Metal film-containing deposition and chamber cleaning

Abstract

Methods of forming a metal-containing layer on a semiconductor substrate are provided that may include performing a plurality of cycles of: (a) flowing a metal-containing precursor together with a reactant into a processing chamber containing a semiconductor substrate; and (b) after (a), flowing a reactant into a processing chamber containing the semiconductor substrate wherein the reactant does not react with the gas phase metal-containing precursor. A method of cleaning a processing chamber is also provided.

Description

Incorporated by Reference The PCT application form is filed concurrently with this specification as a part of this application. Each application to which this application claims the benefit or priority as identified in the concurrently filed PCT application form is incorporated herein by reference in its entirety and for all purposes. Background Art

[0001] In integrated circuit (IC) manufacturing, deposition and etching techniques are used to form patterns of materials, such as for forming metal lines embedded in dielectric layers. Some patterning schemes require conformal deposition of materials, where the deposited layer should follow the contours of raised and / or recessed features on the substrate surface. Atomic layer deposition (ALD) is generally the preferred method for forming conformal films on substrates because ALD relies on the adsorption of one or more reactants (precursors) to the substrate surface, and the subsequent chemical conversion of the adsorbed layer to the desired material. Because ALD uses sequential reactions that occur on the substrate surface, are separated in time, and are generally limited by the amount of adsorbed reactants, the method can provide thin conformal layers with excellent step coverage.

[0002] Chemical vapor deposition (CVD) is another deposition method widely used in semiconductor processing. In CVD, the reaction occurs within the volume of the processing chamber and is not limited by the amount of reactants adsorbed onto the substrate. Therefore, CVD deposited films are generally less conformal than ALD deposited films. CVD is often used in applications where step coverage is less important.

[0003] ALD and CVD may employ plasma to promote the reaction of the deposition precursors, thereby forming the desired film. Methods utilizing plasma are known as plasma enhanced ALD (PEALD) and plasma enhanced CVD (PECVD). Methods that do not employ plasma are known as thermal ALD and thermal CVD.

[0004] Although ALD and CVD are most commonly used for the deposition of silicon-containing films, such as silicon oxide, silicon nitride, and silicon carbide, these methods are also applicable to the deposition of certain metals, notably tungsten and cobalt.

[0005] Some semiconductor manufacturing processes deposit thin films on substrates in a process chamber. The thin film material may also be deposited on the interior surfaces of the process chamber, thereby forming wall deposits. After the wall deposits reach a certain thickness or condition—usually after many wafers have been processed in the process chamber—the deposits may interfere with the deposition process. Therefore, it may be necessary to remove the wall deposits from the interior surfaces of the process chamber.

[0006] The background description provided here is for the purpose of generally presenting the context of the present disclosure. The work of the presently designated inventors is neither explicitly nor implicitly admitted to be prior art against the present disclosure to the extent that it is described in this background section and to aspects of the specification that could not be determined as prior art at the time of filing the application. Summary of the invention

[0007] One aspect relates to a method of forming a metal-containing layer on a semiconductor substrate, wherein the method includes multiple cycles of: (a) flowing a metal-containing precursor and a reactant together into a processing chamber containing the semiconductor substrate; and (b) after (a), flowing the reactant into the processing chamber containing the semiconductor substrate, wherein the reactant does not react with the gas-phase metal-containing precursor.

[0008] In some embodiments, (b) includes reacting the surface-bound metal-containing precursor with a reactant in the absence of a plasma to form a metal-containing layer on the semiconductor substrate.

[0009] In some embodiments, the metal-containing layer formed is a substantially carbon-free molybdenum-containing or tungsten-containing layer having a carbon content of less than about 5 atomic %, wherein the layer is selected from the group consisting of Mo, W, MoN, WN, MoON, WON, MoB, WB, MoSi, WSi layers and combinations thereof.

[0010] In some embodiments, the metal-containing precursor is a halogen-free, carbonyl-free compound comprising at least one ligand bound to a metal selected from the group consisting of molybdenum and tungsten.

[0011] In some embodiments, the halogen-free, carbonyl-free compound does not include metal-carbon bonds and metal-oxygen double bonds.

[0012] In some embodiments, the metal-containing layer is formed to have a carbon content of less than about 2 atomic %.

[0013] In some embodiments, the metal-containing precursor does not include beta-hydrogen atoms.

[0014] In some embodiments, the formed metal-containing layer is selected from the group consisting of Mo, MoN, and MoON.

[0015] In some embodiments, the reactant is hydrogen (H 2 ).

[0016] In some embodiments, the reactants are introduced at a pressure of at least 10 Torr.

[0017] In some embodiments, the reactants are introduced at a pressure of at least 100 Torr.

[0018] Another aspect relates to a method for cleaning a process chamber, wherein the method includes flowing a fluorine-containing substance into the process chamber. The process chamber includes a molybdenum-containing film formed on an inner surface of the process chamber. The method also includes flowing an oxygen-containing substance and a fluorine-containing substance into the process chamber cyclically or simultaneously to clean the process chamber, wherein the molybdenum-containing film is removed from the inner surface of the process chamber.

[0019] In some embodiments, the fluorine-containing species includes nitrogen trifluoride (NF 3 ), molecular fluorine (F 2 ), carbon tetrafluoride (CF 4 ), carbon hexafluoride (C 2 F 6 ), Xenon difluoride (XeF 2 ), fluoromethane (CH 3 F), difluoromethane (CH 2 F 2 ), tetrafluoroethylene (C 2 F 4 ), hexafluoroethane (C 2 F 6 ), octafluoropropane (C 3 F 8 ), sulfur hexafluoride (SF 6 ), fluorine-containing plasma or a mixture thereof.

[0020] In some embodiments, the oxygen-containing species includes oxygen (O 2 ), ozone (O 3 ), carbon monoxide (CO), carbon dioxide (CO 2 ), nitrous oxide (N 2 O), nitrogen dioxide (NO 2 ), oxygen-containing plasma, or a mixture thereof.

[0021] In some embodiments, the method further comprises generating fluorine-containing free radicals in the remote plasma source. The fluorine-containing species comprises fluorine-containing free radicals. The method further comprises generating oxygen-containing free radicals in the remote plasma source. The oxygen-containing species comprises oxygen-containing free radicals.

[0022] In some embodiments, the fluorine-containing species and the oxygen-containing species are cyclically flowed toward the interior surface of the processing chamber.

[0023] In some embodiments, the fluorine-containing species and the oxygen-containing species are co-flowed simultaneously toward the interior surface of the processing chamber.

[0024] In some embodiments, the method further comprises depositing a molybdenum-containing layer on the substrate in the process chamber. After depositing the molybdenum-containing layer on the substrate, a molybdenum-containing film is formed on the inner surface of the process chamber.

[0025] In some embodiments, the molybdenum-containing layer is deposited on the substrate by atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma enhanced chemical vapor deposition (PECVD).

[0026] In some embodiments, the method also includes transferring the substrate out of the processing chamber after depositing the molybdenum-containing layer and before cleaning the processing chamber; and after transferring the substrate out of the processing chamber, adjusting the chamber pressure of the processing chamber to a high pressure regime between about 2 Torr and about 6 Torr or a low pressure regime between about 0.5 Torr and about 2 Torr.

[0027] In some embodiments, the process chamber is cleaned at a first chamber pressure between about 2 Torr and about 6 Torr for a first duration and at a second chamber pressure between about 0.5 Torr and about 2 Torr for a second duration.

[0028] In some embodiments, for the first duration, argon gas flows at a flow rate of about 1 to about 2 standard liters per minute, nitrogen trifluoride gas flows at a flow rate of about 0.5 to about 3 standard liters per minute, and oxygen flows at a flow rate of about 0.5 to about 2 standard liters per minute.

[0029] In some embodiments, for the second duration, argon gas flows at a flow rate of about 0.5 to about 2 standard liters per minute, nitrogen trifluoride gas flows at a flow rate of about 0.5 to about 1.5 standard liters per minute, and oxygen flows at a flow rate of about 0.5 to about 1.5 standard liters per minute.

[0030] In some embodiments, the molybdenum-containing film includes undoped or carbon-doped molybdenum oxide, undoped or carbon-doped molybdenum nitride, undoped or carbon-doped molybdenum oxynitride, or mixtures thereof. In some embodiments, the molybdenum-containing film includes molybdenum metal.

[0031] In some embodiments, the molybdenum-containing film includes carbon, and the oxygen-containing species oxidizes the carbon to remove the carbon from the interior surfaces of the processing chamber.

[0032] In some embodiments, during cleaning of the process chamber, the process chamber is at a temperature of about 200°C to about 650°C.

[0033] In some embodiments, the first duration of cleaning exposes the interior surfaces of the processing chamber to a plasma of a fluorine-containing species and a plasma of an oxygen-containing species, and the second duration of cleaning exposes the interior surfaces of the processing chamber to a fluorine-containing species and an oxygen-containing species in a plasma-free environment.

[0034] In some embodiments, the molybdenum-containing film is formed by reducing a molybdenum oxynitride film by one or more reducing agents, and the one or more reducing agents include nitrogen, argon, hydrogen, ammonia, other hydrogen-containing gases, or mixtures thereof.

[0035] Another aspect relates to a method for cleaning a process chamber, the method comprising providing a process chamber including an inner surface on which a carbon-containing molybdenum nitride film is deposited; exposing the inner surface of the process chamber to fluorine-containing radicals to react with the carbon-containing molybdenum nitride film and remove at least some of the carbon-containing molybdenum nitride film; and exposing the inner surface of the process chamber to oxygen-containing radicals to at least oxidize carbon in the carbon-containing molybdenum nitride film. The fluorine-containing radicals and the oxygen-containing radicals are generated by a remote plasma source fluidically coupled to the process chamber. The fluorine-containing radicals and the oxygen-containing radicals are circulated or co-flowed simultaneously to the inner surface of the process chamber to clean the process chamber.

[0036] In some embodiments, oxidizing the carbon includes generating carbon monoxide, carbon dioxide, or a mixture thereof from the carbon-containing molybdenum nitride film.

[0037] In some embodiments, fluorine-containing radicals and oxygen-containing radicals are generated in a remote plasma source and co-flowed simultaneously into the processing chamber.

[0038] In some embodiments, the process chamber is cleaned at a first chamber pressure between about 2 Torr and about 6 Torr for a first duration and at a second chamber pressure between about 0.5 Torr and about 2 Torr for a second duration.

[0039] In some embodiments, the method further comprises depositing a molybdenum-containing layer on the substrate in the processing chamber. The carbon-containing molybdenum nitride film is formed on the inner surface of the processing chamber. Depositing the molybdenum-containing layer comprises flowing a molybdenum-containing precursor from a first manifold into the processing chamber. The method further comprises removing the carbon-containing molybdenum nitride film from the inner surface of the processing chamber in the processing chamber by flowing fluorine-containing free radicals and oxygen-containing free radicals from a second manifold into the processing chamber.

[0040] Another aspect relates to an apparatus comprising: a processing chamber including a chuck configured to support a substrate; one or more gas outlets coupled to the processing chamber and configured to introduce a fluorine-containing species and an oxygen-containing species into the processing chamber; one or more remote plasma sources fluidly coupled to the processing chamber through one or more gas inlets; one or more second gas outlets coupled to the processing chamber and configured to introduce a molybdenum-containing precursor into the processing chamber; and a controller having at least one processor and a memory. The memory includes computer executable instructions for controlling the at least one processor to: flow the molybdenum-containing precursor into the processing chamber through the one or more second gas outlets to expose the substrate to the molybdenum-containing precursor, wherein a molybdenum-containing film is deposited on an inner surface of the processing chamber; introduce a fluorine-containing source gas into the one or more remote plasma sources and generate a plasma of a fluorine-containing species; introduce an oxygen-containing source gas into the one or more remote plasma sources and generate a plasma of an oxygen-containing species; and flow the plasma of the fluorine-containing species and the plasma of the oxygen-containing species into the processing chamber cyclically or simultaneously through the one or more first gas outlets to remove the molybdenum-containing film from the inner surface of the processing chamber.

[0041] In some embodiments, the apparatus further includes a chamber pressure gauge configured to maintain a first pressure in the processing chamber when a molybdenum-containing precursor flows into the processing chamber, and configured to maintain a second pressure in the processing chamber when a fluorine-containing substance and an oxygen-containing substance flow into the processing chamber, wherein the second pressure is in a low pressure state between about 0.5 Torr and about 2 Torr or in a high pressure state between about 2 Torr and about 6 Torr.

[0042] In some embodiments, the fluorine-containing source gas includes nitrogen trifluoride (NF 3 ), molecular fluorine (F 2 ), carbon tetrafluoride (CF 4 ), carbon hexafluoride (C 2 F 6 ), Xenon difluoride (XeF 2 ), fluoromethane (CH 3 F), difluoromethane (CH 2 F 2 ), tetrafluoroethylene (C 2 F 4 ), hexafluoroethane (C 2 F 6 ), octafluoropropane (C 3 F 8 ), sulfur hexafluoride (SF 6 ) or a mixture thereof.

[0043] In some embodiments, the oxygen-containing source gas includes oxygen (O 2 ), ozone (O 3 ), carbon monoxide (CO), carbon dioxide (CO2 ), nitrous oxide (N 2 O), nitrogen dioxide (NO 2 ) or a mixture thereof.

[0044] Yet another aspect relates to a method of removing a dielectric material from one or more components of a processing chamber, the method comprising: (a) introducing (i) a remote plasma containing a fluorine species and (ii) a thermal etchant into the processing chamber, the thermal etchant undergoing a ligand exchange reaction with a fluorine-containing reaction product of the dielectric material to produce a volatile reaction product, and (b) removing the volatile reaction product from the processing chamber.

[0045] In some embodiments, (a) includes co-flowing the remote plasma with the thermal etchant into the processing chamber.

[0046] In some embodiments, the remote plasma and the thermal etchant may be introduced for about 0.1 to about 600 seconds.

[0047] In some embodiments, (a) includes introducing the remote plasma into the processing chamber at a first time and later introducing the thermal etchant at a second time. The method further includes repeating introducing the remote plasma into the processing chamber at a first time and introducing the thermal etchant at a second time.

[0048] In some embodiments, the remote plasma may be introduced for about 30 to about 300 seconds, and the thermal etchant may be introduced for about 30 to about 300 seconds.

[0049] In some embodiments, (a) further comprises introducing water vapor, methanol, ethanol, or propanol into the process chamber.

[0050] In some embodiments, introducing (i) a remote plasma containing a fluorine species into the processing chamber includes forming a dielectric material containing a fluorine ligand.

[0051] In some embodiments, performing a ligand exchange reaction includes replacing fluorine in a fluorine-containing reaction product with bromine or chlorine.

[0052] In some embodiments, the method further includes, prior to (a), pausing a semiconductor device manufacturing process in the process chamber.

[0053] In some embodiments, the remote plasma is generated by a process gas that includes nitrogen trifluoride, fluorine (F2), tetrafluoromethane, trifluoromethane, difluoromethane, fluoromethane, sulfur hexafluoride, octafluoropropane, octafluorocyclobutane, hexafluorocyclobutene, 1,2,3,3,4-pentafluorocyclobutene-4-yl, fluorine, or a mixture thereof.

