WO2020118100A1

WO2020118100A1 - Void free low stress fill

Info

Publication number: WO2020118100A1
Application number: PCT/US2019/064768
Authority: WO
Inventors: Anand Chandrashekar; Tsung-Han Yang
Original assignee: Lam Research Corp
Current assignee: Lam Research Corp
Priority date: 2018-12-05
Filing date: 2019-12-05
Publication date: 2020-06-11
Anticipated expiration: 2021-06-05
Also published as: KR20210089260A; SG11202106002VA; US20240234208A1; JP2025098141A; KR20250109239A; JP2022510428A; JP7705347B2; US11978666B2; US20220020641A1; CN113166929A; KR102828798B1

Abstract

Provided herein are methods of depositing low stress and void free metal films in deep features and related apparatus. Embodiments of the methods include treating the sidewalls of the holes to inhibit metal deposition while leaving the feature bottom untreated. In subsequent deposition operations, metal precursor molecules diffuse to the feature bottom for deposition. The process is repeated with subsequent inhibition operations treating the remaining exposed sidewalls. By repeating inhibition and deposition operations, high quality void free fill can be achieved. This allows high temperature, low stress deposition to be performed.

Description

VOID FREE LOW STRESS FILL

INCORPORATION BY REFERENCE

[0001] A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in its entirety and for all purposes.

BACKGROUND

[0002] Deposition of conductive materials such as tungsten films is an integral part of many semiconductor fabrication processes. These materials may be used for horizontal interconnects, vias between adjacent metal layers, contacts between metal layers and devices on the silicon substrate, and high aspect ratio features. As devices shrink and more complex patterning schemes are utilized in the industry, deposition of thin films becomes a challenge. These challenges include depositing void free and low stress films.

[0003] The background and contextual descriptions contained herein are provided solely for the purpose of generally presenting the context of the disclosure. Much of this disclosure presents work of the inventors, and simply because such work is described in the background section or presented as context elsewhere herein does not mean that it is admitted to be prior art.

SUMMARY

[0004] One aspect of the disclosure relates to a method including: providing a 3-D structure including metal lines arranged in a staircase pattern, a dielectric material overlying the staircase pattern, and a vertically-oriented feature providing fluidic access to a metal line; depositing a conformal layer of metal in the vertically-oriented feature; exposing the conformal layer of metal feature to inhibition species at first flow rate and first exposure time in a first inhibition operation; after the first inhibition operation, preferentially depositing metal at the bottom of the vertically-oriented feature in a first non-conformal deposition operation, where a temperature of the substrate is at least 400°C during the first non-conformal deposition operation; after the first non-conformal deposition operation, exposing the feature to inhibition species at a second flow rate and second exposure time in a second inhibition operation, where the second flow rate is lower than the first flow rate and/or the second exposure time is lower than the first exposure time; and after the second inhibition operation, depositing metal in the feature at a substrate temperature of at least 400°C in a second non-conformal deposition operation. [0005] In some embodiments the metal is one of tungsten, cobalt, molybdenum, and ruthenium. In some embodiments preferentially depositing metal at the bottom of the feature includes exposing the feature to a metal precursor and a reducing agent, where the volumetric ratio of reducing agent to metal precursor is at least 30:1. In some embodiments preferentially depositing metal at the bottom of the feature includes exposing the feature to a metal precursor at flow rate of no more than 100 seem. In some embodiments the feature is an interconnect feature in a 3D NAND device. In some embodiments the metal is tungsten and the substrate temperature is at least 430°C during deposition. In some embodiments the metal is molybdenum and the substrate temperature is at least 600°C during deposition.

[0006] In some embodiments the inhibition species are nitrogen-containing gas or plasma species. In some embodiments the first inhibition operation treats most of the feature. The method the first inhibition operation treats at least 70% of the feature depth. In some embodiments a substrate temperature during the first inhibition operation is different than during the second inhibition operation.

[0007] Another aspect of the disclosure relates to an apparatus for processing substrates, the apparatus including: (a) a process chamber including at least one station having a pedestal configured to hold a substrate; (b) at least one outlet for coupling to a vacuum; (c) one or more process gas inlets coupled to one or more process gas sources; and (d) a controller for controlling operations in the apparatus, including machine-readable instructions for performing the method of: inletting inhibition species at first flow rate and first exposure time to the process chamber in a first inhibition operation; after the first inhibition operation, inletting a metal precursor and reducing agent to deposit a metal, where a temperature of the pedestal on which the substrate is at least 400°C, in a first non-conformal deposition operation; after the first non-conformal deposition operation, inletting inhibition species to the process chamber at a second flow rate and second exposure time in a second inhibition operation, where the second flow rate is lower than the first flow rate and/or the second exposure time is lower than the first exposure time; and after the second inhibition operation, inletting a metal precursor and reducing agent to deposit a metal, where a temperature of the pedestal on which the substrate is at least 400°C. In some embodiments the metal is tungsten and the substrate temperature is at least 430°C during deposition, in a second non-conformal deposition operation. In some embodiments the volumetric ratio of reducing agent to tungsten precursor is at least 30: 1 during the first and second non-conformal deposition operations. [0008] Another aspect of the disclosure relates to a method including: depositing a conformal layer of metal in a feature on a substrate; treating a portion of the conformal layer to inhibit subsequent tungsten nucleation; after treating the portion of the conformal layer, preferentially depositing tungsten at the bottom of the feature, where a temperature of the substrate is at least 400oc during the deposition; and repeating the treating and depositing operations one or more times to fill the feature with metal.

[0009] These and other aspects are described below with references to the drawings.

