Chamber Conditioning for Remote Plasma Processing

Abstract

The present invention relates to chamber conditioning for remote plasma processing. Methods, systems, and apparatus described herein relate to chamber conditioning for remote plasma processing, and in particular to remote nitrogen-based plasma processing. Certain implementations of the present disclosure relate to remote plasma suppression processing including chamber conditioning for feature fill. Embodiments of the present disclosure relate to exposing a remote plasma processing chamber to a fluorine species prior to nitrogen-based remote plasma processing of a substrate, such as a semiconductor wafer. Intra-wafer uniformity and inter-wafer uniformity are improved.

Description

[0001] This application is a divisional application of the invention patent application with application number 201711372325.2, application date December 19, 2017, applicant is Rum Research Company, and invention name is "Chamber Regulation for Remote Plasma Processing". Technical Field

[0002] The present invention relates to semiconductor manufacturing processes and, more particularly, to chamber conditioning for remote plasma processing. Background Art

[0003] Filling contact holes, trench lines, and other features with various materials is an integral part of the semiconductor manufacturing process. For example, to form horizontal interconnects, vias between adjacent metal layers, contacts between the first metal layer and the device, a metal such as tungsten can be deposited using chemical vapor deposition (CVD) techniques. In a conventional deposition process, a substrate is heated to a predetermined process temperature in a deposition chamber, and a thin layer of tungsten-containing material is deposited, which serves as a seed or nucleation layer. Afterwards, the remaining tungsten-containing material (bulk layer) is deposited on the nucleation layer. Conventionally, the tungsten-containing material is deposited by heating the substrate with hydrogen (H 2 ) Reduction of tungsten hexafluoride (WF 6 ) to form a tungsten-containing material. The tungsten-containing material is deposited on the entire exposed surface area of ​​the substrate including the features and field regions.

[0004] Depositing materials into small and high aspect ratio features can result in the formation of voids and seams within the filled features. Large seams can result in high resistance, contamination, loss of fill material, and otherwise degrade the performance of the integrated circuit. For example, a seam can extend close to the field region after the fill process and then open during the chemical mechanical planarization process. Likewise, voids can cause problems with integration and performance. Summary of the invention

[0005] One aspect of the present disclosure relates to a method of performing a conditioning process on a remote plasma processing chamber, the conditioning process comprising: introducing a fluorine-containing gas into a plasma generator to generate a fluorine-containing conditioning plasma; introducing the fluorine-containing conditioning plasma into the remote plasma processing chamber, wherein the remote plasma processing chamber comprises a substrate support and a showerhead, and the showerhead is disposed between the substrate support and the plasma generator, and wherein during the conditioning process, no manufacturing substrate is present in the remote plasma processing chamber; after performing the conditioning process, introducing a manufacturing substrate into the remote plasma processing chamber; and exposing the manufacturing substrate to the remotely generated nitrogen-based plasma. In some embodiments, the manufacturing substrate comprises one or more features to be filled.

[0006] In some embodiments, N 2In some embodiments, the remotely generated nitrogen-based plasma is generated from a nitrogen-containing compound, and the conditioning process further comprises introducing the nitrogen-containing compound into a plasma generator to generate a fluoride-free nitrogen-based conditioning plasma, and introducing the fluoride-free nitrogen-based conditioning plasma into the remote plasma processing chamber.

[0007] In some embodiments, the method further includes sequentially introducing one or more additional fabricated substrates into the remote plasma processing chamber and exposing each additional fabricated substrate to the remotely generated nitrogen-based plasma. For example, at least three fabricated substrates may be introduced into the remote plasma processing chamber prior to performing another conditioning process.

[0008] In some embodiments, the remotely generated nitrogen-based plasma selectively suppresses nucleation near the feature opening relative to the interior of the feature. In some such embodiments, the method may further include: selectively depositing tungsten or cobalt in the feature interior relative to the vicinity of the feature opening. In some embodiments, the conditioning process may further include forming a fluorine-containing layer on one or more chamber components. In some embodiments, the conditioning process may further include forming an aluminum fluoride layer on one or more chamber components.

[0009] Another aspect of the present disclosure relates to a method that includes performing multiple conditioning and treatment cycles to sequentially process multiple substrates in a remote plasma processing chamber. Each cycle may include: a) performing a conditioning treatment that includes: i) introducing a fluorine-containing gas into a plasma generator to generate a fluorine-containing conditioning plasma; and ii) introducing the fluorine-containing conditioning plasma into the remote plasma processing chamber, wherein the remote plasma processing chamber includes a substrate support and a showerhead, and the showerhead is disposed between the substrate support and the plasma generator, and wherein no manufacturing substrate is present in the remote plasma processing chamber during the conditioning treatment; b) after the conditioning treatment and before repeating the conditioning treatment, performing multiple nitrogen plasma exposure treatments, wherein each nitrogen plasma exposure treatment includes: i) introducing a manufacturing substrate into the remote plasma processing chamber; ii) exposing the manufacturing substrate to a remotely generated nitrogen-based plasma; and iii) removing the manufacturing substrate from the remote plasma processing chamber.

[0010] In some embodiments, N 2The gas generates a remotely generated nitrogen-based plasma. In some embodiments, the remotely generated nitrogen-based plasma is generated by a nitrogen-containing compound, and the conditioning process further includes introducing the nitrogen-containing compound into a plasma generator to generate a fluoride-free nitrogen-based conditioning plasma, and introducing the fluoride-free nitrogen-based conditioning plasma into a remote plasma processing chamber. In some embodiments, the method further includes: sequentially introducing one or more additional manufacturing substrates into the remote plasma processing chamber, and exposing each additional manufacturing substrate to the remotely generated nitrogen-based plasma. For example, at least three manufacturing substrates may be introduced into the remote plasma processing chamber before performing another conditioning process. In some embodiments, the remotely generated nitrogen-based plasma selectively suppresses nucleation near the feature opening relative to the interior of the feature. In some such embodiments, the method may also include selectively depositing tungsten or cobalt in the feature relative to the feature opening and inside the feature. In some embodiments, the conditioning process may further include forming a fluorine-containing layer on one or more chamber components. In some embodiments, the conditioning process may further include forming an aluminum fluoride layer on one or more chamber components.

