Catalyst-Enhanced Seamless Ruthenium Gap Filling

Abstract

To provide methods for selective deposition of a metal film on a metal surface over a dielectric surface.SOLUTION: The present invention provides methods of selectively depositing films. A second metal surface of a substrate, which includes a substrate surface including a first dielectric surface and the second metal surface, is exposed to a precursor of the general formula (I): M-L1(L2)y, causing the film to be selectively deposited on the second metal surface over the first dielectric surface. (M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, and y is a number in the range of from 2 to 8 to form a metal film on the substrate surface, where the L2 comprises 1,5-hexadiene, 1,4-hexadiene, and less than 5% of 1,3-hexadiene).SELECTED DRAWING: Figure 8

Description

Technical Field

[0001]

[0001] Embodiments of the present disclosure generally relate to a method for depositing a metal film. One or more embodiments of the present disclosure are directed to a method for depositing a metal film. One or more embodiments of the present disclosure relate to selective deposition of a metal film.

Background Art

[0002]

[0002] The semiconductor industry is continuously pursuing device miniaturization due to the need for mobile and high-performance systems in emerging industries such as autonomous vehicles, virtual reality, and future mobile devices. To achieve this excellent technology, new high-performance materials are needed to avoid the inherent engineering and physical problems encountered during the rapid reduction of features in microelectronic devices.

[0003]

[0003] Ruthenium is a proposed material for integration due to its high melting point (ability to withstand high current density), exceptional density, and conductivity. Ruthenium and ruthenium-containing thin films have attractive material and conductive properties. Ruthenium films have been proposed for use in front-end to back-end components of semiconductor and microelectronic devices.

[0004]

[0004] Ruthenium thin films are ideally deposited using thin film deposition techniques such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) because of their ability to deposit materials with high throughput and precision.

[0005]

[0005] Deposited ruthenium films often differ from bulk ruthenium materials. In particular, there are challenges in depositing ruthenium films with high purity (>99% Ru) as a gap filling material. In previous solutions that included the use of oxygen reactants, films with greater roughness than the bulk material were produced. Similarly, hydrogen reactants resulted in greater impurities that required subsequent annealing steps. Finally, plasma deposition processes were unable to deposit gap filling materials without creating seams and without potentially damaging underlying substrates.

[0006]

[0006] Accordingly, there is a need for methods and materials for depositing high purity conformal ruthenium films as gap fills.

[0007]

[0007] Accordingly, there is a need for methods and materials for depositing high purity conformal ruthenium films as gap fills. There is also a need for methods and materials for depositing ruthenium films as gap fills without seams or voids.

[0008]

[0008] As semiconductor device designs evolve, precision material fabrication in the semiconductor industry has entered an era of atomic scale dimensions. At the atomic scale, with only dozens of atoms involved, there is little room for error. This unprecedented challenge requires new material processing technologies with atomic level precision. However, the increasing complexity of the processing flows required in atomic scale device manufacturing can significantly reduce throughput and increase manufacturing costs.

[0009]

[0009] Selective deposition techniques offer the possibility of chemical selective atomic layer refinement in semiconductor film patterning. Selective deposition also offers the possibility of a simpler processing flow by eliminating lithography or other processes.

[0010]

[0010] Selective deposition of materials can be achieved in various ways. For example, some processes may have a selectivity specific to a surface based on interfacial chemistry. Such processes are rather rare and usually require multiple surfaces (e.g., metal and dielectric) with significantly different surface energies.

[0011]

[0011] Therefore, there is a need for a method of selectively depositing a metal film on a metal surface over a dielectric surface or vice versa.

Summary of the Invention

[0012]

[0012] One or more embodiments of the present disclosure are directed to a method of forming a film. The method includes exposing a substrate surface to a precursor of the general formula (I): M-L1(L2) y (wherein M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, y is a number in the range of 2 to 8, and L2 includes 1,5 - hexadiene, 1,4 - hexadiene, and less than 5% of 1,3 - hexadiene) to form a film on the substrate surface.

[0013]

[0013] Additional embodiments of the present disclosure are directed to a method of forming a substrate. In one or more embodiments, the method includes exposing a substrate surface to a halogen catalyst to form an activated substrate surface and exposing the activated substrate surface to a precursor of the general formula (I): M-L1(L2) y (wherein M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, y is a number in the range of 2 to 8 for forming a metal film on the substrate surface, and L2 includes 1,5 - hexadiene, 1,4 - hexadiene, and less than 5% of 1,3 - hexadiene).

[0014]

[0014] A further embodiment is directed to a non - transitory computer - readable medium that, when executed by a controller of a processing chamber, causes the processing chamber to perform exposing a substrate surface to a halogen catalyst to form an activated substrate surface and flowing a precursor into a processing space of the processing chamber. The precursor has the general formula (I): M - L1(L2) y (wherein M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, y is a number in the range of 2 - 8, and L2 includes 1,5 - hexadiene, 1,4 - hexadiene, and less than 5% of 1,3 - hexadiene).

[0015]

[0015] To understand the above - described features of the present disclosure in detail, a more specific description of the present disclosure, briefly summarized above, can be obtained by referring to the embodiments. Some embodiments are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings show only typical embodiments of the present disclosure and are therefore not considered to limit the scope of the present disclosure, and the present disclosure may admit other equally effective embodiments.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10A

Figure 10B

Figure 10C

Figure 10D

DETAILED DESCRIPTION OF THE INVENTION

[0017]

[0026] Before describing some exemplary embodiments of the present disclosure, it should be understood that the present disclosure is not limited to the details of the configurations or process routines presented in the following description. The present disclosure is capable of other embodiments and can be practiced or executed in various ways.

[0018]

[0027] As used herein, the terms "substrate", "substrate surface", etc. refer to any substrate or material surface formed on a substrate on which processing is performed. For example, substrate surfaces on which processing can be performed include, but are not limited to, materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, etc., and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials. The substrate includes, but is not limited to, semiconductor wafers. The substrate may be exposed to pretreatment steps such as polishing, etching, reduction, oxidation, hydroxylation (or otherwise generating or grafting target chemical moieties to impart chemical functionality), annealing, and / or baking. In addition to processing directly on the surface of the substrate itself, in the present disclosure, any of the disclosed film processing steps may be performed on an underlying layer formed on the substrate, which is disclosed in more detail below. The term "substrate surface" is intended to include such underlying layers, as the context indicates. Thus, for example, when a film / layer or a partial film / layer is deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a given substrate surface includes depends on what materials are deposited and the specific chemistry used.

[0019]

[0028] As used herein, "atomic layer deposition" or "cyclic deposition" refers to depositing a material layer on a substrate surface by sequential exposure to two or more reactive compounds. The terms "reactive compound", "reactive gas", "reactant species", "precursor", "processing gas", etc., as used herein and in the appended claims, are used interchangeably and mean a substance having species capable of reacting with the substrate surface or a material on the substrate surface in a surface reaction (e.g., chemisorption, oxidation, reduction). The substrate or a part of the substrate is separately exposed to two or more reactive compounds introduced into the reaction zone of the processing chamber. In time-domain ALD processing, the exposure to each reactive compound is separated by a time delay, whereby each compound can adhere to and / or react on the substrate surface and then be purged from the processing chamber. These reactive compounds are said to be continuously exposed to the substrate. In spatial ALD processing, various portions of the substrate surface or a material on the substrate surface are simultaneously exposed to two or more reactive compounds such that any given point on the substrate is not substantially simultaneously exposed to a plurality of reactive compounds. As used herein and in the appended claims, the expression "substantially" as so used means that, as would be understood by one of ordinary skill in the art, a small portion of the substrate may be simultaneously exposed to a plurality of reactive gases due to diffusion, and that such simultaneous exposure is not intended.

[0020]

[0029] In one aspect of time-domain ALD processing, after a first reactive gas (i.e., a first precursor or compound A) is pulsed into the reaction zone, there is a first time delay. Next, a second precursor or compound B is pulsed into the reaction zone, followed by a second delay. During each time delay, a purge gas such as argon is introduced into the processing chamber to purge the reaction zone or, alternatively, to remove any residual reactive compounds or reactive by-products from the reaction zone. Alternatively, the purge gas may flow continuously throughout the deposition process such that only the purge gas flows during the time delay between pulses of the reactive compounds. The reactive compounds are pulsed alternately until a desired film or film thickness is formed on the substrate surface. In either case, the ALD process of pulsing compound A, the purge gas, compound B, and the purge gas is performed periodically. The cycle may start with either compound A or compound B, and the corresponding sequence of the cycle is continued until a film having a predetermined thickness is achieved.

[0021]

[0030] In one embodiment of spatial ALD processing, a first reactive gas and a second reactive gas (e.g., hydrogen gas) are supplied to the reaction zone simultaneously but are separated by an inert gas curtain and / or a vacuum curtain. The substrate is moved relative to the gas supply device such that any given point on the substrate is exposed to the first reactive gas and the second reactive gas.

[0022]

[0031] As used herein, "chemical vapor deposition" refers to a process in which a substrate surface is exposed to a precursor and / or co-reagents simultaneously or substantially simultaneously. As used herein, "substantially simultaneously" refers to either co-flow or where there is an overlap for most of the exposure of the precursor.

[0023]

[0032] The terms "reactive compound", "reactive gas", "reactive species", "precursor", "processing gas", etc. used in this specification and the appended claims are used interchangeably and mean a substance having species capable of reacting with the substrate surface or materials on the substrate surface in surface reactions (e.g., chemisorption, oxidation, reduction).

[0024]

[0033] One or more embodiments of the present disclosure are directed to a process using a reaction chamber having a plurality of gas ports that can be used for introducing different chemical substances or plasma gases. Spatially, these gas ports (also referred to as channels) are separated by an inert purge gas and / or vacuum pumping holes to minimize or eliminate the mixing of gases from different gas ports and generate a gas curtain that avoids unwanted gas-phase reactions. The wafers moving through these various spatially separated ports obtain a plurality of successive surface exposures to different chemical substances or plasma environments such that layer-by-layer film growth or surface etching processes occur in a spatial ALD mode. In one or more embodiments, the processing chamber has a modular architecture on a gas distribution component, and each modular component has independent parameter control (e.g., RF or gas flow) to provide flexibility in controlling, for example, gas flow and / or RF exposure.

[0025]

[0034] One or more embodiments of the present disclosure provide a method for depositing a high-purity metal film. The methods of the various embodiments use atomic layer deposition (ALD) or chemical vapor deposition (CVD) to provide a pure or nearly pure metal film. Exemplary embodiments of the present disclosure refer to the deposition of ruthenium, but the principles of the present disclosure are believed to enable the deposition of high-purity metal films regardless of the metal.

[0026]

[0035] One or more embodiments of the present disclosure provide a method for selectively depositing a metal film on a metal surface on a dielectric surface. One or more embodiments of the present disclosure provide a method for selectively depositing a metal film on a dielectric surface on a metal surface. As used herein and in the appended claims, expressions such as "selectively depositing a film on another surface on one surface" mean that a first amount of the film is deposited on the first surface, a second amount of the film is deposited on the second surface, and the second amount of the film is less than the first amount of the film, or no film is deposited on the second surface.

[0027]

[0036] As used in this way, the expression "over" does not mean the physical orientation of the other surface above one surface, but rather means the relationship of the thermodynamic or mechanical properties of the chemical reaction of the other surface to one surface. For example, selectively depositing a ruthenium film on a metal surface on a dielectric surface means that the ruthenium film is deposited on the metal surface, and little or no ruthenium film is deposited on the dielectric surface, or that the formation of the ruthenium film on the metal surface is thermodynamically or kinetically favorable for the formation of the ruthenium film on the dielectric surface.

