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Definitions

• Tungsten (W) film deposition using chemical vapor deposition (CVD) techniques is an integral part of semiconductor fabrication processes.
• W films may be used as low resistivity electrical connections in the form of horizontal interconnects, vias between adjacent metal layers, and contacts between a first metal layer and devices on a silicon substrate.
• Tungsten films may also be used in various memory applications, including in formation of buried wordline (bWL) architectures for dynamic random access memory (DRAM), word lines for 3D NAND, and logic applications.
• bWL buried wordline
• DRAM dynamic random access memory
• 3D NAND 3D NAND
• logic applications include high resistivity for thinner films.
• Mo molybdenum
• One aspect involves a method for processing substrates, the method including: providing a substrate having an oxide material thereon; depositing at least a portion of an elemental molybdenum layer over the oxide material using a first atomic layer deposition (ALD) process by exposing the oxide material to alternating pulses of a first oxygen-containing molybdenum precursor and a first reducing agent using a first set of process conditions; and modulating the first set of process conditions to increase non-molybdenum content when depositing the portion of the elemental molybdenum layer.
• ALD atomic layer deposition
• the first set of process conditions includes using a flow rate of at least about 1000 seem of the first reducing agent during the first ALD process.
• the first set of process conditions include exposing the substrate to the first reducing agent for at least 1 second during a cycle of the first ALD process.
• the method also includes prior to depositing the portion of the elemental molybdenum layer, exposing the oxide material to a soak gas such as boron-containing gases, tungsten-containing gases, fluorine-containing gases, oxygen-containing gases, chlorine- containing gases, and combinations thereof.
• a soak gas such as boron-containing gases, tungsten-containing gases, fluorine-containing gases, oxygen-containing gases, chlorine- containing gases, and combinations thereof.
• the method also includes, prior to depositing the portion of the elemental molybdenum layer, exposing the oxide material to alternating pulses of a boron- containing gas and a tungsten-containing gas.
• the boron-containing gas includes diborane and the tungsten-containing gas includes tungsten hexafluoride.
• the method also includes prior to depositing the portion of the elemental molybdenum layer, depositing a first layer on the oxide material using a second oxygen- containing molybdenum precursor and a second reducing agent using a second ALD process on the oxide material under a second set of process conditions.
• the second reducing agent is a nitrogen-containing gas, hydrogen, or combinations thereof.
• the second set of process conditions includes depositing at least the portion of the elemental molybdenum layer at a substrate temperature less than about 400°C.
• at least one of the first and the second oxygen-containing molybdenum precursor is a molybdenum oxyhalide.
• the first oxygen-containing molybdenum precursor is a molybdenum oxyhalide, and the first set of process conditions includes using a hydrogen to molybdenum oxyhalide precursor ratio of between about 100:1 and about 10,000:1.
• the second set of process conditions includes increasing flow of a nitrogen-containing gas during the second ALD process.
• the method also includes flowing nitrogen during depositing of the first layer.
• the method also includes soaking the substrate having the oxide material thereon with a soak gas prior to depositing the first layer.
• the soak gas may be any one or more of oxygen, ammonia, or nitrogen.
• the method also includes soaking the substrate having the oxide material thereon with a soak gas after depositing the first layer.
• less than half of the first layer is converted to a converted elemental molybdenum layer during or prior to the first ALD process.
• the converted elemental molybdenum layer may contain more than 1 (atomic) % impurities.
• the impurities may be any of oxygen, chlorine, nitrogen, and combinations thereof.
• the first layer is a crystalline layer.
• the first layer is an amorphous layer.
• the first ALD process and the second ALD process are performed in the same chamber and without exposure to air.
• the first layer is a template for metal grain growth in the elemental molybdenum layer.
• the second ALD process is performed at a temperature less than 400°C.
• the first ALD process is performed at the same temperature as the second ALD process.
• the elemental molybdenum layer is a gradient film, such that at least a first set of cycles of the first ALD process is performed at a temperature less than about 400°C and at least a last set of cycles of the first ALD process is performed at a temperature greater than 400°C.
• deposition of the first layer and deposition of the elemental molybdenum layer are performed in the same chamber. In some embodiments, deposition of the first layer and deposition of the elemental molybdenum layer are performed in different stations of the same chamber.
• deposition of the first layer is performed in a first chamber and deposition of the elemental molybdenum layer is performed in a second chamber.
• the method also includes exposing the first layer to air prior to deposition of the elemental molybdenum layer.
• the elemental molybdenum layer is crystalline.
• the elemental molybdenum layer contains less than 1 (atomic)
• the elemental molybdenum layer is elemental molybdenum.
• Another aspect involves an apparatus for processing substrates, the apparatus including: first and second process chambers each configured to house a substrate; a substrate support in each of the first and the second process chambers; gas inlets configured to direct gas into each of the first and the second process chambers via one or more showerheads; a heater configured to heat the substrate support in each process chamber; and a controller including program instructions for:
• At least one of the one or more showerheads is a single plenum showerhead.
• At least one of the one or more showerheads is a dual plenum showerhead.
• the process chamber is a chamber within a multi-chamber apparatus.
• FIG. 1 Another aspect involves an apparatus for processing substrates, the apparatus including: a process chamber configured to house a substrate; a substrate support in the process chambers; a first gas box including a gas source for containing hydrogen gas; a second gas box including a gas source for containing a molybdenum-containing gas; a third gas box including a gas source for containing a boron-containing or tungsten-containing gas; gas inlets configured to direct gas from each of the first gas box, second gas box, and third gas box into the process chamber via one or more showerheads; and a heater configured to heat the substrate support in each process chamber.
• at least one of the one or more showerheads is a single plenum showerhead.
• At least one of the one or more showerheads is a dual plenum showerhead.
• the process chamber is a chamber within a multi-chamber apparatus.
• Figures 1A and IB are schematic examples of material stacks that include a nucleation layer as a template for metal growth.
• Figures 2A and 2B provide examples of structures in which the material stacks may be employed according to various embodiments.
• Figures 3A, 3B, and 3C are process flow diagrams illustrating operations in methods of depositing a conductive material according to various embodiments.
• Figure 4 is an example of a material stack with a gradient composition in the nucleation layer according to various embodiments.
• Figure 5 is a schematic diagram of an example process chamber for performing disclosed embodiments.
• Figures 6 and 7A-7C are schematic illustrations of example gas flow diagrams for apparatuses that may be used to perform certain disclosed embodiments.
• Figure 8 is a block diagram of a processing system suitable for conducting deposition processes in accordance with embodiments described herein.
• Figure 9 are graphs of atomic content of various elements in stacks deposited in accordance with certain disclosed embodiments.
• Metallization of the gate contact in the 3D NAND transistor involves deposition of a metal that is highly conductive and has low resistivity, particularly in small features.
• Tungsten (W) has been used for metallization in 3D NAND devices and deposition of W for gate contacts involves formation of a titanium nitride (TiN) liner layer followed by a W nucleation layer and finally W bulk layer.
• TiN titanium nitride
• the TiN layer is used as both a barrier layer and an adhesion layer to facilitate effective nucleation of the W nucleation layer, which is used to facilitate formation of high quality bulk W.
• the nucleation layer often includes boron from a boron-containing reactant used to deposit the nucleation layer, and has higher resistivity than bulk W. Because many layers are deposited, the available space for depositing high quality, low resistance bulk W is low, especially as devices continue to shrink.
• Molybdenum (Mo) metallization is an alternative metallization option.
• Mo metallization a liner layer is deposited, followed by a bulk Mo layer.
• process conditions can be controlled to nearly completely convert the liner layer to elemental Mo, thereby allowing more of the space in a feature to be filled with elemental Mo, which has lower resistivity than the combination of a non-converted liner layer and bulk Mo. Overall, this results in elemental Mo being in contact with the gate oxide.
• One function of a 3D NAND device is the ability to retain data in the device.
• One advantage of using a 3D NAND device is its nonvolatility. Data may be written to a transistor in a 3D NAND device and then left unpowered for a period of time; when the 3D NAND device is later powered, the data is expected to still be written to the transistor to thereby function as an effective 3D NAND device.
• the ability of the transistor to retain that data after the period of time has lapsed may be referred to as data retention - e.g., whether the data can effectively be retained in the device.
• One potential way to reduce the oxygen and non-molybdenum component element loss is to supply an overabundance of oxygen and non-molybdenum component elements in the initial gate metal film, or to fabricate the metal-dielectric interface to have a composition similar to TiN W integration schemes that have been used in gate oxide stacks. This may reduce the driving force that leads to loss of oxygen and other non-molybdenum component elements from the gate oxide stack. It is also believed that retaining oxygen or other elements in the nucleation layer can prevent oxygen and other elements from being removed from the dielectric.
• the process conditions for depositing the metal layer cause an interaction between the nucleation layer and dielectric layer such that oxygen is removed from the dielectric layer, whereas when the nucleation layer retains some oxygen or other non-molybdenum component element impurities, the rate of data loss is substantially reduced.
• Memory device electrical performance has also changed due to changing of wordline metals from W to Mo.
• tungsten integration involved a barrier metal such as TiN, tungsten nitride (WN), tungsten carbonitride (WCN), and the like.
• barrier metal such as TiN, tungsten nitride (WN), tungsten carbonitride (WCN), and the like.
• Deposition of TiN barrier layers resulted in exposure to various chemistries, including ammonia (NFb), chlorine (Ch), and hydrochloric acid (HC1) at high temperatures, but the overall process scheme adapted to these exposures such that trace amounts of these elements did not intrinsically harm the control gate or capacitor dielectrics.