BRIEF DESCRIPTION OF DRAWINGS

[0010] Figure 1A shows a schematic example 3D structure structure that may be filled with a conductive material using the feature fill methods described herein.

[0011] Figure IB shows a schematic example of interconnects of the 3D structure after a feature fill process using the methods described herein.

[0012] Figure 2 is a flow diagram illustrating certain operations in a method of filling a feature.

[0013] Figure 3 shows schematic examples of a feature at various stages of a fill process using the methods described herein.

[0014] Figure 4 is a block diagram of a processing system suitable for conducting deposition processes in accordance with embodiments described herein.

[0015] Figure 5 is a diagram of a station suitable for conducting inhibition and deposition processes in accordance with embodiments described herein.

DETAILED DESCRIPTION

[0016] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail to not unnecessarily obscure the present invention. While the invention will be described in conjunction with the specific implementations, it will be understood that it is not intended to limit the invention to the implementations.

[0017] Described herein are methods of feature fill and related systems and apparatus. Examples of applications include logic and memory contact fill, DRAM buried wordline fill, vertically integrated memory gate/wordline fill, and 3-D integration with through- silicon vias (TSVs). In some embodiments, the methods may be used for tungsten feature fill. Such features can include vertical features, such as vias, and horizontal features, such as vertical NAND (VNAND) wordlines.

[0018] In some embodiments, provided herein are methods of depositing low stress and void free metal films in deep features and related apparatus. Embodiments of the methods include treating the sidewalls of the holes to inhibit metal deposition while leaving the feature bottom untreated. In subsequent deposition operations, metal precursor molecules diffuse to the feature bottom for deposition. The process is repeated with subsequent inhibition operations treating the remaining exposed sidewalls. By repeating inhibition and deposition operations, high quality void free fill can be achieved. This allows high temperature, low stress deposition to be performed.

[0019] Figure 1A shows an example structure that may be filled with a conductive material using the feature fill methods described herein. In the example of Figure 1A, the structure 102 is a partially fabricated 3D NAND device. Alternating oxide layers 111 and tungsten or other metal wordlines 140 on a substrate 100 are shown in a staircase structure. Although five wordlines 140 are depicted for ease of illustration, according to various implementations, a structure 102 may include any number of wordlines, such 48 wordlines, 256 wordlines, 512 wordlines, or 1024 wordlines. In some implementations, the feature to be filled is at least 10 microns deep, and may be deeper, e.g., 30 microns deep.

[0020] An oxide layer 122 is deposited over the staircase structure, with features 137 etched in the oxide layer 122. These features 137 may be filled with tungsten or other metal using the methods described herein to provide interconnects to the wordlines 140. Figure IB shows interconnects 142 after a fill process.

[0021] Figure 2 is a flow diagram illustrating certain operations in a method of filling a feature. The method begins at an operation 202 with depositing a conformal layer of material in the feature. This layer can be a nucleation layer or a bulk layer that conformally lines the feature. In certain implementations, operation 202 may be omitted, for example, if the underlying feature surface is sensitive to the subsequent inhibition chemistry. In the example of tungsten, operation 202 may involve exposing the feature to a tungsten precursor, such as tungsten hexafluoride (WFe) and a reducing agent such as hydrogen (¾). Figure 3 shows an example of a feature after conformal deposition (labeled Conformal Depl). Returning to Figure 2, the feature is then exposed to an inhibition chemistry for conformal inhibition of nucleation except at the feature bottom. (204). An example of operation 204 is illustrated in Figure 3 (labeled Conformal Inhibition) with the circles indicating an inhibited surface. An inhibited surface is one on which subsequent nucleation of the tungsten or other material is inhibited, delaying or preventing deposition thereon. As can be seen in Figure 3, most of feature is inhibited except for the feature bottom and a short length of sidewall extending up from the bottom. According to various embodiments, the inhibition may extend up to 99%, 95%, 90%, 80%, 70%, or 60% of the feature depth.

[0022] In some implementations, operation 204 involves exposing the feature to a nitrogen- containing compound such as nitrogen (N2) or ammonia (NH3) in a thermal (non-plasma) operation. In alternate embodiments, the inhibition chemistry may be provided as plasma species generated in a remote or direct plasma generator.

[0023] Returning to Figure 2, a low stress film is deposited at the feature bottom (206). To deposit a low stress film, the feature may be exposed to a precursor and reducing agent in a precursor-depleted regime at high temperatures. The precursor-depleted regime may be characterized as having at a volumetric reducing agenhprecursor flow rate ratio of least 30:1. In some embodiments, a substrate temperature of at least 400°C are used.

[0024] For tungsten deposition with WF₆, substrate temperatures of at least 400°C, or at least 430°C, and no more than 100 seem WF₆ may be used. Chamber pressure may be between 5 and 200 Torr, inclusive. The WF₆ is delivered with Fb and a carrier gas such as argon (Ar). The Fb and carrier gas flows are at least an order of magnitude greater than the precursor flow. Example ranges are below:

WFe flow rate of less than 100 seem;

Fb flow rate between 3000 and 6000 seem;

Ar flow rate between 4000 and 8000 seem.