[0028]

[0037] The selectivity of the deposition process is generally expressed as a multiple of the growth rate. For example, if one surface grows (or is deposited) 25 times faster than another surface, this process is described as having a selectivity of 25:1. Thus, a higher ratio indicates a more selective process.

[0029]

[0038] One or more embodiments of the present disclosure advantageously provide a method for depositing a metal film with high purity. Thus, these high-purity films exhibit properties similar to those of the associated bulk metal material. For example, one or more embodiments of the present disclosure provide a ruthenium film that is smoother and has lower resistance than a ruthenium film deposited by conventional oxygen or hydrogen reactant treatment. One or more embodiments of the present disclosure advantageously provide a metal film that conformally fills gaps without seams.

[0030]

[0039] One or more embodiments of the present disclosure advantageously provide for the selective deposition of a high-purity metal film onto a metal surface on a dielectric surface. For example, the selective deposition of ruthenium onto copper on a dielectric advantageously provides a copper capping layer without additional etching or lithography steps. Additionally, the selective deposition may enable bottom-up gap filling for trenches having metal contacts on the bottom and dielectric sidewalls.

[0031]

[0040] One or more embodiments of the present disclosure advantageously provide for the selective deposition of a high-purity metal film onto a dielectric surface on a metal surface. For example, the selective deposition of a metal onto a dielectric advantageously provides a metal layer on a barrier or other dielectric in back-end applications.

[0032]

[0041] One or more embodiments of the present disclosure utilize spatial ALD processing executed on a processing platform as disclosed herein. Referring to the drawings, FIG. 1 shows a processing platform 100 according to one or more embodiments of the present disclosure. The embodiment shown in FIG. 1 merely represents one possible configuration and should not be construed as limiting the scope of the present disclosure. For example, in one or more embodiments, the processing platform 100 may have a different number of processing chambers, buffer chambers, and robot configurations.

[0033]

[0042] The processing platform 100 includes a central transfer station 110 having a plurality of sides 111, 112, 113, 114, 115, 116. The illustrated central transfer station 110 has a first side 111, a second side 112, a third side 113, a fourth side 114, a fifth side 115, and a sixth side 116. Although six sides are shown here, those skilled in the art will understand that the central transfer station 110 may have any suitable number of sides depending on, for example, the overall configuration of the processing platform 100.

[0034]

[0043] Transfer station 110 has a robot 117 positioned therein. Robot 117 can be any suitable robot capable of moving a wafer during processing. In one or more embodiments, robot 117 has a first arm 118 and a second arm 119. The first arm 118 and the second arm 119 can move independently of the other arm. The first arm 118 and the second arm 119 can move in the x-y plane and / or along the z-axis. In one or more embodiments, robot 117 includes a third arm or a fourth arm (not shown). Each arm can move independently of the other arms.

[0035]

[0044] The first batch processing chamber 120 can be connected to the first side 111 of the central transfer station 110. The first batch processing chamber 120 can be configured to process x wafers at a time during batch time. In one or more embodiments, the first batch processing chamber 120 can be configured to process from about 4 (x = 4) to about 12 (x = 12) wafers simultaneously. In one or more embodiments, the first batch processing chamber 120 is configured to process 6 (x = 6) wafers simultaneously. As will be understood by those skilled in the art, the first batch processing chamber 120 can process multiple wafers between the loading and unloading of individual wafers, but each wafer can be exposed to different processing conditions at any given time. For example, a spatial atomic layer deposition chamber exposes the wafer to different processing conditions in different processing regions as the wafer moves through each region, as shown in FIGS. 2 through 6, such that the processing is completed.

[0036]

[0045] Figure 2 shows a cross-section of a processing chamber 200 including a gas distribution assembly 220 (also referred to as an injector or injector assembly), and a susceptor assembly 240. The gas distribution assembly 220 is any type of gas supply device used within the processing chamber. The gas distribution assembly 220 includes a front face 221 that faces the susceptor assembly 240. The front face 221 may have any number or variety of openings for communicating a gas flow toward the susceptor assembly 240. The gas distribution assembly 220 also includes an outer peripheral edge 224 that is substantially circular in the illustrated embodiment.

[0037]

[0046] The particular type of gas distribution assembly 220 used may vary depending on the particular process being used. Embodiments of the present disclosure are capable of being used with any type of processing system in which the gap between the susceptor and the gas distribution assembly is controlled. A variety of types of gas distribution assemblies (e.g., showerheads) may be utilized, but embodiments of the present disclosure may be particularly useful in a spatial gas distribution assembly having a plurality of substantially parallel gas channels. As used herein and in the appended claims, the expression "substantially parallel" means that the longitudinal axes of the gas channels extend generally in the same direction. There may be some imperfection in the parallelism of the gas channels. In a two-component reaction, the plurality of substantially parallel gas channels may include at least one first reactive gas A channel, at least one second reactive gas B channel, at least one purge gas P channel, and / or at least one vacuum V channel. The gas flowing from one or more of the first reactive gas A channels, one or more of the second reactive gas B channels, and one or more of the purge gas P channels is directed toward the upper surface of the wafer. Some of the gas flow moves horizontally across the wafer surface and exits the processing region through one or more of the purge gas P channels. As the substrate moves from one end of the gas distribution assembly to the other end, the substrate is sequentially exposed to each processing gas, and a layer is formed on the substrate surface.

[0038]

[0047] In one or more embodiments, the gas distribution assembly 220 is a rigid stationary object made of a single injector unit. In one or more embodiments, the gas distribution assembly 220 is composed of a plurality of individual sectors (e.g., injector units 222), as shown in FIG. 3. Whether it is a single object or an object composed of multiple sectors, it can be used with various embodiments of the present disclosure described.

[0039]

[0048] In one or more embodiments, the susceptor assembly 240 is positioned below the gas distribution assembly 220. The susceptor assembly 240 includes an upper surface 241 and at least one recess 242 in the upper surface 241. The susceptor assembly 240 further has a bottom surface 243 and an edge 244. The at least one recess 242 can be of any suitable shape and size according to the shape and size of the substrate 60 to be processed. In the embodiment shown in FIG. 2, the recess 242 has a flat bottom to support the bottom of the wafer, but the bottom of the recess can vary. In one or more embodiments, the recess has a stepped region sized to support the outer edge of the wafer around the outer edge of the recess. The amount of the outer edge of the wafer supported by this step can vary, for example, according to the thickness of the wafer and the presence of features already on the back surface of the wafer.

[0040]

[0049] In one or more embodiments, as shown in FIG. 2, the recess 242 in the upper surface 241 of the susceptor assembly 240 is sized such that the substrate 60 supported within the recess 242 has an upper surface 61 that is substantially coplanar with the upper surface 241 of the susceptor 240. As used in this specification and the appended claims, the term "substantially coplanar" means that the upper surface of the wafer and the upper surface of the susceptor assembly are in the same plane within a range of ±0.2 mm. In one or more embodiments, the upper surfaces are in the same plane within a range of 0.5 mm, ±0.4 mm, ±0.35 mm, ±0.30 mm, ±0.25 mm, ±0.20 mm, ±0.15 mm, ±0.10 mm, or ±0.05 mm.

[0041]

[0050] The susceptor assembly 240 of FIG. 2 includes support posts 260 capable of raising, lowering, and rotating the susceptor assembly 240. The susceptor assembly may include a heater or a gas line or an electrical component inside the center of the support posts 260. The support posts 260 can be a main means of moving the susceptor assembly 240 to an appropriate position by widening or narrowing the gap between the susceptor assembly 240 and the gas distribution assembly 220. The susceptor assembly 240 may further include a fine adjustment actuator 262. The fine adjustment actuator 262 can perform fine adjustment on the susceptor assembly 240 so that a predetermined gap 270 is formed between the susceptor assembly 240 and the gas distribution assembly 220.

[0042]

[0051] In one or more embodiments, the distance of the gap 270 is within the range of about 0.1 mm to about 5.0 mm, or within the range of about 0.1 mm to about 3.0 mm, or within the range of about 0.1 mm to about 2.0 mm, or within the range of about 0.2 mm to about 1.8 mm, or within the range of about 0.3 mm to about 1.7 mm, or within the range of about 0.4 mm to about 1.6 mm, or within the range of about 0.5 mm to about 1.5 mm, or within the range of about 0.6 mm to about 1.4 mm, or within the range of about 0.7 mm to about 1.3 mm, or within the range of about 0.8 mm to about 1.2 mm, or within the range of about 0.9 mm to about 1.1 mm, or is about 1 mm.

[0043]

[0052] The processing chamber 200 shown in the figure is a carousel-type chamber in which the susceptor assembly 240 can hold a plurality of substrates 60. As shown in FIG. 3, the gas distribution assembly 220 can include a plurality of individual injector units 222. Each injector unit 222 is capable of depositing a film on the wafer as the wafer moves below the injector unit. Two pie-shaped injector units 222 are shown positioned substantially on both sides of and above the susceptor assembly 240. The number of injector units 222 is shown for illustrative purposes only. It should be understood that more or fewer injector units 222 may be included. In one or more embodiments, there are a sufficient number of pie-shaped injector units 222 to form a shape that follows the shape of the susceptor assembly 240. In one or more embodiments, each individual pie-shaped injector unit 222 can be moved, removed, and / or replaced individually without affecting any of the other injector units 222. For example, by raising a segment, the robot can access the area between the susceptor assembly 240 and the gas distribution assembly 220 to enable loading / unloading of the substrate 60.

[0044]

[0053] In one or more embodiments, a processing chamber having a plurality of gas injectors can be used to process a plurality of wafers simultaneously such that the wafers undergo the same process flow. For example, as shown in FIG. 4, the processing chamber 200 has four gas injector assemblies and four substrates 60. At the start of processing, the substrates 60 can be placed between the gas distribution assemblies 220. By rotating the susceptor assembly 240 by 45°, each substrate 60 located between the gas distribution assemblies 220 is moved towards the gas distribution assembly 220 as shown by the dotted circle below the gas distribution assembly 220 for film deposition. By further rotating by 45°, the substrate 60 will move away from the gas distribution assembly 220. The number of substrates 60 and the number of gas distribution assemblies 220 may be the same or different. In one or more embodiments, the number of wafers to be processed is the same as the number of gas distribution assemblies. In one or more embodiments, the number of wafers to be processed is a fraction or an integer multiple of the number of gas distribution assemblies. For example, if there are four gas distribution assemblies, the number of wafers to be processed is 4x, where x is an integer value of 1 or more. In an exemplary embodiment, the gas distribution assembly 220 includes eight processing regions separated by gas curtains, and the susceptor assembly 240 can hold six wafers.

[0045]

[0054] The processing chamber 200 shown in FIG. 4 merely represents one possible configuration and should not be considered as limiting the scope of the present disclosure. Here, the processing chamber 200 includes a plurality of gas distribution assemblies 220. In the illustrated embodiment, there are four gas distribution assemblies 220 (also referred to as injector assemblies), which are arranged equidistantly around the processing chamber 200. Although the illustrated processing chamber 200 is octagonal, those skilled in the art will understand that this is one possible shape and should not be considered as limiting the scope of the present disclosure. The illustrated gas distribution assembly 220 is trapezoidal, but it could be a single circular component or, as shown in FIG. 3, could be composed of a plurality of pie-shaped segments.

[0046]

[0055] The embodiment shown in FIG. 4 includes an auxiliary chamber such as a load lock chamber 280 or a buffer station. This chamber 280 is connected to the side of the processing chamber 200, whereby, for example, a substrate (also referred to as substrate 60) can be loaded / unloaded between the processing chamber 200. A wafer robot may be disposed within the chamber 280 to move the substrate onto the susceptor.