[0054] In some embodiments, the thermal etchant includes hydrogen bromide, hydrogen chloride, boron trichloride, or mixtures thereof.

[0055] In some embodiments, the thermal etchant includes boron bromide, phosphorus trichloride, carbon tetrachloride, nitrogen trichloride, or mixtures thereof.

[0056] In some embodiments, the volatile reaction product includes Br or Cl ligands.

[0057] In some embodiments, the chamber temperature is from about 50°C to about 650°C.

[0058] In some embodiments, the chamber pressure is from about 0.5 Torr to about 100 Torr.

[0059] In some embodiments, the etch rate of the dielectric material is from about 500 angstroms / minute to about 1,000 angstroms / minute.

[0060] In some embodiments, the dielectric material includes hafnium oxide, zirconium oxide, tin oxide, aluminum oxide, hafnium nitride, zirconium nitride, aluminum nitride, yttrium oxide, lanthanum oxide, or mixtures thereof.

[0061] In some embodiments, (a) includes exposing the dielectric material in the processing chamber to a remote plasma comprising a fluorine species at a first time and to a thermal etchant at a second time.

[0062] In some embodiments, (a) includes exposing the dielectric material in the processing chamber to a co-flow of the remote plasma and the thermal etchant.

[0063] Yet another aspect relates to a system comprising: a processing chamber configured to perform a device manufacturing operation that deposits a dielectric material on one or more components of the processing chamber; a remote plasma source configured to generate a remote plasma comprising a fluorine-containing species and deliver the remote plasma to the processing chamber; and a controller configured to introduce (a) (i) the remote plasma comprising the fluorine species and (ii) a thermal etchant into the processing chamber, the thermal etchant undergoing a ligand exchange reaction with a fluorine-containing reaction product of the dielectric material to produce a volatile reaction product; and (b) removing the volatile reaction product from the processing chamber.

[0064] In some embodiments, the system further includes a first process gas supply fluidly coupled to the remote plasma source to deliver a process gas to the remote plasma source. The process gas includes nitrogen fluoride, tetrafluoromethane, trifluoromethane, difluoromethane, fluoromethane, sulfur hexafluoride, octafluoropropane, octafluorocyclobutane, hexafluorocyclobutene, 1,2,3,3,4-pentafluorocyclobutene-4-yl, fluorine, or a mixture thereof.

[0065] In some embodiments, the system further includes a second process gas supply source fluidly coupled to the process chamber to deliver a thermal etchant into the process chamber. The thermal etchant includes hydrogen bromide, hydrogen chloride, boron trichloride, or a mixture thereof.

[0066] In some embodiments, the second process gas supply is fluidly coupled to the remote plasma source.

[0067] In some embodiments, the system further includes a vaporization point fluidly coupled to the processing chamber to deliver the thermal etchant into the processing chamber. The thermal etchant includes boron bromide, phosphorus trichloride, carbon tetrachloride, nitrogen trichloride, or a mixture thereof.

[0068] In some embodiments, (a) includes co-flowing the remote plasma with the thermal etchant into the processing chamber.

[0069] In some embodiments, (a) includes introducing a remote plasma into the processing chamber at a first time and later introducing a thermal etchant at a second time.

[0070] In some embodiments, the controller is further configured to control the temperature of chamber (c) to be between about 50°C and about 650°C.

[0071] In some embodiments, the system further includes a vacuum pump to remove volatile reaction products from the process chamber.

[0072] In some embodiments, the controller is further configured to control the pressure of chamber (d) to be between about 0.5 and about 100 Torr.

[0073] In some embodiments, the controller is further configured to control the etch rate of the (e) dielectric material to be between about 500 and about 1,000 angstroms per minute.

[0074] Another aspect is a method for cleaning a process chamber. The method may include heating the process chamber to a predetermined temperature. A plasma stream may be delivered from a remote plasma source through a showerhead into the process chamber to clean the process chamber, wherein the remote plasma source is fluidically coupled to the process chamber through the showerhead and is located upstream of the process chamber. The plasma stream limits the diffusion of gaseous contaminants outside the showerhead.

[0075] In some embodiments, the plasma flow is conveyed in a downward direction or a substantially downward direction.

[0076] In some embodiments, the plasma source includes an inductively coupled plasma, a capacitively coupled plasma reactor, a microwave plasma reactor, a DC plasma reactor, or a laser-created plasma reactor.

[0077] In some embodiments, the plasma flow has a flow rate between about 1 liter / minute and about 50 liters / minute.

[0078] In some embodiments, the plasma stream includes an oxygen-containing species, a fluorine-containing species, and an inert gas.

[0079] In some embodiments, the gaseous pollutant comprises a metal fluoride. For example, the gaseous pollutant comprises aluminum fluoride.

[0080] In some embodiments, the predetermined temperature ranges from about 450°C to about 650°C.

[0081] In some embodiments, the predetermined temperature ranges from 500°C to 600°C.

[0082] In some embodiments, heating the processing chamber includes heating the susceptor.

[0083] In some embodiments, the plasma stream is delivered at a sufficient flow rate to substantially prevent gaseous contaminants from being deposited on the showerhead.

[0084] In some embodiments, the method further includes providing a substrate in a processing chamber. The method further includes depositing a film on the substrate before delivering a plasma stream to clean the processing chamber. Before depositing the film, the processing chamber temperature is maintained at a predetermined temperature. The film is deposited at the predetermined temperature. The method further includes transferring the substrate out of the processing chamber after depositing the film on the substrate and before delivering a plasma stream to clean the processing chamber. Delivering a plasma stream to clean the processing chamber includes removing deposition byproducts from the processing chamber after depositing the film on the substrate.

[0085] Another aspect of the present invention relates to a method for cleaning a processing chamber. The method includes heating a susceptor in the processing chamber to a predetermined temperature and depositing a film on a substrate in a reaction chamber. The method also includes transferring the substrate out of the processing chamber and generating a plasma stream in a remote plasma source. The remote plasma source is coupled to the processing chamber through a showerhead fluid and is located upstream of the processing chamber. The method also includes conveying a plasma stream from the remote plasma source in a downward direction through the showerhead to clean the processing chamber from deposition byproducts formed in the processing chamber during deposition of the film on the substrate. The plasma stream is conveyed at a sufficient flow rate to substantially prevent gaseous contaminants formed in the processing chamber from being deposited on the showerhead.

[0086] In some embodiments, the plasma flow has a flow rate between about 1 liter / minute and about 50 liters / minute.

[0087] In some embodiments, the plasma stream includes an oxygen-containing species, a fluorine-containing species, and an inert gas.

[0088] In some embodiments, the remote plasma source includes an inductively coupled plasma reactor, a capacitively coupled plasma reactor, a microwave plasma reactor, a DC plasma reactor, or a laser generated plasma reactor.

[0089] In some embodiments, the gaseous contaminant comprises a metal fluoride. In some embodiments, the gaseous contaminant comprises aluminum fluoride.

[0090] In some embodiments, the predetermined temperature is in the range of about 450° C. to about 650° C. In some embodiments, the predetermined temperature is in the range of about 500° C. to about 600° C.

[0091] In some embodiments, depositing a film on the substrate includes depositing a silicon-based film on the substrate.Before and during deposition, the susceptor temperature is maintained at a predetermined temperature.

[0092] These and other features of the disclosed embodiments will be described in detail below with reference to the associated drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0093] Figure 1A Examples of molybdenum precursors that may be used in deposition methods according to some embodiments are provided.

[0094] Figure 1B Several specific examples of molybdenum precursors that can be used in the methods according to some embodiments are provided.

[0095] Figure 2 is a process flow diagram of a method of forming a metal-containing film according to some embodiments.

[0096] Figure 3A is a process flow diagram of a method of forming a metal-containing film according to some embodiments.

[0097] Figure 3B and 3C is an example of a timing sequence that may be used to deposit a metal-containing layer.

[0098] Figure 4A A process flow diagram of a method of processing a metal-containing film according to some embodiments.

[0099] Figure 4B A process flow diagram of a method of processing a metal-containing film according to some embodiments.

[0100] Figure 5 is a schematic cross-sectional view of a pMOS device structure including a layer of a substantially carbon-free metal-containing material according to some embodiments.

[0101] Figures 6A-6C is a schematic cross-sectional view of a semiconductor device during fabrication according to some embodiments.

[0102] Figure 7 is a schematic diagram of an apparatus suitable for depositing a film according to some embodiments.

[0103] Figure 8A schematic diagram of a multi-station processing system is shown according to some embodiments.

[0104] Fig. 9 A schematic diagram of a multi-station processing system is shown according to some embodiments.

[0105] Fig.10 A schematic side view with a cross-sectional inset of a fluid mixer is shown according to some embodiments.

[0106] Fig.11A A view of a portion of a dual-plenum showerhead assembly is shown according to some embodiments.

[0107] Fig. 11B A view of a portion of a showerhead faceplate with the showerhead housing detached is shown according to some embodiments.

[0108] Fig.12 Flowchart of an exemplary method for cleaning surfaces within a processing chamber according to some embodiments.

[0109] Fig.13 Flowchart of an exemplary method for cleaning surfaces within a processing chamber according to some embodiments.

[0110] Fig.14 Flowchart of an exemplary method for cleaning interior surfaces of a processing chamber on which a carbon-containing and molybdenum-containing film is deposited, according to some embodiments.

[0111] Fig.15 Flowchart of an exemplary method for cleaning interior surfaces of a processing chamber on which a carbon-containing and molybdenum-containing film is deposited, according to some embodiments.

[0112] Fig.16 is a schematic diagram of an exemplary processing apparatus with a remote plasma source according to some embodiments.

[0113] Fig.17 A flow chart is shown of an example of removing dielectric material according to some embodiments.

[0114] Fig.18 A flow chart is shown of an example of removing dielectric material according to some embodiments.

[0115] Fig.19 A flow chart is shown of an example of removing dielectric material according to some embodiments.

[0116] Fig. 20 A cross section of an exemplary processing chamber using an exemplary remote plasma source according to some embodiments is shown.

[0117] Fig.21A cross-section of one station of a multi-station processing tool using an exemplary remote plasma apparatus is shown in accordance with some embodiments.

[0118] Fig. 22 A flow chart illustrating operation according to an exemplary embodiment is shown.

[0119] Fig.23 A scanning electron microscope (SEM) image of a portion of a ceramic coupon (disposed on a showerhead) after passing through a plasma jet cleaning chamber, according to some embodiments, is shown. DETAILED DESCRIPTION

[0120] In the following description, numerous specific details are set forth to provide a thorough understanding of the embodiments presented. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known processing operations are not described in detail to avoid unnecessarily obscuring the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific embodiments, it should be understood that they are not intended to limit the disclosed embodiments. definition

[0121] The terms "semiconductor wafer," "wafer," "substrate," "wafer substrate," and "partially fabricated integrated circuit" may be used interchangeably. One of ordinary skill in the art will appreciate that the term "partially fabricated integrated circuit" may refer to a semiconductor wafer during any of many stages of integrated circuit fabrication being performed thereon. Wafers or substrates used in the semiconductor device industry typically have a diameter of 200 mm, or 300 mm, or 450 mm. Examples of wafer materials include silicon (Si), gallium arsenide (GaAs), and silicon germanium (SiGe). In addition to semiconductor wafers, other workpieces that may utilize the disclosed embodiments include a variety of articles, such as printed circuit boards, magnetic recording media, magnetic recording sensors, mirrors, optical elements, display devices or components (e.g., backplanes for pixelated display devices), flat panel displays, micromechanical devices, and the like. The workpiece may have a variety of shapes, sizes, and materials.

[0122] As used herein, "semiconductor device manufacturing operations" are operations performed during semiconductor device manufacturing. Typically, the entire manufacturing process includes multiple semiconductor device manufacturing operations, each of which is performed in its own unique semiconductor manufacturing tool, such as a plasma reactor, an electroplating tank, a chemical mechanical planarization tool, a wet etching tool, or the like. Categories of semiconductor device manufacturing operations include subtractive processes (such as etching processes and planarization processes) and additive processes (such as deposition processes (e.g., physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), electrochemical deposition, electroless deposition). In the context of etching processes, substrate etching processes include processes that etch mask layers, or more generally, processes that etch any material layer previously deposited on the substrate surface and / or otherwise left thereon. Such etching processes can etch layer stacks in the substrate.

[0123] In the present invention, the terms "deposit" and "form" are used interchangeably. In addition, the terms "layer", "film" and "thin film" are used interchangeably. It should be understood by those of ordinary skill in the art that "forming" a "layer" in any of the many stages of integrated circuit manufacturing may refer to "depositing" a "film" or "thin film" by one of various film forming methods (e.g., CVD, PECVD, ALD, or PEALD) due to the reduction in feature size in semiconductor devices.

[0124] In the present invention, the terms "clean", "etch" and "remove" are used interchangeably. In the context of etching processes, one of ordinary skill will agree that etching material from the interior surfaces of a processing chamber is equivalent to "cleaning" or "removing" material from the interior surfaces of the processing chamber, thereby leaving the interior surfaces free of material.

[0125] In the present disclosure, the term "remote plasma cleaning" refers to the removal or etching of a layer from an interior surface of a processing chamber using a plasma activated species generated from a remote plasma source. The plasma activated species may include a fluorine-containing species and may actively react with the layer to form non-volatile or volatile reaction products. Nitrogen trifluoride (NF 3 ) or fluorine (F 2 ) may be a process gas supplied to the remote plasma source to generate a fluorine-containing species. The layer may include a metal, a metal alloy, an oxide, a doped or undoped nitride, a doped or undoped carbide, or a mixture thereof.

[0126] In this disclosure, the term "thermal etching" uses a gas phase reagent to react with a substrate surface and chemically and / or thermally etches material from the substrate surface. Thermal etching may also be referred to as "chemical etching". In some cases, thermal etching does not use plasma or free radicals. In some cases, the etching rate of thermal etching is sensitive to temperature and proceeds faster at higher temperatures.

[0127] Methods for depositing metal-containing films (including molybdenum-containing films and tungsten-containing films) on semiconductor substrates are provided. In some embodiments, the films are substantially carbon-free. These methods can be used, for example, to deposit a blanket metal-containing layer on a planar substrate, to deposit a conformal metal-containing layer on a substrate having one or more recessed or protruding features, and to fill recessed features with metal-containing materials. In some embodiments, methods for forming a metal-containing layer on a semiconductor substrate as a liner or diffusion barrier are provided. In some embodiments, methods for forming a substantially metal-containing layer as an electrode layer in a device (e.g., a pMOS device) are provided. In some embodiments, the metal-containing layer can be used as a hard mask.

[0128] The method can be used to deposit a variety of molybdenum-containing and tungsten-containing materials, including but not limited to metallic molybdenum (Mo), molybdenum nitride (MoN), molybdenum boride (MoB), molybdenum silicide (MoSi) and molybdenum oxynitride (MoON), metallic tungsten (W), tungsten nitride (WN), tungsten boride (WB), tungsten silicide (WSi) and tungsten oxynitride (WON), wherein the stoichiometry of these compounds may vary, and the listed chemical formulas do not represent stoichiometry. For example, in various embodiments, MoN can include between about 10 atomic % and about 70 atomic % nitrogen, with the balance being molybdenum.