• Deposition of tungsten layers resulted in exposure of control gate and capacitor dielectrics to a variety of other chemistries, including diborane (B2H6), silane (S1H4), hydrogen (H2), tungsten hexafluoride (WF6) and reaction byproducts including but not limited to fluorine (F2), hydrofluoric acid (HF), boron trifluoride (BF3), silicon tetrafluoride (S1F4) and others.
• B2H6 diborane
• silane S1H4
• H2 hydrogen
• WF6 tungsten hexafluoride
• reaction byproducts including but not limited to fluorine (F2), hydrofluoric acid (HF), boron trifluoride (BF3), silicon tetrafluoride (S1F4) and others.
• Barrier metal layers may be TiN layers deposited using a nitrogen- containing reactant such as NH3 and titanium-containing reactant such as titanium tetrachloride (TiC'U). and H2.
• a nitrogen- containing reactant such as NH3
• titanium-containing reactant such as titanium tetrachloride (TiC'U).
• H2 titanium tetrachloride
• Such deposition can result in incorporation of trace amounts of fluorine, boron, and other non-molybdenum component elements in the device.
• Some devices may perform more optimally with these trace amounts still in the device, even when metallization involves deposition of Mo instead of W.
• some Mo deposition may include barrier layers, some integration schemes may be integrated without barrier layers.
• Mo deposition may involve exposure to NH3, H2, and HC1, process schemes with W deposition also involved such exposures so these gases may not necessarily be intrinsically harmful to the dielectric.
• deposition of Mo also includes exposure to Mo-containing precursors, reaction byproducts such as water (H2O) and nitric oxide (NO), and Mo oxides and suboxides, as well as molybdenum oxynitride (MoOxNy).
• Process schemes with W deposition do not typically involve exposures to these gases that are used in Mo deposition.
• compounds that dielectrics were exposed to during W deposition can be used to modulate the dielectric-Mo interface resulting in good electrical performance for Mo gate oxide stacks.
• Certain disclosed embodiments address these issues in various applications, including but not limited to 3D NAND fabrication of wordlines with a barrier metal, 3D NAND fabrication of wordlines without a barrier metal, DRAM buried wordline with a barrier metal, DRAM buried wordline without a barrier metal, and metal-oxide-semiconductor capacitor (MOSCAP) devices.
• MOSCAP metal-oxide-semiconductor capacitor
• Non-limiting example metal-dielectric interfaces include aluminum oxide- molybdenum (AI2O3-M0) interfaces, silicon oxide-molybdenum (SiC -Mo) interfaces, zirconium oxide-molybdenum (ZrC -Mo) interfaces, and other control gate dielectrics interfaced with metals such as Mo.
• AI2O3-M0 aluminum oxide- molybdenum
• SiC -Mo silicon oxide-molybdenum
• ZrC -Mo zirconium oxide-molybdenum
• other control gate dielectrics interfaced with metals such as Mo.
• Methods may be performed during any operation of depositing metal, including but not limited to before deposition of any metal, before deposition of a metal nucleation layer such as metal oxynitride, after deposition of some metal (including metal oxynitride and bulk metal), after deposition of some of a metal nucleation layer, after deposition of the entire metal nucleation layer and before deposition of bulk metal, throughout or during deposition of the metal nucleation layer, throughout or during deposition of the bulk metal, or after deposition of the bulk metal.
• a metal nucleation layer such as metal oxynitride
• some metal including metal oxynitride and bulk metal
• embodiments involve a substrate having a barrier layer on the dielectric
• methods described herein may be performed on the dielectric before depositing the barrier layer, after depositing the barrier layer, or during deposition of the barrier layer.
• Methods described herein may incorporate one or more of the following elements: oxygen, nitrogen, fluorine, boron, chlorine, and tungsten.
• 3D NAND gate transistors are fabricated using certain disclosed embodiments.
• Various disclosed embodiments involve plasma-free deposition or plasma-less deposition.
• Various disclosed embodiments are thermal processes.
• Certain disclosed embodiments retain impurity content of boron, fluorine, oxygen, nitrogen, chlorine, and other non-molybdenum component elements that may range between less than about 1 atomic % and about 50 atomic % per element type.
• a gradient composition may be formed whereby impurity content near the dielectric-metal interface is greater than in the bulk metal.
• the high impurity content may be between less than about 1 atomic % and about 50 atomic % in the less than about lA to 30A range of Mo-containing material at the dielectric-Mo interface.
• methods involve one or more of the following operations: temperature and/or gas treatment of the substrate (including the dielectric, partial or full barrier layer, partial or full metal nucleation layer, or partial or full metal layer) using particular gases; and deposition whereby at least one of deposition of the initial Mo layers, treatment of the interface between an liner layer and bulk Mo layer, and deposition of bulk Mo layer is modified to increase or retain content of oxygen and other elements in the liner layer.
• deposition of the liner layer may include under-reacting the Mo precursor to retain oxygen in the metal film.
• the quad-station module includes four stations; at least one station may be used to deposit molybdenum in accordance with certain disclosed embodiments.
• one station can be for depositing a liner, another for depositing an optional initiation layer, another for depositing the bulk, and another for depositing an overburden to ensure complete fill of the feature.
• the quad-station module allows depositing a liner and depositing a bulk in two separate stations.
• the station for depositing the liner and/or the bulk can be modulated to reduce deposition temperature (or modulate or perform any other process condition described herein for certain disclosed embodiments) while allowing other stations to deposit at higher deposition temperatures or other process conditions that improve reaction rate to allow higher module throughput.
• Figures 1A and IB are schematic examples of material stacks that include a nucleation layer as a template for metal growth.
• Figures 1A and IB illustrate the order of materials in a particular stack and may be used with any appropriate architecture and application, as described further below with respect to Figures 3 and 4.
• stack 100 includes a substrate 102 which may be a silicon or other semiconductor wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi-conducting material deposited thereon.
• the methods may also be applied to form metallization stack structures on other substrates, such as glass, plastic, and the like.
• the substrate 102 includes silicon.
• a dielectric layer 104 is on the substrate 102.
• the dielectric layer 104 may be deposited directly on a semiconductor surface of the substrate 102, or there may be any number of intervening layers.
• dielectric layers include doped and undoped silicon oxide (SiCh), doped and undoped silicon carbide (SiC), silicon nitride (SiN), and aluminum oxide (AI2O3) layers, with specific examples including doped or undoped layers silicon oxide (S1O2) and AI2O3.
• a stack 100 includes a barrier layer 106 deposited between the nucleation layer 108 and the dielectric layer 104.
• the barrier layer 106 may be a diffusion barrier, an adhesion barrier, or both.
• barrier layers including TiN, Ti/TiN, WN, and WCN.
• the barrier layer 106 is between about 10 A and about 40 A in thickness or between about IOA and about 20A in thickness.
• nucleation layer 108 is deposited on dielectric layer 104 and a metal layer 110 is deposited on nucleation layer 108.
• nucleation layer 108 is deposited on barrier layer 106 and a metal layer 110 is deposited on nucleation layer 108.
• Figures 1A and IB show dielectric-metal interface, i.e., 112a and 112b.
• Certain disclosed embodiments may involve performing a treatment operation before depositing nucleation layer 108, performing a treatment operation after depositing at least some of nucleation layer 108, performing a treatment operation after depositing all of the nucleation layer 108, modulating deposition conditions of the nucleation layer 108, performing a treatment operation before depositing metal layer 110, performing a treatment during deposition of metal layer 110, modulating deposition conditions when depositing at least some of metal layer 110, modulating deposition conditions when depositing all of metal layer 110, or combinations thereof.
• Metal layer 110 can be formed such that it is in contact at dielectric-metal interface 112 with the nucleation layer 108.
• the metal layer 110 deposited on the nucleation layer 108 is the main conductor (also referred to as a bulk conductor or bulk layer) of the structure with the nucleation layer 108 providing a template for metal growth.
• the nucleation layer 108 may be deposited as an amorphous film.
• An amorphous film has no grain structure and as a template for metal growth, low resistivity metal having no grain structure and/or large grains (as opposed to small grains) can be formed. Examples of metal layers include Mo layers.
• the nucleation layer 108 deposited is a metal oxynitride layer, such as a MoO x N y layer.
• some of the nucleation layer 108 may be converted to a pure metal while some of the nucleation layer 108, such as a region at the interface of nucleation layer 108 and dielectric layer 104, may retain non-molybdenum component element impurities such as boron, fluorine, tungsten, oxygen, nitrogen, and chlorine, and some of nucleation layer 108 may not be converted to a pure metal.
• a pure metal may be defined as having a non-molybdenum component element composition of less than about 1%.
• Non-molybdenum component element impurities are intentionally maintained within the nucleation layer 108 at or near the dielectric-metal interface which can reduce the chances of oxide diffusion from the dielectric that can cause data loss.
• the nucleation layer 108 may or may not be the same composition as the metal layer 110.
• the nucleation layer 108 includes multiple layers, or is a gradient layer, or is a layer deposited by repeating at least one ALD cycle with the same precursor and reactant flows in each cycle, and when depositing the metal layer 110, the nucleation layer 108 is modified to result in a gradient, in multiple layers, in a change in morphology, or in the change in the impurity composition of the nucleation layer.
• one or more of the multiple players are gradient layers.
• the nucleation layer 108 may be characterized by its amorphous character, with the metal layer 110 characterized by its lack of grain boundaries.
• the metal of the metal oxynitride layer is the same as that of the pure metal conductor, e.g., a MoO x N y layer may be deposited as a nucleation layer prior to deposition of a Mo layer.
• the metal oxynitride layer may have a different metal than that of the pure conductor, e.g., a W layer may be deposited on a Mo-containing nucleation layer or a Mo layer may be deposited on a W-containing nucleation layer.
• the nucleation layer may be deposited directly on SiC , silicon, or other semiconductor substrate as a template for metal growth.