[0011] Another aspect of the present disclosure relates to a method of conditioning a remote plasma processing chamber by exposing the remote plasma processing chamber to atomic fluorine; after conditioning the remote plasma processing chamber, introducing a substrate having one or more features into the remote plasma processing chamber, each feature including a feature opening; exposing the substrate to nitrogen radicals; selectively inhibiting nucleation of the one or more features on a surface at or near the feature opening, thereby forming a differential inhibition profile in each feature; and depositing a material in the feature according to the differential inhibition profile. Examples of materials include tungsten and cobalt. In some embodiments, the material is deposited in the remote plasma processing chamber. In some embodiments, the material is deposited in a chamber separate from the remote plasma processing chamber.

[0012] Specifically, some aspects of the present invention can be described as follows:

[0013] 1. A method comprising:

[0014] A conditioning process is performed on the remote plasma processing chamber, the conditioning process comprising:

[0015] introducing a fluorine-containing gas into a plasma generator to produce a fluorine-containing conditioning plasma;

[0016] introducing the fluorine-containing conditioning plasma into the remote plasma processing chamber, wherein the remote plasma processing chamber comprises a substrate support and a showerhead, and the showerhead is disposed between the substrate support and the plasma generator, and wherein no manufacturing substrate is present in the remote plasma processing chamber during the conditioning process;

[0017] After performing the conditioning process, introducing a manufacturing substrate into the remote plasma processing chamber; and

[0018] The fabrication substrate is exposed to a remotely generated nitrogen-based plasma.

[0019] 2. The method of clause 1, wherein the fabrication substrate comprises one or more features to be filled.

[0020] 3. The method of clause 1, wherein the remotely generated nitrogen-based plasma is composed of N 2 Gas production.

[0021] 4. A method according to clause 1, wherein the remotely generated nitrogen-based plasma is generated from a nitrogen-containing compound, and the conditioning process further comprises: introducing the nitrogen-containing compound into the plasma generator to generate a fluoride-free nitrogen-based conditioning plasma, and introducing the fluoride-free nitrogen-based conditioning plasma into the remote plasma processing chamber.

[0022] 5. The method of any one of clauses 1 to 4, further comprising: sequentially introducing one or more additional fabricated substrates into the remote plasma processing chamber, and exposing each additional fabricated substrate to the remotely generated nitrogen-based plasma.

[0023] 6. The method of clause 5, wherein at least three fabrication substrates are introduced into the remote plasma processing chamber prior to performing another conditioning process.

[0024] 7. The method of any of clauses 1-4, wherein the remotely generated nitrogen-based plasma selectively suppresses nucleation near a feature opening relative to an interior of the feature.

[0025] 8. The method of clause 6, further comprising: in the feature, selectively depositing tungsten or cobalt in an interior portion of the feature relative to a vicinity of the feature opening.

[0026] 9. The method of any of clauses 1-4, wherein the conditioning process comprises forming a fluorine-containing layer on one or more chamber components.

[0027] 10. The method of any of clauses 1-4, wherein the conditioning process comprises forming an aluminum fluoride layer on one or more chamber components.

[0028] 11. A method comprising:

[0029] A plurality of conditioning and processing cycles are performed to sequentially process a plurality of substrates in a remote plasma processing chamber, wherein each cycle comprises:

[0030] a) performing a conditioning process, which includes:

[0031] i) introducing a fluorine-containing gas into a plasma generator to generate a fluorine-containing conditioning plasma; and

[0032] ii) introducing the fluorine-containing conditioning plasma into the remote plasma processing chamber, wherein the remote plasma processing chamber comprises a substrate support and a showerhead, and the showerhead is disposed between the substrate support and the plasma generator, and wherein no manufacturing substrate is present in the remote plasma processing chamber during the conditioning process; and

[0033] b) performing a plurality of nitrogen plasma exposure processes after the conditioning process and before repeating the conditioning process, each of the nitrogen plasma exposure processes comprising:

[0034] i) introducing a manufacturing substrate into the remote plasma processing chamber;

[0035] ii) exposing the fabrication substrate to a remotely generated nitrogen-based plasma; and

[0036] iii) removing the fabricated substrate from the remote plasma processing chamber.

[0037] 12. The method of clause 11, wherein the fabrication substrate includes one or more features to be filled.

[0038] 13. The method of clause 11, wherein the remotely generated nitrogen-based plasma is N 2 Gas produced.

[0039] 14. A method according to any one of clauses 11-13, wherein the remotely generated nitrogen-based plasma is generated by a nitrogen-containing compound, and the conditioning treatment further comprises: introducing the nitrogen-containing compound into the plasma generator to generate a fluoride-free nitrogen-based conditioning plasma, and introducing the fluoride-free nitrogen-based conditioning plasma into the remote plasma processing chamber.

[0040] 15. A method comprising:

[0041] conditioning the remote plasma processing chamber by exposing the remote plasma processing chamber to atomic fluorine;

[0042] After conditioning the remote plasma processing chamber, introducing a substrate having one or more features into the remote plasma processing chamber, each feature including a feature opening;

[0043] exposing the substrate to nitrogen radicals;

[0044] selectively inhibiting nucleation of the one or more features on the surface at or near the feature opening, thereby forming a differential inhibition profile in each feature; and

[0045] Material is deposited in the feature according to the differential inhibition profile.

[0046] 16. The method of clause 15, wherein the material is tungsten or cobalt.

[0047] 17. A method according to clause 15 or 16, wherein the material is deposited in the remote plasma processing chamber.

[0048] 18. The method of clause 15 or 16, wherein the material is deposited in a chamber separate from the remote plasma processing chamber.

[0049] These and other aspects of the disclosed embodiments are described in further detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 An example of a schematic representation of a feature filling sequence that may employ remote plasma processing is shown.

[0051] Figure 2 and Figure 3 A schematic example of an apparatus for remote plasma processing is shown.

[0052] Figure 4 is a flow chart illustrating an example of a method of remote plasma processing according to certain embodiments.

[0053] Figure 5 is a flow chart illustrating an example of a chamber conditioning method for a remote plasma processing chamber.

[0054] Figure 6 is a graph showing tungsten (W) growth delay on a substrate after various chamber conditioning processes.

[0055] Figure 7is a graph illustrating wafer-to-wafer uniformity with and without a fluorine conditioning operation prior to a nitrogen-based process.

[0056] Figure 8 is a graph showing within-wafer uniformity with and without a fluorine conditioning operation prior to a nitrogen-based process.