[0129] The term "substantially carbon-free" refers to a material having a carbon content of less than about 5 atomic %, wherein hydrogen (if present) is excluded from the calculation. In some embodiments, a substantially carbon-free film is provided that includes less than about 3 atomic % carbon, such as less than about 2 atomic % carbon.

[0130] "Metal", such as "metallic molybdenum" or "metallic tungsten" as used herein, refers to a material consisting essentially of a metal (e.g., Mo or W). Other elements (e.g., B, Si, N, or O) may be present in the metal in small amounts (e.g., less than about 15 atomic %, or less than about 10% in total, excluding hydrogen in the calculation).

[0131] Molybdenum nitride (MoN), molybdenum boride (MoB), molybdenum silicide (MoSi), molybdenum oxynitride (MoON), tungsten nitride (WN), tungsten boride (WB), tungsten silicide (WSi), tungsten oxynitride (WON) refer to materials consisting essentially of the listed elements, wherein the stoichiometry of these compounds may vary and is not determined by the listed chemical formula (e.g., MoN does not necessarily represent a 1:1 Mo:N stoichiometry). Other elements (e.g., boron, silicon, nitrogen, phosphorus, etc.) may be present in these compounds in small amounts, such as less than about 10%, about 5%, or about 1% atomic, wherein hydrogen is excluded from the calculation.

[0132] As used herein, the term "semiconductor substrate" refers to a substrate at any stage of semiconductor device manufacturing, which contains semiconductor material anywhere within its structure. It should be understood that the semiconductor material in the semiconductor substrate does not need to be exposed. A semiconductor wafer with multiple layers of other materials (e.g., dielectrics) covering the semiconductor material is an example of a semiconductor substrate. The following detailed description assumes that the disclosed implementation is implemented on a semiconductor wafer (e.g., a 200mm, 300mm, or 450mm semiconductor wafer). However, the disclosed implementation is not limited thereto. The workpiece can have various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces that can utilize the disclosed implementation include various products, such as printed circuit boards, etc.

[0133] Unless otherwise indicated, the term "about" used in reference to a numerical value includes a range of ±10% of the numerical value being described.

[0134] As used herein, the term "alkyl" refers to a saturated substituent containing exclusively carbon and hydrogen atoms. Alkyl groups include straight chain, branched chain and cyclic groups. Examples of straight chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, etc. Examples of branched chain alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl and tert-butyl. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, etc.

[0135] As used herein, the term "fluoroalkyl" refers to an alkyl group containing one or more fluorine substituents. In some embodiments, the fluoroalkyl group exclusively contains fluorine substituents, such as CF 3 , C 2 F 5 , C 3 F 7 The fluoroalkyl group may be in the form of a straight chain, a branched chain or a ring.

[0136] As used herein, the term "alkylsilyl" refers to SiR 3A group wherein at least one R is an alkyl group and each R is independently selected from H and an alkyl group. Alkylsilyl groups include mono-, di- and tri-alkylsilyl groups. Examples of alkylsilyl groups include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl and ethylsilyl.

[0137] As used herein, the term "alkylamino" refers to NR 2 A group wherein at least one R is an alkyl group and each R is independently selected from H and an alkyl group. Examples of alkylamino substituents include dimethylamino and diethylamino substituents.

[0138] The term "alkoxy" refers to an OR group, wherein R is an alkyl group. Examples of alkoxy groups include methoxy, ethoxy, propoxy.

[0139] The term "independently selected" when referring to the selection of R substituents in a molecule containing multiple R groups means that the selection of R substituents on different atoms of the molecule is independent and that the selection of R substituents on an atom with multiple R substituents is also independent.

[0140] As used herein, the term "metal-organic precursor" refers to a metal-containing compound comprising at least one carbon-containing ligand, wherein the compound does not contain a metal-carbon bond. Deposition of metal-containing films

[0141] One aspect of the present invention relates to the deposition of metal-containing films. In the following description, this is mainly described with reference to molybdenum-containing precursors and films as examples. It should be understood that the general description and principles also apply to tungsten-containing precursors and films.

[0142] There are several issues with depositing molybdenum- and tungsten-containing films with desired properties on semiconductor substrates that have hindered the integration of these films into many device manufacturing process flows. Specifically, the use of halide-containing molybdenum and tungsten CVD and ALD precursors can result in unintentional etching of the substrate. Metal-organic and organometallic precursors can eliminate the integration issues in semiconductor processing caused by halide-containing precursors, but because molybdenum and tungsten form very stable carbide phases, the use of carbon-containing precursors often results in significant carbon incorporation into the formed film. Many applications do not require carbon-containing films because the presence of carbon increases the resistivity of the film and reduces the work function of the film.

[0143] Provided are methods for depositing substantially carbon-free molybdenum-containing and tungsten-containing films. These methods can be used to deposit molybdenum-containing and tungsten-containing materials, such as nitrides, borides, silicides, oxynitrides and combinations thereof. Some materials deposited by these methods are used as MOSFET (metal oxide semiconductor field effect transistor) gate electrode materials. Since carbon has a negative impact on the effective work function in early transition metal films, these methods are conducive to producing films suitable for pMOS structures with high work functions (e.g., greater than about 5eV). Some materials deposited by these methods can also be used as ultra-thin low resistivity liners and / or barrier materials. In some embodiments, these methods are carried out in an integrated multi-chamber device including, for example, a deposition chamber and a plasma treatment chamber, wherein a substantially carbon-free film is deposited by CVD or ALD in the absence of plasma in the deposition chamber, and is treated with plasma in the plasma treatment chamber. Plasma treatment can be used to adjust film composition, densify the formed film and / or adjust the effective work function of the formed material.

[0144] The provided method utilizes a halogen-free molybdenum-containing or tungsten-containing metal organic compound as a CVD or ALD precursor, wherein the metal organic compound does not include a metal-carbon (molybdenum-carbon or tungsten-carbon) bond and does not include a carbonyl (CO) ligand. In addition, in some embodiments, the precursor does not include a β hydrogen atom. Deposition is performed by reacting the precursor with a reactant, in some embodiments, in the absence of a plasma. In some embodiments, the reaction is performed at a temperature below about 450° C., for example, below about 420° C. in the absence of a plasma. Careful selection of the precursor advantageously allows avoiding the incorporation of carbon into the formed film in large quantities, and a film having a carbon content of less than about 5 atomic %, for example, less than about 3 atomic %, can be formed. This result is unexpected because the metal organic precursor contains carbon, and it can be expected that due to the high affinity of molybdenum and tungsten for carbon, carbon incorporation into the film will inevitably occur at a high level. However, it is found that when the metal in the precursor does not form a direct bond with carbon and the precursor does not include a carbonyl ligand, carbon incorporation into the film can be avoided, especially if plasma is not used during the deposition reaction. Another factor that can significantly reduce carbon incorporation into the film is the absence of beta-hydrogen in the ligands of the metal-containing precursor. It is believed that beta-hydrogen can lead to low-energy reaction pathways that lead to carbon incorporation into the film, even under low temperature deposition conditions. The absence of beta-hydrogen can stabilize the ligand against decomposition and allow for complete removal of the ligand during subsequent reaction gas exposure.

[0145] Although thermal (non-plasma) deposition is used in many embodiments, the methods described herein can also be used with plasma-based deposition. In a plasma enhanced CVD process (PECVD), a plasma can be generated or delivered to a process chamber to increase the reaction rate of the reagents and can allow deposition to be performed at lower temperatures. The plasma species can also be used to change the resulting film properties. A plasma enhanced ALD (PEALD) cycle can include the following operations: (i) delivery / adsorption of a precursor, (ii) removal of the precursor from the chamber, (iii) delivery of a second reactant and ignition of the plasma, and (iv) removal of byproducts from the chamber.

[0146] In some embodiments, the metal-containing precursor used herein includes a metal (e.g., molybdenum or tungsten) that forms bonds only with elements selected from N, O, and S. In some embodiments, the precursor preferably does not include a beta hydrogen atom. For example, in some embodiments, the precursor includes a carbon bonded to three alkyl groups at the beta position. In some embodiments, the precursor does not include a metal-oxygen double bond (M=O).

[0147] In some embodiments, precursors useful for deposition include halogen-free molybdenum and tungsten complexes with at least one of a monodentate ligand such as an amine, nitrile, imide, nitride, alkoxide, or thiolate, or a polydentate ligand that is bonded to the metal through an atom of N, O, or S. The ligand preferably does not contain a β-hydrogen atom.

[0148] Examples of suitable molybdenum-containing precursors 1-16 are Figure 1A As shown, each L is a carbon-containing ligand that does not form a metal-carbon bond, wherein m is an integer between 1-4, and n is an integer between 1-4. Each R and R1 are independently selected from the group consisting of alkyl, fluoroalkyl and alkylsilyl. In some embodiments, each R1 is selected so that it does not provide β hydrogen atoms. Examples of such R1 substituents include tert-butyl and trialkylsilyl substituents. It is worth noting that in some embodiments, the R substituents on O and S atoms can provide β hydrogen atoms because β hydrogen is not easily eliminated at these positions and is not expected to cause carbon contamination of the resulting film. In addition, in compounds 7, 8 and 14, the β hydrogen on the alkyl-substituted carbon atom adjacent to the anionic nitrogen is also stabilized, and these stabilized compounds are also suitable for the deposition of the provided film.

[0149] In some embodiments, both R and R1 do not provide β hydrogen atoms. In some embodiments, the precursor does not include β hydrogen atoms. For example, in some embodiments, the precursor is any one of compounds 1, 2, 3, 4, 5, 6, 15 and 16, wherein each of R, R1 and L does not provide β hydrogen atoms.

[0150] More specific examples of molybdenum-containing precursors are Figure 1B As shown, structures 17-20 are depicted. It can be seen that molybdenum forms bonds only with N and O atoms, and the precursor does not contain any hydrogen atoms in the β position. The precursor can be synthesized by reacting a molybdenum starting material, such as a halide-containing molybdenum starting material, with a deprotonated ligand. An exemplary synthesis route is described in U.S. Patent Application Publication No. 2018 / 0355484. It is incorporated herein by reference for the purpose of describing the synthesis route.

[0151] The precursors used for deposition are easily vaporized and are stable at the target temperature and pressure. For example, in some embodiments, the precursors are used for deposition reactions at temperatures below about 450° C., such as below about 420° C. In order to maintain appropriate volatility, in many embodiments discussed herein, a precursor having a molecular weight of less than about 450 g / mol, such as less than about 400 g / mol, is selected.

[0152] Substantially carbon-free molybdenum-containing and tungsten-containing materials can be deposited using the precursors described herein by a variety of deposition methods, such as CVD and ALD. An exemplary method for depositing a molybdenum-containing or tungsten-containing layer is as follows: Figure 2 The process is illustrated in the process flow diagram shown in . The process begins at 201, where a halogen-free molybdenum-containing or tungsten-containing precursor is introduced into a process chamber containing a semiconductor substrate. The precursor does not include metal-carbon bonds and preferably does not include beta hydrogen atoms. The precursor can be introduced in vaporized form into an inert gas flow, such as argon, helium, or nitrogen (N 2 ). In operation 203 (which may occur before, after, or during the introduction of the molybdenum-containing precursor 201), the reactants are introduced into the processing chamber containing the substrate. In some embodiments, the introduction of the metal-containing precursor and the reactants is sequential. The chemical nature of the reactants depends on the chemical nature of the target molybdenum-containing or tungsten-containing film. For example, for the deposition of metal (Mo or W), the second reactant is typically a reducing reactant (e.g., H 2 ). Nitrogen-containing reactants (e.g., NH 3 or N 2 H 4 ) for deposition of metal nitrides. In some embodiments, H 2 As a reactant, metal nitrides are deposited, and the required nitrogen can be provided by the ligand. The deposition of metal borides can use boron-containing reactants (such as B 2 H 6 ). A silicon-containing reactant (e.g., SiH 4 or Si 2 H 6 ) forms metal silicide.

[0153] In some embodiments, the precursor and the reactant are allowed to mix in the body of the treatment chamber. In other embodiments, after the metal-containing precursor has been introduced and adsorbed on the surface of the substrate, the treatment chamber is purged and / or evacuated with an inert gas to remove the unadsorbed precursor from the treatment chamber. In some embodiments, the precursor layer on the substrate is adsorption-limited. In other embodiments, before the treatment chamber is purged and / or evacuated, a thicker precursor layer can be formed on the surface of the substrate. Note that when the precursor and the reactant are introduced in sequence, the order of introduction of the precursor and the reactant can be reversed. In some embodiments, the reactant is first introduced and allowed to be adsorbed on the surface of the substrate. Then, the treatment chamber is purged and / or evacuated to remove the second reactant from the volume of the treatment chamber, and then the precursor is introduced.

[0154] With reference to operation 205, the precursor reacts with the reactant to form a substantially carbon-free molybdenum-containing material layer on the substrate, wherein the reaction occurs on the substrate surface and / or in the body of the processing chamber, and preferably in the absence of plasma. For example, in a CVD process, the precursor and the reactant may be introduced into the body of the processing chamber simultaneously, wherein the reaction occurs continuously on the body or surface of the processing chamber. In an ALD process, the reaction occurs only on the surface and is limited by the amount of adsorbed material on the surface (the amount of precursors and / or the amount of adsorbed reactants). For example, the temperature during the reaction process may be between about 20°C and about 600°C. In some embodiments, low temperature deposition is performed at about 450°C or less, such as about 420°C or less, such as between about 200°C and about 400°C, and is particularly advantageous for depositing substantially carbon-free films. The pressure in the processing chamber may be in the range of about 0.1 Torr to about 100 Torr, such as about 1 Torr to about 60 Torr in thermal ALD, such as about 10 Torr.

[0155] After the reaction is completed, the formed molybdenum-containing or tungsten-containing layer can be optionally treated with a second reactant to modify the layer, as shown in operation 207. The processing can be performed to adjust the properties of the layer, such as densifying the layer, changing the composition or electrical properties of the layer, reducing the resistivity of the layer, etc. In some embodiments, the processing is plasma-assisted. For example, the substrate can be treated with a direct plasma (formed in a compartment containing the substrate) or a remote plasma (formed away from the substrate and introduced into the compartment containing the substrate). In some cases, it is preferred to use a remote plasma because it can reduce damage to the substrate. In one of the preferred embodiments, a substantially carbon-free molybdenum-containing or tungsten-containing layer is deposited in the absence of plasma. The substrate is then transferred to a plasma processing chamber without exposing the substrate to an ambient atmosphere, where the substrate is processed with a plasma processing reactant. The selection of plasma processing reactants depends on the desired characteristics of the final layer. It can be, for example, with a plasma-activated H 2 NH 3 、N2 , BH 3 、SiH 4 , Ar, He and their mixtures are used to treat the substrate.