• W or Mo growth on the nucleation layers is described above, the nucleation layers may serve as a template for low resistivity growth of other metals, such as, cobalt (Co), ruthenium (Ru), nickel (Ni), and alloys including these metals such as MoW.
• the nucleation layer may be any appropriate metal oxynitride or metal nitride layer, including MoOxNy, Mo nitride, tungsten oxynitride, WN, nickel nitride, etc.
• Figures 2A and 2B provide examples of structures in which the stacks may be employed.
• Figure 2A depicts a schematic example of wordlines 210 in a 2D NAND structure 223.
• the wordlines 210 are separated by oxide layers 211 as pillars with gaps 235 between them on substrate 200.
• Figure 2B a detail of the interface between a wordline 210 and oxide layer 211 is shown including a layer of AI2O3 204 and a nucleation layer 208 is shown.
• the nucleation layer 208 may be deposited directly on the oxide layer 211 or on a TiN 204 or other barrier layer as described herein.
• the nucleation layers may be between about IOA and 100 A, or IOA and 50A, for example, for deposition of a wordline 210 of between about 10 nm and 100 nm thick, or about 5 nm thick or less.
• Figure 3A is a process flow diagram illustrating operations in a method of depositing a conductive material in accordance with certain disclosed embodiments.
• a substrate having an oxide surface and/or a barrier layer surface (which may be on an oxide surface) is provided. Examples of process conditions and features of operation 301 are provided further below with respect to Figure 3B.
• the oxide-metal interface is modulated to prevent defects in the oxide. Example methods for performing operation 360 are described below with respect to Figures 3B and 3C.
• a metal layer is formed over the substrate whereby the metal is in contact with the oxide surface or barrier layer surface. Example embodiments for performing operation 370 are further described below with respect to Figures 3B and 3C.
• operations 360 and 370 may be performed at the same time; or in order of operation 360 first followed by operation 370; or operation 370 first followed by operation 360; or a combination of operations 360 and 370 may be performed together (such as alternately; or some operations of operation 360 performed during operation 370; or some operations of operation 370 performed during operation 360.
• Each of operations 301, 360, and 370 may be performed in the same chamber, in a single chamber, in one or more stations of the same chamber, or in one or more stations of different chambers.
• Figure 3B is a process flow diagram illustrating operations in a method of depositing a conductive material. It will be understood that each of operations 301, 303a, 305, 307, and 309 may be each performed in the same chamber as when performing one of the other operations in Figure 3B or may be performed in separate chambers or may be performed using a combination of same and different chambers, and that each of operations 301, 303a, 305, 307, and 309 may be each performed in the same station in a multi-station chamber as when performing one of the other operations in Figure 3B or may be performed in separate stations or may be performed using a combination of same and different stations.
• At least one of the operations in Figure 3B identified as an optional operation is performed.
• Each of the optional operations may be used in combination with other optional operations in Figure 3B; for example, treatment in operation 303a may be performed while omitting modulating process conditions in operations 305 and 309 and omitting the treatment in operation 307.
• a substrate having an oxide surface is provided. This may be the same as operation 301 in Figure 3 A.
• the substrate has a dielectric layer including an oxide surface thereon.
• the substrate is provided in a first process station of a multi-station chamber.
• the substrate may be a silicon wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi-conducting material deposited thereon.
• Non- limiting examples of under-layers include dielectric layers and conducting layers, e.g., silicon oxides, silicon nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers.
• the substrate is the same as substrate 102 in Figures 1A or IB.
• the substrate includes an oxide surface.
• the oxide surface is a part of a dielectric layer, such as dielectric layer 104 in Figure 1A.
• the oxide surface is part of a barrier layer, such as barrier layer 106 in Figure IB.
• the oxide surface includes silicon oxide.
• the oxide surface includes aluminum oxide.
• operation 303a in operation 303a an optional soak treatment is performed.
• the optional soak treatment may be performed to prepare the surface of the oxide surface on the substrate prior to operation 305. Soaking may cause deposition of material in operation 305 to deposit differently or form a different composition on the surface of the oxide.
• operation 303a involves introducing a boron-containing gas, such as diborane (B2H6). Exposure to a boron-containing gas can make the dielectric process history more similar to previous process histories that involved TiN with tungsten integration.
• a boron-containing gas such as diborane (B2H6). Exposure to a boron-containing gas can make the dielectric process history more similar to previous process histories that involved TiN with tungsten integration.
• operation 303 a involves introducing a tungsten-containing or fluorine-containing gas, such as tungsten halides, including but not limited to tungsten hexachloride, tungsten pentachloride, tungsten pentafluoride, and tungsten hexafluoride (WF6).
• tungsten halides including but not limited to tungsten hexachloride, tungsten pentachloride, tungsten pentafluoride, and tungsten hexafluoride (WF6).
• Fluorine exposure can make the dielectric process history more similar to the process history with TiN with tungsten integration. However, exposure may be limited so as not to expose dielectric to too much fluorine, which can be detrimental to device performance, but trace exposure can be advantageous to match the device performance of TiN with W integration.
• operation 303a is performed with two or more temporally separated pulses of gas treatments.
• exposure may alternate between EEHb and WF6 in some embodiments, such as one may do to perform deposition of a W nucleation layer by atomic layer deposition.
• This operation may be performed to make the dielectric process history more similar to the process history of TiN with W integration.
• Any W nucleation layer that may be deposited by performing operation 303a is minimized (e.g., very few cycles, such as between 1 and 5 or 1 and 10 cycles are used) to avoid negative impact of Mo or subsequent metal conductor layer resistivity.
• Ultra-thin W nucleation layer deposited by ALD prior to Mo deposition may reduce Mo resistivity if it provides a template for large-grain or amorphous Mo growth in various embodiments.
• boron-containing and W-containing or fluorine-containing gas exposures are performed simultaneously, similar to a chemical vapor deposition (CVD) type process.
• a combination of ALD and CVD processes may be used.
• Operation 303a may be performed as a separate operation before operation 305 or may be performed during operation 305 such as after some nucleation layer is deposited whereby operation 303a and operation 305 may be performed in temporally alternating operations. In some embodiments, operation 303a is performed periodically throughout other operations performed in Figure 3.
• the soak treatment includes exposing the oxide surface to one or more gases such as oxygen-containing gas, nitrogen-containing gas, or other suitable gas that is capable of changing the interface between the oxide surface and the later deposited material to reduce tunneling of electrons from the oxide in the substrate out of the oxide, and combinations thereof.
• gases such as oxygen-containing gas, nitrogen-containing gas, or other suitable gas that is capable of changing the interface between the oxide surface and the later deposited material to reduce tunneling of electrons from the oxide in the substrate out of the oxide, and combinations thereof.
• Example oxygen-containing gases include oxygen gas.
• Example nitrogen-containing gases include NH3 gas and nitrogen.
• Operation 303a may be performed at any suitable temperature.
• Example non-limiting temperatures include up to about 650°C, or less than about 350°C, or between about 250°C and about 350°C.
• Non-limiting examples of chamber pressure may be up to about 90 Torr, or between about 5 Torr and about 50 Torr, or between about 5 Torr and about 15 Torr, or about 10 Torr.
• Exposure times may vary depending on flow rates. Non-limiting examples of exposure times range from about 0.1 second to about 10 seconds, or between about 0.1 second and about 20 seconds for each gas. For alternating pulses of treatments, each pulse may have any of the above exposure times.
• Overall duration of operation 303a may range from about 0.1 second to about 20 seconds, or between about 0.1 second to about 15 seconds, or between about 0.1 second to about 10 seconds.
• Exposure times for EEFE and hydrogen gas exposure may be between about 0.1 second and about 10 seconds.
• EEFk and hydrogen may be simultaneously flowed to the substrate for between about 0.1 second and about 10 seconds.
• Exposure times for WF6 gas exposure may be between about 0.1 second and about 1 second.
• WF6 may be flowed to the substrate for between about 0.1 second and about 1 second.
• a purge operation may be performed between alternating pulses.
• Purging may involve flowing argon gas or another inert gas for a particular duration, such as between about 0.1 second and about 1 second.
• one cycle of pulses may involve: (1) EEFk and hydrogen dose for between 0.1 second and 10 seconds, (2) purge using argon gas for between 0.1 second and 1 second, (3) WF6 dose between 0.1 second and 1 second, and (4) purge using argon gas for between 0.1 second and 1 second.
• the gas flow of the one or more gases depends on chemistry of one or more gases selected, the oxide surface material, the duration of exposure, the mixture of gases if more than one gas is flowed, and the extent of the soak effect desired for the given substrate. Duration of gas exposure depends on the gas flow, type of gas, and extent of soak effect desired.
• Non-limiting example gas flows for flowing oxygen gas may vary between about 100 seem and about 10,000 seem.
• Example durations for oxygen gas flows include between about 0.1 second and about 30 seconds.
• Non-limiting example gas flows for flowing NEE gas may vary between about 100 seem and about 10,0000 seem.
• Example durations for NEE gas flows include between about 0.1 second and about 30 seconds.
• Non-limiting example gas flows for flowing nitrogen gas may vary between about 100 seem and about 10,000 seem.
• Example durations for nitrogen gas flows include between about 0.1 second and about 30 seconds.
• a conformal nucleation layer is formed by atomic layer deposition (ALD) on the substrate.
• the conformal nucleation layer is deposited on the oxide surface of the substrate provided in operation 301.
• operation 303a and operation 305 are performed in the same chamber, or in the same tool in separate chambers, or without breaking vacuum.
• an air break occurs after operation 303a before operation 305, which may be advantageous as after operation 303 a, exposed boron or fluorine atoms may be on the surface and those atoms may oxidize thereby incorporating oxygen into the device before operation 305, which can enable reduced resistivity of the overall film stack and/or reduce data loss as incorporated non-molybdenum component element elements can help reduce the likelihood of oxide loss or diffusion.