[0025] For Mo deposition, temperatures may be at least 450°C, e.g., between 450°C and 800°C, e.g., between 600°C and 750°C. [0026] Operation 204 may be performed simultaneous exposure of two reactants, such that both reactants are flowed at the same time during deposition. For example, bulk tungsten may be deposited by exposing a substrate to hydrogen (¾) and tungsten hexafluoride (WFe) at the same time.s. Hydrogen and WF₆ (or other metal precursor) react during the exposure to deposit tungsten into the features. In pulsed CVD processes, one reactant is continuously flowed while the other reactant is pulsed, but the substrate is exposed to both reactants during deposition to deposit material during each pulse. For example, a substrate may be exposed to a continuous flow of ¾ while WF₆ is pulsed, and WF₆ and ¾ react during the pulse to deposit tungsten. In some embodiments, operation 204 may involve separate exposures to each reactant such that the reactants are not flowed into the chamber at the same time during deposition. Rather, each reactant flow is introduced to a chamber housing the substrate in temporally separated pulses in sequence, repeated one or more times in cycles. In such embodiments, a precursor-depleted regime may be implemented by using more reducing agent pulses and/or volumetric flow rate during the pulses.

[0027] Deposition in a precursor-depleted regime and high temperature results in a low stress film; however, these conditions also make feature fill challenging as the small amount of precursor available to react will do so at the nearest available reaction surface. Without inhibition, the precursor will be consumed at the feature top, closing off the feature to further diffusion and creating a void. Thus, the inhibition in the previous operation prevents reaction on the sidewall surfaces, guiding the precursor to the bottom of the feature for reaction. This is illustrated in Figure 3 (see Inhibition after Dep2) with the second deposition (Dep2) depositing material at the bottom of the feature. Returning to Figure 2, operations 204 and 206 are repeated one or more times (208). This is illustrated in Figure 3 (Dep2 + Inhibition and Dep3). As depicted in Figure 3, the inhibition wears off during the deposition.

[0028] Each successive inhibition may be considered“less conformal” than the previous deposition in that it extends to shallower depths to accommodate the film growth at the feature bottom. To control inhibition depth, temperature and inhibition gas flow rate may be adjusted with higher temperatures and lower flow rates resulting in shallower depths. However, as substrate temperature is generally determined by the requirements of the deposition, inhibition flow rate may be modified.

[0029] In some implementations, operations 204 and 206 are repeated until the feature is completely filled. In some embodiments, operations 204 and 206 may be repeated to partially fill the feature with bottom up fill, followed by a longer CVD deposition for final feature fill. A non-conformal inhibition may be performed to inhibition deposition at the top of re-entrant features, such as depicted in Figure 3.

[0030] The deposition and inhibition operations may be performed in the same or different process chambers. Further, if performed in a multi-station chamber, they may be performed in the same or different stations. In some embodiments, one or more deposition and inhibition cycles are performed in the same station of a multi-station chamber. For example, a feature fill operation involving six deposition/inhibition cycles, and a final CVD fill operation may be implemented in a four- station chamber as follows:

Station 1 : 2 Deposition/Inhibition cycles

Station 2: 2 Deposition/Inhibition cycles

Station 3 : 2 Deposition/Inhibition cycles

Station 4: CVD deposition

Nucleation Layer Deposition

[0031] In some implementations, the methods described herein involve deposition of a tungsten nucleation layer prior to deposition of a bulk layer. In the examples described herein, the nucleation layer may be deposited as the first conformal deposition or to as a seed layer for the first conformal deposition. A nucleation layer is a thin conformal layer that facilitates subsequent deposition of bulk tungsten-containing material thereon. According to various implementations, a nucleation layer may be deposited prior to any fill of the feature and/or at subsequent points during fill of the feature. In some implementations of the method described herein, a nucleation layer is deposited only at the beginning of feature fill and is not necessary at subsequent depositions.

[0032] In certain implementations, the nucleation layer is deposited using a pulsed nucleation layer (PNL) technique. In a PNL technique, pulses of a reducing agent, optional purge gases, and tungsten-containing precursor are sequentially injected into and purged from the reaction chamber. The process is repeated in a cyclical fashion until the desired thickness is achieved. PNL broadly embodies any cyclical process of sequentially adding reactants for reaction on a semiconductor substrate, including atomic layer deposition (ALD) techniques. Nucleation layer thickness can depend on the nucleation layer deposition method as well as the desired quality of bulk deposition. In general, nucleation layer thickness is sufficient to support high quality, uniform bulk deposition. Examples may range from 10A-100A.

[0033] While examples of PNL deposition are provided above, the methods described herein are not limited to a particular method of tungsten nucleation layer deposition, but include deposition of bulk tungsten film on tungsten nucleation layers formed by any method including PNL, ALD, CVD, and physical vapor deposition (PVD). Moreover, in certain implementations, bulk tungsten may be deposited directly in a feature without use of a nucleation layer. For example, in some implementations, the feature surface and/or an already-deposited under-layer supports bulk tungsten deposition. In some implementations, a bulk tungsten deposition process that does not use a nucleation layer may be performed.

[0034] In various implementations, tungsten nucleation layer deposition can involve exposure to a tungsten-containing precursor such as tungsten hexafluoride (WFe), tungsten hexachloride (WCk), and tungsten hexacarbonyl (W(CO)₆). In certain implementations, the tungsten- containing precursor is a halogen-containing compound, such as WF₆. Organo-metallic precursors, and precursors that are free of fluorine such as MDNOW (methylcyclopentadienyl- dicarbonylnitrosyl-tungsten) and EDNOW (ethylcyclopentadienyl-dicarbonylnitrosyl-tungsten) may also be used.

[0035] Examples of reducing agents can include boron-containing reducing agents including diborane (B2H6) and other boranes, silicon-containing reducing agents including silane (S1H4) and other silanes, hydrazines, and germanes. In some implementations, pulses of tungsten- containing precursors can be alternated with pulses of one or more reducing agents, e.g., S/W/S/W/B/W, etc., W represents a tungsten-containing precursor, S represents a silicon- containing precursor, and B represents a boron-containing precursor. In some implementations, a separate reducing agent may not be used, e.g., a tungsten-containing precursor may undergo thermal or plasma-assisted decomposition.