[0156] An example of a surface-based deposition process for forming a molybdenum-containing or tungsten-containing film on a substrate is provided by Figure 3A The process flow chart shown in is illustrated. In operation 301, a metal-containing precursor layer and / or reactants are formed on the surface of the substrate. In some embodiments, the layer is an adsorption limiting layer. Next, in operation 303, the processing chamber is purged and / or evacuated. This step ensures that the precursor and / or reactants are only present on the surface of the substrate and not in the volume of the processing chamber. Next, in 305, the precursor reacts with the reactant on the surface of the substrate. For example, if only the metal-containing precursor is adsorbed on the surface of the substrate in 301, the reactant can be introduced into the processing chamber and allowed to react with the precursor on the surface. If a metal-containing precursor and reactant layer is formed on the surface of the substrate in 301, the processing conditions can be adjusted in 313 (for example, using temperature increase adjustment) to activate the reaction. Next, in 307, the processing chamber is purged and / or evacuated, and in 309, operations 301-307 are repeated to form more metal-containing material. In some embodiments, each cycle of operations 301-307 deposits an average of about In some embodiments, 1-100, such as 2-100 cycles are performed. For example, 1-20, such as 2-20 cycles may be performed. With a high degree of control over the thickness of the layer, a layer having a thickness of about Between, for example The method can be used to form a conformal layer with excellent step coverage.

[0157] Figure 3B and 3C An example of a reactant sequence that can be used to deposit a metal-containing film is shown. Figure 3B In this example, the metal-containing precursor stream is alternated with a reactant. In this example, the reactant is H 2 An inert gas may flow with the metal-containing precursor. In this example, the metal-containing precursor is charged in a charge volume before entering a station containing a substrate on which a film is to be deposited. Figure 3B The station can then be purged with an inert gas. 2 Exposure and subsequent sweeping. The cycle can then be repeated. The heights and lengths of the various operations are provided for illustrative purposes only and do not reflect actual flow rates or times. In some embodiments, H 2The conversion may be significantly longer than the formulation, for example at least 2, 3, 4 or 5 times longer.

[0158] In some embodiments, the process allows reactants (e.g., hydrogen (H)) to 2 ))Executed when co-flow occurs. Figure 3C Show that H 2 Examples of flow throughout the process include during dosing and in subsequent portions of the cycle where metal-containing precursor is not flowing into the station. According to various embodiments, the inert gas may or may not flow during all or part of the cycle.

[0159] Figure 3C The timing shown may be used in some embodiments where H 2 or other reactants do not react with the gas phase metal precursor. For example, H 2 It does not react with certain gas-phase halogen-free metal organic precursors (e.g., bis(tert-butylimino)bis(tert-butyloxy)molybdenum), but reacts with the deposited film. 2 Or other reactants co-flow with the metal-containing precursor, can improve the yield. Further, the longer part of the cycle used to reduce the deposited film and / or control the oxygen, nitrogen and / or carbon content in the film can be used to improve composition control. As described herein, this can be used to adjust the properties of the film, including density, etch rate, resistivity or effective work function.

[0160] In some embodiments, H 2 or other reactants flow at high pressure, such as at least 10 Torr, at least 20 Torr, at least 50 Torr, at least 100 Torr, at least 200 Torr, or at least 250 Torr. Examples of pressures are between 10 and 300 Torr, inclusive. This can be used for non-co-flow (e.g., Figure 3B ) or co-flow (e.g. Figure 3C ) embodiment. High pressure and / or long conversion operation can promote the reduction of the deposited film.

[0161] In some embodiments, the deposited substantially carbon-free molybdenum- and tungsten-containing films are treated with a second reactant to change a property of the film, such as density, resistivity, or effective work function.

[0162] Figure 4A An exemplary process flow diagram for film modification is provided. The process begins at 401, where a molybdenum-containing precursor is reacted with a reactant to form a substantially carbon-free molybdenum-containing film on a substrate in the absence of a plasma. For example, a halogen-free metal-containing organo-molybdenum precursor may be reacted with NH in the absence of a plasma on the substrate surface. 3 or H 2Next, in operation 403, the film is processed with a plasma-activated nitrogen-containing reactant to increase the nitrogen content in the film. For example, a plasma-activated nitrogen-containing reactant may be used to form a MoN layer. 2 The MoN film is processed by a plasma formed in a treatment gas to increase the nitrogen content in the MoN layer. In some embodiments, the nitrogen content is increased by at least 5%, such as at least 10%, by such processing. The increase in nitrogen content in the MoN layer is associated with an increase in work function. In some embodiments, the increase in work function due to such processing is at least 30 meV, such as about 50 meV to about 200 meV. In some embodiments, the MoN material obtained after processing has a nitrogen content of at least 25 atomic % and a work function of at least about 5.0 eV, such as at least about 5.2 eV.

[0163] Figure 4B The processing diagram shown in FIG. 1 illustrates another example of post-processing. In this example, the processing is as follows: Figure 4A As shown, the process begins at 411 by reacting a molybdenum-containing precursor with a reactant to form a substantially carbon-free molybdenum-containing layer. Next, at 413, the formed layer is processed with a plasma-activated hydrogen-containing reactant to reduce the resistivity of the layer. For example, a plasma-activated hydrogen-containing reactant may be used. 2 The plasma formed in the processing gas of H processes the substantially carbon-free molybdenum nitride layer, thereby significantly reducing the resistivity of the film. In some embodiments, the resistivity can be reduced by at least 20%, such as at least 50%, or even at least 80% by such processing. In some embodiments, H 2 The plasma processing reduces the resistivity of the film by at least two, three, or five times. 2 After plasma processing, a film having a resistivity of less than about 1,000 μΩ·cm, such as less than about 800 μΩ·cm, is obtained. In some embodiments, plasma processing (e.g., using a plasma such as H 2 Plasma processing with hydrogen-containing reactants such as H2O2 is further used to densify the deposited film. For example, the density of the film can be controlled by H2O2. 2 The plasma post-processing is increased by at least 20%, such as by at least 40%.

[0164] The provided substantially carbon-free molybdenum-containing and tungsten-containing films can be deposited on a variety of surfaces, including on metals (e.g., copper, nickel, cobalt, tungsten, etc.), dielectrics (e.g., silicon oxide-based dielectrics, silicon nitrides, silicon carbide, metal oxides, metal nitrides, etc.), and on amorphous silicon and crystalline silicon. In some embodiments, the films are deposited as a liner or diffusion barrier.

[0165] In one implementation, the provided substantially carbon-free metal-containing film is used as a MOSFET gate electrode material. In one example, the provided film is integrated into a pMOS device structure. A schematic cross-sectional view of a pMOS device is shown in FIG. Figure 5 As shown. The device (e.g., a transistor) includes a semiconductor layer 501, a source region 501, a drain region 503, and a gate dielectric layer 505 formed above the semiconductor layer 501, and a channel region 515 is defined in the semiconductor layer 501 between the source region 501 and the drain region 503. The semiconductor layer 501 includes a semiconductor material, such as silicon (Si), germanium (Ge), or silicon germanium (SiGe). In one embodiment, the gate dielectric layer 505 includes a high-k dielectric having a dielectric constant greater than about 3.9. For example, the gate dielectric layer 505 may include a high-k material, such as HfO, HfSiO, HfSiON, etc. The gate dielectric layer is typically very thin, for example, with a thickness between about Layers 509, 511, and 513 are disposed over gate dielectric layer 505 and together form a gate electrode. Layer 509 is an optional capping layer formed directly over and in contact with gate dielectric layer 505. In some embodiments, capping layer 509 includes TiN, TaN, and / or WN and has a thickness between about The thickness of the layer 511 above the capping layer 509 is referred to as a work function metal layer. Layer 511 includes a substantially carbon-free molybdenum-containing or tungsten-containing material as provided herein, wherein the material has a high work function, such as a work function greater than about 4.9 eV, greater than about 5.0 eV, or greater than about 5.1 eV. In some embodiments, layer 511 is a substantially carbon-free MoN layer having an effective work function greater than about 5.0. The substantially carbon-free layer is deposited by the ALD or CVD method described herein, and in some embodiments, is additionally processed with a plasma processing reactant to increase its work function. For example, in some embodiments, a nitrogen-containing reactant (e.g., N) activated by a plasma is used. 2 ) The deposited substantially carbon-free molybdenum-containing or tungsten-containing material is processed to increase the nitrogen content and work function of the formed layer. In some embodiments, layer 511 has about or In one implementation, the work function metal layer 511 has a thickness of about In some embodiments, the substantially carbon-free metal-containing layer 511 is deposited directly on the capping layer 509. When the capping layer 509 is not present, the layer 511 can be deposited directly on the gate dielectric layer 507. Finally, the device can optionally include forming one or more conductive layers 513 on the substantially carbon-free metal-containing layer 511. In some embodiments, the conductive layer 513 includes one or more of TiAl, TiAlC, TiAlON, and / or a conductive metal filler (e.g., Mo, Co, or W). Figure 5 The device shown in is a schematic diagram of a partially fabricated device, which does not depict contacts formed to the source and drain regions, which contacts may be formed after forming the electrode layers.

[0166] The provided substantially carbon-free molybdenum- and tungsten-containing layers can be used in planar pMOS devices, FinFET pMOS devices, or gate-all-around (GAA) pMOS devices. Films having work functions greater than 5.0 eV, such as between about 5.0 eV and about 5.5 eV, can be obtained.

[0167] In another application, substantially carbon-free films are deposited as diffusion barriers on substrates containing recessed features such as vias and trenches. Figure 6A-6B A schematic cross-sectional view of an exemplary substrate during fabrication is shown. Fig. 6A , a substrate including a dielectric layer 601 is provided, wherein the dielectric may be a silicon oxide based interlayer dielectric, such as a low-k dielectric, in which a recessed feature 603 is formed. Figure 6B , a substantially carbon-free molybdenum-containing or tungsten-containing film 605 is conformally deposited over dielectric 601, wherein the film acts as a liner for the recessed features. The conformal film is preferably deposited by ALD using the precursors described herein. In some embodiments, film 605 is deposited directly on the dielectric. In other embodiments, one or more additional layers, such as an adhesion layer, may be formed on the dielectric prior to depositing film 605. Next, reference is made to Figure 6C , the recessed features 603 are filled with a metal 607 (e.g., copper or cobalt). The copper or cobalt may be deposited, for example, by electrodeposition onto a thin conformal metal seed layer (not shown). The resulting structure includes a thin layer of a substantially carbon-free molybdenum- or tungsten-containing layer located between the dielectric layer and the metal-filled via or trench. In some embodiments, the thickness of the film 605 is between about between, for example, between about In some embodiments, film 605 is a diffusion barrier that prevents metals such as copper from diffusing into the dielectric. Examples of suitable diffusion barrier materials include MoN and WN. In some embodiments, film 605 is an adhesion layer that can promote adhesion of a conventional diffusion barrier layer (e.g., TaN, TiN) to a conductive seed layer. Examples of suitable adhesion layer materials include Mo and MoN with a relatively low nitrogen content. In many embodiments, it is preferred that film 605 is a low resistivity film, such as a film having a resistivity of less than about 1000 μΩ·cm, such as less than about 500 μΩ·cm. In some embodiments, these films are formed from substantially carbon-free films deposited using plasma post-processing, wherein the post-processing reduces the resistivity of the deposited film. For example, in some embodiments, the deposited film (e.g., MoN or WN film) is used in a hydrogen-containing gas (e.g., H 2 ) is post-processed with the plasma formed in the Figure 4B described.

[0168] Note that while the description provided herein uses molybdenum deposition as an example, similar precursors and conditions can be used to deposit tungsten-containing layers. Figure 1A and 1B A tungsten-containing precursor of the same structure as shown (with molybdenum replacing tungsten). Experimental Example

[0169] Example 1. Use Figure 1B The bis(tert-butylimino)bis(tert-butyloxy)molybdenum (Compound 19) shown as a molybdenum-containing precursor is used to deposit a substantially carbon-free MoN film on a SiO 2 The substrate is exposed to the precursor 19 in the ALD chamber; the chamber is then purged to remove the non-surface-bound precursor, and the substrate is then exposed to the reactant (NH 3 , H 2 or NH 3 and H 2 The precursors are contacted with the substrate (composition of the precursors, in a mixture or sequentially) to react on the surface of the substrate. The process chamber is purged and the precursor and reactant dosing is repeated. Between 1 and 500 ALD cycles are used. Deposition is performed at a temperature between about 300° C. and about 400° C. in the absence of plasma.

[0170] Compositional analysis of the deposited MoN films by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) showed that the carbon content was between 0.2-2 atomic %. For film thicknesses of 2-10 nm, the film resistivity was 500-4,000 μΩ·cm.

[0171] The 2 nm thick film was subjected to H 2The plasma treatment was carried out for 60 seconds. The films were treated at 400 °C in a 2 The 1 nm film measured by TEM had a resistivity of about 600 μΩ·cm, indicating a 1 / 6 reduction in resistivity compared to the initial 3600 μΩ·cm resistivity of the deposited film.

[0172] Example 2 (Comparative) When a molybdenum precursor is treated with a reactant in a plasma, significant carbon incorporation is demonstrated. Figure 1B The MoC film was deposited on SiO2 using bis(tert-butylimino)bis(tert-butyloxy)molybdenum (compound 19) as a molybdenum-containing precursor. 2 The substrate is exposed to the precursor 19 in the ALD chamber; the chamber is then purged to remove the non-surface-bound precursor, and the substrate is then exposed to the precursor 19 in the H 2 The plasma formed in the reaction chamber is contacted to react the precursor on the substrate surface. The treatment chamber is purged and the precursor and reactant dosing is repeated. 200 ALD cycles are used. Deposition is carried out at a temperature of 250°C. Composition analysis of the 15nm film by X-ray photoelectron spectroscopy shows that Mo is 58 atomic % and C is 41 atomic %. It is believed that the high-energy plasma reactants will cause uncontrolled decomposition of organic ligands, thereby easily forming a highly thermodynamically stable molybdenum carbide film. Therefore, it is difficult to obtain a metallic molybdenum-containing film that is substantially free of carbon using plasma reactants.

[0173] Example 3. A 3 nm substantially carbon-free MoN film was subjected to N 2 The plasma was processed for 150 seconds using a mixture of argon and argon. The plasma was generated remotely at a power of 3 kW. MOS capacitors were fabricated and the effective work function was obtained by extrapolating the flat band voltage versus effective oxide thickness curve to zero. The plasma processed films showed an increase in effective work function of approximately 0.08 eV compared to the unprocessed film. Separate experiments to determine the compositional changes due to plasma processing showed that the nitrogen content was approximately 10% higher after plasma processing. Device

[0174] The deposition methods described herein can be performed in a variety of apparatuses. A suitable apparatus includes: a processing chamber having one or more inlets for introducing reactants; a substrate holder in the processing chamber configured to hold the substrate in place during deposition; and optionally, a plasma generating mechanism configured to generate plasma in the process gas. The apparatus may include a controller having program instructions for causing any of the method steps described herein to be performed.

[0175] For example, in some embodiments, the apparatus includes a controller having program instructions including instructions for: introducing a molybdenum or tungsten precursor into a process chamber, wherein the precursor is any of the precursors described herein; and causing a reaction between the precursor and the reactant to form a substantially carbon-free molybdenum- or tungsten-containing material layer on the substrate. The controller may include program instructions for causing any of the methods described herein.