• process conditions may be modulated to modify the composition of the conformal nucleation layer.
• process conditions may be adjusted to increase non-molybdenum component element content of the conformal nucleation layer, such as the oxygen, chlorine, and/or nitrogen content.
• process conditions may not be modulated in operation 305.
• the substrate may be exposed in cycles such that the substrate is first exposed to a pulse of a suitable metal-containing precursor, then the precursor is optionally purged, then the substrate is exposed to a pulse of a reducing agent, and then the reducing agent is optionally purged, and such cycles may be repeated until a desired thickness of the nucleation layer is formed on the substrate.
• Purging may be performed by flowing an inert gas, such as argon.
• inert gases may also be used as a carrier gas to deliver one or more gases, including but not limited to soak gases, precursor gases, and reactant gases, to the substrate.
• ALD is a technique that deposits thin layers of material using sequential self-limiting reactions.
• an ALD cycle includes operations to deliver and adsorb at least one reactant to the substrate surface, and then react the adsorbed reactant with one or more reactants to form the partial layer of film.
• a MoO x N y deposition cycle may include the following operations: (i) delivery/adsorption of a Mo-containing precursor, (ii) purging of the Mo precursor from the chamber, (iii) delivery of an nitrogen-containing reactant or nitrogen-containing gas, and (iv) purging of the nitrogen-containing reactant from the chamber.
• ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis.
• a substrate surface that includes a population of surface active sites is exposed to a gas phase distribution of a first precursor, such as a Mo-containing precursor, in a dose provided to a chamber housing a substrate.
• Molecules of this first precursor are adsorbed onto the substrate surface, including chemisorbed species and/or physisorbed molecules of the first precursor.
• the adsorbed layer may include the compound as well as derivatives of the compound.
• an adsorbed layer of a Mo-containing precursor may include the Mo- containing precursor as well as derivatives of the Mo-containing precursor.
• the chamber may be evacuated such that the partial pressure of the first precursor in gas phase is sufficiently low to mitigate a reaction.
• a second reactant such as an nitrogen-containing reactant, is introduced to the chamber so that some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed first precursor.
• the chamber may then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness.
• an ALD first precursor dose partially saturates the substrate surface.
• the dose phase of an ALD cycle concludes before the precursor contacts the substrate to evenly saturate the surface.
• the precursor flow is turned off or diverted at this point, and only purge gas flows.
• the ALD process reduces the cycle time and increases throughput.
• precursor adsorption is not saturation limited, the adsorbed precursor concentration may vary slightly across the substrate surface. Examples of ALD processes operating in the sub-saturation regime are provided in U.S. Patent Application No. 14/061,587 (now U.S. Patent No.
• Substrate temperature for nucleation layer deposition may range, for example, from 250°C to about 600°C, or from 300 ° C to 600 ° C, or from 250°C to about 550°C. In some embodiments, lower temperatures may be used. Such temperatures may be less than 500 ° C, less than 550 ° C, less than 450 ° C, less than 400 ° C, or less than 350 ° C. Low temperatures may be used for improved step coverage. In addition, low temperatures may increase the amount of impurities in the nucleation layer, increasing the amorphous character, which in turn may increase grain size of the subsequently deposited conductor. In various embodiments, it may be advantageous to deposit the nucleation layer at low temperatures. Chamber pressure may be between about 5 Torr and about 90 Torr, or between about 5 Torr and about 50 Torr, or between about 20 Torr and about 40 Torr, or about 30 Torr.
• the surface on which the nucleation layer is deposited depends on the particular application.
• the nucleation layer is deposited directly on a dielectric (e.g., silicon oxide, aluminum oxide, silicon nitride, etc.) surface.
• the nucleation layer is deposited on a barrier layer.
• the nucleation layer is deposited before depositing any other metal on the surface.
• the nucleation layer is deposited on a treated dielectric.
• the nucleation layer is deposited on a tungsten nucleation layer.
• the nucleation layer is deposited on an untreated dielectric.
• the nucleation layer is deposited on a treated barrier layer.
• the nucleation layer is deposited on an untreated barrier layer. In some embodiments, the nucleation layer is deposited directly on a TiN or other surface. In some embodiments, the subsequent elemental metal deposition may be performed on any surface.
• the ALD process in operation 305 involves flowing an oxygen-containing Mo precursor and a reducing agent in sequentially alternating pulses or doses.
• the reducing agent is ammonia (NTb) or other nitrogen-containing gas or nitrogen-containing reducing agent such hydrazine (N2H4). Ammonia chemisorption on dielectrics is more favorable than that of hydrogen (H2) for the nucleation layer.
• the reducing agent and precursor are selected such that they react without reducing agent dissociation.
• Ammonia reacts with metal oxychlorides and metal chlorides without dissociation.
• ALD metal oxychlorides that uses hydrogen as a reducing agent; hydrogen dissociates on the surface to form adsorbed atomic hydrogen, which results in very low concentrations of reactive species and low surface coverage during initial nucleation of metal on the dielectric surface.
• NTb and metal oxychloride or metal chloride precursors nucleation delay is reduced or eliminated at deposition temperatures up to hundreds of degrees lower than used by hydrogen reduction of the same metal precursors.
• the reducing agent may be a boron-containing or silicon- containing reducing agent such as B2H6 or SiLL.
• B2H6 or SiLL reducing agents
• metal chloride precursors such as aluminum chloride
• metal oxychlorides such as aluminum oxychlorides
• the B2H6 and SiLL will react with water formed as a byproduct during the ALD process and form solid B2O3 and S1O2, which are insulating and will remain in the film, increasing resistivity.
• Use of U also has greater adhesion over B2H6 and S1H4 ALD processes on certain surfaces including AI2O3.
• metal oxychloride and metal chloride precursors include molybdenum pentachloride (M0CI5), molybdenum oxychlorides such as molybdenum dichloride dioxide (M0O2CI2) and molybdenum oxytetrachloride (MoOCU).
• MoOCU molybdenum pentachloride
• WCU tungsten hexachloride
• WCU tungsten tetrachloride
• WCI2 tungsten dichloride
• WCI2 tungsten oxychlorides
• WOxCly tungsten oxychlorides
• the metal chloride and metal oxychloride may be useful in embodiments in which fluorine incorporation is a concern.
• fluorine-containing precursors such as nitrogen trifluoride (NF3) may be used.
• NF3 nitrogen trifluoride
• metal fluorides such as WFe, molybdenum hexafluoride (M0F6), and molybdenum pentafluoride (M0F5).
• the resulting nucleation layer is generally not a pure elemental film but a metal nitride or metal oxynitride film.
• the nucleation layer is an amorphous layer. Impurities in the film (e.g., oxygen, NH3, chlorine, or other halogen) facilitate growth of an amorphous microstructure.
• the nucleation layer as deposited is an amorphous metal oxynitride layer or an amorphous metal nitride layer.
• the amorphous character templates large grain growth in the subsequently deposited conductor.
• the surface energy of nitride or oxynitride relative to an oxide surface is much more favorable than that of a metal on an oxide surface, facilitating formation of a continuous and smooth film on the dielectric. This allows formation of thin, continuous layers.
• Example thicknesses of the nucleation layer range from 5 ⁇ -30 ⁇ as deposited. Depending on the temperature, this may be about 5-50 ALD cycles for example.
• deposition process conditions are optionally modulated to increase or modulate the amount of non-molybdenum component element elements or “impurities” in the film.
• One technique is to vary exposure times and/or exposure flows during the deposition process.
• the substrate is exposed first to a pulse of a suitable metal- containing precursor, followed by exposure to a pulse of a reducing agent.
• the flow of the reducing agent is modified to retain more impurities from the metal- containing precursor in the resulting metal oxynitride film.
• Example flow rates of reducing agent include about 100 seem to about 40,000 seem. Flow rates are used during reducing agent pulses.
• one or more additive gases are flowed.
• the additive gases may include oxygen-containing gases, nitrogen-containing gases, or combinations thereof.
• Example oxygen-containing gases include oxygen.
• Example nitrogen-containing gases include nitrogen and NEE.
• Additive gases may be continuously flowed, flowed only with the Mo precursor, flowed only with the reducing agent, flowed only with the purge gas, or periodically without being synchronized to either precursor doses, reducing agent doses, or purge gas operations.
• temperature or pressure may be modulated to retain oxygen, nitrogen, and other component elements in the metal oxynitride layer.
• operation 305 may be performed at a temperature up to about 650°C, or less than about 350°C, or between about 200°C and about 550°C, or between about 250°C and about 350°C to retain impurities in the film.
• the chamber pressure can be between about 5 and about 90.
• Another technique for retaining impurity content in the nucleation layer is to change the morphology of the film.
• An amorphous films is more likely to reduce diffusion of impurities out of the film and thus reduce the likelihood of oxygen or other elements from the dielectric from diffusing out of the dielectric, thereby reducing the chances of trapped charge from escaping the dielectric and causing data loss.
• the morphology may be modulated by reducing the temperature of the substrate during film deposition and bulk molybdenum deposition.
• modulating the first few cycles of ALD of operation 305 may involve modulating the first few cycles of ALD of operation 305, in some embodiments, most or all cycles of ALD in operation 305 may be modulated. Any combination of modulated ALD cycles may be performed, including alternating between modulated and non-modulated cycles, such as performing a few cycles of low temperature ALD followed by a few cycles of high temperature ALD and repeating this sequentially, to improve throughput.
• Exposure times for gases used to deposit the nucleation layer may vary depending on flow rates. Non-limiting examples of exposure times range from about 0.1 seconds to about 10 seconds, or between about 0.1 seconds and about 20 seconds for each gas. For alternating pulses of treatments, each pulse may have any of the above exposure times.