[0047]

[0056] The rotation of the carousel (e.g., susceptor assembly 240) may be continuous or intermittent (discontinuous). In continuous processing, the wafer is always rotating and is successively exposed to each injector. In discontinuous processing, the wafer may move to the injector region and stop, and then move to the region 84 between injectors and stop. For example, the carousel can rotate until the wafer moves from the region between injectors through the injector (or stops adjacent to the injector) to the next region between injectors where the carousel can stop again. By stopping between injectors, time can be ensured for performing additional processing routines (e.g., exposure to plasma) between depositions of each layer.

[0048]

[0057] FIG. 5 shows a sector or a part of the gas distribution assembly 220, which may also be referred to as an injector unit. The injector unit 222 may be used individually or in combination with other injector units. For example, as shown in FIG. 6, four of the injector units 222 of FIG. 5 are combined to form a single gas distribution assembly 220 (for clarity, the lines separating the four injector units are not shown). The injector unit 222 of FIG. 5 has both a first reactive gas port 225 and a second gas port 235 in addition to a purge gas port 255 and a vacuum port 245, but not all of these components are necessary for the injector unit 222.

[0049]

[0058] Referring to both FIGS. 5 and 6, a gas distribution assembly 220 according to one or more embodiments may include a plurality of sectors (or injector units 222), each sector being the same or different. The gas distribution assembly 220 is disposed within the processing chamber and includes a plurality of elongated gas ports 225, 235, 245 on the front surface 221 of the gas distribution assembly 220. The plurality of elongated gas ports 225, 235, 245, 255 extend from a region adjacent to the inner peripheral edge 223 to a region adjacent to the outer peripheral edge 224 of the gas distribution assembly 220. The plurality of gas ports shown include a first reactive gas port 225, a second gas port 235, a vacuum port 245 surrounding each of the first reactive gas port and the second reactive gas port, and a purge gas port 255.

[0050]

[0059] Referring to the embodiment shown in FIG. 5 or FIG. 6, even though it has been stated that the port extends at least from around the inner peripheral region to around the outer peripheral region, the port may not simply extend radially from the inner region to the outer region. Since the vacuum port 245 surrounds the reactive gas ports 225 and 235, the port can extend in a tangential direction. In the embodiments shown in FIGS. 5 and 6, the wedge-shaped reactive gas ports 225, 235 are surrounded by the vacuum port 245 on all edges including the edges adjacent to the inner and outer peripheral regions.

[0051]

[0060] Referring to FIG. 5, as the substrate moves along path 227, each portion of the substrate surface is exposed to various reactive gases. Following path 227, the substrate is exposed to, i.e., "encounters", purge gas port 255, vacuum port 245, first reactive gas port 225, vacuum port 245, purge gas port 255, vacuum port 245, second gas port 235, and then vacuum port 245. Thus, at the end of path 227 shown in FIG. 5, the substrate is exposed to the first reactive gas and the second reactive gas, and a layer is formed. The illustrated injector unit 222 forms a quadrant, but may be larger or smaller. The gas distribution assembly 220 shown in FIG. 6 may be considered as four injector units 222 of FIG. 3 connected and combined continuously.

[0052]

[0061] The injector unit 222 of FIG. 5 shows a gas curtain 250 that separates reactive gases. The term "gas curtain" is used to describe any combination of gas flows or vacuums that separate so as not to mix reactive gases. The gas curtain 250 shown in FIG. 5 includes a portion of vacuum port 225 adjacent to the first reactive gas port 225, an intermediate purge gas port 255, and a portion of vacuum port 245 adjacent to the second gas port 235. This combination of gas flow and vacuum can be used to prevent or minimize the gas-phase reaction between the first reactive gas and the second reactive gas.

[0053]

[0062] Referring to FIG. 6, the combination of gas flow and vacuum from the gas distribution assembly 220 forms separations in a plurality of processing regions 350. The processing regions are roughly defined around the individual gas ports 225, 235 and are accompanied by gas curtains 250 therebetween. The embodiment shown in FIG. 6 consists of eight separate processing regions 350, with eight separate gas curtains 250 therebetween. The processing chamber may have at least two processing regions. In one or more embodiments, there are at least 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 processing regions.

[0054]

[0063] During processing, the substrate can be exposed to one or more processing regions 350 at any given point in time. However, the portions exposed to the various processing regions have a gas curtain separating the two. For example, when the front edge of the substrate enters the processing region including the second gas port 235, the central portion of the substrate is under the gas curtain 250, and the rear edge of the substrate is within the processing region including the first reactive gas port 225.

[0055]

[0064] For example, a factory interface (shown in FIG. 4), which can be a load lock chamber 280, is shown connected to the processing chamber 200. The substrate 60 is shown superimposed on the gas distribution assembly 220 to provide a reference frame. The substrate 60 can often be placed on a susceptor assembly so as to be held near the front face 221 of the gas distribution assembly 220. The substrate 60 is loaded into the processing chamber 200 via the factory interface and placed on a substrate support or susceptor assembly (see FIG. 4). Since the substrate 60 is adjacent to the first reactive gas port 225 and is disposed between the two gas curtains 250a, 250b, it can be shown as being positioned within the processing region. By rotating the substrate 60 along the path 227, the substrate will move counterclockwise through the processing chamber 200. Thus, the substrate 60 will be exposed to all the processing regions including the intervening processing regions from the first processing region 350a to the eighth processing region 350h.

[0056]

[0065] One or more embodiments of the present disclosure are directed to a processing chamber 200 having a plurality of processing regions 350a - 350h, where each processing region is separated from an adjacent region by a gas curtain 250. For example, the processing chamber shown in FIG. 6. The number of gas curtains and processing regions within the processing chamber can be any suitable number depending on the gas flow arrangement. The embodiment shown in FIG. 6 has eight gas curtains 250 and eight processing regions 350a - 350h.

[0057]

[0066] Referring again to FIG. 1, the processing platform 100 includes a processing chamber 140 connected to the second side surface 112 of the central transfer station 110. The processing chamber 140 of one or more embodiments is configured to expose a wafer to a process of processing the wafer before and after the process in the first batch processing chamber 120. The processing chamber 140 of one or more embodiments includes an annealing chamber. The annealing chamber may be a furnace annealing chamber or a rapid thermal annealing chamber, or may be another chamber configured to hold a wafer at a predetermined temperature and pressure and supply a gas flow to the chamber.

[0058]

[0067] In one or more embodiments, the processing platform further includes a second batch processing chamber 130 connected to the third side surface 113 of the central transfer station 110. The second batch processing chamber 130 can be configured in the same manner as the first batch processing chamber 120, or can be configured to perform different processes or process different numbers of substrates.

[0059]

[0068] The second batch processing chamber 130 may be the same as or different from the first batch processing chamber 120. In one or more embodiments, the first batch processing chamber 120 and the second batch processing chamber 130 are configured such that x (the number of wafers in the first batch processing chamber 120) and y (the number of wafers in the second batch processing chamber 130) are the same, and the first batch time and the second batch time (of the second batch processing chamber 130) are the same, so that the same process is performed on the same number of wafers at the same batch time. In one or more embodiments, the first batch processing chamber 120 and the second batch processing chamber 130 are configured to have different numbers of wafers (x and y are not equal), different batch times, or both.

[0060]

[0069] In the embodiment shown in FIG. 1, the processing platform 100 includes a second processing chamber 150 connected to the fourth side surface 114 of the central transfer station 110. The second processing chamber 150 may be the same as or different from the processing chamber 140.

[0061]

[0070] The processing platform 100 may include a controller 195 (connection not shown) connected to the robot 117. The controller 195 may be configured to move wafers between the processing chamber 140 and the first batch processing chamber 120 using the first arm 118 of the robot 117. In one or more embodiments, the controller 195 is further configured to move wafers between the second processing chamber 150 and the second batch processing chamber 130 using the second arm 119 of the robot 117.

[0062]

[0071] In one or more embodiments, the controller 195 is connected to the susceptor assembly 240 and the gas distribution assembly 220 of the processing chamber 200. The controller 195 may be configured to rotate the susceptor assembly 240 around a central axis. The controller may be further configured to control the gas flow in the gas ports 225, 235, 245, 255. In one or more embodiments, the first reactive gas port 225 supplies a flow of metal precursor. In one or more embodiments, the second reactive gas port 235 supplies a flow of reactant. In one or more embodiments, other gas ports (not labeled) may supply a flow of plasma. The first reactive gas port 225, the second reactive gas port 235, and the other reactive gas ports (not labeled) can be arranged in any processing order.

[0063]

[0072] The processing platform 100 may include a first buffer station 151 connected to the fifth side 115 of the central transfer station 110 and / or a second buffer station 152 connected to the sixth side 116 of the central transfer station 110. The first buffer station 151 and the second buffer station 152 can perform the same or different functions. For example, the buffer station may hold a cassette of wafers, and the wafers are processed and returned to the original cassette. Alternatively, the first buffer station 151 may hold unprocessed wafers, and the wafers are moved to the second buffer station 152 after being processed. In one or more embodiments, one or more of the buffer stations are configured to pre-process, pre-heat, or clean the wafers before and after processing.

[0064]

[0073] In one or more embodiments, the controller 195 is configured to use the first arm 118 of the robot 117 to move wafers between the first buffer station 151 and one or more of the processing chamber 140 and the first batch processing chamber 120. In one or more embodiments, the controller 195 is configured to use the second arm 119 of the robot 117 to move wafers between the second buffer station 152 and one or more of the second processing chamber 150 or the second batch processing chamber 130.

[0065]

[0074] The processing platform 100 may further include one or more slit valves 160 between the central transfer station 110 and any of the processing chambers. In the illustrated embodiment, there is a slit valve 160 between each of the processing chambers 120, 130, 140, 150 and the central transfer station 110. The slit valve 160 can be opened and closed to isolate the environment in the processing chamber from the environment in the central transfer station 110. For example, if a processing chamber generates plasma during processing, it may be useful to close the slit valve of that processing chamber to prevent the floating plasma from damaging the robot in the transfer station.

[0066]

[0075] In one or more embodiments, the processing chambers cannot be easily removed from the central transfer station 110. To enable maintenance to be performed on any of the processing chambers, each processing chamber may further include a plurality of access doors 170 on the sides of the processing chamber. The access doors 170 enable manual access to the processing chamber without removing the processing chamber from the central transfer station 110. In the illustrated embodiment, each side of each processing chamber has an access door 170 except for the side connected to the transfer station. Including a very large number of access doors 170 can complicate the configuration of the processing chamber used because the hardware inside the chamber has to be configured to be accessible through the doors.

[0067]

[0076] The processing platform of one or more embodiments includes a water box 180 connected to the central transfer station 110. The water box 180 can be configured to supply coolant to any or all of the processing chambers. Although it is referred to as a "water" box, those skilled in the art will understand that any coolant can be used.

[0068]

[0077] In one or more embodiments, due to the size of the processing platform 100, it becomes possible for the connection part to accommodate power via a single power connector 190. The single power connector 190 is attached to the processing platform 100 and supplies power to each of the processing chamber and the central transfer station 110.

[0069]

[0078] In one or more embodiments, the processing platform 100 can be connected to the factory interface 102, thereby making it possible to load wafers or wafer cassettes onto the processing platform 100. The robot 103 within the factory interface 102 can be moved to transfer wafers or cassettes in and out of the buffer stations 151, 152. The robot 117 within the central transfer station 110 can move wafers or cassettes within the processing platform 100. In one or more embodiments, the factory interface 102 is a transfer station of another cluster tool.

[0070]

[0079] In one or more embodiments, the processing platform 100 or the first batch processing chamber 120 is connected to a controller. The controller may be the same controller 195 or a different controller. The controller can be connected to the susceptor assembly and the gas distribution assembly of the first batch processing chamber 120 and has one or more configurations. This configuration may include, but is not limited to, a first configuration for rotating the susceptor assembly around the central axis, a second configuration for supplying the flow of metal precursors to the processing region, a third configuration for supplying the flow of reactants to the processing region, and a fourth configuration for supplying plasma to the processing region.