[0036] According to various implementations, hydrogen may or may not be ran in the background. Further, in some implementations, deposition of a tungsten nucleation layer may be followed by one or more treatment operations prior to tungsten bulk deposition. Treating a deposited tungsten nucleation layer to lower resistivity may include pulses of reducing agent and/or tungsten precursor. Bulk Deposition

[0037] In many implementations, tungsten bulk deposition can occur by a CVD process in which a reducing agent and a tungsten-containing precursor are flowed into a deposition chamber to deposit a bulk fill layer in the feature. An inert carrier gas may be used to deliver one or more of the reactant streams, which may or may not be pre-mixed. Unlike PNL or ALD processes, this operation generally involves flowing the reactants continuously until the desired amount is deposited. In certain implementations, the CVD operation may take place in multiple stages, with multiple periods of continuous and simultaneous flow of reactants separated by periods of one or more reactant flows diverted.

[0038] Various tungsten-containing gases including, but not limited to, WF₆, WCk, and W(CO)₆ can be used as the tungsten-containing precursor. In certain implementations, the tungsten-containing precursor is a halogen-containing compound, such as WF₆. In certain implementations, the reducing agent is hydrogen gas, though other reducing agents may be used including silane (SiFfl), disilane (SUFL) hydrazine (N2H4), diborane (B2H6) and germane (GeFL). In many implementations, hydrogen gas is used as the reducing agent in the CVD process. In some other implementations, a tungsten precursor that can decompose to form a bulk tungsten layer can be used. Bulk deposition may also occur using other types of processes including ALD processes.

[0039] It should be understood that the tungsten films described herein may include some amount of other compounds, dopants and/or impurities such as nitrogen, carbon, oxygen, boron, phosphorous, sulfur, silicon, germanium and the like, depending on the particular precursors and processes used. The tungsten content in the film may range from 20% to 100% (atomic) tungsten. In many implementations, the films are tungsten-rich, having at least 50% (atomic) tungsten, or even at least about 60%, 75%, 90%, or 99% (atomic) tungsten.

[0040] While the description above focuses on tungsten feature fill, aspects of the disclosure may also be implemented in filling features with other materials. For example, feature fill using one or more techniques described herein may be used to fill features with other materials including other tungsten-containing materials (e.g., tungsten nitride (WN) and tungsten carbide (WC)), titanium-containing materials (e.g., titanium (Ti), titanium nitride (TiN), titanium silicide (TiSi), titanium carbide (TiC) and titanium alumide (TiAl)), tantalum-containing materials (e.g., tantalum (Ta), and tantalum nitride (TaN)), nickel-containing materials (e.g., nickel (Ni) and nickel silicide (NiSi), cobalt-containing materials (e.g., cobalt (Co)), ruthenium-containing materials (e.g., ruthenium (Ru)) and molybdenum-containing materials (e.g., molybdenum (Mo)).

[0041] CVD and ALD deposition of these materials can include using any appropriate precursors. For example, CVD and ALD deposition of tungsten nitride can include using tungsten-containing and nitrogen-containing compounds. CVD and ALD deposition of titanium- containing layers can include using precursors containing titanium with examples including tetrakis(dimethylamino)titanium (TDMAT) and titanium chloride (TiCL), and if appropriate, one or more co-reactants. CVD and ALD deposition of tantalum-containing layers can include using precursors such as pentakis-dimethylamino tantalum (PDMAT) and TaFs and, if appropriate, one or more co-reactants. CVD and ALD deposition of cobalt-containing layers can include using precursors such as Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt, bis(cyclopentadienyl)cobalt, and dicobalt hexacarbonyl butylacetylene, and one or more co reactants.

[0042] Examples of cobalt precursors dicarbonyl cyclopentadienyl cobalt, cobalt carbonyl, a cobalt ami din ate precursor, a cobalt diazadienyl complex, and a cobalt amidinate/guanidinate precursor.

[0043] Examples of ruthenium precursors that may be used for oxidative reactions include (ethylbenzyl)( 1 -ethyl- 1 ,4-cyclohexadienyl)Ru(0), 2,3-dimethyl- 1 ,3-butadienyl)Ru(0)tricarbonyl, (l,3-cyclohexadienyl)Ru(0)tricarbonyl, and (cyclopentadienyl)(ethyl)Ru(II)dicarbonyl.. Examples of ruthenium precursors that may be used for oxidative reactions include (ethylbenzyl)(l -ethyl- l,4-cyclohexadienyl)Ru(0), (l-isopropyl-4-methylbenzyl)(l,3- cyclohexadienyl)Ru(O), 2,3-dimethyl-l,3-butadienyl)Ru(0)tricarbonyl, (1,3- cyelohexadienyl)Ru(0)tricarbonyl, and (cyclopentadienyl)(ethyl)Ru(II)dicarbonyl. Examples of ruthenium precursors that react with non-oxidizing reactants are bis(5-methyl-2,4- hexanediketonato)Ru(II)dicarbonyl and bis(ethylcyclopentadienyl)Ru(II).

[0044] Examples of nickel precursors include cyclopentadienylallylnickel (CpAllylNi) and MeCp₂Ni.