[0057] Fig. 9 is a graph showing wafer-to-wafer uniformity with and without periodic fluorine conditioning operations prior to nitrogen-based processing of multiple wafers.

[0058] Fig.10 is a flow chart illustrating an example of a method of filling a feature with a material, according to certain embodiments.

[0059] Fig.11A A schematic example of a multi-station arrangement is shown.

[0060] Fig. 11B A schematic example of a multi-chamber device is shown. DETAILED DESCRIPTION

[0061] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other cases, well-known processing operations are not described in detail so as not to unnecessarily obscure the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific embodiments, it should be understood that this is not intended to limit the disclosed embodiments.

[0062] The methods, systems, and apparatus described herein relate to chamber conditioning for remote plasma processing, particularly nitrogen-based remote plasma processing. Certain implementations of the present disclosure relate to remote plasma suppression processing for feature filling including chamber conditioning. However, it should be understood that the chamber conditioning methods described herein can be used for a variety of other applications.

[0063] Filling a feature with material can result in the formation of voids and seams within the filled feature. Voids are unfilled areas within a feature. For example, voids can form when the deposited material forms a pinch point within the feature, thereby closing off the unfilled space within the feature and preventing reactants from entering and depositing. Seams are elongated areas within a feature that can be characterized by an elongated void, a series of smaller voids, or a grain boundary.

[0064] There are several possible reasons for voids and seams to form. One is an overhang at the feature opening. An overhang can be formed by a previous layer (e.g., a diffusion barrier) or in the initial stages of deposition of the fill material. Another reason for voids or seams to form is the curved or arched sidewalls of the feature hole, which are also called arched features. In features with an overhang or in an arched feature, the cross-sectional dimensions of the cavity to be filled near the opening are smaller than the cross-sectional dimensions inside the feature. Shrinkage within the feature also creates challenges for filling.

[0065] Even if void-free fill is achieved, a seam may pass through the central axis of a via, trench, line, or other feature. This is because growth may start at the sidewall until the grains come into contact as they grow from the opposing sidewalls. The seam may allow for the capture of impurities including fluorine-containing compounds such as hydrofluoric acid (HF). During chemical mechanical planarization (CMP), intracrystalline segregation (coring) may propagate from the seam. According to various embodiments, the methods described herein may reduce or eliminate void and seam formation.

[0066] Embodiments of the present disclosure relate to preferentially inhibiting film growth at portions of a feature. Such preferential inhibition, which may also be referred to as selective inhibition, selective passivation, differential inhibition, or differential passivation, includes inhibiting nucleation at a portion of a feature without inhibiting nucleation (or inhibiting nucleation to a lesser extent) at the remainder of the feature. For example, in some embodiments, a feature is preferentially inhibited at a feature opening, while further nucleation is not inhibited within the feature. In some embodiments, a feature is preferentially inhibited at a feature contraction, while further nucleation within the feature is not inhibited.

[0067] Selective inhibition is further described below and may involve, for example, selectively exposing a portion of a feature to an activated species of a plasma. In certain embodiments, for example, a feature opening is selectively exposed to a plasma consisting of molecular nitrogen (N 2 ) generated by a plasma. As discussed further below, a desired inhibition profile in a feature can be formed by appropriate selection of one or more of the inhibition chemistry, substrate bias power, plasma power, process pressure, exposure time, and other process parameters.

[0068] Figure 1 An example of a schematic representation of a feature filling sequence that can employ remote plasma processing is shown. Figure 1In the example of FIG. 1 , tungsten (W) deposition for fabricating a word line (WL) is shown. The WL structure 100 is provided with a liner layer surface 102. The liner surface 102 may be, for example, titanium nitride (TiN) or tungsten nitride (WN). Next, a W nucleation layer 104 is conformally deposited on the liner 102 throughout the structure 100. Note that in some processes, this operation of depositing a conformal nucleation layer may be omitted. Next, the structure is exposed to an inhibition chemical to selectively inhibit a portion 106 of the structure 100. In this example, a portion 104a beyond the column constriction 151 is not inhibited. As shown in the figure, inhibition involves exposure to a chemical composed of, for example, N 2 , forming gas (N 2 +H 2 ) or NH 3 Such gases produce remotely generated plasma.

[0069] Next, a chemical vapor deposition (CVD) process is performed to selectively deposit tungsten according to the inhibition profile: bulk tungsten 108 is preferentially deposited on the uninhibited portion 104a of the nucleation layer so that the hard-to-fill area behind the constriction is filled, without depositing on the inhibited portion 106. The remainder of the feature is then filled with bulk tungsten 110. The same CVD process used to selectively deposit tungsten can be used for the remainder of the feature, a different CVD process using different chemistries or process conditions and / or performed after the nucleation layer is deposited can be used.

[0070] Figure 1 is an example of a feature filling process that can use a nitrogen-based remote plasma. Other examples can be found in U.S. Patent Publication Nos. 20130171822, 20160056077, and 20160190008, and U.S. Patent No. 9,349,637, which are incorporated herein by reference. Specifically, U.S. Patent Publication Nos. 2013017182 and 20160190008 are incorporated by reference to describe methods of tungsten feature filling using a nitrogen-based remote plasma, and U.S. Patent Publication No. 20160056077 and U.S. Patent No. 9,349,637 are incorporated herein by reference to describe methods of cobalt feature filling using a nitrogen-based remote plasma. Embodiments of the present disclosure include feature filling of these and other materials using a nitrogen-based remote suppression process.

[0071] Figure 2 and Figure 3 A schematic example of an apparatus for remote plasma processing is shown. First, Figure 2, the apparatus 200 includes a chamber 218 having a base 220, a showerhead 214, and a remote plasma generator 206. In some embodiments, the apparatus may include an in-situ plasma generator (not shown). The apparatus 200 also includes a system controller 222 for receiving input and / or supplying control signals. The system controller is further described below.

[0072] A gas (e.g., a nitrogen-based gas, a fluorine-containing gas, an inert gas (such as argon, helium, etc.), etc.) is supplied to the remote plasma generator 206 as a process gas from one or more sources 202, which may be one or more tanks. Any suitable remote plasma generator may be used to activate the process gas prior to introducing the process gas into the chamber 218. For example, a remote plasma cleaning (RPC) unit may be used, such as the MKS Instruments, all available from Andover, Massachusetts. i Type AX7670, eTypeAX7680, ex Type AX7685, hf-s Type AX7645. RPC units are usually stand-alone units that generate weakly ionized plasma using supplied process gas.