• Exposure times for NFL and hydrogen gas exposure depend on the particular application and can range widely.
• hydrogen gas exposure may be at least about 30 seconds or longer.
• Non-limiting examples of exposure times include between about 0.1 second and about 60 seconds, between about 0.1 second and about 50 seconds, and at least about 30 seconds.
• NFb and hydrogen may be simultaneously flowed to the substrate for at least about 30 seconds, or between about 0.1 second and about 50 seconds.
• Exposure times for an oxygen-containing Mo precursor (such as one having a formula MoOxCly) gas exposure may be between about 0.1 second and about 10 seconds.
• an oxygen-containing Mo precursor may be flowed to the substrate for between about 0.1 second and about 10 seconds.
• a purge operation may be performed between alternating pulses.
• Purging may involve flowing argon gas or an other inert gas for a particular duration, such as between about 0.1 second and about 5 seconds.
• one cycle of pulses may involve: (1) NFL and hydrogen dose for between 0.1 second and 10 seconds, (2) purge using argon gas for between 0.1 seconds and 5 seconds, (3) MoOxCly dose between 0.1 seconds and 10 seconds, and (4) purge using argon gas for between 0.1 seconds and 5 seconds.
• a soak treatment is optionally performed. In some embodiments, this soak is performed in addition to or instead of operation 303 without modulating process conditions in operation 305 or with modulating process conditions in operation 305. In various embodiments, the soak treatment performed can use any one or more of the techniques described above with respect to operation 303a.
• Operation 307 may be performed as a separate operation after operation 305 or may be performed during operation 305 such as after some nucleation layer is deposited whereby operation 307 and operation 305 may be performed in temporally alternating operations. In some embodiments, operation 307 is performed periodically throughout other operations performed in Figure 3B. Operation 307 may be performed after depositing some main conductor layer material in operation 309, or before any main conductor layer material is deposited in operation 309. [0116] In operation 309, the main conductor layer is formed. In various embodiments, the main conductor layer is formed by ALD while modulating process conditions. In various embodiments, deposition is performed over, on, or directly on the nucleation layer.
• the main conductor layer may be referred to as the bulk layer or the metal layer.
• the main conductor layer is a Mo layer.
• the main conductor layer is an elemental Mo layer.
• the amount of impurities in the main conductor layer is less than about 1%.
• the main conductor layer is deposited by ALD using alternating pulses of an oxygen-containing metal precursor (such as a metal oxyhalide) and a reducing agent.
• an oxygen-containing metal precursor such as a metal oxyhalide
• the main conductor layer is deposited by ALD using an oxygen-containing Mo precursor and hydrogen as the reducing agent.
• a purge gas may be used; any purge gas described above with respect to operation 305 may be used in operation 309.
• any Mo precursor described above with respect to operation 305 may be used in operation 309.
• the Mo precursor may be a molybdenum oxyhalide.
• the molybdenum oxyhalide is a molybdenum oxychloride (MoOxCly).
• metal oxychloride and metal chloride precursors that may be employed in operations 305 and 309 include molybdenum pentachloride (MoCb) and molybdenum hexachloride (MoCE), molybdenum oxychlorides such as molybdenum dichloride dioxide (M0O2CI2) and molybdenum oxytetrachloride (MoOCU).
• tungsten pentachloride WCb
• WCE tungsten hexachloride
• WCE tungsten tetrachloride
• WCI2 tungsten dichloride
• WCI3 tungsten oxychlorides
• WOxCly tungsten oxytetrachloride
• the impurities present may include oxygen, chlorine, and nitrogen. It is believed that chlorine is more likely to be removed from the nucleation layer first during deposition of the main conductor layer, such as when a higher temperature is used for deposition. Following chlorine, oxygen and/or nitrogen may be removed thereafter. Without being bound by a particular theory, it is believed that reducing the rate of deposition of the main conductor layer reduces the amount of impurities that leave the nucleation layer.
• Modulating process conditions in operation 309 helps retain the impurity content of the nucleation layer deposited in operation 307 so that the nucleation layer does not completely or mostly convert to metal during operation 309.
• Operation 309 is performed under process conditions such that after operation 309, the resulting nucleation layer composition after operation 309 is a metal to impurity atomic ratio of between about 100:1 and about 1:4, or a Mo to oxygen atomic ratio of between about 100:1 and about 1:4.
• Modulating process conditions can be performed in various ways.
• One way is to perform two or more different sets of ALD cycles such that the first few cycles of deposition do not change the composition of the conductor layer, thereby retaining the impurities incorporated during deposition of the nucleation layer in operation 307.
• the first few cycles may refer to the first to the tenth or the first to the twentieth cycles of ALD in operation 309.
• the first few cycles may refer to the cycles sufficient to deposit up to 30% of the feature with main conductor layer material.
• the conditions during these first few cycles may be modulated to prevent the impurities from escaping the nucleation layer.
• deposition is performed at a lower temperature to reduce the amount of impurities removed from the nucleation layer.
• Example temperatures may be less than 500 ° C, less than 550 ° C, less than 450 ° C, less than 400 ° C, or less than 350 ° C.
• the lower temperature may be used to reduce the amount of nucleation layer converted to an elemental film such that the amount of impurities or non-molybdenum component elements within the nucleation layer is maintained or is greater than about 1% or at least greater than 0%.
• the reducing agent may be hydrogen (3 ⁇ 4).
• the temperature may be the same temperature as used in operation 305 in some embodiments.
• the metal precursor may also be the same or a different precursor than in employed in operation 305. In some embodiments, the same precursor is used, with only the reducing agent changed.
• operation 309 may or may not deposit an appreciable amount of film of the main conductor.
• subsequent sets of ALD cycles may be performed at higher temperatures, such as between about 350°C and about 700°C. Higher temperatures allow for increased deposition rate of the main conductor layer, particularly Mo, as some Mo precursors may be more efficient and more reactive at higher temperatures.
• Another technique is to modulate precursor and reducing agent flows to change the rate of deposition of the main conductor layer.
• Precursor flows may be increased relative to reducing agent flows such that the reducing agent flow is insufficient to convert adsorbed precursor; reducing agent flows may be reduced while keeping precursor flows constant such that there is insufficient reducing agent to convert adsorbed precursors to metal.
• example precursor to reducing agent flow ratios may be between about 1:1000 and about 1:10,000.
• hydrogen reducing agent flow is reduced, example reducing agent to precursor flow ratios may be between about 1:10 and about 1 : 1000.
• a gradient film may be formed using certain disclosed embodiments where the impurity level of the metal-containing film near the dielectric layer or barrier layer is higher while the impurity level decreases in the metal-containing film as the distance from the dielectric layer is increased such that fewer impurities or no impurities are in the last few cycles of metal deposited in the main conductor layer.
• Gradient films may be deposited by using various different sets of ALD cycles during deposition.
• ALD cycles are modulated by changing chamber pressure instead of or in addition to changing temperature and/or precursor flows and/or reactant flows.
• chamber pressure may be reduced to slow the deposition rate of the main conductor layer to reduce the conversion of the nucleation layer to elemental metal.
• Example reduced pressures may be between about 5 and about 20 Torr or at least about 30-80% less than the pressure used for deposition of the nucleation layer.
• Exposure times for gases used to deposit the main conductor layer may vary depending on flow rates. Non-limiting examples of exposure times range from about 0.1 second to about 10 seconds, or between about 0.1 second and about 20 seconds for each gas. For alternating pulses of treatments, each pulse may have any of the above exposure times.
• Exposure times for hydrogen gas exposure may be between about 0.1 second and about 10 seconds.
• hydrogen may be flowed to the substrate for between about 0.1 second and about 10 seconds.
• Exposure times for an oxygen-containing Mo precursor (such as one having a formula MoOxCly) gas exposure may be between about 0.1 second and about 2 seconds.
• an oxygen-containing Mo precursor may be flowed to the substrate for between about 0.1 second and about 2 seconds.
• a purge operation may be performed between alternating pulses.
• Purging may involve flowing argon gas or another inert gas for a particular duration, such as between about 0.1 second and about 5 seconds.
• one cycle of pulses may involve: (1) hydrogen dose for between 0.1 second and 10 seconds, (2) purge using argon gas for between 0.1 second and 5 seconds, (3) MoOxCly dose between 0.1 second and 2 seconds, and (4) purge using argon gas for between 0.1 second and 5 seconds.
• FIG. 3C shows an example process flow diagram for performing certain disclosed embodiments.
• Operation 301 may be the same as operation 301 in Figures 3A and 3B.
• Operation 303b involves performing treatment on an oxide surface of a semiconductor substrate. This oxide surface may be aluminum oxide or silicon oxide in some embodiments and may be performed using any of the techniques described above with respect to operation 303a.
• operation 303b involves exposing the oxide surface to EEFk and WF6.
• a conformal nucleation layer of Mo is deposited by ALD on the treated oxide surface. This may be performed using any of the techniques described with respect to Figure 3B.
• operation 305 involves depositing a MoO x N y film by ALD on a B2H6 and WF6-treated oxide surface.
• a partial main conductor layer is deposited at low temperature by ALD.
• Lower temperature here prevents converting MoOxNy deposited in operation 305 from completely converting to Mo metal.
• Low temperature may be between about less than 500°C.
• operation 319b the rest of the main conductor layer is deposited at high temperature by ALD.
• operation 319b involves deposited bulk Mo metal by using an oxygen-containing Mo precursor and hydrogen at temperatures greater than 540°C.
• boron-containing gas doses may result in exposure of between about 1E16 atoms/cm 2 and about 1E21 atoms/cm 2 of boron.
• fluorine-containing gas doses may result in exposure of between about 1E16 atoms/cm 2 and about 1E21 atoms/cm 2 of fluorine.