[0045] Examples of molybdenum precursors include molybdenum hexafluoride (MoFe), molybdenum pentachloride (MoCL), molybdenum dichloride dioxide (M0O2CI2), molybdenum tetrachloride oxide (MoOCL), and molybdenum hexacarbonyl (Mo(CO)e) may be used. Examples of co-reactants can include N2, NEL, N2H4, N2H6, SiEL, SEEL, ELEL, EL, and AICL. [0046] The metal-containing precursor may be reacted with a reducing agent as described above. In some embodiments, ¾ is used as a reducing agent for bulk layer deposition to deposit high purity films.

Inhibition of nucleation

[0047] Inhibition can involve exposure to activated species that passivate the feature surfaces. For example, in certain implementations, a tungsten (W) surface can be passivated by exposure to a nitrogen-based or hydrogen-based plasma. In some implementations, inhibition can involve a chemical reaction between activated species and the feature surface to form a thin layer of a compound material such as tungsten nitride (WN) or tungsten carbide (WC). In some implementations, inhibition can involve a surface effect such as adsorption that passivates the surface without forming a layer of a compound material. Activated species may be formed by any appropriate method including by plasma generation and/or exposure to ultraviolet (UV) radiation. In some implementations, the substrate including the feature is exposed to a plasma generated from one or more gases fed into the chamber in which the substrate sits. In some implementations, one or more gases may be fed into a remote plasma generator, with activated species formed in the remote plasma generator fed into a chamber in which the substrate sits. The plasma source can be any type of source including radio frequency (RF) plasma source or microwave source. The plasma can be inductively and/or capacitively-coupled. Activated species can include atomic species, radical species, and ionic species. In certain implementations, exposure to a remotely-generated plasma includes exposure to radical and atomized species, with substantially no ionic species present in the plasma such that the inhibition process is not ion- mediated. In other implementations, ion species may be present in a remotely-generated plasma. In certain implementations, exposure to an in-situ plasma involves ion-mediated inhibition.

[0048] For W surfaces, exposure to nitrogen-based and/or hydrogen-based plasmas inhibits subsequent tungsten deposition on the W surfaces. Other chemistries that may be used for inhibition of tungsten surfaces include oxygen-based plasmas and hydrocarbon-based plasmas. For example, molecular oxygen or methane may be introduced to a plasma generator. Nitrogen- containing chemistries also inhibit nucleation of other metals described herein including Mo, Co, and Al. As used herein, a nitrogen-based plasma is a plasma in which the main non-inert component is nitrogen. An inert component such as argon, xenon, or krypton may be used as a carrier gas. In some implementations, no other non-inert components are present in the gas from which the plasma is generated except in trace amounts. In some implementations, inhibition chemistries may be nitrogen-containing, hydrogen-containing, oxygen-containing, and/or carbon-containing, with one or more additional reactive species present in the plasma.

[0049] Using a NF3 plasma, for example, where activated fluorine radicals react with and remove tungsten at the feature opening, the nitrogen generated from the NF3 plasma can cause nitridation of the tungsten surface forming tungsten nitride. Subsequent deposition of tungsten on a nitrided surface is significantly delayed, compared to on a regular bulk tungsten film. A longer delay allows the feature to stay open for longer before pinching off, and promoting fill improvement because more WF₆ molecules can reach the inside of the feature and deposit tungsten. In addition to NF3, fluorocarbons such as CF4 or C2F8 may be used. However, in certain implementations, the inhibition species are fluorine-free to prevent etching during inhibition.

[0050] In certain implementations, UV radiation and/or thermal energy may be used instead of or in addition to plasma generators to provide activated species. In addition to tungsten surfaces, nucleation may be inhibited on liner/barrier layers surfaces such as TiN and/or WN surfaces. Any chemistry that passivates these surfaces may be used. For TiN and WN, this can include exposure to nitrogen-based or nitrogen-containing chemistries. In certain implementations, the chemistries described above for W may also be employed for TiN, WN, or other liner layer surfaces. In some implementations, inhibition involves exposure to NH3 in a non-plasma operation.

[0051] Tuning an inhibition profile can involve appropriately controlling an inhibition chemistry, substrate bias power, plasma power, process pressure, exposure time, and other process parameters. For in situ plasma processes (or other processes in which ionic species are present), a bias can be applied to the substrate. Substrate bias can, in some implementations, significantly affect an inhibition profile, with increasing bias power resulting in active species deeper within the feature. For 3-D structures in which selectivity is desired in a lateral direction (tungsten deposition preferred in the interior of the structure), but not in a vertical direction, increased bias power can be used to promote top-to-bottom deposition uniformity.

[0052] While bias power can be used in certain implementations as the primary or only knob to tune an inhibition profile for ionic species, in certain situations, tuning an inhibition profile uses other parameters in addition to or instead of bias power. These include remotely generated non-ionic plasma processes and non-plasma processes. Also, in many systems, a substrate bias can be easily applied to tune selectivity in vertical but not lateral direction. Accordingly, for 3-D structures in which lateral selectivity is desired, parameters other than bias may be controlled, as described above.

[0053] Inhibition chemistry can also be used to tune an inhibition profile, with different ratios of active inhibiting species used. For example, for inhibition of W surfaces, nitrogen may have a stronger inhibiting effect than hydrogen; adjusting the ratio of N2 and H2 gas in a forming gas- based plasma can be used to tune a profile. The plasma power may also be used to tune an inhibition profile, with different ratios of active species tuned by plasma power. For example, in certain implementations described herein, nitrogen radical formation and resultant W-N formation and the related passivation effect can be modulated by varying the plasma power. Varying plasma power can also allow control of the resistivity of the final W film.

[0054] Process pressure can be used to tune a profile, as pressure can cause more recombination (deactivating active species) as well as pushing active species further into a feature. Process time may also be used to tune inhibition profiles, with increasing treatment time causing inhibition deeper into a feature.