[0073] In some embodiments, the process gas flows from the remote plasma generator 206 through the connection line 208 into the chamber 218, where the mixture is distributed through the showerhead 214. In some embodiments, one or more inert gas sources 212 can be connected to the mixing bowl 210 and then mixed with the plasma species downstream of the remote plasma generator 206.

[0074] The chamber 218 may include sensors 224 for sensing various process parameters such as the extent of deposition or etching, concentration, pressure, temperature, etc. The sensors 224 may provide information about chamber conditions to the system controller 222 during processing. Examples of sensors 224 include mass flow controllers, pressure sensors, thermocouples, etc. The sensors 224 may also include infrared detectors or optical detectors to monitor the presence of gases in the chamber and control measures.

[0075] Various volatile materials can be exhausted from the chamber 218. Moreover, the process is carried out at certain predetermined pressure levels in the chamber 218. A vacuum outlet 226, which can be a vacuum pump, can be used to control the pressure and exhaust the gas as appropriate.

[0076] The plasma species generated in the remote plasma generator may include ionic species and neutral species (eg, atoms and free radicals). The showerhead 214 may effectively block the flow of ionic species so that only neutral species enter the chamber 218. The showerhead may be an aluminum (Al) showerhead or an aluminum-containing showerhead.

[0077] Figure 3 Another example apparatus for remote plasma processing according to certain disclosed embodiments is shown. Figure 3 A cross-sectional view of an inductively coupled plasma etching apparatus 390 suitable for practicing certain embodiments herein is schematically shown, an example of which is manufactured by Lam Research Corp. of Fremont, California. MaxExtremeFill TM Reactor. Although an ICP reactor is described herein, in some embodiments, it should be understood that a capacitively coupled plasma reactor may also be used.

[0078] Inductively coupled plasma device 390 includes an entire processing chamber structurally defined by chamber wall 391 and dome 392 for igniting plasma. Chamber wall 391 can be made of stainless steel or Al. Elements for plasma generation include coil 394, which is positioned around dome 392 and above showerhead 395. In some embodiments, no coil is used. Coil 394 is made of a conductive material and includes at least one complete turn. Figure 3 The example of the coil 394 shown includes three turns. The cross-section of the coil 394 is represented by symbols, and the coil with an "X" extends rotationally into the page, while the coil with a "●" extends rotationally out of the page. The elements for plasma generation also include an RF power supply 341 configured to supply RF power to the coil 394. Generally speaking, the RF power supply 341 is connected to the matching circuit 339 via connection 345. The matching circuit 339 is connected to the coil 394 via connection 333. In this way, the RF power supply 341 is connected to the coil 394. RF power is supplied from the RF power supply 341 to the coil 394 so that RF current flows through the coil 394. The RF current flowing through the coil 394 generates an electromagnetic field around the coil 494. The electromagnetic field generates an inductively coupled plasma within the dome 392, thereby generating ion species and neutral species (such as free radicals).

[0079] RF power supply 341 can provide RF power at any suitable frequency. In some embodiments, RF power supply 341 can be configured to control high-frequency and low-frequency RF power sources independently of each other.

[0080] The showerhead 395 distributes the processing gas toward the substrate 397. Figure 3In the illustrated embodiment, substrate 397 is located below showerhead 395 and is shown resting on base 396. Showerhead 395 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to substrate 397. Figure 2 As in the example of FIG. 3 , the showerhead 395 can be used as an ion filter, thereby allowing only neutral species to reach the substrate 397. The showerhead can be an Al showerhead or an aluminum-containing showerhead. The base 396 is configured to receive and hold the substrate 397.

[0081] Gas (e.g., nitrogen-containing gas, inert gas, or fluorine-containing gas) can flow into the processing chamber through one or more main gas flow inlets 393 located in the dome and / or through one or more side gas flow inlets (not shown). Similarly, although not explicitly shown, similar gas flow inlets can be used to supply processing gas to the capacitively coupled plasma processing chamber. In some embodiments for the capacitively coupled plasma processing chamber, the gas can be injected through the center and / or edge of the nozzle through the nozzle. A vacuum pump (e.g., a one-stage or two-stage mechanical dry pump and / or a turbomolecular pump 398a) can be used to extract the processing gas from the processing chamber 391 and maintain the pressure in the processing chamber 391. A valve control pipeline can be used to connect the vacuum pump fluid to the processing chamber 391 to selectively control the application of the vacuum environment provided by the vacuum pump. This can be done using a closed-loop control flow restriction device (e.g., a throttle valve (not shown) or a swing valve (not shown)) during the operation of the plasma treatment. Similarly, a vacuum pump and a valve-controlled fluid connection connected to the capacitively coupled plasma processing chamber can also be used. Volatile byproducts can be removed from the processing chamber 391 through port 398b. The device 390 also includes a system controller 399 for receiving input and / or providing control signals. The system controller is described further below.

[0082] Figure 4 A general process flow diagram representing a method 400 of remote plasma processing is illustrated in accordance with certain embodiments. First, condition a chamber. Block 401. The method of conditioning a chamber is further described below. Figure 2 and 3 Examples of chambers are described. Figure 4 In some embodiments, a dummy substrate (also referred to as a test substrate) that does not require additional processing can be positioned in the chamber. The term "manufacturing substrate" is used herein to distinguish wafers and other substrates that are undergoing processing to be manufactured into devices (e.g., semiconductor logic and memory devices) from dummy or test substrates.

[0083] The nth substrate is then positioned in the chamber (block 403), with n=1 being the first substrate after chamber conditioning. As further described below, the nth substrate may be positioned in the chamber (block 403), with n=1 being the first substrate after chamber conditioning.max The chamber conditioning is performed on the nth substrate. The nth substrate is then exposed to a remotely generated nitrogen-based plasma. (Block 405). A nitrogen-based plasma is a plasma in which the primary chemically reactive species is nitrogen (typically in the form of nitrogen radicals). Other plasma species (e.g., inert gas species) may be present. In some implementations, other than nitrogen radicals, there are no non-inert components in the gas from which the plasma is generated, except for trace amounts of non-inert components. In some embodiments, the nitrogen-based plasma is halogen-free. In many embodiments, the nitrogen-based plasma is composed of N 2 gas formation, but other nitrogen gases may also be used, such as forming gas, NH 3 or N 2 H 2 The nth substrate is removed from the chamber. (Block 407). It should be noted that in some embodiments, various other processing operations may be performed while the nth substrate is in the chamber. These include deposition of material on the substrate or etching of deposited material.