[0071]

[0080] One or more embodiments are directed to a non-transitory computer-readable medium including instructions that, when executed by a controller of a processing chamber, cause the processing chamber to expose a substrate surface to a halogen catalyst to form an activated substrate surface and to flow a precursor into a processing space of the processing chamber having the substrate, the precursor having the general formula (I): M-L1(L2) y (wherein M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, y is a number in the range of 2 to 8, and L2 includes 1,5-hexadiene, 1,4-hexadiene, and less than 5% 1,3-hexadiene).

[0072]

[0081] FIG. 7 shows a process flow diagram illustrating a generalized method for forming a metal film on a substrate according to one or more embodiments of the present disclosure. Method 700 generally begins with an operation 702 in which a substrate on which a metal film is to be formed is disposed within a processing chamber. As used herein, "substrate surface" refers to any substrate surface on which a layer may be formed. The substrate surface may have one or more features formed therein, one or more layers formed thereon, and combinations thereof. In one or more embodiments, the substrate (or substrate surface) may be pre-treated, for example, by polishing, etching, reduction, oxidation, halogenation, hydroxylation, annealing, baking, etc. prior to deposition of the metal film.

[0073]

[0082] In one or more embodiments, the substrate can be any substrate that can have materials deposited thereon, such as a silicon substrate, a Group III-V compound substrate, a silicon germanium (SiGe) substrate, an epitaxial substrate, a silicon-on-insulator (SOI) substrate, a display substrate such as a liquid crystal display (LCD), a plasma display, an electroluminescence (EL) lamp display, a solar array, a solar panel, a light-emitting diode (LED) substrate, a semiconductor wafer, etc. In one or more embodiments, one or more additional layers may be disposed on the substrate such that a metal film can be at least partially formed on the substrate. For example, in one or more embodiments, a layer including a metal, a nitride, an oxide, etc., or a combination thereof can be disposed on the substrate, and a metal film can be formed on such one or more layers.

[0074]

[0083] In one or more embodiments, in operation 703, the substrate is optionally exposed to a blocking compound. This processing step, which is described in more detail below, can be useful for controlling the selectivity of deposition processes on the substrate, including both metal and dielectric surfaces.

[0075]

[0084] In one or more embodiments, in operation 704, a metal film is formed on a substrate. In one or more embodiments, the metal film can be formed by a periodic deposition process such as atomic layer deposition (ALD). In one or more embodiments, the formation of the metal film by the periodic deposition process can generally include separately exposing the substrate to two or more process gases. In embodiments of time-domain ALD, each exposure to a process gas is separated by a time delay / pause, which allows the components of the process gas to adhere to and / or react on the substrate surface. Alternatively, or in combination, in one or more embodiments, a purge may be performed before and after exposing the substrate to the process gas, and an inert gas is used for the purge. For example, a first process gas can be supplied to the processing chamber, and then a purge with an inert gas can be performed. Next, a second process gas can be supplied to the processing chamber, and then a purge with an inert gas can be performed. In one or more embodiments, the inert gas may be continuously supplied to the processing chamber, and the first process gas can be administered or pulsed into the processing chamber, and then the second process gas can be administered or pulsed into the processing chamber. In such embodiments, there may be a delay or pause between the administration of the first process gas and the administration of the second process gas, which allows a continuous flow of inert gas to purge the processing chamber between the administrations of the process gases.

[0076]

[0085] In embodiments of spatial ALD, each exposure to a process gas is performed simultaneously on different portions of the substrate such that (when only two reactive gases are used) one portion of the substrate is exposed to the first reactive gas and a different portion of the substrate is exposed to the second reactive gas. The substrate is moved relative to the gas supply system such that each point thereon is continuously exposed to both the first reactive gas and the second reactive gas. In any embodiment of time-domain ALD or spatial ALD processing, this sequence can be repeated until a predetermined layer thickness is formed on the substrate surface.

[0077]

[0086] As used herein, "pulse" or "dose" is intended to refer to the amount of source gas introduced intermittently or discontinuously into the processing chamber. The amount of a particular compound within each pulse can vary over time depending on the duration of the pulse. A particular process gas can include a single compound or a mixture / combination of two or more compounds (e.g., the process gases described below).

[0078]

[0087] The duration of each pulse / dose is variable and can be adjusted, for example, to conform to the spatial volume of the processing chamber and the capabilities of the vacuum system connected to the processing chamber. Further, the dosing time of the process gas can vary depending on the flow rate of the process gas, the temperature of the process gas, the type of control valve, the type of processing chamber used, and the ability of the components of the process gas to adsorb on the substrate surface. The dosing time can also vary based on the type of layer being formed and the shape of the device being formed. The dosing time must be long enough to supply an amount of compound sufficient to substantially adsorb / chemisorb over the entire surface of the substrate and form a layer of the process gas components thereon.

[0079]

[0088] In one or more embodiments, in operation 704, the process of forming a metal film can be initiated by exposing the substrate to a first reactive gas. In one or more embodiments, the first reactive gas includes a halogen catalyst. In other embodiments, the first reactive gas includes an alkyl halide catalyst.

[0080]

[0089] As used herein, the term "halide" refers to a two-phase entity, one part of which is a halogen atom and the other part of which is an element or radical less electronegative than the halogen for making a fluoride, chloride, bromide, iodide, or astatide compound. A halide ion is a halogen atom with a negative charge. As known to those skilled in the art, halide anions include fluoride (F-), chloride (Cl-), bromide (Br-), iodide (I-), and astatide (At-).

[0081]

[0090] Unless otherwise specified, the terms "lower alkyl", "alkyl", or "alk" as used herein alone or as part of another group include both straight-chain hydrocarbons and branched-chain hydrocarbons containing 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethyl-pentyl, nonyl, decyl, undecyl, dodecyl, and various branched-chain isomers thereof. Such groups can optionally contain up to 1 to 4 substituents.

[0082]

[0091] In one or more embodiments, in operation 704, the process of forming the metal film is initiated by exposing the substrate to a first reactive gas containing an alkyl halide catalyst. In one or more embodiments, the first reactive gas contains an alkyl halide catalyst and is exposed to the substrate for a first period as shown in operation 706.

[0083]

[0092] In one or more embodiments, the alkyl halide catalyst can be any suitable reactant for adsorbing a layer of halogen onto the substrate for a subsequent reaction. In one or more embodiments, the alkyl halide catalyst contains carbon and halogen. In one or more embodiments, the halogen includes bromine or iodine. In one or more embodiments, the halogen is insoluble in the metal film. As used in this regard, the halogen that is insoluble in the metal film contains about 2% or less, about 1% or less, or about 0.5% or less of the metal film on an atomic basis. In one or more embodiments, the alkyl halide catalyst has the general formula R-X, where R is an alkyl, alkenyl, aryl, or other carbonaceous group. In one or more embodiments, R contains 1 to 2, 1 to 4, or 1 to 6 carbon atoms.

[0084]

[0093] In one or more embodiments, the alkyl halide catalyst comprises, or consists essentially of, iodoethane (H5C2I) or diiodomethane (CH2I2). As used in this context, an alkyl halide catalyst consisting essentially of the species described contains more than 95%, 98%, 99%, or 99.5% of the species described on a molar basis, excluding inert diluent gas.

[0085]

[0094] In one or more embodiments, the alkyl halide catalyst is delivered to the processing chamber as an alkyl halide catalyst-containing gas. In one or more embodiments, the alkyl halide catalyst-containing gas can be supplied in one or more pulses or continuously. In one or more embodiments, the flow rate of the alkyl halide catalyst-containing gas can be in the range of about 1 to about 5000 sccm, or in the range of about 2 to about 4000 sccm, or in the range of about 3 to about 3000 sccm, or in the range of about 5 to about 2000 sccm, but can be any suitable flow rate not limited thereto. The alkyl halide catalyst-containing gas is provided at a pressure in the range of about 5 mTorr to about 25 Torr, or in the range of about 100 mTorr to about 20 Torr, or in the range of about 5 Torr to about 20 Torr, or in the range of about 50 mTorr to about 2000 mTorr, or in the range of about 100 mTorr to about 1000 mTorr, or in the range of about 200 mTorr to about 500 mTorr, but can be provided at any suitable pressure not limited thereto.

[0086]

[0095] The period during which the substrate is exposed to the alkyl halide catalyst-containing gas can be any suitable amount of time necessary to allow the alkyl halide catalyst to form a suitable adsorption layer on the substrate surface. For example, the processing gas can be flowed into the processing chamber over a period of about 0.1 seconds to about 90 seconds. In some time-domain ALD processes, the alkyl halide catalyst-containing gas is exposed to the substrate surface for a time in the range of about 0.1 seconds to about 90 seconds, or in the range of about 0.5 seconds to about 60 seconds, or in the range of about 1 second to about 30 seconds, or in the range of about 2 seconds to about 25 seconds, or in the range of about 3 seconds to about 20 seconds, or in the range of about 4 seconds to about 15 seconds, or in the range of about 5 seconds to about 10 seconds.

[0087]

[0096] In one or more embodiments, an inert gas can be additionally provided to the processing chamber simultaneously with the halogenated alkyl catalyst-containing gas. The inert gas may be mixed with the halogenated alkyl catalyst-containing gas (e.g., as a dilution gas), or may be provided separately, may be pulsed, or may have a constant flow rate. In one or more embodiments, the inert gas is flowed into the processing chamber at a constant flow rate in the range of about 1 to about 10,000 sccm. The inert gas may be any inert gas, such as argon (Ar), helium (He), neon (Ne), or a combination thereof.

[0088]

[0097] The temperature of the substrate during deposition can be controlled, for example, by setting the temperature of the substrate support or susceptor. In one or more embodiments, the substrate is maintained at a temperature in the range of about 0°C to about 600°C, or in the range of about 25°C to about 500°C, or in the range of about 50°C to about 450°C, or in the range of about 100°C to about 400°C, or in the range of about 100°C to about 200°C, or in the range of about 250°C to about 350°C. In one or more embodiments, the substrate is maintained at a temperature below the decomposition temperature of the metal precursor. In one or more embodiments, the substrate is maintained at a temperature below the decomposition temperature of the halogenated alkyl catalyst. In one or more embodiments, the substrate is maintained at a temperature between the decomposition temperature of the halogenated alkyl catalyst and the decomposition temperature of the metal precursor.

[0089]

[0098] In one or more embodiments, the substrate is maintained at about 400°C or less, or about 350°C or less, or less than about 300°C. In one or more embodiments, the substrate is maintained at about 250°C or more, or about 300°C or more, or about 350°C or more. In one or more embodiments, the substrate is maintained at a temperature of about 280°C.

[0090]

[0099] In addition to the above, additional processing parameters can be adjusted while exposing the substrate to a gas containing an alkyl halide catalyst. For example, in one or more embodiments, the processing chamber can be maintained at a pressure in the range of about 0.2 to about 100 Torr, or about 0.3 to about 90 Torr, or about 0.5 to about 80 Torr, or about 1 to about 50 Torr.

[0091]

[0100] Next, at 708, (especially in time-domain ALD), the processing chamber may be purged using an inert gas (in spatial ALD processing, this may not be necessary because there is a gas curtain separating the reactive gases). The inert gas can be any inert gas (e.g., argon, helium, neon, etc.). In one or more embodiments, the inert gas may be the same as the inert gas supplied to the processing chamber during exposure of the substrate to the alkyl halide catalyst in operation 706, or alternatively it may be different therefrom. In embodiments where the inert gases are the same, the purge may be performed by diverting the first processing gas from the processing chamber and allowing the inert gas to flow through the processing chamber, purging any excess first processing gas component or reaction by-products from the processing chamber. In one or more embodiments, the inert gas may be supplied at the same flow rate as the flow rate used in relation to the first processing gas described above, or, in one or more embodiments, the flow rate may be increased or decreased. For example, in one or more embodiments, the inert gas may be supplied to the processing chamber at a flow rate of about 0 to about 10,000 sccm to purge the processing chamber. In spatial ALD, a purge gas curtain is maintained between the flows of the reactive gases, and it may not be necessary to purge the processing chamber. In one or more embodiments of spatial ALD processing, the processing chamber or a region of the processing chamber may be purged with an inert gas.

