate <b>236</b> before entering the chamber <b>216</b>. The baffle plate <b>236</b> is utilized to prevent gases injected into the chamber <b>216</b> from blowing off gases adsorbed onto the surface of the substrate. The baffle plate <b>236</b> may include a mixing lip <b>284</b> to re-direct gases toward the center of the plenum <b>288</b> and into the process chamber <b>216</b>.

[0035] Disposed within processing chamber <b>216</b> is a heater/lift assembly <b>246</b> that includes a wafer support pedestal <b>248</b>. The heater/lift assembly <b>246</b> may be moved vertically within the chamber <b>216</b> so that a distance between support pedestal <b>248</b> and vacuum lid assembly <b>220</b> may be controlled. The support pedestal may include an embedded heater element, such as a resistive heater element or heat transfer fluid, utilized to control the temperature thereof. Optionally, a substrate disposed on the support pedestal <b>248</b> may be heated using radiant heat. The support pedestal <b>248</b> may also be configured to hold a substrate thereon, such as by a vacuum chuck, by an electrostatic chuck, or by a clamp ring.

[0036] Disposed along the side walls <b>214</b><i>b </i>of the chamber <b>216</b> proximate the lid assembly <b>220</b> is a pumping channel <b>262</b>. The pumping channel <b>262</b> is coupled by a conduit <b>266</b> to a pump system <b>218</b> which controls the amount of flow from the processing chamber <b>216</b>. A plurality of supplies <b>268</b><i>a</i>, <b>268</b><i>b </i>and <b>268</b><i>c </i>of process and/or other fluids, are in fluid communication with one of valves <b>232</b> through a sequence of conduits (not shown) formed through the housing <b>214</b>, lid assembly <b>220</b>, and gas manifold <b>234</b>. The processing system <b>210</b> may include a controller <b>270</b> which regulates the operations of the various components of system <b>210</b>. The processing system <b>210</b> as described in FIG. 2 is more fully described in U.S. patent application (Ser. No. 10/016,300) entitled “Lid Assembly For A Processing System To Facilitate Sequential Deposition Techniques” to Tzu et al. filed on Dec. 12, 2001, which claims priority to U.S. Provisional Application Serial No. 60/305,970 filed on Jul. 16, 2001, which are both incorporated by reference in its entirety to the extent not inconsistent with the present disclosure.

[0037] Other processing system may also be used to perform cyclical deposition. For example, another processing system which may also be used is the processing system disclosed in U.S. patent application (Ser. No. 10/032,284) entitled “Gas Delivery Apparatus and Method For Atomic Layer Deposition” to Chen et al. filed on Dec. 21, 200, which claims priority to U.S. Provisional Patent Application (Serial No. Unknown) entitled “Method and Apparatus for Atomic Layer Deposition” to Chen et al. filed on Oct. 26, 2001, which are both incorporated by reference in its entirety to the extent not inconsistent with the present disclosure.

[0038] Deposition Processes

[0039] Processing system <b>100</b> as described in FIGS. 1 and 1A and processing system <b>210</b> as described in FIG. 2 may be used to implement the following exemplary process for cyclical deposition utilizing three or more precursors. It should also be understood that the following processes may be performed in other chambers as well, such as batch processing systems.

[0040] One embodiment of the present method involves cyclical deposition of a ternary material layer by delivering three precursors to a substrate in which delivery of two of the three precursors at least partially overlap. The term “ternary material” as used herein is defined as a material comprising three major elements. The composition and structure of precursors on a surface during cyclical deposition is not precisely known. Not wishing to be bound by theory, FIGS. <b>3</b>A-C are simplified cross-sectional views illustrating one embodiment of exposing the substrate structure <b>300</b> to three precursors in which delivery of two of the three precursors at least partially overlap. The substrate structure <b>300</b> refers to any workpiece upon which film processing is performed and may be used to denote a substrate, such as a semiconductor substrate or a glass substrate, as well as other material layers formed on the substrate, such as a dielectric layer or other layers.

[0041] In FIG. 3A, a first precursor <b>310</b> is adsorbed on the substrate structure <b>300</b> by introducing a pulse of the first precursor <b>310</b> into a process chamber, such as process chamber <b>100</b> shown in FIGS. 1 and 1A and such as process chamber <b>210</b> shown in FIGS. 2. The first precursor <b>310</b> may comprise atoms of an element (labeled as A) with one or more reactive species (labeled as R₁). The first precursor may be provided with or without the aid of a carrier gas. Examples of carrier gases which may be used include, but are not limited to, helium (He), argon (Ar), nitrogen (N₂), hydrogen (H₂), and mixtures thereof. It is believed that a layer <b>315</b>, which may be about a monolayer or may be more or less than a monolayer, of the first precursor <b>310</b> may be adsorbed onto the surface of the substrate structure <b>300</b> during a given pulseAny of the first precursor <b>310</b> not adsorbed will flow out of the chamber as a result of the vacuum system, carrier gas flow, and/or purge gas flow. The terms “adsorption” or “adsorb” as used herein are defined to include chemisorption, physisorption, or any attractive and/or bonding forces which may be at work and/or which may contribute to the bonding, reaction, adherence, or occupation of a portion of an exposed surface of a substrate structure.