[0084] At decision block 409, it is determined whether n=n max If not, the process returns to block 403 where another substrate is placed in the chamber. max , then at decision block 411, it is determined whether more substrates are to be processed. If so, the process returns to block 401 for chamber conditioning. Otherwise, the process is complete and all substrates in the run have been processed.

[0085] Chamber conditioning involves exposing the chamber to a remotely generated fluorine-containing plasma. Such as nitrogen trifluoride (NF 3 ), fluorine (F 2 ), sulfur hexafluoride (SF 6 ) or carbon tetrafluoride (CF 4 ) can be provided to the remote plasma generator. Fluorine species, typically neutral species such as atomic fluorine, regulate the chamber. In some embodiments, the plasma in the regulated chamber does not have ionized species. Species generated by inert gases may be present.

[0086] In some embodiments, the chamber conditioning process includes exposure to a remotely generated fluorine-free nitrogen plasma prior to and / or after exposure to the fluorine-containing plasma. Figure 5 is a flow chart illustrating an example of a method 500 for chamber conditioning of a remote plasma processing chamber including these operations. 2 Gas remotely generated plasma. Block 501. Although Figure 5 N is provided 2 As an example, but in Figure 5The same gas used for remote nitrogen-based plasma treatment of the substrate is used in blocks 501 and 505 (e.g., Figure 4 405 in the above). Thus, in other embodiments, the plasma in these boxes may be generated from other nitrogen-containing gases as described above. Next, the chamber is exposed to a plasma remotely generated from a F-containing gas. Box 503. The chamber is then exposed to a remotely generated N 2 Plasma. Block 505. Typically, the duration of block 505 is shorter than the duration of blocks 501 or 503. The operations in method 500 are described below with reference to Figure 6-8 Further description.

[0087] As mentioned above about Figure 1 As indicated, in some embodiments, N 2 Plasma is used to suppress the growth of tungsten or cobalt. Figure 6 is a graph showing the tungsten (W) growth delay on a substrate after various chamber conditioning processes. The remote plasma processing chamber is conditioned in the absence of a substrate and then the substrate is exposed to N in the remote plasma processing chamber. 2 Remote plasma (i.e., N 2 The substrate is then exposed to a tungsten deposition chemistry such as WF 6 / H 2 . Measure the growth delay of tungsten, i.e. N 2 A measure of the efficiency of a plasma process.

[0088] Three chamber conditioning protocols were performed: (1) N 2 / NF 3 ,(2)N 2 / NF 3 / N 2 (short), and (3) only N 2 Only N 2 processing results in very low growth latency. In contrast, NF 3 Treatment significantly increased the growth delay (from less than 10 s to more than 100 s).

[0089] Without being bound by a particular theory, it is believed that the fluorine reacts with components in the chamber and forms a passivation layer, such as aluminum fluoride (AlF 3 In the absence of such a passivation layer, nitrogen radicals (N * ) may be lost due to interaction with the showerhead and in some cases with other components of the chamber. Back Figure 6 , in NF 3 The short N after 2 The plasma reduces the N 2Plasma efficacy, as measured by W growth retardation. However, in some embodiments, in NF 3 The short N after 2 The plasma may help return the chamber to the N 2 Wafer-to-wafer uniformity can be improved due to the conditions experienced during plasma processing.

[0090] According to various embodiments, chamber conditioning may passivate one or more of the showerhead, chamber walls, and other hardware components in the chamber. The surfaces of these components may contribute to the nitrogen radical loss rate, which results in wafer-to-wafer non-uniformity as well as intra-wafer non-uniformity. The result is a more uniform and more stable nitrogen radical flux in subsequent nitrogen remotely generated plasma processing operations. In addition, by controlling the nitrogen radical loss rate, the conditioning may be used in conjunction with other result-effective variables (e.g., time, power, and temperature) to control the total amount of inhibition on the substrate in a nitrogen inhibition process.

[0091] Although the chamber conditioning described above uses remote plasma, in some embodiments, the conditioning process may employ a non-plasma process prior to a nitrogen-based remote plasma processing operation. In some other embodiments, the conditioning process may employ a non-plasma process prior to a nitrogen-based remote plasma processing operation. For example, a fluorine-containing thermal deposition process may be used to deposit a passivation layer on chamber components prior to using a nitrogen radical treatment. The passivation layer may be a fluorine-containing layer that limits N radical loss. In some embodiments, if the conditioning process does not affect the wafer or if the chamber conditioning process may be used to process the wafer, the wafer may be present in the chamber during the conditioning process.

[0092] The processes described herein provide improved wafer-to-wafer uniformity and improved within-wafer (center-to-edge) uniformity. Figure 7 is a graph illustrating wafer-to-wafer uniformity with and without a fluorine conditioning operation prior to a nitrogen-based process. Five wafers were processed (N was generated remotely). 2 plasma + subsequent tungsten deposition) to produce each of curves 701 and 703. Curve 701 represents the case where no fluorine (NF 3 Curve 703 represents the tungsten growth delay of five wafers processed with fluorine (NF 3 ) Adjust the tungsten growth delay of the five wafers after treatment. 3 The wafer-to-wafer non-uniformity (WtW Nu%) of the conditioned wafers was 18%, while that of the NF 3 The wafer-to-wafer non-uniformity of the processed wafers after conditioning was only 2%.

[0093] Figure 8is a graph showing the within-wafer uniformity with and without a fluorine conditioning operation prior to a nitrogen-based process. Curve 801 represents the within-wafer uniformity without a fluorine (NF 3 Curve 803 shows the tungsten thickness of a 300 mm wafer processed under the condition of fluorine (NF 3 ) adjustment of the tungsten thickness on the 300 mm wafer processed later. The wafer non-uniformity (WiWNu%) is 3 The wafers processed under the condition of adjustment are 6%, and the 3 For wafers processed after conditioning, only 3% did so.