• W and/or Mo-containing gas doses may result in exposure of between about 1E16 atoms/cm 2 and about 1E21 atoms/cm 2 of W or Mo respectively.
• FIG 4 shows an example of a zoomed in schematic illustration of a stack 400 having substrate 102 (which may be the same as substrate 102 in Figure 1A) where the dielectric-metal interface 112 between dielectric layer 104 and Mo nucleation layer 108 after deposition of metal layer 110.
• Dielectric-metal interface 112 is the same as dielectric-metal interface 112 in Figure 1A;
• dielectric layer 104 may be the same as dielectric layer 104 in Figures 1A and IB;
• Mo nucleation layer 108 may be the same as nucleation layer 108 in Figures 1A and IB;
• metal layer 110 may be the same as metal layer 110 in Figures 1A and IB.
• Mo nucleation layer 108 includes a gradient such that region 450 of the Mo nucleation layer 108 either has increased amounts of “impurities” or non-molybdenum component elements such as boron, tungsten, fluorine, oxygen, nitrogen, or chlorine, while the remainder of Mo nucleation layer 108 is converted to Mo metal when metal layer 110 is deposited.
• impurities or non-molybdenum component elements such as boron, tungsten, fluorine, oxygen, nitrogen, or chlorine
• metal layer 110 is deposited.
• 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. The process can be performed on multiple deposition stations in parallel.
• a nucleation layer deposition process is performed at a first station that is one of two, five, or even more deposition stations positioned within a single deposition chamber. For example, nucleation layer deposition may be performed at a first station, followed by lower temperature hydrogen reduction of a metal precursor at a second station, followed by high temperature hydrogen reduction of a metal precursor at a third station.
• Each station may have independent temperature control.
• various steps for the process are performed at two different stations of a deposition chamber.
• the substrate may be exposed to NEE in a first station using an individual gas supply system that creates a localized atmosphere at the substrate surface, and then the substrate may be transferred to a second station to be exposed to a metal halide, metal oxyhalide, metal chloride, metal fluoride, or metal oxychloride precursor to deposit the nucleation layer.
• the substrate may then be transferred back to the first station for a second exposure of NEE. Then the substrate may be transferred to the second station for exposure to the metal precursor.
• the substrate may also be exposed to NEE at another station following the first metal chloride or metal oxychloride deposition.
• nucleation layer deposition process is performed at a first station and a higher temperature treatment is performed at a second station such that Nfb is plumbed to the second station for the treatment.
• the third station may be used to deposit bulk.
• multiple chambers are used to perform the methods described herein.
• deposition of the nucleation layer may be performed in a first chamber and deposition of the bulk metal layer performed in a second chamber.
• the two chambers may be connected to a common vacuum chamber such that the substrate can be transferred between them without exposure.
• the chambers are not connected under vacuum, with the substrate exposed to air during transfer. Any oxidation can be reduced in the subsequent processing as described above.
• Figure 5 depicts a schematic illustration of an embodiment of an atomic layer deposition (ALD) process station 500 having a process chamber body 502.
• a plurality of process stations 500 may be included in a tool environment.
• Figure 6 depicts an embodiment of a system 600.
• one or more hardware parameters of process station 500 including those discussed in detail below may be adjusted programmatically by one or more computer controllers 550.
• Process station 500 fluidly communicates with reactant delivery system 50 lfor delivering process gases to a distribution showerhead 506.
• Reactant delivery system 50 l includes a mixing vessel 504 for blending and/or conditioning process gases, such as an oxygen-containing Mo precursor gas, or NFb and/or nitrogen gas, for delivery to distribution showerhead 506.
• One or more mixing vessel inlet valves 520 may control introduction of process gases to mixing vessel 504. Gases are delivered to process chamber body 502 and may react in processing region 507.
• the embodiment of Figure 5 includes a vaporization point 503 for vaporizing liquid reactant to be supplied to the mixing vessel 504 with valve 505 directing reactants from the mixing vessel 504 to the process chamber body 502.
• vaporization point 503 may be a heated vaporizer.
• the saturated reactant vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc.
• delivery piping downstream of vaporization point 503 may be heat traced.
• mixing vessel 504 may also be heat traced.
• piping downstream of vaporization point 503 has an increasing temperature profile extending from approximately 100°C to approximately 150°C at mixing vessel 504.
• liquid precursor or liquid reactant may be vaporized at a liquid injector.
• a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel.
• a liquid injector may vaporize the reactant by flashing the liquid from a higher pressure to a lower pressure.
• a liquid injector may atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. Smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce alength of piping downstream from vaporization point 503.
• a liquid injector may be mounted directly to mixing vessel 504.
• a liquid injector may be mounted directly to distribution showerhead 506.
• a liquid flow controller (LFC) upstream of vaporization point 503 may be provided for controlling a mass flow of liquid for vaporization and delivery to process station 500.
• the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC.
• a plunger valve of the LFC may then be adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.
• PID proportional-integral-derivative
• the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be performed by disabling a sense tube of the LFC and the PID controller.
• Distribution showerhead 506 distributes process gases toward substrate 512.
• the substrate 512 is located beneath distribution showerhead 506 and is shown resting on a pedestal 508.
• Distribution showerhead 506 may have any suitable shape, and may have any suitable number and arrangement of ports for distributing process gases to substrate 512.
• pedestal 508 may be raised or lowered to expose substrate 512 to a volume between the substrate 512 and the distribution showerhead 506. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller 550.
• pedestal 508 may be temperature controlled via heater 510. In some embodiments, the pedestal 508 may be heated to a temperature of between 50°C and 700°C, depending on the chamber and its function in the overall deposition process. For example, some chambers may have a pedestal 508 set to a temperature of between 250°C and about 400°C, such as for deposition of a nucleation layer or initial ALD cycles of a main conductor layer; some chambers may have a pedestal 508 set to a temperature between about 350°C and about 700°C or greater than about 400°C for some deposition of main conductor layers particularly those that are deposited using oxygen-containing Mo precursors such as M0O2CI2.
• pressure control for process station 500 may be provided by butterfly valve 518. As shown in the embodiment of Figure 5, butterfly valve 518 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 500 may also be adjusted by varying a flow rate of one or more gases introduced to the process station 500.
• a position of distribution showerhead 506 may be adjusted relative to pedestal 508 to vary a volume between the substrate 512 and the distribution showerhead 506. Further, it will be appreciated that a vertical position of pedestal 508 and/or distribution showerhead 506 may be varied by any suitable mechanism within the scope of the present disclosure.
• pedestal 508 may include a rotational axis for rotating an orientation of substrate 512. It will be appreciated that, in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers 550.
• instructions for a controller 550 may be provided via input/output control (IOC) sequencing instructions.
• the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe.
• process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase.
• instructions for setting one or more reactor parameters may be included in a recipe phase.
• a first recipe phase may include instructions for setting a flow rate of an inert and/or an NH3 and/or nitrogen reactant gas, instructions for setting a flow rate of a carrier gas (such as argon), instructions for igniting a plasma, and time delay instructions for the first recipe phase.
• a second recipe phase may include instructions for setting a flow rate of an inert and/or metal halide or metal oxyhalide precursor gas, instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for a second recipe phase.
• a third, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the third recipe phase.
• a fourth recipe phase may include instructions for modulating a flow rate of reducing agent gas, instructions for modulating the flow rate of a carrier or purge gas, and time delay instructions for the fourth recipe phase.
• a fifth, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a second metal halide or metal oxyhalide reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the fifth recipe phase. It will be appreciated that these recipe phases may be further subdivided and/or iterated in any suitable way within the scope of the disclosed embodiments.
• the controller 550 may include any of the features described below with respect to system controller 829 of Figure 8.
• FIG. 6 shows a schematic illustration of a line diagram of gas source and line configuration for a single station of an apparatus suitable for performing certain disclosed embodiments. While only one station is depicted, it will be understood that an apparatus may include one or more of these identical, similar, or different modules for processing substrates.
• a single station chamber may be used with a single station to process only one substrate per chamber at a time.
• a single station is a station within a multi-station chamber having two or more stations, such as four stations. While a single station is shown, in some embodiments, multiple stations may be used where gas sources are configured to inlet certain gases to some stations but not other stations.
• process chamber 602 includes a showerhead 606, and a movable pedestal 608 for holding a substrate 612.
• Pressure control for the process chamber 602 may be provided by butterfly valve 618 to keep the process under vacuum.
• the microvolume 607 generated between showerhead 606 and movable pedestal 608 may be modulated by moving the movable pedestal 608 vertically to narrow and widen the space between the showerhead 606 and the movable pedestal 608, thereby changing the partial pressure of various gases in the microvolume 607.
• showerhead 606 may be a dual plenum showerhead as depicted by the two arrows, which shows that gas flows may enter the showerhead using different lines, and may also exit the showerhead using different lines, which may be performed to reduce the likelihood of gases interacting with each other in the lines. That is, in some embodiments, gases selected to be introduced in the same line may be selected such that they do not interact with each other and thus cannot result in formation of excess byproducts or deposited materials within the lines, which may contribute to the formation of defects on the substrate 612. In some embodiments, showerhead 606 may be heated. In some embodiments, showerhead 606 is both heated and is a dual-plenum showerhead.
• Upstream of showerhead 606 is a manifold 686 which may be used to collect gases prior to delivery to the showerhead.
• the manifold is configured such that gases from different lines do not interact with each other but can be separately delivered to the showerhead 606 and can also be controlled with upstream and downstream valves (not shown).
• showerhead 606 may be a single plenum or multi-plenum showerhead.
• a multi-plenum showerhead may be a dual plenum showerhead or triple plenum showerhead.
• a dual plenum showerhead may allow flow of W and/or fluorine-containing gases, Mo-containing precursor, and hydrogen in one plenum while a second plenum is used to flow boron-containing gases, hydrogen, Ntb, and argon.