[0042] After the pulse of the first precursor <b>310</b> is introduced into the chamber, a purge gas is introduced. Examples of purge gases which may be used include, but are not limited to, helium (He), argon (Ar), nitrogen (N₂), hydrogen (H₂), and mixtures thereof. The purge gas may be provided as a pulse or may be provided as a continuous flow into the chamber. The purge gas and the carrier gas may comprise different gas flows or may comprise the same gas flow. If the purge gas and the carrier gas comprise different gas flows, the purge gas and the carrier gas preferably comprise the same type of gas.

[0043] Referring to FIG. 3B, after a purge gas has been introduced, a pulse of a second precursor <b>320</b> and a pulse of a third precursor <b>330</b> are introduced into the process chamber. The second precursor <b>320</b> may comprise atoms of an element (labeled as B) with one or more reactive species (labeled as R₂) and the third precursor <b>330</b> may comprise atoms of an element (labeled as C) with one or more reactive species (labeled as R₃). The second precursor <b>320</b> and the third precursor <b>330</b> may be provided with or without the aid of a carrier gas. Examples of carrier gases which may be used include, but are not limited to, helium (He), argon (Ar), nitrogen (N₂), and hydrogen (H₂), and mixtures thereof.

[0044] It is believed, that the second precursor <b>320</b> and the third precursor <b>330</b> compete with one another to adsorb onto and to react with the first precursor <b>310</b>. The reaction of the first precursor <b>310</b> with the second precursor <b>320</b> and the reaction of the first precursor <b>310</b> with the third precursor <b>330</b> forms a ternary compound <b>340</b> comprising element A, element B, and element C and forms by-products <b>350</b>. The amount of the second precursor <b>320</b> reacting with the first precursor <b>310</b> in comparison to the amount of the third precursor <b>330</b> reacting with the first precursor <b>310</b> depends, along with other factors discussed herein, on the ratio of the second precursor versus the third precursor introduced into the chamber. Therefore, a layer <b>335</b>, which may be about a monolayer or may be more or less than a monolayer, of the combination of the second precursor <b>320</b> and the third precursor <b>330</b> may adsorb on the first precursor <b>310</b> and a monolayer <b>345</b> or less of the ternary compound <b>340</b> may form during one cycle. Therefore, sequential delivery of pulses of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time,is believed to result in the alternating adsorption of a layer of a first precursor and of a layer of a second precursor and a third precursor to form a layer of a ternary material.

[0045] After a pulse of the second precursor <b>320</b> and the third precursor <b>330</b>, a purge gas is introduced. Thereafter, as shown in FIG. 3C, the cycle of delivering three precursor to the substrate structure <b>300</b> may be repeated, if necessary, until a desired thickness of the ternary material <b>340</b> is achieved. In general, the composition of the ternary material <b>340</b> may be represented by the following expression AB_xC_yin which the atomic ratio of element A to element B to element C is 1 to X to Y in which X and Y may be any fraction including whole numbers, or mixed numbers.

[0046] In FIGS. <b>3</b>A-<b>3</b>C, formation of the ternary material layer is depicted as starting with the adsorption of a layer of the first precursor <b>310</b> on the substrate structure <b>300</b> followed by a layer of the combination of the second precursor <b>320</b> and the third precursor <b>330</b>. Alternatively, formation of the ternary material layer may start with the adsorption of a layer of the combination of the second precursor <b>320</b> and the third precursor <b>330</b> on the substrate structure <b>300</b> followed by adsorption of a layer of the first precursor <b>310</b>. In another theory, the precursors may be in an intermediate state when on a surface of the substrate. In addition, the deposited ternary compound <b>340</b> may also contain more than simply element A, element B, and element C due to other elements and/or by-products incorporated into the film. Furthermore, one or more of the precursors may be plasma enhanced. However, the second precursor <b>320</b> and the third precursor <b>330</b> are preferably introduced without a plasma to reduce the likelihood of co-reaction between the second precursor <b>320</b> and the third precursor <b>330</b>.

[0047] The amount of element B and the amount of element C in the ternary material may be varied by adjusting one or more variety of parameters. For example, the flow ratio of element B to element C between cycles may be varied. The flow ratio of element B to element C is not necessarily a one-to-one relationship of the amount of element B and element C incorporated into the ternary material. Other parameters which may affect incorporation of element B and element C in the ternary material include the substrate heater temperature, the pressure, and the amount and sequence of the overlap of element B to element C. Furthermore, the composition of the ternary material layer may be tuned so that the ternary material layer may comprise varying amounts of the three elements through the depth of the ternary material layer which is described in further detail elsewhere herein.