[0176] Figure 7 An example of a deposition apparatus suitable for depositing molybdenum-containing films using the provided methods is shown. Figure 7 Schematically illustrated is an embodiment of a processing station 700 that can be used to deposit materials using ALD and / or CVD (either of which can optionally be plasma enhanced). It should be noted that in many embodiments, plasma enhancement of the deposition reaction is avoided to prevent incorporation of carbon into the film. For simplicity, the processing station 700 is depicted as a stand-alone processing station having a processing chamber body 702 for maintaining a low pressure environment. However, it should be understood that multiple processing stations 700 can be included in a common processing tool environment. In addition, it should be understood that in some embodiments, one or more hardware parameters of the processing station 700, including those discussed in detail below, can be programmatically adjusted by one or more computer controllers.

[0177] The reactant delivery system 701 delivers the process gas to the distribution showerhead 706 of the process station 700. The reactant delivery system 701 includes a mixing vessel 704 for blending and / or conditioning the process gas for delivery to the showerhead 706. One or more mixing vessel inlet valves 720 can control the introduction of the process gas to the mixing vessel 704. Similarly, the showerhead inlet valve 705 can control the introduction of the process gas to the showerhead 706.

[0178] Some metal-containing precursors may be stored in solid or liquid form prior to vaporization at a processing station and subsequently transported to a processing station. Figure 7Embodiments include a vaporization point 703, which is used to vaporize solid reactants to be supplied to a mixing container 704. In some embodiments, the vaporization point 703 can be a heated evaporator. In some embodiments, an inert gas stream flows through a heated solid molybdenum or tungsten precursor at less than atmospheric pressure, or bubbles through a heated liquid molybdenum or tungsten precursor, and transports the precursor vapor to a processing chamber. The precursor vapor produced from such an evaporator will condense in a downstream delivery conduit. Incompatible gases exposed to condensed reactants can produce small particles. These small particles may block the conduit, hinder valve operation, contaminate the substrate, etc. Some methods for dealing with these problems involve cleaning and / or evacuating the delivery conduit to remove residual reactants. However, cleaning the delivery conduit can increase the processing station cycle time and reduce the processing station throughput. Therefore, in some embodiments, the delivery conduit downstream of the vaporization point 703 can be heat traced. In some examples, the mixing container 704 can also be heat traced. In one non-limiting example, the conduit downstream of the vaporization point 703 has an increasing temperature profile from about 100° C. to about 200° C. at the mixing vessel 704 .

[0179] Showerhead 706 distributes processing gas toward substrate 712. Figure 7 In the illustrated embodiment, substrate 712 is positioned below showerhead 706 and is shown as resting on pedestal 708. It should be appreciated that showerhead 706 may have any suitable shape and may have any suitable number and arrangement of ports to distribute process gases to substrate 712. Although not explicitly shown, in some embodiments, showerhead 706 is a dual-chamber showerhead including at least two types of conduits, wherein a first type of conduit is dedicated to the delivery of a molybdenum-containing or tungsten-containing precursor vapor, and a second type of conduit is dedicated to a reaction (e.g., H 2 NH 3 In these embodiments, the molybdenum-containing precursor and the reactant are not allowed to mix in the conduit before entering the processing chamber, and if delivered to the chamber continuously, the conduit is not shared.

[0180] In some embodiments, microvolume 707 is located below showerhead 706. Performing ALD and / or CVD processing in a microvolume rather than in the entire volume of the processing station can reduce reactant exposure and sweep or purge time (i.e., the duration of the sweep or purge operation), can reduce the time to change processing conditions (e.g., pressure, temperature, etc.), can limit the exposure of the processing station robot to the processing gas, etc. Exemplary microvolume sizes include, but are not limited to, volumes between 0.1 liters and 2 liters. This microvolume also affects productivity throughput. When the deposition rate per cycle decreases, the cycle time is also reduced. In some cases, for a given target film thickness, the effect of the cycle time reduction is significant enough to increase the overall yield of the module.

[0181] In some embodiments, the pedestal 708 can be raised or lowered to expose the substrate 712 to the microvolume 707 and / or to change the volume of the microvolume 707. For example, during a substrate transfer phase, the pedestal 708 can be lowered so that the substrate 712 can be loaded on the pedestal 708. During a deposition process phase, the pedestal 708 can be raised to position the substrate 712 within the microvolume 707. In some embodiments, the microvolume 707 can completely surround the substrate 712 and a portion of the pedestal 708 to form an area of ​​high flow impedance during the deposition process.

[0182] Optionally, the pedestal 708 can be lowered and / or raised during portions of the deposition process to adjust the process pressure, reactant concentration, etc. within the microvolume 707. In one case where the process chamber body 702 is maintained at a base pressure during the deposition process, lowering the pedestal 708 can allow the microvolume 707 to be evacuated. Exemplary ratios of microvolume to process chamber volume include, but are not limited to, volume ratios between 1:700 and 1:10. It should be understood that in some embodiments, the pedestal height can be programmatically adjusted by a suitable computer controller.

[0183] Although the exemplary microvolume variations described herein relate to a height-adjustable pedestal, it should be understood that in some embodiments, the position of the showerhead 706 can be adjusted relative to the pedestal 708 to change the volume of the microvolume 707. In addition, it should be understood that the vertical position of the pedestal 708 and / or showerhead 706 can be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 708 may include a rotation axis for rotating the orientation of the substrate 712 in a suitable direction. It should be understood that in some embodiments, one or more of these exemplary adjustments can be performed programmatically by one or more appropriate computer controllers.

[0184] Back to Figure 7In the embodiment shown, the showerhead 706 and the base 708 are in electrical communication with the RF power source 714 and the matching network 716 for powering the plasma. In other embodiments, a device without a plasma generator is used to deposit a molybdenum-containing or tungsten-containing film using the provided method. In some embodiments, the energy of the plasma can be controlled by controlling one or more of the pressure of the processing station, the concentration of the gas, the radio frequency (RF) source power, the RF source frequency, and the plasma power pulse timing. For example, the RF power source 714 and the matching network 716 can be operated at any suitable power to form a plasma with a component of a desired free radical substance. Similarly, the RF power source 714 can provide RF power of any appropriate frequency. In some embodiments, the RF power source 714 can be configured to control a high-frequency RF power source and a low-frequency RF power source that are independent of each other. Exemplary low-frequency RF frequencies may include, but are not limited to, frequencies between 50kHz and 700kHz. Exemplary high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8MHz and 2.45GHz. It should be understood that any suitable parameters may be adjusted discretely or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power may be pulsed intermittently to reduce ion bombardment of the substrate surface relative to a continuously powered plasma. In some embodiments, the plasma is used to post-treat the deposited substantially carbon-free film.

[0185] In some embodiments, the plasma can be monitored in situ by one or more plasma monitors. In one case, the plasma power can be monitored by one or more voltage and current sensors (e.g., VI probes). In another case, the plasma density and / or the concentration of the process gas can be measured by one or more optical emission spectrometer sensors (OES). In some embodiments, one or more plasma parameters can be adjusted programmatically based on the measurement results from such an in-situ plasma monitor. For example, an OES sensor can be used in a feedback loop to provide programmatic control of the plasma power. It should be understood that in some embodiments, other monitors can be used to monitor plasma and other processing characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0186] In some embodiments, plasma can be controlled via input / output control (IOC) sequencing instructions. In one example, instructions for setting the plasma conditions of the plasma treatment stage may be included in the corresponding plasma activation recipe stage of the deposition process recipe. In some cases, the treatment recipe stages may be arranged in sequence so that all instructions for the deposition treatment stage are executed simultaneously with the treatment stage. In some embodiments, instructions for setting one or more plasma parameters may be included in the recipe stage before the plasma treatment stage. For example, the first recipe stage may include instructions for setting the flow rate of an inert gas and / or a reactant gas, instructions for setting a plasma generator to a power set point, and time delay instructions for the first recipe stage. The second subsequent recipe stage may include instructions for enabling a plasma generator and time delay instructions for a second recipe stage. The third recipe stage may include instructions for disabling a plasma generator and time delay instructions for a third recipe stage. It should be understood that these recipe stages may be further subdivided and / or iterated in any suitable manner within the scope of the present disclosure.

[0187] In some embodiments, the susceptor 708 can be temperature controlled by a heater 710. Additionally, in some embodiments, pressure control of the deposition processing station 700 can be provided by a butterfly valve 718. Figure 7 In the embodiment shown in FIG. 7 , butterfly valve 718 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, the pressure control of the process station 700 can also be adjusted by changing the flow rate of one or more gases introduced into the process station 700.

[0188] Figure 8 A schematic diagram of an embodiment of a multi-station processing tool 800 is shown, which has an inbound load lock 802 and an outbound load lock 804, one or both of which may include a remote plasma source. Such a tool can be used to process substrates using the methods provided herein. At atmospheric pressure, a robot 806 is configured to move a wafer from a box loaded by a wafer boat 808 into the inbound load lock 802 via an atmospheric port 810. The wafer is placed on a pedestal 812 in the inbound load lock 802 by the robot 806, the atmospheric port 810 is closed, and the load lock is evacuated. When the inbound load lock 802 includes a remote plasma source, the wafer can be exposed to a remote plasma treatment in the load lock before being introduced into the processing chamber 814. In addition, the wafer can also be heated in the inbound load lock 802, for example to remove moisture and adsorbed gases. Next, a chamber transfer port 816 leading to the processing chamber 814 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal at the first station shown in the reactor for processing. Although Figure 8The illustrated embodiment includes a load lock, but it will be appreciated that in some embodiments, wafers may be allowed to enter the processing station directly.

[0189] The depicted processing chamber 814 contains four processing stations, Figure 8 In the embodiment shown, the stations are numbered 1 to 4. Each station has a heated susceptor (shown as 818 for station 1) and a gas line inlet. It should be understood that in some embodiments, each processing station can have different or multiple uses. Although the processing chamber 814 depicted includes four stations, it should be understood that the processing chamber according to the present disclosure can have any suitable number of stations. For example, in some embodiments, the processing chamber can have five or more stations, while in other embodiments, the processing chamber can have three or fewer stations.

[0190] Figure 8 Also depicted is an embodiment of a wafer handling system 890 for transferring wafers within the processing chamber 814. In some embodiments, the wafer handling system 890 can transfer wafers between various processing stations and / or between a processing station and a load lock. It should be understood that any suitable wafer handling system can be used. Non-limiting examples include a wafer turntable and a robot for handling wafers. Figure 8 Also depicted is an embodiment of a system controller 850 for controlling processing conditions and hardware states of the processing tool 800. The system controller 850 may include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. The processor 852 may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0191] In some embodiments, the system controller 850 controls all activities of the processing tool 800. The system controller 850 executes system control software 858 stored in the mass storage device 854, loaded into the memory device 856, and executed on the processor 852. The system control software 858 can include instructions for controlling timing, mixing of gases, chamber and / or station pressures, chamber and / or station temperatures, purge conditions and timing, wafer temperature, RF power level, RF frequency, substrate, pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by the processing tool 800. The system control software 858 can be configured in any suitable manner. For example, various processing tool component subroutines or control objects can be written to control the operation of the processing tool components necessary to perform various processing tool processes according to the disclosed methods. The system control software 858 can be encoded in any suitable computer-readable programming language.

[0192] In some embodiments, the system control software 858 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of the ALD process may include one or more instructions for execution by the system controller 850. Instructions for setting the processing conditions for the ALD process stage may be included in the corresponding ALD recipe stage. In some embodiments, the ALD recipe stages may be arranged sequentially so that all instructions for the ALD process stage are executed simultaneously with the process stage.

[0193] In some embodiments, other computer software and / or programs stored on the mass storage device 854 and / or the memory device 856 associated with the system controller 850 may be employed. Examples of programs or program segments used for this purpose include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

[0194] The substrate positioning program may contain program code for processing tool components used to load a substrate into the pedestal 818 and control the spacing between the substrate and other parts of the processing tool 800.

[0195] The process gas control program may include code for controlling gas composition and flow rate and optionally for flowing gas into one or more process stations prior to deposition to stabilize the pressure in the process station. The process gas control program may include code for controlling gas composition and flow rate within any disclosed range. The pressure control program may include code for controlling the pressure within the process station by adjusting, for example, a throttle valve in an exhaust system of the process station, gas flow into the process station, etc. The pressure control program may include code for maintaining the pressure in the process station within any disclosed pressure range.

[0196] The heater control program may include code for controlling the flow of current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (e.g., helium) to the substrate. The heater control program may include instructions for maintaining the temperature of the substrate within any disclosed range.

[0197] The plasma control program may include code for setting the RF power level and frequency applied to the processing electrodes in one or more processing stations, for example using any RF power level disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0198] In some embodiments, there may be a user interface associated with the system controller 850. The user interface may include a display screen, a graphical software display of apparatus and / or processing conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, and the like.

[0199] In some embodiments, the parameters adjusted by the system controller 850 may relate to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF power level, frequency, and exposure time), etc. These parameters may be provided to the user in the form of a recipe that may be entered using the user interface.

[0200] Signals for monitoring the process may be provided from various process tool sensors by analog and / or digital input connections of the system controller 850. Signals for controlling the process may be output via analog and / or digital output connections of the process tool 800. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (e.g., manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with the data from these sensors to maintain process conditions.

[0201] Any suitable chamber may be used to implement the disclosed embodiments. Exemplary deposition equipment includes, but is not limited to, Product range of devices, facts The product line is available from Lam Research Corp. (Fremont, California). Two or more stations can perform the same function. Similarly, two or more stations can perform different functions. Each station can be designed / configured as needed to perform a specific function / method.

[0202] In some embodiments, the apparatus includes a process chamber for depositing films that are substantially free of carbon, and a different process chamber configured for processing these films with a remote plasma to densify the films, reduce the resistivity of the films, or increase their work function. In some embodiments, the apparatus is programmed or configured to transfer a substrate from a deposition process chamber to a plasma processing process chamber without exposing the substrate to ambient atmosphere, moisture, or oxygen.

[0203] Fig. 9is a block diagram of a processing system suitable for performing thin film deposition processing according to certain embodiments. System 900 includes a transport module 903. The transport module 903 provides a clean, pressurized environment to minimize the risk of contamination when the substrate being processed moves between the various reactor modules. According to certain embodiments, mounted on the transport module 903 are two multi-station reactors 909 and 910, each reactor capable of performing ALD and / or CVD. Reactors 909 and 910 may include multiple stations 911, 913, 915 and 917, which may perform operations sequentially or non-sequentially according to the disclosed embodiments. These stations may include a heated pedestal or substrate support, one or more gas inlets or nozzles, or a dispersion plate.

[0204] Mounted on the transfer module 903 may also be one or more single or multi-station modules 907 that are capable of performing plasma or chemical (non-plasma) pre-cleaning, or any other processing associated with the disclosed method. In some cases, the module 907 may be used for various processing, such as preparing a substrate for a deposition process. The module 907 may also be designed / configured to perform various other processing, such as etching or polishing. The system 900 also includes one or more wafer source modules 901, in which wafers are stored before and after processing. An atmospheric manipulator (not shown) in the atmospheric transfer chamber 919 may first move the wafer from the source module 901 to the load lock 921. The wafer transfer device (typically a robot arm unit) in the transfer module 903 moves the wafer from the load lock 921 to the modules mounted on the transfer module 903 and between the modules mounted on the transfer module 903.

[0205] In various embodiments, the system controller 929 is used to control the process conditions during the deposition process. The controller 929 will generally include one or more memory devices and one or more processors. The processor may include a CPU or calculator, analog and / or digital input / output connections, a stepper motor controller board, and the like.