• Manifold 686 may be configured so that it is close in distance to the showerhead 606 to allow for high pressured volumes of gases to accumulate before a valve is released to deliver high pressure gas to the microvolume 607.
• the configuration shown in Figure 6 includes multiple gas sources, which for purposes of this example, will be referred to as being associated with a particular gas.
• the gas sources may include any suitable gas used as a precursor or reactant for performing certain disclosed embodiments, and the configuration may be selected such that that deliver gases to one line are less likely to interact with each other or cause deposition of films than if mixed with gas sources delivered to the other line, and vice versa.
• three gas sources are shown as being delivered to a single line, and only two separate lines are depicted, one or more gas sources may be delivered to a single line, and two or more separate lines may all be delivered to the manifold 686 before being introduce to the showerhead 606.
• Argon gas source 621a, WF6 gas source 631a, and Mo-containing precursor gas source 641a are included in gas box 682 separate from top plate 684. Argon gas source 621a, WF6 gas source 631a, and Mo-containing precursor gas source 641a are each delivered via its corresponding line to a line 690 to be delivered to the manifold 686.
• B2H6 gas source 651a Diborane (B2H6) gas source 651a, NH3 gas source 661a, and argon gas source 671a are also provided in gas box 682.
• B2H6 gas source 651a, NH3 gas source 661a, and argon gas source 671a are each delivered via its corresponding line to a line 695 to be delivered to the manifold 686.
• Flow of argon from argon gas source 621 a is controlled by argon control valve 620a prior to delivery to an argon charge volume 621b such that argon can accumulate in argon charge volume 621b prior to delivery to the showerhead 606; that is, although the gas box 682 may be physically farther away from the process chamber 602, having the argon charge volume 621b in closer vicinity to the showerhead 606 and having argon outlet valve 620b to control the flow of argon from the argon charge volume 621b allows for better control and increased pressure of argon that can be delivered to the showerhead 606, and therefore delivered to the substrate 612.
• flow of WF6 from WF6 gas source 631a is controlled by WF6 control valve 630a prior to delivery to WF6 charge volume 631b such that tungsten can accumulate in WF6 charge volume 631b prior to delivery to the showerhead 606; that is, although the gas box 682 may be physically farther away from the process chamber 602, having the WF6 charge volume 631b in closer vicinity to the showerhead 606 and having WF6 outlet valve 630b to control the flow of WFe from the WF6 charge volume 631b allows for better control and increased pressure of WF6 that can be delivered to the showerhead 606, and therefore delivered to the substrate 612.
• Mo-containing precursor control valve 640a Flow of Mo-containing precursor from Mo-containing precursor gas source 641a is controlled by Mo-containing precursor control valve 640a prior to delivery.
• Mo-containing precursor can pass through a plasma generated prior to delivery to the process chamber 602.
• Mo-containing precursor is delivered from a remote source.
• Molybdenum-containing precursor outlet valve 640b may be used to control flow after Mo-containing precursor flows through the line towards the showerhead to modulate the flow and increase pressure of the Mo-containing precursor introduced to the showerhead 606.
• Flow of argon gas, WF6, and Mo-containing precursor accumulates via line 690 to manifold 686, where it is delivered to showerhead 606 separate from gases that are delivered via line 695 to prevent interactions between, for example, WF6 and B2H6, which can form tungsten in the lines.
• Flow of B2H6 from B2H6 gas source 651a is controlled by B2H6 control valve 650a prior to delivery of B2H6 to B2H6 charge volume 651b such that B2H6 can accumulate in B2H6 charge volume 651b prior to delivery to showerhead 606.
• gas box 682 may be physically farther away from the process chamber 602 than manifold 686, having B2FF charge volume 65 lb in closer vicinity to showerhead 606 and having B2H6 outlet valve 650b to control the flow of B2H6 from the B2H6 charge volume 651b allows for better control and increased pressure of B2H6 that can be delivered to the showerhead 606 via manifold 686.
• Flow of NFb from NFb gas source 661 a is controlled by NFb control valve 660a prior to delivery of NFb to NFb charge volume 661b, such that NFb can accumulate in NFb charge volume 661b prior to delivery to showerhead 606.
• gas box 682 may be physically farther away from the process chamber 602 than manifold 686, having NFb charge volume 661b in closer vicinity to showerhead 606 and having NFb outlet valve 660b to control the flow of NFb from the NFb charge volume 661b allows for better control and increased pressure of NFb that can be delivered to the showerhead 606 via manifold 686.
• Flow of argon from argon gas source 671 a is controlled by argon control valve 670a prior to delivery to an argon charge volume 671b such that argon can accumulate in argon charge volume 671b prior to delivery to the showerhead 606; that is, although the gas box 682 may be physically farther away from the process chamber 602, having the argon charge volume 671b in closer vicinity to the showerhead 606 and having argon outlet valve 670b to control the flow of argon from the argon charge volume 671b allows for better control and increased pressure of argon that can be delivered to the showerhead 606, and therefore delivered to the substrate 612.
• gas Once gas accumulates and is pressurized in charge volumes and can be controlled via outlet valves, the flow of gases to the manifold 686 can increase, thereby increasing the volume and the pressure of gases introduced to microvolume 607.
• Such embodiments may be particular suitable for processing substrates for forming 3D NAND structures.
• Apparatuses disclosed herein may be set a subatmospheric pressures, such as less than about 760 Torr, or less than about 600 Torr, to keep the substrate under vacuum. Some partial pressures of gases may be delivered up to about 1500 Torr to the substrate for a 300 mm wafer.
• the movable pedestal combined with the charge volume, line, and manifold configuration can collectively cause introduction of gases to the microvolume having a partial pressure less than about 1 Torr to greater than about 90 Torr.
• the partial pressure may be between less than 1 Torr for a 3 Torr chamber with diluted flow, or the partial pressure may be greater than 90 Torr for a 90 Torr chamber with pure flow (without carrier gas).
• FIG. 7A shows a schematic illustration of a line diagram of gas source and line configuration for a single station of an apparatus suitable for performing certain disclosed embodiments.
• “CV” used in drawings herein refer to charge volumes. While only one station is depicted, it will be understood that an apparatus may include one or more of these identical, similar, or different modules for processing substrates.
• a single station chamber may be used with a single station to process only one substrate per chamber at a time.
• a single station is a station within a multi-station chamber having two or more stations, such as four stations. While a single station is shown, in some embodiments, multiple stations may be used where gas sources are configured to inlet certain gases to some stations but not other stations.
• process chamber 702 includes a showerhead 706, and a movable pedestal 708 for holding a substrate 712.
• Pressure control for the process chamber 702 may be provided by butterfly valve 718 to keep the process under vacuum.
• the microvolume 707 generated between showerhead 706 and movable pedestal 708 may be modulated by moving the movable pedestal 708 vertically to narrow and widen the space between the showerhead 706 and the movable pedestal 708, thereby changing the partial pressure of various gases in the microvolume 707.
• showerhead 706 may be a dual plenum showerhead as depicted by the two arrows, which shows that gas flows may enter the showerhead using different lines, and may also exit the showerhead using different lines, which may be performed to reduce the likelihood of gases interacting with each other in the lines. That is, in some embodiments, gases selected to be introduced in the same line may be selected such that they do not interact with each other and thus cannot result in formation of excess byproducts or deposited materials within the lines, which may contribute to the formation of defects on the substrate 712. In some embodiments, showerhead 706 may be heated. In some embodiments, showerhead 706 is both heated and is a dual-plenum showerhead.
• Upstream of showerhead 706 is a manifold 786 which may be used to collect gases prior to delivery to the showerhead.
• the manifold is configured such that gases from different lines do not interact with each other but can be separately delivered to the showerhead 706 and can also be controlled with upstream and downstream valves (not shown).
• showerhead 706 may be a single plenum or multi-plenum showerhead.
• a multi-plenum showerhead may be a dual plenum showerhead or triple plenum showerhead.
• a dual plenum showerhead may allow flow of W- and/or fluorine-containing gases, Mo-containing precursor, and hydrogen in one plenum while a second plenum is used to flow boron-containing gases, hydrogen, NH3, and argon.
• Manifold 786 may be configured so that it is close in distance to the showerhead 706 to allow for high pressured volumes of gases to accumulate before a valve is released to deliver high pressure gas to the microvolume 707.
• the configuration shown in Figure 7 includes multiple gas sources, which for purposes of this example, will be referred to as being associated with a particular gas.
• the gas sources may include any suitable gas used as a precursor or reactant for performing certain disclosed embodiments, and the configuration may be selected such that that deliver gases to one line are less likely to interact with each other or cause deposition of films than if mixed with gas sources delivered to the other line, and vice versa.
• three gas sources are shown as being delivered to a single line, and only two separate lines are depicted, one or more gas sources may be delivered to a single line, and two or more separate lines may all be delivered to the manifold 786 before being introduce to the showerhead 706.
• Argon gas sources and optionally hydrogen gas sources are included in gas box 782a.
• Argon gas sources and optionally hydrogen gas sources deliver argon gas and optionally hydrogen as respectively via its corresponding line to be delivered to the manifold 786.
• Molybdenum precursor gas source is included in gas box 782b.
• a Mo-containing precursor gas is delivered via its corresponding line to be delivered to the manifold 786.
• Ammonia and argon gas sources are included in gas box 782c separate from gas boxes 782a and 782b. Ammonia and argon are flowed from these gas sources via its corresponding line to be delivered to manifold 786.
• a chamber purge top plate may be used as shown in Figure 7B whereby argon gas sources are used.
• Flow of argon gas or optionally hydrogen, Mo-containing precursor, and NFb are separated to reduce interactions between, for example, Mo-containing precursor and hydrogen, which can form Mo in the lines.