[0048] Preferably, there is a co-reaction of the first precursor <b>310</b> with the second precursor <b>320</b> and a co-reaction of the first precursor <b>310</b> with the third precursor <b>330</b> with a limited or no co-reaction of the second precursor <b>320</b> with the third precursor <b>330</b> to limit gas phase reactions between the second precursor <b>320</b> and the third precursor <b>330</b>. Because of the highly reactive nature of precursors containing halogens, such as metal halides and derivatives thereof, the second precursor <b>320</b> and the third precursor <b>330</b> preferably do not comprise halogens to reduce the likelihood of gas phase reactions between the second precursor <b>320</b> and the third precursor <b>330</b>. The deposition of the ternary compound may proceed by sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time, to the substrate structure <b>300</b>. The second precursor and the third precursor may be introduced through the chamber lid assembly through separate flow paths by separate valves or may be introduced through the chamber lid assembly through the same flow path by the same valve or separate valves. Preferably, the second precursor and the third precursor are introduced into the chamber by separate valves in fluid communication with separate flow paths through the chamber lid assembly.

[0049]FIG. 4A is a graph of an exemplary process of sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time. One cycle <b>400</b> comprises providing a continuous flow <b>442</b> of a purge gas <b>440</b> to the chamber. During the continuous flow <b>442</b> of the purge gas <b>440</b>, a pulse <b>412</b> of a first precursor <b>410</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>442</b> of the purge gas <b>440</b> by opening and closing a valve providing the first precursor. After the pulse <b>412</b> of the first precursor <b>410</b>, the flow <b>442</b> of the purge gas <b>440</b> continues into the chamber without any precursor introduced into the chamber. Then, during the continuous flow <b>442</b> of the purge gas <b>440</b>, a pulse <b>422</b> of a second precursor <b>420</b> and a pulse <b>432</b> of a third precursor <b>430</b> are introduced simultaneously into the chamber and dosed into the stream of the continuous flow <b>442</b> of the purge gas <b>440</b> by opening a valve providing the second precursor and a valve providing the third precursor substantially at the same time and, then, by closing the valve providing the second precursor and the valve providing the third precursor substantially at the same. After the pulse <b>422</b> of the second precursor <b>420</b> and the pulse <b>432</b> of the third precursor <b>430</b>, the flow <b>442</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. The cycle <b>400</b> may be repeated to deposit a desired thickness of the ternary material layer.

[0050]FIG. 4B is a graph of another exemplary process of sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time. One cycle <b>402</b> comprises providing a continuous flow <b>444</b> of a purge gas <b>440</b> to the chamber. During the continuous flow <b>444</b> of the purge gas <b>440</b>, a pulse <b>414</b> of a first precursor <b>410</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>444</b> of the purge gas <b>440</b> by opening and closing a valve providing the first precursor. After the pulse <b>414</b> of the first precursor <b>410</b>, the flow <b>444</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. Then, during the continuous flow <b>444</b> of the purge gas <b>440</b>, a pulse <b>424</b> of a second precursor <b>420</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>444</b> of the purge gas <b>440</b> by opening a valve providing the second precursor. Prior to the end of the pulse <b>424</b> of the second precursor <b>420</b>, a pulse <b>434</b> of a third precursor is introduced into the chamber and dosed into the stream of the continuous flow <b>444</b> of the purge gas <b>440</b> by opening a valve providing the third precursor. Then, the valve providing the second precursor is closed followed by closing the valve providing the third precursor. After the pulse <b>434</b> of the third precursor <b>430</b>, the flow <b>444</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. The cycle <b>402</b> may be repeated to deposit a desired thickness of the ternary material layer.

[0051]FIG. 4C is a graph of still another exemplary process of s sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time,. One cycle <b>404</b> comprises providing a continuous flow <b>446</b> of a purge gas <b>440</b> to the chamber. During the continuous flow <b>446</b> of the purge gas <b>440</b>, a pulse <b>416</b> of a first precursor <b>410</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>446</b> of the purge gas <b>440</b> by opening and closing a valve providing the first precursor. After the pulse <b>416</b> of the first precursor <b>410</b>, the flow <b>446</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. Then, during the continuous flow <b>446</b> of the purge gas <b>440</b>, a pulse <b>426</b> of a second precursor <b>420</b> is bled into the chamber prior to a pulse <b>436</b> of a third precursor <b>430</b> and dosed into the stream of the continuous flow <b>446</b> of the purge gas <b>440</b> by opening a valve providing the second precursor. The pulse <b>436</b> of the third precursor <b>430</b> is then introduced into the chamber and dosed into the stream of the continuous flow <b>446</b> of the purge gas <b>440</b> by opening a valve providing the third precursor. Then, the valve providing the second precursor and the valve providing the third precursor are closed substantially at the same time. After the pulse <b>426</b> of the second precursor <b>420</b> and the pulse <b>436</b> of the third precursor <b>430</b>, the flow <b>446</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. The cycle <b>404</b> may be repeated to deposit a desired thickness of the ternary material layer.