[0206] The controller 929 can control all of the activities of the deposition apparatus. The system controller 929 executes system control software, which includes a set of instructions for controlling timing, mixtures of gases, chamber pressure, room temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored in a memory device associated with the controller 929 may be employed in some embodiments.

[0207] There will typically be a user interface associated with the controller 929. The user interface may include a display screen, a graphical software display of the apparatus and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, and the like.

[0208] The system control logic can be configured in any suitable manner. In general, the logic can be designed or configured in hardware and / or software. The instructions for controlling the drive circuit can be hard-coded or provided as software. The instructions can be provided by "programming". Such programming is understood to include any form of logic, including hard-coded logic in digital signal processors, application-specific integrated circuits, and other devices with specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that can be executed on a general-purpose processor. The system control software can be encoded in any suitable computer-readable programming language.

[0209] The computer program code for controlling the precursor flow and other processes in the process sequence can be written in any commonly used computer readable programming language: for example, assembly language, C, C++, Pascal, Fortran or others. The compiled object code or script is executed by the processor to perform the tasks identified in the program. Also as indicated, the program code can be hard-coded.

[0210] Controller parameters are related to process conditions such as, for example, process gas composition and flow rate, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of recipes and can be input using the user interface. Signals for monitoring the process can be provided through analog and / or digital input connections of the system controller 929. Signals for controlling the process are output through analog and digital output connections of the deposition apparatus 900.

[0211] 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 the operation of chamber components necessary to perform deposition processes (and in some cases other processes) in accordance with the disclosed embodiments. Examples of programs or program segments for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0212] In some implementations, the controller 929 is part of a system, which can be part of the above examples. Such a system can include a semiconductor processing device, which includes one or more processing tools, one or more processing chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronic devices for controlling their operations before, during, and after processing semiconductor wafers or substrates. The electronic device can be referred to as a "controller", which can control various components or subcomponents of one or more systems. Depending on the processing requirements and / or the type of system, the controller 929 can be programmed to control any of the processes disclosed herein, including controlling process gas delivery, 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, position and operation settings, wafer transfer in and out of tools and other transfer tools and / or load locks connected to or connected to a specific system through an interface.

[0213] In a broad sense, a controller can be defined as an electronic device with various integrated circuits, logic, memory and / or software that receives instructions, issues instructions, controls operations, enables cleaning operations, enables endpoint measurements, etc. The integrated circuit can include a chip in the form of firmware that stores program instructions, a digital signal processor (DSP), a chip defined as an application specific integrated circuit (ASIC), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions can be instructions transmitted to the controller in the form of various separate settings (or program files), which define operating parameters for performing specific processing on or for a semiconductor wafer or system. In some embodiments, the operating parameters can be part of a recipe defined by a process engineer for completing one or more processing steps during the preparation of one or more (kinds) of layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0214] In some implementations, the controller may be part of or coupled to a computer that is integrated with, coupled to, or connected to the system or a combination thereof via a network. For example, the controller may be in the "cloud" or all or part of a wafer fab host system, thereby allowing remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, check the history of past manufacturing operations, check trends or performance criteria for multiple manufacturing operations, change parameters of a current process, set processing steps to follow the current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide a processing recipe to the system via a network, which may include a local network or the Internet. The remote computer may include a user interface that allows input or programming of parameters and / or settings, which are then transmitted from the remote computer to the system. In some examples, the controller receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be for the type of process to be performed and the type of tool to which the controller is configured to connect or control the tool type. Thus, as described above, the controller may be distributed, for example, by including one or more discrete controllers that are networked together and work toward a common goal (e.g., processing and control as described herein). An example of a distributed controller for these purposes may be one or more integrated circuits on the chamber that communicate with one or more remote integrated circuits (e.g., at a platform level or as part of a remote computer) that are combined to control the processing within the chamber.

[0215] Example systems may include, but are not limited to, plasma etch chambers or modules, deposition chambers or modules, spin cleaning chambers or modules, metal plating chambers or modules, cleaning chambers or modules, chamfer edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, CVD chambers or modules, ALD chambers or modules, atomic layer etch (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing system that may be associated with or used in the preparation and / or manufacture of semiconductor wafers.

[0216] As described above, depending on one or more processing steps to be performed by the tool, the controller can communicate with one or more of the following: other tool circuits or modules, other tool components, combination tools, other tool interfaces, adjacent tools, adjacent tools, tools located throughout the factory, a host computer, another controller, or tools used in material handling to move containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing facility. Fluid mixer

[0217] In another aspect, a fluid mixer for mixing a carrier gas and a metal-containing precursor prior to delivery to a process chamber is provided. The fluid mixer is suitable for improving the uniformity of delivery of the metal-containing precursor to a showerhead and can be used for any metal-containing precursor, including but not limited to the molybdenum and tungsten precursors described herein.

[0218] Examples of molybdenum-containing precursors for ALD or CVD of molybdenum or molybdenum-containing materials include the precursors described above as well as MoF 6 、MoCl 5 , molybdenum dioxide dichloride (MoO 2 Cl 2 ), molybdenum oxychloride (MoOCl 4 ) and molybdenum hexacarbonyl (Mo(CO) 6 ). Formula Mo x O x H z Other Mo oxyhalides where H is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)), and x, y, and z are any numbers greater than zero, can form stable molecules. These include molybdenum tetrafluoride (MoOF 4 ), molybdenum dioxide dibromide (MoO 2 Br 2 ) and molybdenum oxide iodide MoO 2 I and Mo 4 O 11 I. Organometallic precursors may also be used with examples including Mo precursors having cyclopentadienyl ligands. Other examples include the formula Mo 2 L n wherein each L is independently selected from an amidate ligand, an amidinate ligand and a guanidinate ligand, and wherein n is 2-5. 2 L nThe precursor includes multiple molybdenum-molybdenum bonds (e.g., double bonds or any multiple bonds with a bond order of 2-5). Further examples include heteroleptic molybdenum compounds containing halides (i.e., compounds with different types of ligands). Specific examples of such precursors are compounds including molybdenum, at least one halide that forms a bond with molybdenum, and at least one organic ligand having any of the elements N, O, and S, wherein an atom of any of these elements forms a bond with the molybdenum. Examples of suitable organic ligands that provide nitrogen or oxygen bonding include amidinates, amidates, iminopyrrolidinates, diazadienes, beta-iminoamides, alpha-imino alkoxides, beta-amino alkoxides, beta-diketiminates, beta-ketoiminates, beta-diketonates, amines, and pyrazolates. Examples of suitable organic ligands that provide sulfur bonding include thioethers, thiolates, dithiolenes, dithiolates, and a-imino thiolenes. These ligands may be substituted or unsubstituted. In some embodiments, the ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The organic ligands can be neutral or anionic (e.g., monoanionic or dianionic), and the platinum can be in various oxidation states, such as +1, +2, +3, +4, +5, and +6.

[0219] When metal precursor vapor is delivered to shower head, it is usually with carrier gas flow (such as N2, argon, helium, etc.), mixes to provide the precursor of desired concentration.This mixing is usually performed in a fluid mixer, and this mixer has the outlet connected to shower head.It should be noted that in many embodiments, metal precursor vapor is delivered to mixing tube together with the first carrier gas flow, and is then diluted by the second carrier gas flow.For the sake of clarity, this more concentrated metal-containing precursor flow in the carrier gas will be referred to as metal precursor flow, and the carrier gas flow not including the precursor will be referred to as carrier gas flow.

[0220] One of the problems that may be encountered in the mixing process of these flows is the uneven delivery of metal precursors to the nozzles. For example, the peripheral area near the edge of the nozzle can receive a metal precursor flow with a lower concentration than the more central part of the nozzle. This in turn may lead to an uneven distribution of the metal precursor in the processing chamber. A fluid mixer is provided, which is configured to improve the uniformity of mixing of the metal precursor with the carrier gas. In some embodiments, the fluid mixer delivers the metal precursor so that the concentration of the metal precursor at all nozzle outlets differs by no more than 2 volume %. In the described implementation, the fluid mixer includes: (a) an outer fluid conduit, which includes: an inlet for allowing the carrier gas to enter the outer fluid conduit, a mixing zone for mixing the carrier gas with the metal-containing precursor, and an outlet for removing the carrier gas mixed with the metal-containing precursor from the outer fluid conduit; (b) an inner fluid conduit at least partially located inside the outer conduit, wherein the inner fluid conduit includes an inlet for allowing the metal-containing precursor to enter the inner fluid conduit, and an outlet configured to release the metal-containing precursor into the outer fluid conduit, wherein the distance from the inlet of the inner fluid conduit to the inlet of the outer fluid conduit is greater than the distance from the outlet of the inner fluid conduit to the inlet of the outer fluid conduit, thereby supporting opposite flows of the carrier gas and the metal-containing precursor in the fluid mixer, wherein the distance refers to the distance in the z direction.

[0221] The fluid mixer described in Fig.10 , which shows a schematic side view of the fluid mixer 1001, and a cross-sectional view of a portion showing the inlet of the inner fluid conduit. Fig.10, the outer fluid conduit 1003 has a generally cylindrical shape and has an inlet (not shown) at the top of the outer fluid conduit 1003 for allowing a carrier gas to enter. The inlet of the outer fluid conduit is connected to a carrier gas source. The flow of the carrier gas (without the metal precursor) is indicated by a downward arrow 1005. The outlet 1007 of the outer fluid conduit 1003 is located opposite to the inlet at the bottom of the outer fluid conduit 1003. The outlet is suitable for connecting to a nozzle (not shown) and delivering a mixed stream 1009 containing a metal precursor and a carrier gas to the nozzle. The inner fluid conduit 1011 is (at least partially) located inside the outer fluid conduit and has a coaxial portion with the outer fluid conduit 1003. The inner fluid conduit 1011 has an inlet 1013, which is configured to allow a metal precursor from a metal precursor source to enter. The metal precursor is usually mixed with a carrier gas and flows into the inner fluid conduit, but the metal precursor concentration of this flow is higher than the target concentration of the nozzle and needs to be further diluted with a carrier gas in the mixing tube. The flow of metal precursor entering the inner fluid conduit 1011 is shown by arrow 1015. The outlet 1017 of the inner fluid conduit 1011 is configured to release the metal-containing precursor flowing upward as shown by arrow 1019 into the outer fluid conduit 1003, where the metal precursor flow mixes with the carrier gas flow. It is worth noting that the distance 1018 in the z-direction (vertical direction) from the inlet 1013 of the inner fluid conduit 1011 to the outlet 1017 of the inner fluid conduit 1013 is less than the distance from the inlet 1013 of the inner fluid conduit 1011 to the inlet (not shown) of the outer fluid conduit 1003 located at the top of the outer fluid conduit 1003. This configuration can support the relative flow of the carrier gas (shown by the downward arrow 1005) and the metal-containing precursor (shown by the upward arrow 1019), so that the mixing of the flows is more effective.

[0222] The outer fluid conduit 1003 has a mixing zone 1021 in which the metal-containing precursor and the carrier gas flow are allowed to mix unrestricted to form a mixed flow, as shown by the downward arrow 1023. It is important to provide a mixing zone of sufficient length because the mixing that occurs in this zone will affect the uniformity of the precursor concentration in the nozzle. In some embodiments, the length of the mixing zone L1 in the z direction is at least about 102 mm, such as at least about 127 mm. For example, at a flow rate of 1,000 sccm and an outer tube outer diameter of approximately 41 mm, a mixing zone of about 102 mm long provides sufficient mixing. In some embodiments, the ratio of the length L1 of the flow mixing zone in the z direction to the inner diameter of the outer fluid conduit 1003 is at least about 2, such as at least about 3.

[0223] In some embodiments, for example, Fig.10In the embodiment shown in , the outer fluid conduit 1003 also has a restriction 1025, wherein the mixed flow 1023 is confined to a plurality of narrower channels located inside the outer fluid conduit 1003. For example, in some embodiments, the restriction comprises six narrower non-connected channels that convey the mixed flow to the outlet 1007. The restriction has a length L2 in the z direction (e.g., between about 1 mm and about 5 mm). The mixed flow within the restriction is represented by a downward arrow 1027.

[0224] In some embodiments, the fluid mixer 1001 is designed so that the outlet 1017 of the inner fluid conduit 1013 includes a flow diverter 1029, which is configured to divert the metal-containing precursor flow before the metal-containing precursor flow is mixed with the carrier gas flow in the outer fluid conduit 1003, so that the diverted metal-containing precursor flow maintains a velocity component in the outer fluid conduit in the opposite direction to the velocity direction of the carrier gas flow.

[0225] The fluid diverter can include two parallel flow limiting plates, which are configured to limit the flow of the metal-containing precursor between the plates. For example, the upward flow of the metal-containing precursor can be turned in the lateral direction, making a turn less than 90 degrees, thereby retaining the velocity component opposite to the carrier gas flow in the downward direction. Maintaining this opposite velocity component is an important factor in improving mixing efficiency. In some embodiments, the flow diverter 1029 includes a delivery tee with multiple (e.g., six) evenly spaced radial openings.

[0226] In some implementations, the ratio of the inner diameter of the outer fluid conduit to the inner diameter of the inner fluid conduit is between about 1.5 and about 10, such as between about 1.5 and about 5. In a specific example, the inner diameter of the outer fluid conduit is about 40.5 mm, and the inner diameter of the inner fluid conduit is about 4.8 mm. In some implementations, the total length of the fluid mixer in the z direction is between about 76 mm and about 510 mm, such as between about 102 mm and about 508 mm, such as about 124.5 mm. The fluid mixer can be made of various materials compatible with the metal-containing precursor, including aluminum, stainless steel, and ceramic. Multi-chamber sprinkler

[0227] On the other hand, a multi-plenum showerhead for delivering a plurality of reactants to a processing chamber is provided. The showerhead can be used for delivering any combination of reactants, including but not limited to molybdenum-containing and tungsten-containing precursors described herein. In some embodiments, the multi-plenum showerhead includes (a) a showerhead panel, which includes a first plurality of conduits for delivering a first reactant and a second plurality of conduits for delivering a second reactant, wherein the first plurality of conduits are configured to be fluidically isolated from the second plurality of conduits; and (b) a showerhead housing positioned around the periphery of the showerhead panel, wherein the showerhead panel can be releasably attached to the showerhead panel. Because the showerhead is configured to have a removable panel, the cleaning of the panel, which usually contains very small channels, can be efficiently performed. For example, the panel can be cleaned with a solvent, such as by immersing the panel in a solvent and / or cleaning the channel with a solvent. In some embodiments, the panel includes an opening having a diameter of about 1 mm or less, such as an opening of 0.5 mm or less, which can be effectively cleaned after the panel is removed from the base.

[0228] In some embodiments, the multi-plenum showerhead is a dual-plenum showerhead, wherein the first plurality of conduits are configured to deliver reactants (e.g., H 2 NH 3 、SiH 4 , B 2 H 6 , hydrocarbons, etc.) and a second plurality of conduits are configured to deliver a metal-containing precursor (e.g., a molybdenum- or tungsten-containing precursor).