• gas Once gas accumulates and is pressurized in charge volumes and can be controlled via outlet valves, the flow of gases to the manifold 786 can increase, thereby increasing the volume and the pressure of gases introduced to microvolume 707.
• Such embodiments may be particular suitable for processing substrates for forming 3D NAND structures.
• Apparatuses disclosed herein may be set a subatmospheric pressures, such as less than about 760 Torr, or less than about 600 Torr, to keep the substrate under vacuum. Some partial pressures of gases may be delivered up to about 1500 Torr to the substrate for a 300 mm wafer.
• the movable pedestal combined with the charge volume, line, and manifold configuration can collectively cause introduction of gases to the microvolume having a partial pressure less than about 1 Torr to greater than about 90 Torr.
• the partial pressure may be between less than 1 Torr for a 3 Torr chamber with diluted flow, or the partial pressure may be greater than 90 Torr for a 90 Torr chamber with pure flow (without carrier gas).
• FIG. 7C shows an example schematic illustration of a line diagram of gas source and line configuration for a single station of an apparatus suitable for performing certain disclosed embodiments.
• “Stn2,” “Stn3,” and “Stn4,” refer to stations that may be those such as process chamber body 502 of Figure 5, process chamber 602 of Figure 6, and process chamber 702 of Figure 7A.
• Gas box 792a includes argon and hydrogen gas sources and gas box 792b includes Mo-containing gas source, which are each delivered to different charge volumes and manifolds of corresponding stations to allow performance of different operations in different stations, each set under different process conditions.
• Hardware such as those described above can be used to implement treatment of memory device wordline dielectric surfaces to boron, fluorine, tungsten-containing species and other non molybdenum component element sources prior to deposition of a nucleation layer such as MoO x N y and/or main conductor layer of elemental Mo.
• These example chambers and systems can be used to deliver B2H6, hydrogen, and argon to semiconductor substrates in either an ALD or CVD mode.
• gas charge volume(s) are used to deliver pulses of gas mixtures having B2H6, hydrogen, argon, nitrogen, and combinations thereof to semiconductor wafers in an ALD mode.
• BH X adsorbed boron hydride
• hardware such as described above can be used to deliver WF6-argon (WF6-Ar) to a semiconductor substrate in ALD or CVD mode.
• gas charge volume(s) are used to deliver pulses of WF6-Ar gas mixtures to semiconductor wafers in ALD mode (W and F exposure). Tungsten hexafluoride exposure can cause tungsten fluoride (WFx) to be adsorbed on the wafer surface.
• the adsorbed WF X can diffuse into the substrate directly or react further.
• hardware is configured to deliver one or more ALD pulses of (B2H6-H2-Ar-N2) gas mixtures alternatively with pulses of (WF6-Ar).
• this causes a WF6 reaction with Fh, ELFk, or BFL which can result in formation of W metal, tungsten boride (WB X ), WF X sub-fluorides and adsorbed F, HF, and adsorbed hydrogen.
• W metal, WB X , WF X , F, and HF are available on the semiconductor surface and can diffuse into the substrate.
• gas delivery hardware can be used to expose a semiconductor surface to pulses of WF6/Ar and B2H6/H2/NH3 through independent WF6-Ar gas charge volumes, B2H6/H2/N2/Ar gas charge volumes, and B/H2/Ar gas charge volumes feeding into a showerhead above a wafer.
• a single plenum showerhead is used.
• a dual plenum showerhead is used.
• a dual plenum showerhead may include WF6/Ar + MoOxCly + H2 in one plenum and B2FL/H2/NFL/Ar in the other, which may be used to avoid upstream reaction of Mo or W precursor with NH3 and B2H6).
• gas charge volumes can be used with continuous trickle purge sweeping control valve outlets.
• WF6/Ar, B2H6/H2/Ar/N2, and B/H2/Ar gas delivery hardware can be used in a single-wafer or multi-station deposition chamber.
• WF6/Ar, B2H6/H2/Ar/N2, and B/H2/Ar gas delivery hardware can be used at a first deposition station in a multi-station deposition chamber.
• one or more chambers can be configured to cause W-F-B exposure on semiconductor substrates.
• One or more chambers may be configured to cause nucleation layer, MoO x N y , or MoOxNy deposition on semiconductor substrates.
• One or more chambers may be configured to cause metallic Mo deposition on semiconductor substrates.
• One or more chambers may be configured to cause deposition of MoO x N y and metallic Mo.
• FIG. 8 is a block diagram of a processing system suitable for conducting deposition processes in accordance with embodiments described herein.
• the system 800 includes a transfer module 803
• the transfer module 803 provides a clean, pressurized environment to minimize the risk of contamination of substrates being processed as they are moved between the various reactor modules.
• Mounted on the transfer module 803 is a multi-station reactor 809 capable of performing ALD depositions as described herein.
• Multi-station reactor 809 may include multiple stations 811, 813, 815, and 817 that may sequentially perform these operations.
• multi-station reactor 809 could be configured such that stations 811 and 813 perform nucleation layer deposition, and stations 813 and 815 perform bulk layer deposition.
• Each deposition station may include a heated wafer pedestal and a showerhead, dispersion plate or other gas inlet.
• the transfer module 803 may be one or more single or multi-station modules 807 capable of performing plasma or chemical (non-plasma) pre-cleans.
• the module may also be used for various other treatments, e.g., reducing agent soaking.
• the system 800 also includes one or more (in this case two) wafer source modules 801 where wafers are stored before and after processing.
• An atmospheric robot (not shown) in the atmospheric transfer chamber 819 first removes wafers from the source modules 801 to loadlocks 821.
• a wafer transfer device (generally a robot arm unit) in the transfer module 803 moves the wafers from loadlocks 821 to and among the modules mounted on the transfer module 803.
• a high temperature showerhead is employed.
• NEE and metal oxychloride or metal chloride precursors can be used in a single plenum showerhead without ammonium chloride (NEECl) condensation.
• dual-plenum showerheads may be used in which NEE is delivered through one plenum and metal chloride or oxychloride precursors can be delivered through the other plenum.
• depositing both metal (nitride) nucleation and pure metal in a single process chamber facilitates the conversion of the as-deposited metal + Ox + NHx + CL nucleation film to pure metal by high-temperature reaction with EE, metal (oxychloride), and their byproducts (HC1, OCl x , Metal-CL, ). This may be done in a multi-station reactor with low-temperature at the first deposition station and low or higher temperatures at subsequent deposition stations as described above.
• the individual deposition stations in a multi-station deposition reactor can be isolated from each other by shaping the showerheads and pedestals such that in a pedestal-up process position, the two assemblies create a small process volume above the wafer and a very narrow gap to isolate the process volume from the main chamber.
• the narrow gap at the edge of the process volume can be augmented with an inert gas purge barrier to make it difficult for gas to diffuse from the main chamber into the process volume.
• the narrow gap at the edge of the process volume can also incorporate a local pumping plenum to prevent process gas from entering the main chamber. This can eliminate the risk of deposition or particle generation in the main chamber.
• the narrow edge gap by itself can eliminate the risk of gas from the main chamber diffusing back into the wafer processing volume such there is no station to station cross talk.
• a system includes two different deposition chambers.
• two deposition chambers may be mounted on transfer module 803.
• each deposition chamber may be a single or multi station chamber.
• two deposition chambers not under common vacuum may be employed.
• a system controller 829 is employed to control process conditions during deposition.
• the controller will typically include one or more memory devices and one or more processors.
• the processor may include a central processing unit (CPU) or computer, analog and/or digital input/output connections, stepper motor controller boards, etc.
• the controller may control all of the activities of the deposition apparatus.
• the system controller executes system control software including sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels if used, wafer chuck or pedestal position, and other parameters of a particular process.
• RF radio frequency
• 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.
• System control logic may be configured in any suitable way.
• 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. Alternatively, the control logic may be hard coded in the controller.
• the computer program code for controlling the deposition 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.
• the controller parameters relate to process conditions such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, 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.
• Signals for monitoring the process may be provided by analog and/or digital input connections of the system controller.
• the signals for controlling the process are output on the analog and digital output connections of the deposition apparatus.
• 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 described herein. 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.
• a controller 829 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 829 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, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency 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.
• temperature settings e.g., heating and/or cooling
• RF radio frequency
• 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.
• the controller 829 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.
• the controller 829 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.
• 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.
• 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.
• the controller may be distributed, such as by including 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.
• 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 physical vapor deposition (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.
• PVD physical vapor deposition
• CVD chemical vapor deposition
• ALD atomic layer etch
• ALE atomic layer etch
• 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.
• the controller 829 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 and flow rates 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.
• Lithographic patterning of a film typically includes 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.
• a tool such as an RF or microwave plasma resist stripper.
• FIG. 9 shows the results from the evaluation at the Mo-oxide interface between the MoOxNy and the dielectric layer.
• a dotted vertical line depicts an approximation of the interface between MoOxNy nucleation layer on the left and dielectric oxide on the right.
• a main conductor layer Mo was deposited on MoOxNy nucleation layer using an oxygen-containing Mo precursor and a reduced hydrogen dose. The results showed low oxygen content at the Mo-oxide interface.
• a main conductor layer Mo was deposited on MoOxNy nucleation layer using an oxygen-containing Mo precursor and an even further reduced (13% less than 910) hydrogen dose.
• Arrow 922 shows the oxide content at the interface being greater than in 910.
• a main conductor layer Mo was deposited on MoOxNy nucleation layer using an oxygen-containing Mo precursor and an even further reduced (26% less than 910) hydrogen dose.
• Arrow 931 shows even greater oxygen content in the main conductor layer Mo than in 910 or 920.
• arrow 932 also shows greater (though still low amounts ol) chlorine at the interface.
• hydrogen dose e.g., flow rate and/or exposure duration

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