[0052]FIG. 4D is a graph of still another exemplary process of sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time. One cycle <b>406</b> of sequential delivery comprises providing a continuous flow <b>448</b> of a purge gas <b>440</b> to the chamber. During the continuous flow <b>448</b> of the purge gas <b>440</b>, a pulse <b>418</b> of a first precursor <b>410</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>448</b> of the purge gas <b>440</b> by opening and closing a valve providing the first precursor. After the pulse <b>418</b> of the first precursor <b>410</b>, the flow <b>448</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. Then, during the continuous flow <b>448</b> of the purge gas <b>440</b>, a pulse <b>428</b> of a second precursor <b>420</b> and a pulse <b>438</b> of a third precursor <b>430</b> are introduced simultaneously into the chamber and dosed into the stream of the continuous flow <b>448</b> of the purge gas <b>440</b> by opening a valve providing the second precursor and a valve providing the third precursor substantially at the same. The pulse <b>428</b> of the second precursor <b>420</b> is dragged behind the pulse <b>438</b> of the third precursor <b>430</b> by closing the valve providing the third precursor prior to closing the valve providing the second precursor. After the pulse <b>428</b> of the third precursor <b>420</b>, the flow <b>448</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. The cycle <b>406</b> may be repeated to deposit a desired thickness of the ternary material layer.

[0053]FIG. 4E is a graph of still another exemplary process of sequentially delivering a first precursor and delivering a second precursor and a third precursor within the scope of the present invention. One cycle <b>409</b> comprises providing a continuous flow <b>449</b> of a purge gas <b>440</b> to the chamber. During the continuous flow <b>449</b> of the purge gas <b>440</b>, a pulse <b>419</b> of a first precursor <b>410</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>449</b> of the purge gas <b>440</b> by opening and closing a valve providing the first precursor. After the pulse <b>419</b> of the first precursor <b>410</b>, the flow <b>449</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. Then, during the continuous flow <b>449</b> of the purge gas <b>440</b>, a pulse <b>429</b> of a second precursor <b>420</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>449</b> of the purge gas <b>440</b> by opening a valve providing the second precursor. . At the end of the pulse <b>429</b> of the second precursor, a pulse <b>439</b> of a third precursor <b>430</b> is introduced into the chamber and dosed into the stream of the continuous flow <b>448</b> of the purge gas <b>440</b> by closing a valve providing the second precursor and by opening a valve providing the third precursor substantially at the same time. Then, the valve providing the third precursor is closed. After the pulse <b>439</b> of the third precursor <b>430</b>, the flow <b>449</b> of the purge gas <b>440</b> continues into the chamber without any precursors introduced into the chamber. The cycle <b>409</b> may be repeated to deposit a desired thickness of the ternary material layer.

[0054] Referring to FIG. 4A, in one embodiment, the pulse <b>412</b> of the first precursor <b>410</b> is evacuated from a processing zone adjacent the substrate prior to introduction of the pulse <b>422</b> of the second precursor <b>420</b> and the pulse <b>432</b> of the third precursor <b>430</b>. In another embodiment, the pulse <b>412</b> of the first precursor <b>410</b> along with the pulse <b>422</b> of the second precursor <b>420</b> and the pulse <b>432</b> of the third precursor <b>430</b> may be present at the same time in a processing zone adjacent the substrate in which the pulse <b>412</b> of the first precursor <b>410</b> is at one portion of the substrate and the pulse <b>422</b> of the second precursor <b>420</b> and the pulse <b>432</b> of the third precursor <b>430</b> are at another portion of the substrate. Similarly in reference to FIGS. <b>4</b>B-<b>4</b>E, the pulse of the first precursor and the pulses of the second and third precursors may be present in the processing zone separately or may be present in the processing zone together with the pulse of the first precursor at one portion of the substrate and the pulse of the second precursor and the third precursor at another portion of the substrate.

[0055] FIGS. <b>4</b>A-<b>4</b>D are graphs of exemplary processes of sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time. Other embodiments of sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time, are within the scope of the present disclosure. Not wishing to be bound by theory, it is believed sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time, may provide a true ternary material layer comprising layers containing at the atomic level elements of the first precursor, the second precursor, and the third precursor. Not wishing to be bound by theory, it is believed that for sequential introduction of three precursors in which the pulses do not overlap in time (i.e., a first precursor, followed by the second precursor, followed by the third precursor or first precursor, followed by the second precursor, followed by the first precursor, followed by the third precursor), it is uncertain whether there is formation of a layer comprising amounts of elements A, B, and C. It is also believed that delivering pulses of a second precursor and a third precursor, in which the pulses of the second precursor and the third precursor at least partially overlap in time, aids in reducing the amount of precursor impurities incorporated into the deposited film due to the competitive nature of the second precursor versus the third precursor for the first precursor. In another aspect, cyclical deposition of a ternary material of three elements by exposing the substrate to three precursors in which the delivery of pulses of two of the three precursors at least partially overlap increases the throughput of cyclical deposition in comparison to a sequential introduction of the three precursors without any overlap of the pulses.