[0055] In some implementations, non-conformal inhibition can be achieved by in a mass transport limited regime. In this regime, the inhibition rate inside the feature is limited by amounts of and/or relative compositions of different inhibition material components (e.g., an initial inhibition species, activated inhibition species, and recombined inhibition species) that diffuse into the feature. In certain examples, inhibition rates depend on various components’ concentrations at different locations inside the feature.

[0056] Mass transport limiting conditions may be characterized, in part, by overall inhibition concentration variations. In certain implementations, a concentration is less inside the feature than near its opening resulting in a higher inhibition rate near the opening than inside. This in turn leads to preferential inhibition near the feature opening. Mass transport limiting process conditions may be achieved by supplying limited amounts of inhibition species into the processing chamber (e.g., use low inhibition gas flow rates relative to the cavity profile and dimensions), while maintaining relative high inhibition rates near the feature opening to consume some activated species as they diffuse into the feature. In certain implementation, a concentration gradient is substantial, which may be caused relatively high inhibition kinetics and relatively low inhibition supply. In certain implementations, an inhibition rate near the opening may also be mass transport limited. [0057] In addition to the overall inhibition concentration variations inside features, inhibition profile may be influenced by relative concentrations of different inhibition species throughout the feature. These relative concentrations in turn can depend on relative dynamics of dissociation and recombination processes of the inhibition species. As described above, an initial inhibition material, such as molecular nitrogen, can be passed through a remote plasma generator and/or subjected to an in-situ plasma to generate activated species (e.g., atomic nitrogen, nitrogen ions). However, activated species may recombine into less active recombined species (e.g., nitrogen molecules) and/or react with W, WN, TiN, or other feature surfaces along their diffusion paths. As such, different parts of the feature may be exposed to different concentrations of different inhibition materials, e.g., an initial inhibition gas, activated inhibition species, and recombined inhibition species. This provides additional opportunities for controlling inhibition profile. For example, activated species are generally more reactive than initial inhibition gases and recombined inhibition species. Furthermore, in some cases, the activated species may be less sensitive to temperature variations than the recombined species. Therefore, process conditions may be controlled in such a way that removal is predominantly attributed to activated species. As noted above, some species may be more reactive than others. Furthermore, specific process conditions may result in activated species being present at higher concentrations near features’ openings than inside the features. For example, some activated species may be consumed (e.g., reacted with feature surface materials and/or adsorbed on the surface) and/or recombined while diffusing deeper into the features, especially in small high aspect ratio features. Recombination of activated species can also occur outside of features, e.g., in the showerhead or the processing chamber, and can depends on chamber pressure. Therefore, chamber pressure may be controlled to adjust concentrations of activated species at various points of the chamber and features.

[0058] In certain implementations, the substrate can be heated up or cooled down before inhibition. A predetermined temperature for the substrate can be selected to induce a chemical reaction between the feature surface and inhibition species and/or promote adsorption of the inhibition species, as well as to control the rate of the reaction or adsorption. For example, a temperature may be selected to have high reaction rate such that more inhibition occurs near the opening than inside the feature. Furthermore, a temperature may be also selected to control recombination of activated species (e.g., recombination of atomic nitrogen into molecular nitrogen) and/or control which species (e.g., activated or recombined species) contribute predominantly to inhibition. In certain implementations, a substrate is maintained at less than about 300°C, or more particularly at less than about 250°C, or less than about 150°C, or even less than about 100°C. In other implementations, a substrate is heated to between about 300°C and 450°C or, in more specific implementations, to between about 350°C and 400°C. Other temperature ranges may be used for different types of inhibition chemistries. In some embodiments, the inhibition temperature may be the same as the deposition temperature, which may be relatively high to deposit a low stress film. However, in some embodiments, a multi station chamber is used with deposition and inhibition performed in different stations. This can facilitate temperature differences between the operations.

[0059] As indicated above, in some embodiments, thermal inhibition processes are used. Thermal inhibition processes can involve exposing the feature to a nitrogen-containing compound such as ammonia (N¾) or hydrazine (N2H4) to conformally or non-conformally inhibit the feature. In some embodiments, the thermal inhibition processes are performed at temperatures ranging from 250°C to 450°C. At these temperatures, exposure of a previously formed tungsten nucleation layer to NH3 results in an inhibition effect. Other potentially inhibiting chemistries such as nitrogen (N2) or hydrogen (¾) may be used for thermal inhibition at higher temperatures (e.g., 900°C). For many applications, however, these high temperatures exceed the thermal budget. In addition to ammonia, other hydrogen-containing nitriding agents such as hydrazine may be used at lower temperatures appropriate for back end of line (BEOL) applications.

[0060] As the thermal inhibition processes do not use a plasma, a bias power on the substrate cannot be used to tune the inhibition profile. However, by appropriately tuning one or more of chamber pressure, flow rate, dose time, and temperature, the inhibition profile can be tuned as desired. As described above, in some embodiments, a mass transport limited regime is employed. Chamber pressure may range from 0.5 Torr to 40 Torr in some embodiments. As noted above, flow rates of the inhibition gas can depend on a size of the chamber, reaction rates, and other parameters. A flow rate can be selected in such a way that more inhibition material is concentrated near the opening than inside the feature. In certain embodiments, these flow rates cause mass-transport limited selective inhibition.