[0229] Fig.11A A view of a portion of a dual plenum showerhead 1101 is shown, comprising a panel 1103 and a housing 1105 attached to the panel 1103, wherein the housing 1105 is positioned around the periphery of the panel 1103. The top of the panel 1103 contains a large number of openings for conduits 1107, which are configured to deliver metal-containing precursors through the panel. The metal-containing precursors are delivered downwardly to the panel and are limited on the sides by the showerhead housing. The panel 1103 also contains a plurality of fluid conduits 1106, wherein the fluid conduits 1106 are not in fluid communication with the metal precursor conduits 1107. The conduits 1106 are configured to receive reactants (e.g., H) from a reactant delivery ring 1109 located in the housing 1105. 2 NH 3 The reactant is transported to the treatment chamber by the reactant conduit 1106. The reactant conduit 1106 has a plurality of outlets (not shown) at the bottom of the panel 1103, which are configured to transport the reactant to the treatment chamber. In some embodiments, these outlets have a diameter of about 1 mm or less or 0.5 mm or less. The outlets of the metal precursor conduit and the reactant conduit lead to the treatment chamber. The conduit is designed so that the metal precursor and the reactant do not contact each other in the body of the shower head 1101.

[0230] While the showerhead panel 1103 is used to distribute and deliver the metal precursor and reactant to the processing chamber without mixing them, the showerhead housing 1105 is used to limit the volume for the metal precursor above the showerhead panel 1103 and accommodate a delivery ring 1109 configured to deliver the reactant to the reactant conduit 1106 of the showerhead panel 1103. The flow of the reactant passing through is shown by arrows 1110. The housing can also include a heater 1111, which can be annular and embedded in a recess formed in the housing. The housing typically also includes a ledge 1113 for supporting an O-ring or other seal for sealing the showerhead to the metal precursor delivery line. Fig. 11B Shown is a portion of the sprayhead panel 1103 and the sprayhead housing 1105 after the sprayhead panel 1103 has been released from the housing 1105 (e.g., for cleaning). This view shows the removable fasteners 1115 that fit into openings in the housing 1105 and are configured to removably attach the housing 1105 to the panel 1103 using the openings around the perimeter of the panel 1103.

[0231] The showerhead faceplate can be made of any material that is compatible with the metal-containing precursor, such as aluminum, stainless steel, and ceramic materials. Further implementation plans

[0232] The apparatus and processes described herein can be used in conjunction with photolithographic patterning tools or processes, e.g., for preparing or manufacturing semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, though not necessarily, these apparatus and processes will be used or operated together in a common manufacturing facility. Photolithographic patterning of films typically involves some or all of the following steps, each of which enables multiple available tools: (1) applying photoresist to a workpiece, i.e., a substrate, using a spin coating or spray coating tool; (2) curing the photoresist using a hot plate or oven or UV curing tool; (3) exposing the photoresist to visible light or UV, or eUV, or x-rays using a tool such as a wafer stepper; (4) developing the resist to selectively remove the resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern to 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. Process chamber cleaning

[0233] Also provided herein is a method for cleaning the interior of a processing chamber and / or components in a processing chamber. Some semiconductor device manufacturing operations may involve various deposition processes to deposit various films to form integrated circuits and related devices by various methods (including CVD, PECVD, ALD or PEALD). The result of the deposition process is that various materials are not only deposited on the substrate on which the various materials are to be deposited, but also deposited on the inner surface of the processing chamber where the deposition process is performed. Therefore, deposits from various materials are formed on the inner surface of the processing chamber, including the inner wall of the processing chamber or the surface of one or more components in the processing chamber, and the deposited materials may accumulate over time to form films or particles. In addition, the deposited materials may be dissolved, separated, thermally desorbed or evaporated by subsequent processing in the processing chamber, thereby contaminating the substrate or the features formed on the substrate. This contamination is a cause of low production yield / yield or equipment reliability problems. Accumulated materials are regularly removed to avoid contamination of the processing chamber.

[0234] The methods described herein can be used to remove contaminants after depositing metal-containing films, including those deposited by the methods described above. They can also be used to remove contaminants caused by depositing other types of films, including dielectric films as described further below.

[0235] One method of removing contaminants deposited on an inner surface in a processing chamber may involve introducing a plasma containing a fluorine (F) species. Free radicals may be one or more species generated in a plasma, and the plasma activated species may include free radicals. Free radicals may be referred to as free radical species. The species may include a source gas, a plasma (e.g., free radicals, ions, charged neutral species), or a mixture thereof. In some embodiments, the plasma may include free radicals, ions, charged neutral species, or a mixture thereof. In one example, the fluorine-containing species includes a fluorine-containing source gas, a fluorine-containing plasma (e.g., free radicals, ions, charged neutral species), or a mixture thereof. In another example, the oxygen-containing species includes an oxygen-containing source gas, an oxygen-containing plasma (e.g., free radicals, ions, charged neutral species), or a mixture thereof.

[0236] For this type of cleaning, one or more source gases (eg, cleaning gases) (including nitrogen trifluoride (NF 3 ), fluorine (F 2 ), carbon tetrafluoride (CF 4 ), carbon hexafluoride (C 2 F 6 ), octafluoropropane (C 3 F 8), other fluorine-containing compounds (i.e., fluorine-containing reactants) or mixtures thereof) can be supplied to a plasma source. The plasma source can be an inductively coupled plasma reactor, a capacitively coupled plasma reactor, a microwave plasma reactor, a DC plasma reactor, or a laser-generated plasma reactor. The plasma generated from the plasma source can include one or more free radicals and can flow into the processing chamber to remove accumulated materials deposited on the inner surface of the processing chamber. Cleaning of Molybdenum-containing membranes

[0237] Molybdenum nitride (MoN x , 0<X≤2) can be used for gate electrode stacks in transistor structures. Gate electrode stacks based on molybdenum nitride films can provide suitable work functions for metal oxide semiconductor field effect transistors (MOSFETs). Some applications (including fin field effect transistor (finFET) structures and dynamic random access memory (DRAM) bit structures) may involve depositing MoN x film to form a gate electrode stack. MoN x It can also be used for film patterning due to its selectivity in wet etching.

[0238] MoN x The film may be deposited using one or more molybdenum-containing precursors by any suitable deposition method, such as ALD, PEALD, CVD, or PECVD. The deposition method may include the above referenced Figures 1A-11B The cleaning methods are not limited to films deposited by these methods, and any of them can be used in films deposited by any suitable method. x Clean the chamber after the membrane.

[0239] MoN x The film can be formed not only on the surface where MoN x The film may be formed on the substrate, and may also be formed on the inner surface of the process chamber. The inner surface includes the inner wall of the process chamber, or the surface of any component that may be located in the process chamber. For example, the inner surface may include the inner wall surface of the process chamber, the outer surface of the showerhead, the outer surface of the susceptor, the surface of the gas pipeline, the surface of the nozzle, the surface of the lift pin, and the surface of other chamber components. x After the film is formed, MoN may also be deposited on the inner surface of the process chamber. x and other materials that may have been deposited or etched in the processing chamber, which may be periodically cleaned from the interior surfaces to avoid further contamination of the substrate during subsequent semiconductor manufacturing processing. Processing Flow

[0240] Fig.12A flow chart 1200 of an exemplary method for cleaning the interior surface of a processing chamber according to some embodiments is shown. In optional operation 1210, a substrate may be provided in a processing chamber for depositing a molybdenum-containing layer on the substrate. In some embodiments, a substrate having one or more features may be transferred in the processing chamber. For example, the one or more features on the substrate may be one or more partially fabricated integrated circuits. Prior to optional operation 1210, the substrate may be cleaned to remove any undesirable layers deposited on the substrate.

[0241] In optional operation 1220, a molybdenum-containing layer may be deposited in one or more features on the substrate. The molybdenum-containing layer may include metallic molybdenum, molybdenum nitride (MoN x ), molybdenum oxynitride (MoO x N y , 0≤x≤1, y=1-x), molybdenum oxide (MoO x , 0≤x≤1), molybdenum oxycarbonitride (MoN x O y C z , 0≤x≤1, 0≤y≤1, y=1-x) or a mixture thereof. In some embodiments, the molybdenum-containing layer may be doped or undoped. For example, the molybdenum-containing layer may be doped with carbon.

[0242] The molybdenum-containing layer can be deposited using a molybdenum-containing precursor in a vapor deposition process, such as ALD, PEALD, CVD or PECVD. In general, the molybdenum-containing precursor can include molybdenum in a wide range of oxidation states from 0 to +6. In some embodiments, the molybdenum compound has molybdenum in a low oxidation state of +3, +4 and +5. The provided method is particularly useful for depositing molybdenum-containing materials from halogen-containing molybdenum-containing compounds, because silicon-containing reactants can contribute to halogen removal, but halogen-free molybdenum-containing precursors can also be used. Suitable molybdenum-containing precursors include molybdenum halides and oxyhalides, such as fluorides, chlorides, bromides, oxyfluorides, oxychlorides and oxybromides, wherein molybdenum can be in any oxidation state from +2 to +6.

[0243] The molybdenum-containing precursor used to deposit the molybdenum-containing layer may include the precursors discussed above. In some embodiments, the molybdenum-containing precursor includes a molybdenum halide precursor and a molybdenum oxyhalide precursor. Examples of molybdenum halide precursors include molybdenum chloride. Molybdenum chloride is represented by the formula MoCl x , wherein x is 2, 3, 4, 5 or 6, and comprises molybdenum dichloride (MoCl 2 ), molybdenum trichloride (MoCl 3 ), molybdenum tetrachloride (MoCl 4 ), molybdenum pentachloride (MoCl 5 ) and molybdenum hexachloride (MoCl 6 In some embodiments, MoCl is used. 5 or MoCl 6Although the description mainly refers to MoCl x Precursors are generally used, but in other embodiments, other molybdenum halide precursors may be used. The molybdenum halide precursor is of the formula MoX z , wherein X is a halogen (e.g., fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)), and z is 2, 3, 4, 5, or 6. MoX z Examples of precursors include molybdenum fluoride (MoF 6 In some embodiments, MoX without fluorine is used. z Precursors are used to prevent fluorine etching or incorporation. In some embodiments, bromine-free and / or iodine-free MoX z Precursors to prevent etching or bromine or iodine incorporation.

[0244] The molybdenum oxyhalide precursor is of the formula MoO y X z , wherein X is a halogen (fluorine (F), chlorine (Cl), bromine (Br) or iodine (I)), y and z are values ​​greater than 0, such that MoO y X z Examples of molybdenum oxyhalide precursors include molybdenum oxytetrafluoride (MoOF 4 ), molybdenum oxychloride (MoOCl 4 ), molybdenum dioxide dichloride (MoO 2 Cl 2 ), molybdenum dioxide dibromide (MoO 2 Br 2 ) and molybdenum iodide (MoO 2 I and Mo 4 O 11 I).

[0245] In some embodiments, the precursor has a molecular weight of less than about 450 g / mol, such as less than about 400 g / mol.

[0246] In some embodiments, the molybdenum-containing precursor has the formula MoX n Y m , wherein X is a chalcogen (e.g., oxygen or sulfur), Y is a halogen (e.g., fluorine, chlorine, bromine, or iodine), n is 0, 1, or 2, and m is 2, 3, 4, 5, or 6. Examples of halogen-containing molybdenum-containing precursors include, but are not limited to, MoCl 5 、Mo 2 Cl 10 、MoO 2 Cl 2 and MoOCl 4 Another example of a halogen-containing molybdenum-containing precursor is MoF 6 .

[0247] In some embodiments, the molybdenum-containing precursor includes a carbonyl ligand. An example of a carbonyl-containing precursor is Mo(CO) 6 .

[0248] Different molybdenum-containing precursors are described in U.S. patent application No. 62 / 816,648, filed on March 11, 2019, and entitled “Precursors for deposition of molybdenum-containing films,” and U.S. patent application No. 63 / 366,888, filed on June 23, 2022, and entitled “Remote plasma low temperature atomic layer deposition of metals,” the entire contents of each of which are incorporated herein by reference for all purposes.

[0249] In some embodiments, the molybdenum-containing layer can be formed in one or more features of the substrate by ALD. In some embodiments, thermal ALD can be used to form the molybdenum-containing layer. In thermal treatment, plasma is not used. ALD is a surface-mediated deposition technique in which reactant batches are introduced into the processing chamber in sequence. For example, the molybdenum-containing layer can be deposited using a sequential batching of one or more cycles of molybdenum-containing precursors and one or more co-reactants. In one example, the molybdenum-containing precursor can be pulsed at elevated temperatures and adsorbed on the substrate to form the molybdenum-containing layer. The molybdenum-containing precursor may include hydrocarbons, and the carbon in the molybdenum-containing precursor may not be completely removed when the molybdenum-containing layer is deposited. Therefore, carbon may remain in the molybdenum-containing layer deposited on the inner surface. For example, the molybdenum-containing layer may be undoped or doped with carbon. For example, carbon may be contained in the molybdenum-containing layer as a contaminant or dopant. In another example, carbon may be a very thin layer present on the surface of the molybdenum-containing layer.

[0250] In some embodiments, the molybdenum-containing layer may include molybdenum oxynitride (MoO x N y ). For example, MoO x N y The layer can be formed by using a molybdenum halide or molybdenum oxyhalide precursor as a precursor and oxygen (O 2 ) and nitrogen (N 2 ) is formed by flowing as a co-reactant. MoO x N yThe layer can be formed by flowing a molybdenum precursor as described in U.S. Patent Application No. 62 / 816,648, filed on March 11, 2019, and entitled “precursors for deposition of molybdenum-containing films” (the entire contents of which are incorporated by reference for all purposes). A mixture of oxygen and nitrogen having a predetermined mixing ratio can be introduced into the process chamber to react with the precursor to deposit MoO. x N y The substrate may be heated to about 150° C. to about 650° C. The processing chamber may be pressurized to a pressure between about 1 Torr and about 200 Torr. In some embodiments, the MoO may be reduced by flowing one or more reducing agents (e.g., nitrogen, argon, hydrogen, ammonia, other hydrogen-containing gases, and mixtures thereof) at a temperature of about 150° C. to about 650° C. x N y MoN x membrane.

[0251] In operation 1230, a molybdenum-containing film is formed on the inner surface of the treatment chamber. The molybdenum-containing film may constitute an undesirable molybdenum-containing material formed on the inner surface (e.g., chamber wall, top plate, shower head, substrate support, gas line, and other areas of the treatment chamber). In operation 1220, a molybdenum-containing precursor may flow onto the substrate to form a molybdenum-containing layer. In some embodiments, depending on the parameters used to deposit the molybdenum-containing layer, one or more molybdenum-containing precursors may also be delivered to a position other than the substrate in the treatment chamber, such as a chamber wall, a remote area away from the substrate, or a surface of one or more chamber components (e.g., a pedestal, shower head, gas line, etc.). The one or more molybdenum-containing precursors will form a deposit in the form of a layer or particles. When one or more molybdenum-containing precursors are deposited in the treatment chamber or as a certain number of substrates deposit a molybdenum-containing layer, the deposit may accumulate over a period of time. After a certain number of substrates are deposited with a molybdenum-containing layer, or after a certain deposition or processing time in the treatment chamber is met, the substrate can be removed from the treatment chamber to clean the inner surface of the treatment chamber. In one example, a molybdenum-containing layer may be formed according to operation 120. In some embodiments, the presence of the molybdenum-containing film on the inner surface prior to cleaning the inner surface may be attributed to the molybdenum-containing layer remaining from the etching operation. In some embodiments, the molybdenum-containing film on the inner surface of the processing chamber may include a carbon-containing and molybdenum-containing layer, such as undoped or carbon-doped MoO x , undoped or carbon-doped MoN x , undoped or carbon-doped MoO x N yor platinum metal. After the substrate is removed from the processing chamber, the chamber pressure can be adjusted to a certain pressure range before cleaning the inner surface of the processing chamber. In some embodiments, the processing chamber pressure range is between about 2 Torr and about 6 Torr, between about 2.5 Torr and about 5.5 Torr, between about 3 Torr and about 5 Torr, between about 0.5 Torr and about 2 Torr, between about 0.5 Torr and about 1.8 Torr, or between about 0.5 Torr and about 1.6 Torr.