[0056]FIG. 4E is a graph of one exemplary process of sequentially delivering a first precursor, a second precursor, and a third precursor in which there is no purge gas which separates the flow of the second precursor and the third precursor. Not wishing to be bound by theory, although pulses of the second precursor and the third precursor do not overlap, it is believed that sequentially delivering a first precursor, a second precursor, and a third precursor in which there is no purge gas which separates the flow of the second precursor and the third precursor may provide conformal growth of a ternary material layer with improved throughput in comparison to prior processes of sequentially introducing multiple precursors. Other embodiments of sequentially delivering three or more precursors in which at least two of the precursors are not separated by a flow of a purge gas are possible.

[0057] The processes as described in referenced to FIG. 4A-<b>4</b>E comprise providing a continuous purge gas. The processes as disclosed herein may also comprise providing a purge gas in pulses. For example, FIG. 4F is a graph of an exemplary process similar to the process as described in FIG. 4A in which the purge gas is provided in pulses. One cycle <b>401</b> of sequential delivery of a first precursor, a second precursor, and a third precursor, in which pulses of the second precursor and the third precursor at least partially overlap in time comprises introducing a pulse <b>413</b> of a first precursor <b>410</b> into the chamber by opening and closing a valve providing the first precursor. After the pulse <b>413</b> of the first precursor <b>410</b>, a pulse <b>443</b>A of a purge gas <b>440</b> is introduced into the chamber by opening and closing a valve providing the purge gas. After the pulse <b>443</b>A of the purge gas <b>440</b>, a pulse <b>423</b> of a second precursor <b>420</b> and a pulse <b>433</b> of a third precursor <b>430</b> are introduced simultaneously into the chamber by opening a valve providing the second precursor and a valve providing the third precursor substantially at the same time and, then, by closing the valve providing the second precursor and the valve providing the third precursor substantially at the same. After the pulse <b>423</b> of the second precursor <b>420</b> and the pulse <b>433</b> of the third precursor <b>430</b>, another pulse <b>443</b>B of the purge gas <b>440</b> is introduced into the chamber by opening and closing the valve providing the purge gas. The cycle <b>401</b> may be repeated to deposit a desired thickness of the ternary material layer. In other embodiments, introduction of the pulses of the purge gas may overlap with the pulses of the precursors.

[0058] FIGS. <b>4</b>A-<b>4</b>F show each cycle starting with delivery of a pulse of a first precursor followed by delivery of a pulse of a second precursor and a pulse of a third precursor. Alternatively, formation of a ternary material layer may start with the delivery of a pulse of a second precursor and a pulse of a third precursor followed by a pulse of a first precursor. FIGS. <b>2</b>A-<b>2</b>F show the duration of pulses of precursors and/or a purge gas provided over a relative length of time. In other embodiments, other relative lengths of time are possible for the duration of the pulses. In addition, FIGS. <b>4</b>A-<b>4</b>E show introducing a pulse of a first precursor and providing a continuous flow of a purge gas in which the continuous flow is started at the same time as the pulse of a first precursor. In other embodiments, a continuous flow of a purge gas may be established prior to any precursor being introduced.

[0059] In one embodiment, the flow ratio of pulses of the precursors may be provided at a first ratio during initial cycles to form a first sub-layer having a first composition and the pulses of the precursor may be provided at a second ratio during final cycles to form a sub-layer having a second composition. For example, the flow ratio of the second precursor <b>420</b> (FIG. 4) and the third precursor <b>430</b> (FIG. 4) may be varied to tune the composition of the ternary material layer. In another embodiment, the pulses of the precursors may be provided at a first sequence during initial cycles to form a first sub-layer having a first composition and the pulses of the precursors may be provided at a second sequence during later cycles to form a second sub-layer.