[0094] Return to reference Figure 4 , every n max The appropriate n max Will depend on the chamber, the specific conditioning process, the specific process, and on the tolerances for wafer-to-wafer non-uniformity and wafer-to-wafer non-uniformity. In some embodiments, it may be possible to perform a 100% scalar flow rate after each wafer (so that n max Yes 1) Condition the chamber. More typically, the chamber may be conditioned only once after remote plasma processing of multiple wafers (eg, every 3, 4, 5, 7, 10, 15 wafers, etc.). Fig. 9 Graph showing wafer-to-wafer uniformity with and without periodic fluorine conditioning operations prior to nitrogen-based processing of multiple wafers. 2 plasma + subsequent tungsten deposition) to produce each of curves 901 and 903. Curve 901 represents the 3 Curve 903 shows the tungsten growth delay of the twenty-five wafers processed after the fluorine (NF) conditioning. 3 ) adjustment. 3 The wafer-to-wafer non-uniformity (WtW Nu%) of the wafer processed under the condition of adjustment is 36.5%. 3 The wafer-to-wafer non-uniformity for wafers processed without conditioning was only 5.7%.

[0095] Fig. 9 Curve 901 of FIG. 9 also provides evidence that, in some embodiments, it is useful to not terminate the conditioning process with a remotely generated plasma containing fluorine. This is because there is a sharp drop in the tungsten growth delay from wafer 1 to wafer 7, indicating that the presence of a certain amount of fluoride on the chamber components consumes N * free radicals, thus causing drift in the process. 2 Plasma stop chamber tuning can mitigate this drift effect.

[0096] References Figure 2 and 3 Examples of chambers that can be regulated according to the methods described herein are described. Figure 1 As described, a remotely generated nitrogen-based plasma may be used to selectively suppress the growth of tungsten, cobalt, or other materials in a feature. Fig.10 is a flow chart illustrating an example of a method of filling a feature with a material according to certain embodiments. The methods described herein can be used to fill vertical features such as tungsten vias and horizontal features such as vertical NAND (VNAND) word lines. These methods can be used for conformal fill and bottom-up fill / inside-out fill. Application examples include logic and memory contact fill, DRAM buried word line fill, vertical integrated memory gate and word line fill, and 3-D integration using through silicon vias.

[0097] First, a remote plasma process is performed in a chamber conditioned to selectively inhibit deposition in a feature. (Block 1001). Block 1001 is performed in a chamber conditioned with a fluorine-containing compound as described above. In some embodiments, a chamber component includes a fluorine-containing passivation layer (e.g., AlF 3 ). This operation creates an "inhibition profile" in the feature, where deposition is preferentially inhibited at one or more locations in the feature relative to one or more other locations.

[0098] Next, selective deposition of material is performed according to the inhibition profile. Box 1003. Box 1003 may include one or more chemical vapor deposition (CVD) and / or atomic layer deposition (ALD) processes, including thermal CVD processes, plasma enhanced CVD processes, and / or ALD processes. The deposition is selective because the material preferentially grows on smaller portions and non-inhibited portions of the feature. In some embodiments, box 1003 involves selectively depositing the material in the bottom or inner portion of the feature until reaching or passing the constriction. After selective deposition according to the inhibition profile, the method may continue at box 1005 with filling the rest of the feature. In some embodiments, box 1005 may involve continuing the CVD deposition process started at box 1003. Such a CVD process may result in deposition on the inhibited portion of the feature, wherein nucleation on the inhibited portion occurs more slowly than nucleation on the non-inhibited portion of the feature. In some embodiments, box 1005 may involve depositing a nucleation layer on at least the inhibited portion of the feature.

[0099] For tungsten deposition, a tungsten precursor and a reducing agent may be used. Examples of precursors include tungsten hexafluoride (WF 6 ), tungsten hexachloride (WCl 6 ), tungsten pentachloride (WCl 5), organometallic precursors, and fluorine-free precursors (e.g., MDNOW (methylcyclopentadienyl-dicarbonylnitrosyl-tungsten) and EDNOW (ethylcyclopentadienyl-dicarbonylnitrosyl-tungsten)). In addition, although hydrogen can be used as a reducing agent in the deposition, other reducing agents including silanes can be used in addition to or in place of hydrogen. In another embodiment, tungsten hexacarbonyl (W(CO)) can be used with or without a reducing agent. 6 ). In CVD technology, WF 6 and H 2 Or other reactants are introduced into the reaction chamber at the same time. This will produce a continuous chemical reaction of the mixed reactant gas, thereby continuously forming a tungsten film on the substrate surface. The method of depositing a tungsten film using CVD is described in U.S. Patent Application Nos. 12 / 202,126, 12 / 755,248 and 12 / 755,259, and the entire contents of these patent applications are incorporated herein by reference for the purpose of describing the tungsten deposition process. According to various embodiments, the method described herein is not limited to a specific method of filling features, but may include any appropriate deposition technique. In some embodiments, a nucleation layer is deposited using the PNL technique. In the PNL technique, a reducing agent, an optional purge gas, and a pulse of a tungsten-containing precursor can be sequentially injected into the reaction chamber and removed therefrom. The process is repeated in a cyclic manner until the desired thickness is reached. PNL broadly embodies any cyclic process of continuously adding reactants for reacting on a semiconductor substrate, including ALD technology. The PNL technique for depositing a tungsten nucleation layer is described in U.S. Patents 6,635,965, 7,589,017, 7,141,494, 7,772,114, 8,058,170, and 8,623,733 and U.S. Patent Publication No. 20100267230, which are incorporated herein by reference in their entirety for the purpose of describing tungsten deposition processes.

[0100] In some embodiments, block 1005 includes repeating blocks 1001 and 1003 one or more times. In addition, in some embodiments, block 1005 may include a non-conformal etch, as described in U.S. Patent Publication No. 20130302980, which is incorporated herein by reference in its entirety for the purpose of describing non-conformal etching in a fill process.

[0101] Precursors useful for cobalt deposition are described in US Pat. No. 9,349,637, which is incorporated herein by reference in its entirety for purposes of describing cobalt feature filling.