[0092]

[0101] The flow of the inert gas can facilitate the removal of any excess first processing gas component and / or excess reaction by-products from the processing chamber and prevent unwanted gas-phase reactions of the first and second processing gases.

[0093]

[0102] Next, in operation 710, the substrate is exposed to a second process gas for a second time. The second process gas includes a precursor that reacts with the adsorbed layer of halogen on the substrate surface to deposit a metal film. In one or more embodiments, the second reactive gas may also be referred to as a precursor gas.

[0094]

[0103] In one or more embodiments, the precursor can be any suitable precursor for reacting with the adsorbed halogen layer on the substrate. In one or more embodiments, the precursor includes a metal and at least two ligands. In one or more embodiments, the metal includes one or more metal atoms.

[0095]

[0104] In one or more embodiments, the metal is selected from molybdenum (Mo), ruthenium (Ru), cobalt (Co), copper (Cu), platinum (Pt), nickel (Ni), or tungsten (W). In other embodiments, the metal is selected from ruthenium (Ru), tungsten (W), or molybdenum (Mo). In one or more particular embodiments, the metal includes ruthenium (Ru).

[0096]

[0105] In one or more embodiments, the precursor includes a plurality of at least two organic ligands. In one or more embodiments, the precursor includes a metal M, an aromatic ligand L1, and an aliphatic ligand L2. In one or more particular embodiments, the precursor includes ruthenium, an aromatic ligand L1, and an aliphatic ligand L2. In some embodiments, the precursor includes two or more aliphatic ligands L2. In one or more embodiments, the precursor includes 2 to 8 aliphatic ligands L2. When two or more aliphatic ligands L2 are present, the L2 ligands may be the same or different.

[0097]

[0106] In one or more embodiments, the precursor has the general formula (I): M-L1(L2) y(wherein M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, and y is a number in the range of 2 to 8 including 2 to 6 and 2 to 5).

[0098]

[0107] In one or more embodiments, the aromatic ligand L1 contains a π - electron system selected from η 2 , η 4 , η 6 , and η 8 . In some embodiments, the aromatic ligand L1 contains 1 - methyl - 4 - isopropylbenzene.

[0099]

[0108] In one or more embodiments, the aliphatic ligand L2 contains an aliphatic diene. In one or more embodiments, the aliphatic ligand L2 contains one or more of 1,5 - hexadiene, 1,4 - hexadiene, and 1,3 - hexadiene. In one or more embodiments, the aliphatic ligand L2 contains less than 5% of 1,3 - hexadiene, including less than about 4% of 1,3 - hexadiene, less than about 3% of 1,3 - hexadiene, less than about 2% of 1,3 - hexadiene, and less than about 1% of 1,3 - hexadiene.

[0100]

[0109] In one or more embodiments, the method includes forming a film on a substrate surface by exposing the substrate surface to a precursor of the general formula (I): M - L1(L2) y (wherein M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, y is a number in the range of 2 to 8, and L2 contains 1,5 - hexadiene, 1,4 - hexadiene, and less than 5% of 1,3 - hexadiene).

[0101]

[0110] In one or more embodiments, the precursor comprises a metal M, an aromatic ligand L1, and at least two aliphatic ligands L2. In one or more embodiments, the aliphatic ligand L2 further comprises an asymmetric cyclic diene. In one or more embodiments, the asymmetric cyclic diene comprises one or more of 3-(2-propenyl)-cyclohexene, 1-(2-propenyl)-cyclohexene, 1,3-propadiene-cyclohexane, and 1,2-divinylcyclohexane.

[0102]

[0111] Without wishing to be bound by theory, it is believed that controlling the ratio of hexadiene isomers in the mixture of L2 aliphatic ligands produces gap filling with excellent performance. Thus, in one or more embodiments, the ratio of 1,5-hexadiene to the other L2 aliphatic ligands present in the precursor should exceed 50%. In some embodiments, the ratio of 1,5-hexadiene to the other L2 aliphatic ligands present in the precursor is in the range of about 50:50 to about 60:40. In one or more embodiments, y is a number in the range of 2 to 6, and the ratio of 1,5-hexadiene to the total of 1,4-hexadiene, 1,3-hexadiene, and the asymmetric cyclic diene is in the range of about 50:50 to about 60:40. In one or more embodiments, the asymmetric cyclic diene comprises one or more of 3-(2-propenyl)-cyclohexene, 1-(2-propenyl)-cyclohexene, 1,3-propadiene-cyclohexane, and 1,2-divinylcyclohexane. Thus, in one or more embodiments, y is a number in the range of 2 to 6, and the ratio of 1,5-hexadiene to the total of 1,4-hexadiene, 1,3-hexadiene, 3-(2-propenyl)-cyclohexene, 1-(2-propenyl)-cyclohexene, 1,3-propadiene-cyclohexane, and 1,2-divinylcyclohexane is in the range of about 50:50 to about 60:40.

[0103]

[0112] In one or more embodiments, the metal of the precursor corresponds to the metal of the deposited metal film. In one or more embodiments, the metal is selected from molybdenum (Mo), ruthenium (Ru), cobalt (Co), copper (Cu), platinum (Pt), nickel (Ni), or tungsten (W). In one or more embodiments, the metal of the precursor has an oxidation state of zero. In other words, in one or more embodiments, the metal precursor comprises a zero-valent metal complex.

[0104]

[0113] During exposure of the substrate to the precursor gas, additional processing parameters can be adjusted. For example, in one or more embodiments, the processing chamber can be maintained at a pressure in the range of about 0.2 to about 100 Torr, or about 0.3 to about 90 Torr, or about 0.5 to about 80 Torr, or about 1 to about 50 Torr.

[0105]

[0114] In one or more embodiments, the precursor is delivered to the processing chamber as a precursor gas. The precursor gas may be supplied in one or more pulses or continuously. The flow rate of the precursor gas can be any suitable flow rate including, but not limited to, the range of about 1 to about 5000 sccm, or about 2 to about 4000 sccm, or about 3 to about 3000 sccm, or about 5 to about 2000 sccm. The precursor gas can be provided at any appropriate pressure including, but not limited to, the range of about 5 mTorr to about 25 Torr, or about 100 mTorr to about 20 Torr, or about 5 Torr to about 20 Torr, or about 50 mTorr to about 2000 mTorr, or about 100 mTorr to about 1000 mTorr, or about 200 mTorr to about 500 mTorr.

[0106]

[0115] In one or more embodiments, the period during which the substrate is exposed to the metal precursor gas can be any suitable time necessary to allow the metal precursor to react with the adsorbed halogen on the substrate surface. For example, the process gas may be flowed into the processing chamber over a period of from about 0.1 second to about 90 seconds. In some time-domain ALD processes, the precursor gas is exposed to the substrate surface for a time in the range of about 0.1 second to about 90 seconds, or in the range of about 0.5 second to about 60 seconds, or in the range of about 1 second to about 30 seconds, or in the range of about 2 seconds to about 25 seconds, or in the range of about 3 seconds to about 20 seconds, or in the range of about 4 seconds to about 15 seconds, or in the range of about 5 seconds to about 10 seconds.

[0107]

[0116] In one or more embodiments, an inert gas can be additionally supplied to the processing chamber simultaneously with the precursor gas. The inert gas may be mixed with the precursor gas (e.g., as a diluent gas), or may be provided separately, may be pulsed, or may be at a constant flow rate. In one or more embodiments, the inert gas is flowed into the processing chamber at a constant flow rate in the range of about 1 to about 10000 sccm. The inert gas can be any inert gas (e.g., argon, helium, neon, nitrogen, or a combination thereof, etc.).

[0108]

[0117] In one or more embodiments, in operation 712, the processing chamber may be purged using an inert gas. As the inert gas, for example, an inert gas such as argon (Ar), helium (He), neon (Ne), etc. can be used. In one or more embodiments, the inert gas may be the same as the inert gas supplied to the processing chamber during a previous processing routine, or alternatively, it may be different. In embodiments where the inert gas is the same, the purge may be performed by diverting the second processing gas from the processing chamber and allowing the inert gas to flow through the processing chamber, purging any excess second processing gas component or reaction by - product from the processing chamber. In one or more embodiments, the inert gas may be supplied at the same flow rate as that used in conjunction with the second processing gas described above, or in one or more embodiments, the flow rate may be increased or decreased. For example, in one or more embodiments, the inert gas may be supplied to the processing chamber at a flow rate greater than 0 sccm and up to about 10,000 sccm to purge the processing chamber.

[0109]

[0118] The general embodiment of the processing method shown in FIG. 7 includes only two pulses of the reactive gas, but this is merely illustrative, and it will be understood that additional pulses of the reactive gas may be used. In one or more embodiments, this method is performed without using an oxygen - containing reactive gas. The sub - steps of operation 704 include cycles. The cycles may be performed in any order as long as the reactive gas is separated by purging of the processing chamber. In one or more embodiments, the metal film is deposited at a rate of about 0.2 Å / cycle or more, about 0.3 Å / cycle or more, about 0.4 Å / cycle or more, about 0.5 Å / cycle or more, about 0.6 Å / cycle or more, about 0.7 Å / cycle or more, about 0.8 Å / cycle or more, about 0.9 Å / cycle or more, about 1.0 Å / cycle or more, or about 1.2 Å / cycle or more.

[0110]

[0119] The deposition process is carried out as a heat treatment without using plasma reactants. In other words, in one or more embodiments, this method is carried out without plasma.

[0111]

[0120] In one or more embodiments, at decision point 714, it is determined whether the metal film has reached a predetermined thickness. If the predetermined thickness is not achieved, method 700 returns to operation 704 and continues forming the metal film until the predetermined thickness is reached. When the predetermined thickness is reached, method 700 can end or proceed to operation 716 for optional further processing (e.g., bulk deposition of another metal film). In one or more embodiments, the metal film may be deposited to form a total layer thickness of about 10 Å to about 10,000 Å, or in one or more embodiments, about 10 Å to about 1000 Å, or in one or more embodiments, about 50 Å to about 5,000 Å.

[0112]

[0121] In one or more embodiments, the metal layer comprises about 75 atomic % or more ruthenium, or about 80 atomic % or more ruthenium, or about 85 atomic % or more ruthenium, or about 90 atomic % or more ruthenium, or about 95 atomic % or more ruthenium.

[0113]

[0122] In one or more embodiments, the metal layer comprises about 10 atomic % or less oxygen, or about 9 atomic % or less oxygen, or about 8 atomic % or less oxygen, or about 7 atomic % or less oxygen, or about 6 atomic % or less oxygen, or about 5 atomic % or less oxygen, or about 4 atomic % or less oxygen, or about 3 atomic % or less oxygen.

[0114]

[0123] In one or more embodiments, the metal layer comprises about 0.02 to about 5 atomic % iodine, or about 1 atomic % or less iodine.

[0115]

[0124] In one or more embodiments, the metal layer comprises about 20 atomic % or less carbon, or about 15 atomic % or less carbon, or about 10 atomic % or less carbon, or about 5 atomic % or less carbon.

[0116]

[0125] In one or more embodiments, the metal layer comprises at least about 90 atomic % ruthenium, at most about 3 atomic % oxygen, at most about 1 atomic % iodine, and at most about 10 atomic % carbon.