[0060]FIG. 5 is a schematic cross-sectional view of one example of tuning the composition of a ternary material layer <b>540</b>. For example, initial cycles may comprise pulsing in the second precursor and the third precursor in which the pulses comprise a ratio of the second precursor to the third precursor to deposit a bottom sub-layer <b>560</b> with the composition of AB_X1C_Y1over a substrate structure <b>500</b>. Then, final cycles may comprise pulsing in the second precursor and the third precursor in which the ratio of the second precursor to the third precursor is increased to deposit a top sub-layer <b>570</b> with the composition of AB_X2C_Y2in which X2&gt;X1. Thus, a ternary material layer <b>540</b> comprising a bottom sub-layer (AB_X1C_Y1) <b>560</b> and a top sub-layer (AB_X2C_Y2) <b>570</b> in which X2&gt;X1 is formed. The ternary material layer <b>540</b> may be tuned to more or less than two different sub-layers and may be tuned to any ratio of element A to element B to element C for each of these sub-layers as desired for a particular application. For example, the second precursor and the third precursor may be introduced into the chamber at a flow ratio of the second precursor and the third precursor of about 0 to about 1 to provide a sub-layer having the composition AC_Y. Therefore, the ternary material layer may comprise a sub-layer of two elements. However, the ternary material layer <b>540</b> as a whole comprises three elements. In addition, the ternary material layer <b>540</b> may be gradually tuned to provide a graded layer comprising a plurality of sub-layers providing a gradually altering composition. Not wishing to be bound by theory, it is believed that a graded layer may provide a film having improved stress characteristics. In addition, it is believed that a graded layer may provide improved adhesion of the sub-layers with one another.

[0061]FIG. 6 is a flow chart illustrating one embodiment of a process utilizing a continuous flow of a purge gas to deposit a ternary material layer with a tuned composition or a variable content composition. These steps may be performed in a chamber, such as chamber <b>100</b> described in reference to FIGS. 1 and 1A and chamber <b>210</b> described in reference to FIG. 2. As shown in step <b>602</b>, a substrate is provided to the process chamber. The process chamber conditions, such as for example the substrate temperature and pressure, may be adjusted. In step <b>604</b>, a purge gas stream is established within the process chamber. Referring to step <b>606</b>, after the purge gas stream is established within the process chamber, a pulse of a first precursor is added or dosed into the purge gas stream. In step <b>608</b>, after the pulse of the first precursor, a pulse of a second precursor and a third precursor is dosed into the purge gas stream at a first ratio of the second precursor to the third precursor. Step <b>606</b> and step <b>608</b> are repeated until a predetermined number of cycles are performed to form a first sub-layer. Referring to step <b>610</b>, after a predetermined number of cycles of step <b>606</b> and step <b>608</b> are performed, a pulse of the first precursor is dosed into the purge gas stream. In step <b>612</b>, after the pulse of the first precursor, a pulse of the second precursor and the third precursor is dosed into the purge gas stream at a second ratio of the second precursor to the third precursor. Step <b>610</b> and step <b>612</b> are repeated until a predetermined number of cycles are performed to form a second sub-layer. Other embodiments include depositing a ternary material layer with a tuned composition comprising more than two sub-layers. Other embodiments of a process utilizing a continuous flow of a purge gas are possible to deposit a ternary material layer with a tuned composition. For example, the second precursor and the third precursor may be introduced in partially overlapping pulses.

[0062]FIG. 7 is a flow chart illustrating one embodiment of a process utilizing pulses of a purge gas to deposit a ternary material layer with a tuned composition or a variable content composition. These steps may be performed in a chamber, such as chamber <b>100</b> described in reference to FIGS. 1 and 1A and chamber <b>210</b> described in reference to FIG. 2. As shown in step <b>702</b>, a substrate is provided to the process chamber. The process chamber conditions, such as for example the substrate temperature and pressure, may be adjusted. In step <b>704</b>, a pulse of a purge gas is provided to the process chamber. Referring to step <b>706</b>, after the pulse of the purge gas of step <b>704</b> is introduced, a pulse of a first precursor is provided to the process chamber. In step <b>708</b>, after the pulse of the first precursor is provided, another pulse of the purge gas is provided to the process chamber. In step <b>710</b>, after the pulse of the purge gas of step <b>708</b> is introduced, a pulse of a second precursor and a third precursor is provided to the process chamber at a first ratio of the second precursor to the third precursor. Steps <b>704</b>, <b>706</b>, <b>708</b>, <b>710</b> are repeated until a predetermined number of cycles are performed to form a first sub-layer. Referring to step <b>712</b>, after a predetermined number of cycles of steps <b>704</b>, <b>706</b>, <b>708</b>, <b>710</b> are performed, another pulse of the purge gas is provided to the process chamber. Referring to step <b>714</b>, after the pulse of the purge gas of step <b>712</b> is introduced, a pulse of the first precursor is provided to the process chamber. In step <b>716</b>, after the pulse of the first precursor is provided, another pulse of the purge gas is provided to the process chamber. In step <b>718</b>, after the pulse of the purge gas of step <b>716</b> is introduced, a pulse of the second precursor and the third precursor is provided to the process chamber at a second ratio of the second precursor to the third precursor. Steps <b>712</b>, <b>714</b>, <b>716</b>, and <b>718</b> are repeated until a predetermined number of cycles are performed to form a second sublayer. Other embodiments include depositing a ternary material layer with a tuned composition or variable content composition comprising more than two sub-layers. Also, other embodiments of a process utilizing pulses of a purge gas are possible to deposit a ternary material layer with a tuned composition or variable content composition. For example, the second precursor and the third precursor may be introduced in partially overlapping pulses.