[0102] CVD and ALD deposition of other materials may include the use of any suitable precursors. For example, CVD and ALD deposition of tungsten nitride may include the use of halogen-containing compounds and halogen-free tungsten-containing compounds and nitrogen-containing compounds as further described below. CVD and ALD deposition of titanium-containing layers may include the use of precursors containing titanium, examples of which include tetrakis(dimethylamino)titanium (TDMAT) and titanium chloride (TiCl 4 ) and, if appropriate, one or more co-reactants. CVD and ALD deposition of tantalum-containing layers may include the use of materials such as penta(dimethylaminotantalum) (PDMAT) and TaF 5 and, if appropriate, one or more co-reactants. CVD and ALD deposition of cobalt-containing layers may include the use of precursors such as tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt, bis(cyclopentadienyl)cobalt, and dicobalt hexacarbonylbutylacetylene and one or more co-reactants. CVD and ALD deposition of nickel-containing layers may include the use of precursors such as cyclopentadienyl allyl nickel (CpAllylNi) and MeCp 2 Examples of co-reactants may include N 2 ,NH 3 、N 2 H 4 、N 2 H 6 、SiH 4 、Si 3 H 6 , B 2 H 6 , H 2 and AlCl 3 .

[0103] Back to Fig.10 According to various embodiments, the deposition in block 1003 may occur in the same or a different chamber as the remote plasma treatment of block 1001. In the latter case, the wafer or other substrate is transferred to another chamber prior to block 1003. Furthermore, in some embodiments, blocks 1001 and 1003 may be performed in the same station or different stations of a multi-station chamber.

[0104] Fig.11AAn example of a multi-station apparatus 1100 is shown. Apparatus 1100 includes a processing chamber 1101 and one or more boxes 1103 (e.g., front opening standard boxes) for holding substrates to be processed and substrates that have completed processing. Chamber 1101 may have multiple stations, such as two stations, three stations, four stations, five stations, six stations, seven stations, eight stations, ten stations, or any other number of stations. The number of stations is generally determined by the complexity of the processing operations and the number of these operations that can be performed in a shared environment. Fig.11A A processing chamber 1101 is shown with six stations labeled 1111 to 1116. All stations in a multi-station apparatus 1100 with a single processing chamber 1103 are exposed to the same pressure environment. However, each station may have a designated reactant distribution system and a dedicated plasma generator and pedestal (e.g., Figure 2 and 3 The local plasma and heating conditions achieved by the plasma generator and susceptor shown.

[0105] The substrate to be processed is loaded from one of the cassettes 1103 into the station 1111 through a load lock arrangement 1105. An external robot 1107 may be used to transfer substrates from the cassettes 1103 into the load locks 1105. In the depicted embodiment, there are two separate load locks 1105. These are typically equipped with substrate transfer devices to move substrates from the load locks 1105 to the station 1111 (once the pressure has equilibrated to a level corresponding to the internal environment of the processing chamber 1103) and from the station 1116 back into the load locks 1105 for removal from the processing chamber 1103. An internal robot 1109 is used to transfer substrates between the processing stations 1111-1116 and to support some of the substrates during processing, as described below.

[0106] In some embodiments, one or more stations may be reserved for heating the substrate. Such a station may have heating lamps (not shown) located above the substrate and / or a heated pedestal (similar to a Figure 2 and 3 1. For example, station 1111 may receive a substrate from a load lock and be used to preheat the substrate before being further processed. Other stations may be used to fill high aspect ratio features, including remote plasma processing, deposition, or selective removal operations.

[0107] After the substrate is heated or otherwise processed at station 1111, the substrate is moved successively to processing stations 1112, 1113, 1114, 1115, and 1116, which may or may not be arranged sequentially. The multi-station apparatus 1100 is configured so that all stations are exposed to the same pressure environment. In this way, the substrate is transferred from station 1111 to other stations in chamber 1101 without the need for a transfer port such as a load lock.

[0108] An internal robot 1109 is used to transfer substrates between stations 1111-1116. In the example of Figure 11, the robot 1109 includes a fin having at least one arm for each processing station (shown extending between stations). Any suitable transfer mechanism may be used.

[0109] In some embodiments, one or more stations may be used to fill features with tungsten-containing materials. For example, station 1112 may be used for an initial deposition operation, station 1113 may be used for a selective suppression operation, and station 1114 may be used for a selective deposition operation. In embodiments using a deposition-removal cycle, station 1114 may be used for another deposition operation, and station 1115 may be used for a selective removal operation. Station 1116 may be used for a final fill operation. It should be understood that any configuration of stations specified for a particular process (e.g., heating, suppression, deposition, and removal) may be used.

[0110] Fig. 11B 1 is a schematic diagram of a usable multi-chamber device 1120 according to certain embodiments. As shown, the device 1120 has three separate chambers 1121, 1123 and 1125. Each of these chambers is shown as having two bases. It should be understood that the device can have any number of chambers (e.g., one, two, three, four, five, six, etc.), and each chamber can have any number of stations (e.g., one, two, three, four, five, six, etc.). Each chamber 1121-1125 has its own pressure environment, which is not shared between chambers. Each chamber can have one or more corresponding transfer ports (e.g., loading locks). The device can also have a shared substrate handling robot 1127 for transferring substrates between the transfer ports of one or more boxes 1129.

[0111] As described above, a separate chamber can be used for remote plasma processing and deposition of tungsten-containing materials and / or selective removal of these deposited materials in subsequent operations. Separating operations into different chambers can help significantly increase processing speeds by maintaining the same environmental conditions in each chamber. In other words, the chamber does not need to change its environment from conditions for remote plasma processing to conditions for deposition or selective removal and back, which may involve different reactants, different temperatures, pressures, and other process parameters. In some embodiments, it is faster to transfer a partially manufactured semiconductor substrate between two or more different chambers than to change the environmental conditions of these chambers.

[0112] Back to Figure 2 In some embodiments, a system controller 222 is used to control the process parameters. Figure 3 In the process, a system controller 399 may be used to control process parameters.

[0113] In some embodiments, a system controller (e.g., system controller 222 or system controller 399, which may include one or more physical or logical controllers) controls some or all operations of the processing chamber. The system controller may include one or more memory devices and one or more processors. In some embodiments, when performing the disclosed embodiments, the device (e.g., device 200 or device 390) includes a switching system for controlling flow rate and duration. In some embodiments, the device may have a switching time of up to about 500 ms or up to about 750 ms. The switching time may depend on the flow chemistry, the selected formulation, the reactor architecture, and other factors.

[0114] In some implementations, the system controller is part of a system, which can be part of the above examples. Such a system can include a semiconductor processing device, which includes one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronic devices for controlling their operation before, during, and after the processing of semiconductor wafers or substrates. The electronic device can be referred to as a "controller", which can control various components or subcomponents of one or more systems. Depending on the processing requirements and / or the type of system, the controller can be programmed to control any process disclosed herein, including the delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer delivery in and out of tools and other delivery tools and / or load locks connected to a specific system or interfaced with a specific system.