[0117]

[0126] In one or more embodiments, the metal layer has a resistivity of at most about 40 μΩ·cm, or at most about 35 μΩ·cm, or at most about 30 μΩ·cm, or at most about 25 μΩ·cm, or at most about 20 μΩ·cm. In one or more embodiments, the metal layer comprises ruthenium and has a resistivity of at most about 40 μΩ·cm, or at most about 35 μΩ·cm, or at most about 30 μΩ·cm, or at most about 25 μΩ·cm, or at most about 20 μΩ·cm.

[0118]

[0127] In one or more embodiments, the metal film is further processed by annealing the metal film. Without being bound by theory, it is believed that annealing the film at a high temperature in an argon (Ar) or hydrogen (H2) atmosphere reduces carbon and halogen impurities in the metal film. In one or more embodiments, the metal film is annealed in an atmosphere containing argon or hydrogen gas (H2) to reduce the atomic concentration of carbon and / or halogen impurities.

[0119]

[0128] The metal film deposited by one or more embodiments is smoother than a film deposited by a known oxygen-based deposition process. In one or more embodiments, the metal film has a surface roughness of at most about 10%, at most about 8%, at most about 5%, or at most about 2% of the thickness of the metal film.

[0120]

[0129] The purity of the metal film is high. In one or more embodiments, the metal film has a carbon content of at most about 2%, at most about 1%, or at most about 0.5% on an atomic basis. In one or more embodiments, the metal film has a halogen content of at most about 1%, or at most about 0.5% on an atomic basis. In one or more embodiments, the metal film has a purity of at least about 95%, at least about 97%, at least about 99%, at least about 99.5%, or at least about 99.9% on an atomic basis.

[0121]

[0130] One or more embodiments of the present disclosure selectively deposit a first metal film on a second metal surface on a first dielectric surface. These methods are similar to method 700 described above, except that the provided substrate includes a first dielectric surface and a second metal surface. The first metal (of the metal film) and the second metal (of the substrate surface) may be the same metal or different metals. In one or more embodiments, the first metal is molybdenum (Mo), ruthenium (Ru), cobalt (Co), copper (Cu), platinum (Pt), nickel (Ni), or tungsten (W), and the second metal is tungsten (W), cobalt (Co), or copper (Cu).

[0122]

[0131] In one or more embodiments, the first dielectric surface can be formed from any suitable dielectric material. In one or more embodiments, the dielectric material includes nitrogen atoms or oxygen atoms. Without being bound by theory, these materials are thought to react with the alkyl halide catalyst and prevent the halogen from adsorbing onto the substrate surface to catalyze the reaction with the metal precursor. Thus, if a metal film is formed on the dielectric surface at all, it is only a little.

[0123]

[0132] In one or more embodiments, the deposition temperature is less than the decomposition temperature of the alkyl halide catalyst. Again, without being bound by theory, when the alkyl halide catalyst decomposes, the halogen is available for reaction with the metal precursor on all surfaces (regardless of composition) and is thought to result in metal film deposition on all substrate surfaces, including the dielectric surface. In one or more embodiments, the deposition temperature is greater than or equal to the decomposition temperature of the alkyl halide catalyst.

[0124]

[0133] One or more embodiments of the present disclosure selectively deposit a first metal film on a first dielectric surface on a second metal surface. These methods are similar to method 700 described above, except that the provided substrate includes a first dielectric surface and a second metal surface and the substrate is exposed to a blocking compound in operation 703.

[0125]

[0134] In one or more embodiments, in operation 703, a substrate including at least a second metal surface and a first dielectric surface is exposed to a blocking compound. The blocking compound can be any suitable compound for blocking deposition on the second metal surface. In one or more embodiments, the blocking compound includes at least one triple bond between two carbon atoms. In other words, in one or more embodiments, the blocking compound includes an alkyne. In one or more embodiments, the blocking compound has the general formula R’≡R”. In one or more embodiments, R’ and R” are the same. In one or more embodiments, R’ and / or R” are an alkyl or other carbonaceous group. In one or more embodiments, the blocking compound includes 4 to 12 carbon atoms. In one or more embodiments, R’ and / or R” are linear. In one or more embodiments, R’ and / or R” are branched. In one or more embodiments, the blocking compound includes 3 - hexyne.

[0126]

[0135] The first metal (of the metal film) and the second metal (of the substrate surface) may be the same metal or different metals. In one or more embodiments, the first metal is molybdenum (Mo), ruthenium (Ru), cobalt (Co), copper (Cu), platinum (Pt), nickel (Ni), or tungsten (W), and the second metal is tungsten (W), cobalt (Co), or copper (Cu).

[0127]

[0136] The first dielectric surface may be formed from any suitable dielectric material. In one or more embodiments, the dielectric material includes a nitrogen atom or an oxygen atom.

[0128]

[0137] As described above, in one or more embodiments, the deposition temperature is equal to or higher than the decomposition temperature of the alkyl halide catalyst. In one or more embodiments, the deposition temperature is about 250 °C or higher, about 260 °C or higher, about 270 °C or higher, about 280 °C or higher, about 290 °C or higher, or about 300 °C or higher. In one or more embodiments, the deposition temperature ranges from about 250 °C to about 450 °C, or from about 300 °C to about 400 °C. In one or more embodiments, the deposition temperature is about 350 °C.

[0129]

[0138] As described above, without being bound by theory, it is believed that these materials react with the alkyl halide catalyst, preventing the halogen from adsorbing onto the substrate surface and catalyzing the reaction with the metal precursor. Therefore, even if a metal film is formed on the dielectric surface, it is only a very small amount.

[0130]

[0139] However, in one or more embodiments, when the deposition temperature exceeds the decomposition temperature of the alkyl halide catalyst, halogen atoms are deposited on the entire substrate surface, thereby enabling deposition onto the dielectric surface. In one or more embodiments, the metal surface, and thus the metal film formed thereon, is blocked by the blocking compound such that, if any, it is only a very small amount. Therefore, the deposition of the metal film is selective with respect to the dielectric surface on the metal surface.

[0131]

[0140] Generally speaking, in one or more embodiments, the deposition of a high-purity metal film can be understood as follows. A substrate maintained at the deposition temperature is exposed to an alkyl halide catalyst (R-X) to adsorb R and X onto the substrate. Here, R is a carbonaceous group and X is a halogen. In one or more embodiments, X is a halogen selected from one or more of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At). R desorbs in the form of R-R or R-, leaving X adsorbed on the substrate. The substrate is then exposed to a precursor, M-L1(L2) y(where M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, and y is a number in the range of 2 to 8 including 2 to 6 and 2 to 5) is exposed. In one or more embodiments, L2 comprises 1,5 - hexadiene, 1,4 - hexadiene, and less than 5% 1,3 - hexadiene. In other embodiments, the aliphatic ligand L2 further comprises an asymmetric cyclic diene. In some embodiments, the asymmetric cyclic diene comprises one or more of 3 - (2 - propenyl) - cyclohexene, 1 - (2 - propenyl) - cyclohexene, 1,3 - propadiene - cyclohexane, and 1,2 - divinylcyclohexane.

[0132]

[0141] In one or more embodiments, M - L1(L2) y reacts with adsorbed X to form M - X on the substrate surface and releases L1(L2) y . M - X reacts with other M - X moieties on the substrate to form M - M. This reaction generates either X - X or X -. X - X may be desorbed and purged. X may remain on the surface to react further with M - L1(L2) y .

[0133]

[0142] In one or more embodiments, this general mechanism depends on several premises. First, X is insoluble in M. Without intending to be bound by theory, the insolubility of X means that X is not found in significant amounts in the final metal film. It is possible to ignore this premise (e.g., using a halogen soluble in M), but using a halogen (X) soluble in M is thought to provide a metal film of lower purity. Second, with respect to the bond strength, M - L1(L2) y is weaker than M - X which is weaker than M - M. Again, without intending to be bound by theory, these thermodynamic relationships ensure that the reactions identified above are thermodynamically favorable. Finally, M - L1(L2) yis thermally stable at the deposition temperature. In other words, the thermal decomposition temperature of the metal precursor is higher than the deposition temperature. The theory here is that when the metal precursor decomposes, the deposited film typically contains a significant amount of the precursor ligands L1 and (L2), which are seen as carbon impurities. y It is stated that it contains.

[0134]

[0143] In one or more embodiments, surprisingly, a process comprising a precursor of general formula (I) M-L1(L2), y a halogenated alkyl catalyst, and processing conditions that meet all of the above requirements has been found to deposit a high-purity metal film and is particularly suitable for seamless gap filling processes.

[0135]

[0144] Further, surprisingly, when the deposition temperature is below the thermal decomposition temperature of a halogen catalyst, such as a halogenated alkyl catalyst, the deposition process has been found to be selective for the metal surface over the dielectric surface without the need for the use of a blocking layer.

[0136]

[0145] Further, surprisingly, when the deposition temperature is above the thermal decomposition temperature of a halogen catalyst, such as a halogenated alkyl catalyst, it has been found that the deposition process can be made selective by exposing the metal surface to a small alkyne blocking compound.

[0137]

[0146] One or more embodiments of the present disclosure advantageously provide a method for depositing a conformal metal film on a substrate including a high aspect ratio structure. As used in this context, the term "conformal" means that the thickness of the metal film is uniform across the substrate surface. As used herein and in the appended claims, the term "substantially conformal" means that the thickness of the metal film varies by no more than about 10%, 5%, 2%, 1%, or 0.5% relative to the average thickness of the film. In other words, a film that is substantially conformal has a conformality of greater than about 90%, 95%, 98%, 99%, or 99.5%.

[0138]

[0147] One or more embodiments of the present disclosure are directed to a memory device including a ruthenium conductive layer. In one or more embodiments, the ruthenium conductive layer includes ruthenium of about 90 at% or more, oxygen of about 3 at% or less, iodine of about 1 at% or less, and carbon of about 10 at% or less, and has a resistivity of about 40 μΩ·cm or less.

[0139]

[0148] In one or more embodiments, the ruthenium conductive layer is formed on a barrier layer. The barrier layer of one or more embodiments has a thickness of about 10 Å, 20 Å, 30 Å, 40 Å, or 50 Å or less. In one or more embodiments, the ruthenium conductive layer is formed on a substrate without an intervening barrier layer.

[0140]

[0149] The above disclosure relates to the deposition of a metal film by a continuous pulse of reactants. The following disclosure relates to the deposition of a metal film by a simultaneous or constant flow process. In one or more embodiments, the continuous pulse method is an ALD method. In one or more embodiments, the simultaneous or constant flow method is a CVD method. Although the processing steps are different, many of the reactants and processing parameters are similar.

[0141]

[0150] FIG. 8 shows a process flow diagram showing a generalized method 800 for forming a metal film on a substrate according to one or more embodiments of the present disclosure. FIG. 9 shows an exemplary substrate for processing according to one or more embodiments of the present disclosure. Method 800 generally begins with an operation 810 in which a substrate 900 on which a metal film is to be formed is placed in a processing chamber.

[0142]

[0151] Referring to FIG. 9, an exemplary substrate 900 is shown. In one or more embodiments, the substrate 900 has a substrate surface 905 having at least one feature 910 therein. The feature 910 has sidewalls 912, 914 and a bottom 916. In one or more embodiments, a dielectric material 920 forms the sidewalls 912, 914 and a metal material 930 forms the bottom 916.

[0143]

[0152] In one or more embodiments, the substrate 900 may undergo a pretreatment step. At 815, the substrate may optionally have one or more layers formed on the substrate surface.

[0144]

[0153] In one or more examples, a metal nitride liner is deposited within the feature 910. In one or more examples, the metal nitride liner includes titanium nitride. In one or more embodiments, the metal nitride liner has a thickness in the range of about 15 Å to about 40 Å. In one or more embodiments, the metal nitride liner has a thickness of about 20 Å or about 30 Å.