[0063] One example of a specific ternary compound with may be formed by overlapping pulses of two precursors is tungsten boron silicon (WB_xSi_y) utilizing a tungsten precursor, a boron precursor, and a silicon precursor. The tungsten boron silicon (WB_xSi_y) may comprise tungsten to boron to silicon in a ratio in which “X” is between about to 0.0 and about 0.35 and in which “Y” is between about 0.0 and about 0.20. In one embodiment, tungsten boron silicon (WB_xSi_y) is formed by overlapping pulses of the boron precursor and the silicon precursor. Applications of tungsten boron silicon (WB_xSi_y) include, but are not limited to, use as a nucleation layer to aid deposition of material thereover, such as tungsten, or use as a barrier layer to prevent diffusion of a metal deposited thereover, such as copper, aluminum, or combinations thereof.

[0064] The tungsten precursor preferably comprise tungsten hexafluoride (WF₆). Other examples of tungsten precursors include, but are not limited to, tungsten carbonyl (W(CO)₆), tungsten hexachloride (WCl₆), and derivatives thereof. The boron precursor preferably comprises diborane (B₂H₆). Other examples of boron precursors include, but are not limited to diborane (B₂H₆), triborane (B₃H₉), tetraborane (B₄H₁₂), pentaborane (B₅H₁₅), hexaborane (B₆H₁₈), heptaborane (B₇H₂₁), octaborane (B₈H₂₄), nanoborane (B₉H₂₇), decaborane (B₁₀H₃₀), and derivatives thereof. The silicon precursor preferably comprises silane (SiH₄) to reduce the likelihood of a co-reaction between the boron precursor and the silicon precursor. Other silicon precursors include, but are not limited to, disilane (Si₂H₆), chlorosilane (SiH₃Cl), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiHCl₃), silicon tetrachloride (SiCl₄), hexachlorodisilane (Si₂Cl₆), and derivatives thereof.

[0065] Another example of a specific ternary compound which may be formed by overlapping pulses of two precursors is titanium silicon nitride (TiSi_xN_y) utilizing a titanium precursor, a silicon precursor, and a nitrogen precursor. The titanium silicon nitride (TiSi_xN_y) may comprise titanium to silicon to nitrogen in a ratio in which “X” is between about 0.0 and about 2.0 and in which “Y” is between about 0.0 and about 1.0. In one embodiment, titanium silicon nitride (TiSi_xN_y) is formed by overlapping pulses of the silicon precursor and the nitrogen precursor. Applications of titanium silicon nitride (TiSi_xN_y) include, but are not limited to, use as a barrier layer for subsequent deposition of a metal layer thereover, such as a layer comprising copper, aluminum, or combinations thereof.

[0066] The titanium precursor preferably comprises titanium tetrachloride (TiCl₄). Examples of other titanium precursors include, but are not limited to, titanium iodide (Til₄), titanium bromide (TiBr₄), other titanium halides, tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), other metal organic compounds, and derivatives thereof. The silicon precursor preferably comprises silane (SiH₄) to reduce the likelihood of a co-reaction between the silicon precursor and the nitrogen precursor. Other silicon precursors include, but are not limited to disilane (Si₂H₆), chlorosilane (SiH₃Cl), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiHCl₃), silicon tetrachloride (SiCl₄), hexachlorodisilane (Si₂Cl₆), and derivatives thereof. The nitrogen precursor preferably comprises ammonia (NH₃). Examples of other nitrogen precursors include, but are not limited to hydrazine (N₂H₄), other N_xH_ycompounds with x and y being integers, dimethyl hydrazine ((CH₃)₂N2H2), t-butylhydrazine (C₄H₉N₂H₃), phenylhydrazine (C₆H₅N₂H₃), 2,2′-azoisobutane ((CH₃)₆C₂N₂), ethylazide (C₂H₅N₃), and derivatives thereof.

[0067] Another example of a specific ternary compound which may be formed by overlapping pulses of two precursors is tantalum silicon nitride (TaSi_xN_y) utilizing a tantalum precursor, a silicon precursor, and a nitrogen precursor. The tantalum silicon nitride (TaSi_xN_y) may comprise tantalum to silicon to nitrogen in a ratio in which “X” is between about 0.0 and about 1.0 and in which “Y” is between about 0.0 and about 2.0. In one embodiment, tantalum silicon nitride (TaSi_xN_y) is formed by overlapping pulses of the silicon precursor and the nitrogen precursor. Applications of tantalum silicon nitride (TaSi_xN_y) include, but are not limited to, use as a barrier layer for subsequent deposition of a metal layer thereover, such as a layer comprising copper, aluminum, or combinations thereof.