[0115] In general, a system controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include a chip in the form of firmware that stores program instructions, a digital signal processor (DSP), a chip defined as an application specific integrated circuit (ASIC), and / or one or more microprocessors, or a microcontroller that executes program instructions (e.g., software). The program instructions may be instructions delivered to the controller in the form of various individual settings (or program files) that define operating parameters for performing a particular process on or for a semiconductor wafer or system. In some embodiments, the operating parameters may be part of a recipe defined by a process engineer to accomplish one or more processing steps during the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0116] In some implementations, the system controller may be part of or coupled to a computer that is integrated with the system, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the "cloud" or in all or part of a wafer fab host system that may allow remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, study trends or performance metrics from multiple manufacturing operations, change the parameters of the current processing, set the processing steps to follow the current processing, or start a new processing. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system via a network (which may include a local network or the Internet). The remote computer may include a user interface that enables input or programming of parameters and / or settings, which are then delivered from the remote computer to the system. In some examples, the system controller receives instructions in the form of data that specify the parameters of each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool, and the controller is configured to interface with or control the tool. Thus, as described above, the system controller may be distributed, for example, by including one or more discrete controllers networked together and working toward a common purpose, such as the processes and controls described herein. An example of a distributed controller for such a purpose is one or more integrated circuits on a chamber that communicate with one or more integrated circuits located remotely (e.g., at a platform level or as part of a remote computer), which combine to control the process on the chamber.

[0117] Example systems may include, but are not limited to, plasma etch chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, cleaning chambers or modules, chamfer edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, CVD chambers or modules, ALD chambers or modules, ALE chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing system that may be associated with or used in the manufacture and / or preparation of semiconductor wafers.

[0118] As described above, depending on one or more processing steps to be performed by the tool, the controller can communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, a host computer, another controller, or tools used in material transport to transport wafer containers to and from tool locations and / or load ports in a semiconductor manufacturing facility.

[0119] The apparatus / process described above may be used in conjunction with a photolithographic patterning tool or process, for example, for preparing or manufacturing semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, although not necessarily, such tools / processes will be performed or used in a common manufacturing facility. Photolithographic patterning of a film generally includes some or all of the following steps, each of which is implemented using a number of possible tools: (1) applying a photoresist to a workpiece (i.e., a substrate) using a spin coating or spray coating tool; (2) curing the photoresist using a hot plate or oven or a UV curing tool; (3) exposing the photoresist to visible light or UV light or X-ray light using a tool such as a wafer stepper; (4) developing the resist to selectively remove the resist, thereby patterning it using a tool such as a wet bench; (5) transferring the resist pattern to an underlying film or workpiece by using a dry etching tool or a plasma assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

[0120] in conclusion

[0121] Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it is apparent that certain changes and modifications may be implemented within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and devices of the disclosed embodiments. Therefore, the embodiments of the present invention should be considered illustrative rather than restrictive, and the disclosed embodiments are not limited to the details given herein.

Claims

1. A plasma treatment method, comprising: A conditioning process is performed on the remote plasma processing chamber, the conditioning process comprising: introducing a fluorine-containing gas into a plasma generator to produce a fluorine-containing conditioning plasma and introducing the fluorine-containing conditioning plasma into a remote processing chamber; reacting fluorine species in the fluorine-containing conditioning plasma with surfaces of the remote plasma processing chamber to form a fluorine-containing passivation layer on the surfaces of the remote plasma processing chamber; and introducing a fluorine-free nitrogen-containing compound into the plasma generator to produce a fluorine-free nitrogen-containing conditioning plasma and introducing the fluorine-free nitrogen-containing conditioning plasma into the remote processing chamber, Wherein during the conditioning process, no manufacturing substrate is present in the remote plasma processing chamber.

2. The method according to claim 1, characterized in that The fluorine-containing passivation layer is an aluminum fluoride layer.

3. The method of claim 1, wherein introducing the fluorine-free nitrogen-containing conditioning plasma is performed after forming a fluorine-containing passivation layer on the surface of the remote plasma processing chamber.

4. The method according to claim 1, wherein the fluorine-containing gas is selected from nitrogen trifluoride (NF3), fluorine (F2), sulfur hexafluoride (SF6) or carbon tetrafluoride (CF4).

5. The method of claim 1 further comprising, after the conditioning process, treating the substrate with a plasma to inhibit metal nucleation.

6. The method of claim 5, wherein the fabricated substrate includes one or more features to be filled with metal, each feature including a feature opening and processing the fabricated substrate includes selectively inhibiting metal nucleation proximate the feature opening.

7. The method of claim 5, wherein the metal nucleation inhibiting plasma is generated from a nitrogen containing gas.

8. The method of claim 5, further comprising depositing a metal on the fabrication substrate after treating the fabrication substrate with the plasma to inhibit metal nucleation.

9. The method of claim 8, wherein the metal is tungsten or cobalt.

10. A plasma treatment method, comprising: providing a plasma generator having an inlet and an outlet, wherein the plasma generator is configured to receive a process gas from one or more sources at the inlet, generate plasma from the process gas, and output the plasma to a connection line that provides a connection to a processing chamber; introducing a fluorine-containing gas into the plasma generator to generate a fluorine-containing plasma, and exhausting the fluorine-containing plasma from the plasma generator into the processing chamber in the absence of a manufacturing substrate in the processing chamber; as well as After exhausting the fluorine-containing plasma from the plasma generator, a fluorine-free nitrogen-containing gas is introduced into the plasma generator to generate a fluorine-free nitrogen-containing conditioning plasma, and the fluorine-free nitrogen-containing conditioning plasma is introduced into the processing chamber without a fabrication substrate in the processing chamber.

11. The method according to claim 10, wherein the fluorine-containing gas is selected from nitrogen trifluoride (NF3), fluorine (F2), sulfur hexafluoride (SF6) or carbon tetrafluoride (CF4).

12. The method of claim 10, wherein the nitrogen-containing gas is N2 or NH3.

13. The method of claim 10, further comprising depositing metal on the fabrication substrate.

14. The method according to claim 13, characterized in that The metal is tungsten or cobalt.

Images