[0145]

[0154] In one or more embodiments, a seed layer is deposited on the substrate surface. In one or more embodiments, the seed layer is a conformal layer. In one or more embodiments, the seed layer is continuous. In one or more embodiments, the thickness of the seed layer is in the range of about 1 nm to about 5 nm, or in the range of about 1 nm to about 4 nm. In one or more embodiments, the seed layer includes a ruthenium layer deposited by a known atomic layer deposition method. In one or more embodiments, the seed layer is deposited by an ALD cycle that includes alkyl halide catalyst exposure with precursor exposure and intervening purges. In one or more embodiments, the seed layer is deposited by an ALD cycle that includes ammonia plasma exposure with precursor exposure and intervening purges.

[0146]

[0155] In one or more embodiments, the precursor has the general formula (I): M-L1(L2) y(wherein M is a metal, L1 is an aromatic ligand, L2 is an aliphatic ligand, and y is a number in the range of 2 to 8 including 2 to 6 and 2 to 5). In one or more embodiments, the aliphatic ligand L2 includes an aliphatic diene. In one or more embodiments, the aliphatic ligand L2 includes one or more of 1,5 - hexadiene, 1,4 - hexadiene, and 1,3 - hexadiene. In one or more embodiments, the aliphatic ligand L2 includes less than 5% of 1,3 - hexadiene, including less than about 4% of 1,3 - hexadiene, less than about 3% of 1,3 - hexadiene, less than about 2% of 1,3 - hexadiene, and less than about 1% of 1,3 - hexadiene. In one or more embodiments, the precursor includes a metal, M, and an aromatic ligand L1, and at least two aliphatic ligands L2. In one or more embodiments, the aliphatic ligand L2 further includes an asymmetric cyclic diene. In one or more embodiments, the asymmetric cyclic diene includes one or more of 3 - (2 - propenyl) - cyclohexene, 1 - (2 - propenyl) - cyclohexene, 1,3 - propadiene - cyclohexane, and 1,2 - divinylcyclohexane.

[0147]

[0156] In one or more embodiments, in operation 820, the substrate is optionally exposed to a blocking compound. This processing step, which is described in more detail below, can be useful for controlling the selectivity of deposition processes on the substrate, including both metal and dielectric surfaces.

[0148]

[0157] In one or more embodiments, in 830, a metal film is formed on the substrate. The process of forming the metal film can be initiated by immersing the substrate in a catalyst gas in operation 830. In one or more embodiments, the catalyst gas includes an alkyl halide catalyst and is exposed to the substrate for a first period, as shown in operation 840.

[0149]

[0158] In one or more embodiments, a halogen catalyst, such as an alkyl halide catalyst, can be any suitable reactant for adsorbing a layer on a substrate for a subsequent reaction. In other words, when the substrate is immersed in a halogen catalyst, such as an alkyl halide catalyst, an activated substrate surface is formed. Halogen catalysts, such as alkyl halide catalysts, are described above and elsewhere in this specification.

[0150]

[0159] In one or more embodiments, a halogen catalyst, such as an alkyl halide catalyst, can be supplied to the processing chamber in one or more pulses or continuously. In one or more embodiments, a halogen catalyst, such as an alkyl halide catalyst, is supplied with an inert carrier gas and is referred to as an alkyl halide catalyst-containing gas. The flow rate and pressure of the halogen catalyst, such as an alkyl halide catalyst, or the halogen catalyst, such as an alkyl halide catalyst, can be any suitable values. Exemplary flow rates and pressures disclosed elsewhere in this specification for a halogen catalyst, such as an alkyl halide catalyst-containing gas, are also applicable in this embodiment.

[0151]

[0160] In one or more embodiments, the time for which the substrate is immersed in a halogen catalyst, such as an alkyl halide catalyst, can be any suitable time required for the halogen catalyst to form a suitable adsorption layer on the substrate surface. For example, the halogen catalyst can immerse the substrate for a period exceeding about 3 seconds or a period exceeding about 5 seconds. In one or more embodiments, the immersion period ranges from about 3 seconds to about 60 seconds.

[0152]

[0161] In one or more embodiments, an inert gas can be additionally supplied to the processing chamber simultaneously with the halogen catalyst, such as an alkyl halide catalyst-containing gas. The inert gas can be mixed with the halogen catalyst (e.g., as a dilution gas), or can be provided separately, can be pulsed, or can be at a constant flow rate. The inert gas can be any inert gas (e.g., argon, helium, neon, nitrogen, or a combination thereof, etc.).

[0153]

[0162] In one or more embodiments, in operation 850, the substrate is exposed to a second process gas during a second period. The second process gas includes a metal precursor that reacts with an adsorbed layer of alkyl halide catalyst or halogen on the substrate surface to deposit a metal film. The second reactive gas is also referred to as a metal precursor gas.

[0154]

[0163] In one or more embodiments, the metal precursor can be any suitable precursor for reacting with an adsorbed alkyl halide catalyst layer or halogen layer on the substrate. Suitable metal precursors are described elsewhere in this specification.

[0155]

[0164] In one or more embodiments, the metal precursor is delivered to the processing chamber as a metal precursor gas. The metal precursor gas may be supplied in one or more pulses or continuously. The flow rate and pressure of the metal precursor gas can be any suitable flow rate and pressure. Exemplary values of the flow rate and pressure are described elsewhere in this specification.

[0156]

[0165] In one or more embodiments, the period during which the substrate is exposed to the metal precursor gas can be any suitable time necessary to allow the metal precursor to react with the adsorbed halogen on the substrate surface. For example, the process gas may be flowed into the processing chamber for a period of about 60 seconds or more. In one or more embodiments, the exposure period to the metal precursor is about 100 seconds, about 200 seconds, about 300 seconds, about 400 seconds, or about 500 seconds.

[0157]

[0166] The temperature of the substrate during exposure to the metal precursor can be controlled, for example, by setting the temperature of the substrate support or susceptor. This temperature is also referred to as the deposition temperature. In one or more embodiments, the substrate is maintained at a temperature below the decomposition temperature of the metal precursor. In one or more embodiments, the substrate is maintained at a temperature below the decomposition temperature of the alkyl halide catalyst. In one or more embodiments, the substrate is maintained at a temperature between the decomposition temperature of the alkyl halide catalyst and the decomposition temperature of the metal precursor.

[0158]

[0167] In one or more embodiments, the substrate is maintained at about 400 °C or less, or about 350 °C or less, or about 300 °C or less, or about 250 °C or less, or about 200 °C or less. In one or more embodiments, the substrate is maintained at about 150 °C or more, or about 200 °C or more, or about 250 °C or more, or about 300 °C or more, or about 350 °C or more. In one or more embodiments, the substrate is maintained at a temperature of about 225 °C or about 280 °C.

[0159]

[0168] In one or more embodiments, the deposition process is performed as a heat treatment without using plasma reactants. In other words, in one or more embodiments, this method is performed without plasma.

[0160]

[0169] In one or more embodiments, at operation 860, it is determined whether the metal film has reached a predetermined thickness. If the predetermined thickness has not been achieved, method 800 returns to 850 and continues to expose the substrate to the metal precursor until the predetermined thickness is reached. When the predetermined thickness is reached, method 800 can end or proceed to 870 for any further processing. In one or more embodiments, the metal film may be deposited to form a total layer thickness of about 10 Å to about 10,000 Å, or in one or more embodiments, about 20 Å to about 1000 Å, or in one or more embodiments, about 50 Å to about 200 Å.

[0161]

[0170] One or more embodiments of the present disclosure selectively deposit a metal film on a metal surface on a first dielectric surface. These methods are similar to method 800 described above. The provided substrate includes a dielectric surface and a metal surface. In one or more embodiments, the substrate as shown in FIG. 9 is processed to selectively form bottom-up gap filling on the metal surface at the bottom 916 of the feature 910.

[0162]

[0171] The metal of the metal film and the metal on the substrate surface may be the same metal or different metals. The dielectric surface can be formed from any suitable dielectric material. In one or more embodiments, the dielectric material contains nitrogen atoms or oxygen atoms. Without being bound by theory, these materials are thought to react with the alkyl halide catalyst and prevent the halogen from adsorbing onto the substrate surface to catalyze the reaction with the metal precursor. Therefore, even if a metal film is formed on the dielectric surface, it is only a little.

[0163]

[0172] In one or more embodiments, the deposition temperature is below the decomposition temperature of the halogen catalyst, such as the alkyl halide catalyst. Again, without intending to be bound by theory, when the alkyl halide catalyst decomposes, the halogen is available for reaction with the metal precursor on all surfaces (regardless of composition) and is thought to result in metal film deposition on all substrate surfaces, including the dielectric surface. In one or more embodiments, the deposition temperature is above the decomposition temperature of the halogen catalyst, such as the alkyl halide catalyst.

[0164]

[0173] One or more embodiments of the present disclosure advantageously provide a method for controlling the deposition of a metal film. In one or more embodiments, the deposition rate is controlled. In one or more embodiments, the deposition position is controlled.

[0165]

[0174] The methods of various embodiments form the metal film using atomic layer deposition (ALD) or chemical vapor deposition (CVD) methods. The above disclosure describes an exemplary ALD process with respect to FIG. 7 and an exemplary CVD process with respect to FIG. 8.

[0166]

[0175] As described above, the generalized deposition processes shown in FIGS. 7 and 8 are performed as heat treatments without using plasma reactants. The use and effects of plasma and other additional reactants are further discussed below.

[0167]

[0176] One or more embodiments of the present disclosure advantageously provide a method for depositing a metal film within a substrate feature or other structure. Exemplary features or structures include, but are not limited to, trenches and vias.

[0168]

[0177] One or more embodiments of the present disclosure advantageously provide a deposition control method for reducing film deposition outside a target feature and near a feature opening. Without being bound by theory, reducing deposition within these regions enables faster gap filling within the target feature and is thought to reduce clogging near the feature opening and the formation of voids or seams within the feature.

[0169]

[0178] Referring to FIGS. 7 and 8, without limiting the scope of the above disclosure, both the ALD and CVD processes described above utilize an alkyl halide catalyst and a metal precursor to deposit a metal film. Without being bound by theory, the alkyl halide catalyst is thought to function as a catalyst in the deposition of the metal film. Thus, as particularly demonstrated by the CVD process, a single exposure of the substrate surface to the alkyl halide catalyst can be used to deposit a metal film having a thickness greater than 10 nm.

[0170]

[0179] One or more embodiments of the present disclosure advantageously provide a deposition control method for reducing the activity of a catalyst in a predetermined region of a substrate surface. In one or more embodiments, the activity of the catalyst is reduced. In one or more embodiments, the activity of the catalyst is eliminated.

[0171]

[0180] Referring to FIGS. 10A - 10D, an exemplary substrate 400 during processing, according to one or more embodiments of the present disclosure, is shown. The substrate 1000 shown in FIGS. 10A - 10D is simplified for illustrative purposes. As described above and as shown in FIG. 9, in one or more embodiments, the substrates of the present disclosure include features or structures not shown in FIGS. 10A - 10D.

[0172]

[0181] In FIG. 10A, the substrate 1000 includes a substrate surface 1010. In FIG. 4B, the substrate surface 1010 is exposed to a halogen catalyst, such as an alkyl halide catalyst, to form an activated surface 1020. As described above, the halogen catalyst, such as the alkyl halide catalyst 1040, adsorbs on the substrate surface 1010 to form an activated substrate surface 1020.

[0173]

[0182] In FIG. 10C, a predetermined region of the activated surface 1020 is exposed to an inactivation treatment to form an inactivated surface 1030. The halogen catalyst shown in FIGS. 10B and 10C, such as the alkyl halide catalyst 1040, is shown as circular or oval, but it is not intended to convey a specific molecular shape. Similarly, the difference between the circular shape shown in FIGS. 10B and 10C and the oval shape shown in FIG. 10C only means to convey the activity and / or relative concentration of the alkyl halide catalyst on the substrate surface.