[0068] The tantalum precursor preferably comprises tantalum pentachloride (TaCl₅). Examples of other tantalum precursors include, but are not limited to tantalum fluoride (TaF₅), tantalum bromide (TaBr₅), pentadimethylamino-tantalum (PDMAT; Ta(NMe₂)₅), pentaethylmethylamino-tantalum (PEMAT; Ta[N(C₂H₅CH₃)₂]₅), pentadiethylamino-tantalum (PDEAT; Ta(NEt₂)₅,), TBTDET (Ta(NEt₂)₃NC₄H₉or C₁₆H₃₉N₄Ta), and derivatives thereof. The silicon precursor preferably comprises silane (SiH₄) to reduce the likelihood of a co-reaction between the silicon precursor and the nitrogen precursor.

[0069] Other silicon precursors include, but are not limited to chlorosilane (SiH₃Cl), dichlorosilane (SiH₂C₂), trichlorosilane (SiHCl₃), silicon tetrachloride (SiCl₄), hexachlorodisilane (Si₂Cl₆), and derivatives thereof. The nitrogen precursor preferably comprises ammonia (NH₃). Examples of other nitrogen precursors include, but are not limited to hydrazine (N₂H₄), other N_xH_ycompounds with x and y being integers, dimethyl hydrazine ((CH₃)₂N2H2), t-butylhydrazine (C₄H₉N₂H₃), phenylhydrazine (C₆H₅N₂H₃), 2,2′-azoisobutane ((CH₃)₆C₂N₂), ethylazide (C₂H₅N₃), and derivatives thereof.

[0070] Still another example of a specific ternary compound which may be formed by overlapping pulses of two precursors is silicon oxynitride (SiO_xN_y) utilizing a silicon precursor, an oxygen precursor, and a nitrogen precursor. The silicon oxynitride may comprise silicon to oxygen to nitrogen in a ratio in which “X” is between about 0.0 and about 2.0 and in which “Y” is between about 0 and about 1.33. For example, when X is about 2.0 and Y is about 0.0, the silicon oxynitride will comprise SiO₂. For example, when X is about 0.0 and Y is about 1.33, the silicon oxynitride will comprise Si₃N₄. In one embodiment, silicon oxynitride (SiO_xN_y) is formed by overlapping pulses of the oxygen precursor and the nitrogen precursor. Applications of silicon oxynitride include, but are not limited to, use as an anti-reflective coating, a dielectric layer, or a barrier layer.

[0071] The silicon precursor preferably comprises silicon tetrachloride (SiCl₄). Other silicon precursors include, but are not limited to silane (SiH₄), disilane (Si₂H₆), chlorosilane (SiH₃Cl), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiHCl₃), hexachlorodisilane (Si₂Cl₆), and derivatives thereof. The oxygen precursor preferably comprises water vapor (H₂O). Other oxygen precursors include, but are not limited to, oxygen gas (O₂) and ozone (O₃). The nitrogen precursor preferably comprises ammonia (NH₃). Examples of other nitrogen precursors include, but are not limited to hydrazine (N₂H₄), other N_xH_ycompounds with x and y being integers, dimethyl hydrazine ((CH₃)₂N2H2), t-butylhydrazine (C₄H₉N₂H₃), phenylhydrazine (C₆H₅N₂H₃) 2,2′-azoisobutane ((CH₃)₆C₂N₂), ethylazide (C₂H₅N₃), and derivatives therof.

[0072] Still another example of a specific ternary compound which may be formed by overlapping pulsesof two precursors is hafnium silicon oxide (HfSi_xO_y) utilizing a hafnium precursor, a silicon precursor, and a oxygen precursor. The hafnium silicon oxide may comprise hafnium to silicon to oxygen in a ratio in which “X” is between about 0.0 and about 0.5 and in which “Y” is between about 0.0 and about 1.0. In one embodiment, hafnium silicon oxide (HfSi_xO_y) is formed by overlapping pulses of the silicon precursor and the oxygen precursor. Applications of hafnium silicon oxide include, but are not limited to, use as a high-k dielectric material layer.

[0073] Examples of a hafnium precursor includes, but is not limited to, hafnium tetrachloride (HfCl₄) and derivatives thereof. The silicon precursor preferably comprises silane (SiH₄) to reduce the likelihood of a co-reaction between the silicon precursor and the oxygen precursor. Other silicon precursors include, but are not limited to disilane (Si₂H₆), chlorosilane (SiH₃Cl), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiHCl₃), silicon tetrachloride (SiCl₄), hexachlorodisilane (Si₂Cl₆), and derivatives thereof. The oxygen precursor preferably comprises water vapor (H₂O). Other oxygen precursors include, but are not limited to, oxygen gas (O₂) and ozone (O₃).

[0074] While foregoing is directed to the preferred embodiment 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.