[0061] Increased pressures and decreased flow rates and dose times result in more non- conformal (i.e., more selective to the feature opening) inhibition profile. Higher pressures result in lower mean free path, while lower flow rates and dose times limit the amount of molecules to be consumed. Increased temperatures result in a more non-conformal inhibition profile with more inhibition molecules consumed at the top of the feature. The profile may be tuned as described above depending on if and were a pinch point is in a feature. Example dose times range from .5 second to 10 seconds.

[0062] In some embodiments, inhibition can involve a chemical reaction between the thermal inhibitor species and the feature surface to form a thin layer of WN compound material. In some embodiments, inhibition can involve a surface effect such as adsorption that passivates the surface without forming a layer of a compound material.

[0063] If a metal nucleation layer is present, it may be exposed to Ntb or other inhibition vapor to inhibit the feature. In some embodiments, if a bulk tungsten or tungsten-containing layer is present, a reducing agent/tungsten-containing precursor/nitrogen-containing inhibition chemistry may be employed to form WN on the bulk layer. These reactants may be introduced in sequence (e.g., B2H6/WF6/NH3 pulses) or simultaneously. Any appropriate reducing agent (e.g., diborane or silane) and any appropriate tungsten-containing precursor (e.g., tungsten hexafluoride or tungsten hexacarbonyl) may be used. A thermal process may be used to avoid damage that may arise from the use of a plasma.

[0064] In the methods described herein, inhibition profile may be controlled by temperature and/or flow rates of the inhibition gas. The higher temperatures used for deposition of low stress film can result in more inhibition species being consumed at the top of the feature. For deeper inhibition (such as used in the inhibition operations of the early cycles), higher flow rates may be used. Flow rates of the inhibition gas can depend on a size of the chamber, reaction rates, and other parameters. A flow rate can be selected in such a way that more inhibition material is concentrated near the opening than inside the feature. Exposure time can also be selected to result in a particular inhibition profile. Example exposure times can range from about 10 s to 500 s, depending on desired selectivity and feature depth. The flow rate and/or exposure time may be decreased with successive cycles to result in shallower inhibition.

Apparatus

[0065] Any suitable chamber may be used to implement the disclosed embodiments. Example deposition apparatuses include various systems, e.g., ALTUS^® and ALTUS^® Max, available from Lam Research Corp., of Fremont, California, or any of a variety of other commercially available processing systems.

[0066] Figure 4 is a block diagram of a processing system suitable for conducting deposition processes in accordance with embodiments. The system 400 includes a transfer module 403. The transfer module 403 provides a clean, pressurized environment to minimize risk of contamination of substrates being processed as they are moved between various reactor modules. Mounted on the transfer module 403 is a multi-station reactor 409 capable of performing ALD and CVD and inhibition processes according to embodiments. Multi-station reactor 409 may include multiple stations 411, 413, 415, and 417 that may sequentially perform operations in accordance with disclosed embodiments. For example, multi-station reactor 409 could be configured such that station 411 performs ALD nucleation and inhibition, stations 413 and 415 each perform multiple CVD and inhibition cycles, and station 417 performs CVD. In another example, multi-station reactor 409 is configured such that station 411 performs ALD nucleation, station 413 performs inhibition, station 415 performs ALD or CVD deposition, and station 417 performs CVD.

[0067] Stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate. An example of a deposition station 500 is depicted in Figure 5, including substrate support 502 and showerhead 503. A heater may be provided in pedestal portion 501. The pedestal 501 may include a chuck for clamping the wafer. In certain embodiments, an electrostatic or mechanical chuck may be used rather than a vacuum chuck to facilitate providing a low pressure environment. Gases may be exhausted out of deposition station 500 by an exhaust (not shown).

[0068] Also mounted on the transfer module 403 may be one or more single or multi-station modules 407 capable of performing plasma or chemical (non-plasma) pre-cleans. The module may also be used for various treatments to, for example, prepare a substrate for a deposition process. The system 400 also includes one or more wafer source modules 401, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 419 may first remove wafers from the source modules 401 to loadlocks 421. A wafer transfer device (generally a robot arm unit) in the transfer module 403 moves the wafers from loadlocks 421 to and among the modules mounted on the transfer module 403.

[0069] In various embodiments, a system controller 429 is employed to control process conditions during deposition. The controller 429 will typically include one or more memory devices and one or more processors. A processor may include a CPU or computer, analog and/or digital input/output connections, stepper motor controller boards, etc.

[0070] The controller 429 may control all of the activities of the deposition apparatus. The system controller 429 executes system control software, including sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the controller 429 may be employed in some embodiments.

[0071] Typically there will be a user interface associated with the controller 429. The user interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0072] System control logic may be configured in any suitable way. In general, the logic can be designed or configured in hardware and/or software. The instructions for controlling the drive circuitry may be hard coded or provided as software. The instructions may be provided by “programming.” Such programming is understood to include logic of any form, including hard coded logic in digital signal processors, application-specific integrated circuits, and other devices which have specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general purpose processor. System control software may be coded in any suitable computer readable programming language.

[0073] The computer program code for controlling the germanium-containing reducing agent pulses, hydrogen flow, and tungsten-containing precursor pulses, and other processes in a process sequence can be written in any conventional computer readable programming language: for example, assembly language, C, C++, Pascal, Fortran, or others. Compiled object code or script is executed by the processor to perform the tasks identified in the program. Also as indicated, the program code may be hard coded.

[0074] The controller parameters relate to process conditions, such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe, and may be entered utilizing the user interface.

[0075] Signals for monitoring the process may be provided by analog and/or digital input connections of the system controller 429. The signals for controlling the process are output on the analog and digital output connections of the system 400.