[0174]

[0183] In FIG. 10D, the substrate 1000 is exposed to a metal precursor to form a metal film 1050. As shown in FIG. 10D, the thickness T1 of the metal film 1050 on the activated surface 1020 is greater than the thickness T2 of the metal film 1050 on the inactivated surface 1030.

[0175]

[0184] In one or more embodiments, the inactivation treatment reduces the concentration of the halogen catalyst, such as the alkyl halide catalyst, on the activated surface 1020. In one or more embodiments, the inactivation treatment reduces the catalytic activity of the halogen catalyst, such as the alkyl halide catalyst, on the activated surface 1020.

[0176]

[0185] In one or more embodiments, the method described above with respect to FIGS. 10A - 10D is modified to include a passivation treatment before exposure to a halogen catalyst, such as an alkyl halide catalyst. In this regard, the passivation treatment can be understood to "super - activate" a predetermined region of the substrate surface 1010 before exposure to the halogen catalyst, such as an alkyl halide catalyst. When exposed to the halogen catalyst, such as an alkyl halide catalyst, the "super - activated" surface forms a catalyst with a higher concentration or activity than the surface that has not been exposed to the passivation treatment. The difference in concentration and / or activity between the surfaces can be used to control deposition. In one or more embodiments, the surface may be further passivated as described above with respect to FIGS. 10C - 10D.

[0177]

[0186] The thickness T1 is greater than the thickness T2. Thus, one or more embodiments of the present disclosure advantageously provide a deposition control method for controlling the amount of deposition in a predetermined region of the substrate surface.

[0178]

[0187] In one or more embodiments, the ratio of T1:T2 is about 1:1 or more, about 2:1 or more, about 3:1 or more, about 4:1 or more, about 5:1 or more, or about 10:1 or more. In one or more embodiments, little or no metal deposition occurs on the passivated surface 1030. In other words, in one or more embodiments, the thickness T2 is about 0. In other words, the amount of the metal film 1050 deposited on the passivated surface 1030 is essentially nil. As used in this regard, "essentially nil" means that the metal film on the passivated surface covers less than 5%, less than 2%, less than 1%, or less than 0.5% of the passivated surface.

[0179]

[0188] The thickness of the metal film 1050 deposited on the activated surface 1020 and the passivated surface 1030 is directly proportional to the deposition rate on the activated surface 1020 and the passivated surface 1030. Thus, one or more embodiments of the present disclosure advantageously provide a deposition control method for controlling the deposition rate in a predetermined region of the substrate surface.

[0180]

[0189] In one or more embodiments, the entire substrate surface is exposed to the passivation treatment. Using one or more embodiments of the present disclosure, the deposition amount over the entire substrate can be controlled. Using one or more embodiments of the present disclosure, the deposition rate over the entire substrate can be controlled.

[0181]

[0190] In one or more embodiments (not shown), the substrate 1000 includes one or more features. In one or more embodiments, the passivated surface 1030 is the surface outside one or more features. In one or more embodiments, the passivated surface 1030 is the surface near the upper part of the sidewalls of one or more features.

[0182]

[0191] Without being bound by theory, it is believed that the surfaces near the substrate features and the upper surfaces of the sidewalls of those features are more highly activated (showing greater deposition) due to the plurality of exposed surfaces in the vicinity. The greater the deposition on these surfaces, the higher the likelihood that the feature will close before a sufficient amount of film is formed inside the feature. When the feature closes, seams or voids are often formed. Thus, in one or more embodiments, the passivated surface 1030 is the surface near the upper part of one or more features. Further, in one or more embodiments, the passivated surface 1030 is the surface close to the substrate features. In one or more embodiments, the metal film deposited in the feature has few seams or voids. In one or more embodiments, the metal film deposited in the feature has substantially no seams or voids. As used in this context, the expression "substantially seam-free" means that the gap formed in the film between the sidewalls is less than about 1% of the cross-sectional area of the sidewalls.

[0183]

[0192] In one or more embodiments, a predetermined region of the substrate is exposed to hydrogen gas without using plasma.

[0184]

[0193] In one or more embodiments, a hydrogen gas pulse is introduced into the ALD deposition cycle described above. In other words, the substrate may be exposed to a pulse sequence of an alkyl halide catalyst, purge, hydrogen gas, purge, metal precursor, and purge. In one or more embodiments, the substrate is exposed to an additional pulse of hydrogen gas and then purged after being exposed to the metal precursor. In one or more embodiments, the substrate is exposed to an additional pulse of hydrogen gas and then purged after being exposed to the alkyl halide catalyst. In one or more embodiments, the purge phase between each exposure to the metal precursor and / or the alkyl halide catalyst is performed in some, but not all, cycles.

[0185]

[0194] In one or more embodiments, a hydrogen gas exposure is introduced into the CVD deposition cycle described above. In other words, the substrate can be immersed in an alkyl halide catalyst, exposed to hydrogen gas, and exposed to a metal precursor. In one or more embodiments, the substrate is exposed to hydrogen gas before being exposed to the metal precursor. In one or more embodiments, hydrogen gas and the metal precursor are flowed simultaneously.

[0186]

[0195] In one or more embodiments, a predetermined region of the substrate is exposed to a plasma containing one or more of hydrogen (H2), ammonia (NH3), or argon (Ar). In one or more embodiments, the plasma used to inactivate the surface is a low-power plasma. In one or more embodiments, the plasma has a power in the range of about 50 W to about 500 W, about 50 W to about 300 W, about 50 W to about 200 W, or about 50 W to about 100 W.

[0187]

[0196] In one or more embodiments, the plasma exposure time is about 30 seconds or less, about 20 seconds or less, about 15 seconds or less, about 10 seconds or less, about 5 seconds or less, or about 2 seconds or less.

[0188]

[0197] In one or more embodiments, the plasma is a capacitively coupled plasma (CCP). In one or more embodiments, the plasma is an inductively coupled plasma (ICP). In one or more embodiments, the plasma is a direct plasma generated within the processing environment. In one or more embodiments, the plasma is a remote plasma generated outside the processing environment.

[0189]

[0198] In one or more embodiments, the plasma pulse is introduced into the ALD deposition cycle described above. In one or more embodiments, the plasma pulse replaces the hydrogen gas pulse described above with respect to the ALD deposition cycle.

[0190]

[0199] In one or more embodiments, the plasma pulse is introduced into the CVD deposition cycle described above. In one or more embodiments, the plasma pulse replaces the hydrogen gas exposure described above with respect to the CVD deposition cycle.

[0191]

[0200] The use of the terms "a," "an," "the," and similar referents in the context of describing the materials and methods discussed herein (especially in the context of the following claims) is to be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by the context. The recitation of numerical ranges herein is merely intended to serve as a shorthand for referring individually to each value falling within the range unless otherwise indicated herein, and each value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by the context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is merely intended to better illustrate the materials and methods and is not limiting of the scope unless otherwise claimed. No language in this specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0192]

[0201] Throughout this specification, references to "one embodiment", "a particular embodiment", "one or more embodiments", or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of the phrases "in one or more embodiments", "in a particular embodiment", "in one embodiment", or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the present disclosure. In one or more embodiments, the particular features, structures, materials, or characteristics are combined in any suitable manner.

[0193]

[0202] Although the disclosure of this specification has been described with reference to particular embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the methods and apparatuses of the present disclosure without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is intended to cover modifications and variations that come within the scope of the appended claims and their equivalents.

Claims

1. 1. A method for selectively depositing a film, comprising: forming an activated substrate surface on a substrate having a first dielectric surface and a second metallic surface by exposing the substrate surface to a halogen catalyst; exposing the first dielectric surface to a passivation treatment to reduce a concentration of a halogen catalyst on the first dielectric surface; The second metal surface is represented by the general formula (I): M-L １ (L ２ ) ｙ (wherein M is a metal and L １ is an aromatic ligand, L ２ is an aliphatic ligand, y is a number ranging from 2 to 8, L ２ selectively depositing the film on the second metal surface over the first dielectric surface by exposing the film to a precursor having a molar ratio of 1,5-hexadiene, 1,4-hexadiene, and less than 5% of 1,3-hexadiene; The method includes:

2. 2. The method of claim 1, wherein the metal M is selected from one or more of molybdenum (Mo), ruthenium (Ru), cobalt (Co), copper (Cu), platinum (Pt), nickel (Ni), or tungsten (W).

3. The method of claim 1 , wherein the substrate surface has at least one feature formed therein, the at least one feature having a sidewall and a bottom.

4. aromatic ligand L １ η ２ , η ４ , η ６ , and η ８ The method of claim 1 , comprising a π-electron system selected from:

5. aromatic ligand L １ The method of claim 4, wherein comprises 1-methyl-4-isopropylbenzene.

6. aliphatic ligand L ２ The method of claim 1 , further comprising an asymmetric cyclic diene.

7. 7. The method of claim 6, wherein the asymmetric cyclic diene comprises one or more of 3-(2-propenyl)-cyclohexene, 1-(2-propenyl)-cyclohexene, 1,3-propadiene-cyclohexane, and 1,2-divinylcyclohexane.

8. 7. The method of claim 6, wherein y is a number ranging from 2 to 6, and the ratio of 1,5-hexadiene to the sum of 1,4-hexadiene, 1,3-hexadiene and asymmetric cyclic dienes is in the range of from about 50:50 to about 60:

40.

9. The method of claim 3 , further comprising depositing a metal nitride liner on the at least one feature.

10. The method of claim 1 , further comprising depositing a seed layer on the substrate surface prior to exposing the substrate surface to the halogen catalyst.

11. The method of claim 1 , wherein exposing the substrate surface to the halogen catalyst comprises immersing the substrate in an alkyl halide catalyst.

12. 12. The method of claim 11, wherein the alkyl halide catalyst comprises iodoethane or diiodomethane.

13. The method of claim 1, wherein the second metal surface has a higher concentration or activity of halogen catalyst than the first dielectric surface after exposure to the deactivation treatment, and the difference in concentration and / or activity between the first dielectric surface and the second metal surface is used to control deposition.

14. A processing method comprising the steps of: exposing the substrate surface to a halogen catalyst to form an activated substrate surface; The activated substrate surface is treated with the general formula (I): M-L １ (L ２ ) ｙ (wherein M is a metal and L １ is an aromatic ligand, L ２ is an aliphatic ligand, y is a number ranging from 2 to 8 for forming a metal film on the substrate surface, and L ２ containing 1,5-hexadiene, 1,4-hexadiene, and less than 5% 1,3-hexadiene; wherein the substrate surface has at least one feature formed therein, the at least one feature having a sidewall and a bottom, the metal film fills the at least one feature, and the metal film is substantially seam and void free.

15. aromatic ligand L １ η ２ , η ４ , η ６ , and η ８ The method of claim 14 , comprising a π-electron system selected from:

16. The method of claim 14 , wherein exposing the substrate surface to the halogen catalyst comprises immersing the substrate in an alkyl halide catalyst.

17. 1. A non-transitory computer readable medium comprising instructions that, when executed by a controller of a processing chamber, cause the processing chamber to: exposing the substrate surface to a halogen catalyst to form an activated substrate surface; Flowing a precursor into a process space of the process chamber having the substrate, the precursor having a general formula (I): M-L １ (L ２ ) ｙ (wherein M is a metal and L １ is an aromatic ligand, L ２ is an aliphatic ligand, y is a number ranging from 2 to 8, L ２ comprising 1,5-hexadiene, 1,4-hexadiene, and less than 5% 1,3-hexadiene; A non-transitory computer-readable medium that causes the following operations to be performed:

18. 20. The non-transitory computer readable medium of claim 17, wherein exposing the substrate surface to the halogen catalyst comprises immersing the substrate in an alkyl halide catalyst.

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