[0076] The system software may be designed or configured in many different ways. For example, various chamber component subroutines or control objects may be written to control operation of the chamber components necessary to carry out the deposition processes in accordance with the disclosed embodiments. Examples of programs or sections of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0077] In some implementations, a controller 429 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and/or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the“controller,” which may control various components or subparts of the system or systems. The controller 429, depending on the processing requirements and/or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and/or load locks connected to or interfaced with a specific system.

[0078] Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and/or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or dies of a wafer.

[0079] The controller 429, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller 429 may be in the“cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and/or settings, which are then communicated to the system from the remote computer. In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps 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 that the controller is configured to interface with or control. Thus as described above, the controller may be distributed, such as by comprising one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

[0080] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a PVD chamber or module, a CVD chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and/or manufacturing of semiconductor wafers.

[0081] As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and/or load ports in a semiconductor manufacturing factory. [0082] The controller 429 may include various programs. A substrate positioning program may include program code for controlling chamber components that are used to load the substrate onto a pedestal or chuck and to control the spacing between the substrate and other parts of the chamber such as a gas inlet and/or target. A process gas control program may include code for controlling gas composition, flow rates, pulse times, and optionally for flowing gas into the chamber prior to deposition in order to stabilize the pressure in the chamber. A pressure control program may include code for controlling the pressure in the chamber by regulating, e.g., a throttle valve in the exhaust system of the chamber. A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas such as helium to the wafer chuck.

[0083] Examples of chamber sensors that may be monitored during deposition include mass flow controllers, pressure sensors such as manometers, and thermocouples located in the pedestal or chuck. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain desired process conditions.

[0084] The foregoing describes implementation of disclosed embodiments in a single or multi chamber semiconductor processing tool. The apparatus and process described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically comprises some or all of the following steps, each step provided with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma- assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

Claims

1. A method comprising:

providing a a 3-D structure on a substrate, the 3-D structure comprising metal lines arranged in a staircase pattern, a dielectric material overlying the staircase pattern, and a vertically-oriented feature having feature sidewalls and a feature bottom and providing fluidic access to a metal line at the feature bottom;

depositing a conformal layer of metal in the vertically-oriented feature;

exposing the conformal layer of metal to inhibition species at a first flow rate and a first exposure time in a first inhibition operation;

after the first inhibition operation, preferentially depositing metal at the bottom of the vertically-oriented feature in a first non-conformal deposition operation, wherein a temperature of the substrate is at least 400°C during the first non-conformal deposition operation;

after the first non-conformal deposition operation, exposing the vertically- oriented feature to inhibition species at a second flow rate and a second exposure time in a second inhibition operation, wherein the second flow rate is lower than the first flow rate and/or the second exposure time is lower than the first exposure time;

and after the second inhibition operation, depositing metal in the feature at a substrate temperature of at least 400°C in a second non-conformal deposition operation.

2. The method of claim 1, wherein the metal is one of tungsten, cobalt, molybdenum, and ruthenium.

3. The method of claim 1 or 2, wherein preferentially depositing metal at the bottom of the feature comprises exposing the feature to a metal precursor and a reducing agent, wherein the volumetric ratio of reducing agent to metal precursor is at least 30: 1.

4. The method of any of claims 1-3, wherein preferentially depositing metal at the bottom of the feature comprises exposing the feature to a metal precursor at flow rate of no more than 100 seem.

5. The method of any of the above claims, wherein the feature is an interconnect feature in a 3D NAND device.

6. The method of any of the above claims, wherein the metal is tungsten and the substrate temperature is at least 430°C during deposition.

7. The method of any of claims 1-5, wherein the metal is molybdenum and the substrate temperature is at least 600°C during deposition.

8. The method of any of the above claims wherein the inhibition species are nitrogen- containing gas or plasma species.

9. The method of any of the above claims, wherein the first inhibition operation treats most of the feature.

10. The method of any of the above claims, wherein the first inhibition operation treats at least 70% of the feature depth.

11. The method of any of the above claims, wherein a substrate temperature during the first inhibition operation is different than during the second inhibition operation.

12. An apparatus for processing substrates, the apparatus comprising:

(a) a process chamber comprising at least one station having a pedestal configured to hold a substrate;

(b) at least one outlet for coupling to a vacuum;

(c) one or more process gas inlets coupled to one or more process gas sources; and

(d) a controller for controlling operations in the apparatus, comprising machine-readable instructions for:

inletting inhibition species at first flow rate and first exposure time to the process chamber in a first inhibition operation;

after the first inhibition operation, inletting a metal precursor and reducing agent to deposit a metal, wherein a temperature of the pedestal on which the substrate is at least 400°C, in a first non-conformal deposition operation;

after the first non-conformal deposition operation, inletting inhibition species to the process chamber at a second flow rate and second exposure time in a second inhibition operation, wherein the second flow rate is lower than the first flow rate and/or the second exposure time is lower than the first exposure time; and

after the second inhibition operation, inletting a metal precursor and reducing agent to deposit a metal, wherein a temperature of the pedestal on which the substrate is at least 400°C, in a second non-conformal deposition operation.

13. The apparatus of claim 12, wherein the volumetric ratio of reducing agent to tungsten precursor is at least 30:1 during the first and second non-conformal deposition operations.

14. A method comprising: depositing a conformal layer of metal in a feature on a substrate; treating a portion of the conformal layer of metal to inhibit subsequent tungsten nucleation; after treating the portion of the conformal layer, preferentially depositing tungsten at the bottom of the feature, wherein a temperature of the substrate is at least 400°C during the deposition; and repeating the treating and depositing operations one or more times to fill the feature with metal.