[0252] After the molybdenum-containing film is formed on the inner surface of the processing chamber, a fluorine-containing source gas and an oxygen-containing source gas may be supplied to a plasma source to generate a plasma including fluorine-containing species and oxygen-containing species in operation 1240. As described below, the fluorine-containing source gas and the oxygen-containing source gas may be supplied in a circulating flow or a co-flow.

[0253] In some embodiments, the fluorine-containing source gas may include nitrogen trifluoride, fluorine (F 2 ), molecular fluorine, carbon tetrafluoride, carbon hexafluoride, xenon difluoride, fluoromethane, difluoromethane, tetrafluoroethylene, hexafluoroethane, octafluoropropane, sulfur hexafluoride, or a mixture thereof. In some embodiments, the oxygen-containing source gas may include oxygen, ozone, carbon monoxide, carbon dioxide, nitrous oxide, nitrogen dioxide, or a mixture thereof. In some embodiments, the one or more source gases may be supplied together with an inert gas (i.e., a carrier gas), such as argon, helium, neon, krypton, xenon, or a mixture thereof. One or both of the fluorine-containing source gas and the oxygen-containing source gas may be mixed with an inert gas. Each of the fluorine-containing source gas and the oxygen-containing source gas may be ignited to generate a plasma including a fluorine-containing substance (e.g., a free radical) and an oxygen-containing substance (e.g., a free radical). The fluorine-containing free radical may be a fluorine-containing substance generated by the plasma, and may also include ions, charged neutral substances, or a mixture thereof. The oxygen-containing free radical may be an oxygen-containing substance generated by the plasma, and may also include ions, charged neutral substances, or a mixture thereof.

[0254] The plasma may be generated in situ at a processing area adjacent to where the deposition or etching operation occurs. Alternatively, the plasma may be generated from a remote plasma source. The remote plasma source may be located upstream of the processing chamber and may be separated from the processing chamber by a showerhead. In some embodiments, the remote plasma source may be a subunit that is removably bolted to the side of the plasma processing chamber. The remote plasma source may be configured so that the plasma from the remote plasma source may flow in a horizontal or vertical direction, depending on the position of the remote plasma source relative to the showerhead and / or the pedestal. In one example, the plasma may be supplied laterally to the showerhead from a remote plasma source disposed on one side of the processing chamber.

[0255] The fluorine-containing source gas and the oxygen-containing source gas may be provided to the processing chamber cyclically or simultaneously (co-flow), as will be described below. Circular Flow

[0256] In operation 1240, a fluorine-containing source gas and an oxygen-containing source gas may be cyclically supplied to a plasma source to generate a fluorine-containing species and an oxygen-containing species. In operation 1250, the fluorine-containing species and the oxygen-containing species generated in the plasma source may also be cyclically introduced into the processing chamber. In some embodiments, the cyclic flow may include two operations: (a) supplying a fluorine-containing source gas in a plasma source to generate fluorine-containing free radicals (operation 1240), and introducing the fluorine-containing species into the processing chamber (operation 1250), followed by (b) supplying an oxygen-containing source gas in a plasma source to generate an oxygen-containing species (operation 1240), and introducing the oxygen-containing species into the processing chamber (operation 1250). In other embodiments, the fluorine-containing source gas may be supplied to the plasma source after the oxygen-containing source gas is supplied to the plasma source.

[0257] In some embodiments, before providing the fluorine-containing free radicals and the oxygen-containing free radicals to the processing chamber, an appropriate amount of one or more inert gases may be premixed with each of the fluorine-containing source gas and the oxygen-containing source gas. In some embodiments, one of these substances may be provided to the processing chamber without energizing the plasma. In one example, the fluorine-containing substance (e.g., fluorine-containing free radicals) and the oxygen-containing source gas (e.g., ozone) from the plasma may be cyclically flowed into the processing chamber. In another example, the fluorine-containing source gas (e.g., fluorine (F)) may be premixed with the fluorine-containing source gas (e.g., fluorine (F)). 2 )) and oxygen-containing species (e.g., oxygen-containing free radicals) can be cyclically flowed into the processing chamber. Regardless of the type of species introduced, the fluorine-containing species and the oxygen-containing species can be cyclically flowed toward the inner surface of the processing chamber. One or both of the fluorine-containing species and the oxygen-containing species can react with the molybdenum-containing film, thereby removing the molybdenum-containing film from the inner surface. For example, the fluorine-containing species can react with the molybdenum in the molybdenum-containing film to form molybdenum fluoride, such as molybdenum hexafluoride (MoF 6 ), which may be volatile and can be removed from the processing chamber by a vacuum pump. The oxygen-containing species circulated into the processing chamber may oxidize the carbon or carbon-containing constituents in the molybdenum-containing film to generate volatile byproducts (e.g., carbon monoxide (CO) or carbon dioxide (CO 2 )) to remove carbon, thereby accelerating the decomposition of the molybdenum-containing film on the inner surface. common flow

[0258] In operation 1240, the fluorine-containing substance and the oxygen-containing free radicals may co-flow toward the inner surface of the processing chamber at the same time. For this co-flow, a fluorine-containing source gas, an oxygen-containing source gas, and an inert gas may be provided simultaneously in the plasma source. In some embodiments, more than one fluorine-containing source gas and / or more than one oxygen-containing source gas may be provided. The fluorine-containing source gas and the oxygen-containing source gas may be pre-mixed before they are supplied to the plasma source. Alternatively, they may be provided separately until they reach the entrance of the plasma source, where they co-flow simultaneously. By igniting a plasma from a mixture of source gas and inert gas, a plasma including a fluorine-containing substance and an oxygen-containing substance may be generated in the plasma source. In operation 150, the fluorine-containing substance and the oxygen-containing substance generated in the plasma source may be simultaneously directed to the inner surface of the processing chamber to remove the molybdenum-containing film. In some embodiments, one of the substances may be provided to the processing chamber without exciting the plasma. In one example, a fluorine-containing substance (e.g., a fluorine-containing plasma) and an oxygen-containing source gas (e.g., ozone) from a plasma may flow into the processing chamber together. In another example, a fluorine-containing source gas (eg, fluorine) and an oxygen-containing species (eg, an oxygen-containing plasma) may be co-flowed into the processing chamber.

[0259] In operation 1250, in some embodiments, volatile reaction byproducts (e.g., molybdenum hexafluoride) may be produced from the reaction between the fluorine-containing species and molybdenum and may be removed from the process chamber by a vacuum pump. The oxygen-containing species may oxidize carbon or carbon-containing constituents that may be present in the molybdenum-containing film and may produce other volatile reaction byproducts (e.g., CO or CO 2 ), thereby accelerating the decomposition of the molybdenum-containing film. The carbon concentration on the inner surface can be reduced to zero or near zero content, thereby making the inner surface free of contaminants. For co-flow, volatile molybdenum fluoride by-products and volatile carbon-containing by-products (e.g., CO or CO 2 ) can occur essentially simultaneously.

[0260] After the molybdenum-containing film is removed from the interior surface by circulating flow or simultaneous co-flow, an optional purge operation may follow by pulsing one or more inert gases (e.g., helium, neon, argon, krypton, xenon, or mixtures thereof) into the processing chamber to remove any residual fluorine-containing species, oxygen-containing species, or any reaction byproducts from the processing chamber.

[0261] In optional operation 160, a substrate may be provided in a processing chamber for subsequent operations. For example, the substrate may be transported by a transfer tool to deposit a molybdenum-containing layer on the substrate. The molybdenum-containing layer may be deposited by ALD, PEALD, CVD, PECVD, or any suitable deposition process. Processing conditions for circulating or co-flowing

[0262] Fig.13A flow chart 1300 is shown of an exemplary method of cleaning surfaces within a processing chamber according to some embodiments. Fig.13 The optional operations 1310, 1320 and 1330 in the embodiment may be substantially equivalent to Fig.12 The optional operations 1210, 1220 and 1230 in the embodiment will be described below, and further description of the optional operations 1310, 1320 and 1330 will be omitted.

[0263] In operation 1340, one or more fluorine-containing source gases (e.g., NF 3 ) and one or more oxygen-containing source gases (e.g., O 2 ) is supplied to a remote plasma source where a plasma comprising fluorine-containing species and oxygen-containing species can be generated and maintained. 3 Gas and O 2 The gas may be supplied to the remote plasma source as a source gas. The remote plasma source may also be supplied with an inert gas such as helium, neon, argon, krypton, xenon, or a mixture thereof. 3 , O 2 The flow ratio between the fluorine-containing source gas, the oxygen-containing source gas and one or more inert gases can be adjusted as needed. In some embodiments, the fluorine-containing source gas, the oxygen-containing source gas and one or more inert gases can be introduced according to the circulating flow or simultaneous co-flow as discussed above. Certain processing conditions, such as the flow rate of the source gas and one or more inert gases, the chamber pressure and the substrate temperature, can be provided for the circulating flow or simultaneous co-flow, which may be individually or collectively beneficial to the cleaning (etching) ability of the fluorine-containing species and the oxygen-containing species produced in the plasma source (e.g., a remote plasma source). In some embodiments, Table 1 includes a processing condition setting A in a higher chamber pressure range, which includes processing conditions A1-A3. In some embodiments, Table 2 includes a processing condition setting B in a lower chamber pressure range, which includes processing conditions B1-B3.

[0264] The processing conditions in Tables 1 and 2 can be designed based on the location and / or composition of the molybdenum-containing film on the inner surface of the processing chamber. In some embodiments, a higher chamber pressure may result in reduced ionization and increased recombination of the source gas. For example, the chamber pressure can be adjusted to about 2 Torr to about 6 Torr, about 2.5 Torr to about 5.5 Torr, or about 3 Torr to about 5 Torr (as shown in Table 1) to facilitate the removal of molybdenum-containing films (e.g., MoN) located on or near the susceptor or carrier ring. x). In some embodiments, a lower chamber pressure can be advantageous for increasing ionization of the source gas and reducing recombination. Reducing recombination can be advantageous for removing molybdenum-containing films formed on the top plate or other internal surfaces where species (e.g., free radicals and / or ions) take a relatively long time to travel to. For example, the presence of chamber components or structures in the processing chamber (e.g., a showerhead) can delay or hinder the transfer of fluorine-containing species and / or oxygen-containing species to the top plate or other isolated areas. In this case, the increased number of free radicals or ions due to reduced recombination can more effectively remove molybdenum-containing films. For example, in removing molybdenum-containing films (e.g., MoO) deposited on areas where species take a long time to travel, x ), a lower chamber pressure range of about 0.5 Torr to about 2 Torr, about 0.5 Torr to about 1.8 Torr, or about 0.5 Torr to about 1.6 Torr (as shown in Table 2) may be required. In some embodiments, the presence of a carrier gas can provide the same effect as reducing the chamber pressure. For example, the flow rate of the inert gas in Table 2 is higher than that in Table 1, and can further improve the ionization of the source gas and reduce recombination compared to Table 1.

[0265] According to some embodiments, one or more processing conditions may involve removing the molybdenum-containing film. For the circulating flow, in some embodiments, the fluorine-containing source gas and the oxygen-containing source gas may be cyclically supplied to the plasma source according to any of the processing conditions listed in Tables 1 and 2. In some embodiments, the fluorine-containing source gas and the oxygen-containing source gas may be supplied to the plasma source under different processing conditions. One or more inert gases may be mixed with each of the fluorine-containing and oxygen-containing source gases. For co-flow, according to any of the processing conditions in Tables 1 and 2, the fluorine-containing source gas, the oxygen-containing source gas, and the inert gas may be supplied to the plasma source as a co-flow at the same time. In some embodiments, the co-flow may be repeated more than once according to another processing condition in Tables 1 and 2. [Table 1] - Processing conditions of fluorine-containing and oxygen-containing source gases *slm = standard liters per minute [Table 2] - Treatment conditions of fluorine-containing and oxygen-containing source gases

[0266] Operation 1340 may be followed by operation 1350, in which the fluorine-containing substance and the oxygen-containing substance produced in operation 1340 may be introduced into the processing chamber. The fluorine-containing substance and the oxygen-containing substance may be introduced into the processing chamber in the same manner as the fluorine-containing source gas and the oxygen-containing source gas are supplied to the plasma source. For the circulating flow, the first source gas (e.g., the fluorine-containing source gas) flowing at a flow rate according to one of the processing conditions in A1-A3 and B1-B3 is mixed with an inert gas flowing at an appropriate flow rate and supplied to the plasma source, and then the first substance produced by the first source gas may flow into the processing chamber. Subsequently, the second source gas (e.g., the oxygen-containing source gas, which flows at a flow rate selected in the processing conditions for the first source gas) is mixed with an inert gas flowing at an appropriate flow rate and supplied to the plasma source, wherein the second substance is produced and flows into the processing chamber to clean the inner surface of the processing chamber. In some embodiments, the total flow rate of the inert gas mixed with the first source gas and the second source gas may correspond to the inert gas flow rate in the processing conditions selected for the first source gas.

[0267] For co-flow, the first source gas, the second source gas, and the inert gas may be co-flown into a plasma source (e.g., a remote plasma source) to produce a mixture including the first species and the second species, which are simultaneously flowed toward the processing chamber. When the molybdenum-containing film is exposed to the fluorine-containing species and the oxygen-containing species, the molybdenum-containing film may be removed from the inner surface.

[0268] After the cleaning operation, an optional sweeping operation may be performed. In addition, operations 1340 and / or 1350 may be repeated once or more than once. In optional operation 1360, a new substrate may be transferred to a processing chamber for subsequent operations, such as deposition or etching operations. For example, a molybdenum-containing layer may be deposited on a new substrate. Circulation flow for removal of carbon and molybdenum containing films

[0269] Fig.14 1400 is a flow chart of an exemplary method for cleaning the interior surface of a processing chamber on which a carbon-containing and molybdenum-containing film is deposited, according to some embodiments. The operations in flow chart 1400 can be performed according to a circulation flow. The operations in flow chart 1400 can be performed in a different order and / or with fewer or additional operations. Flow chart 1400 begins with operation 1410, in which a fluorine-containing source gas (e.g., NF 3 ) may be provided to a plasma source according to one of the processing conditions described in A1-A3 and B1-B3 in Tables 1 and 2, thereby generating fluorine-containing species. An appropriate portion of an inert gas (selected for the fluorine-containing source gas in operation 1410) may also be provided to mix with the fluorine-containing source gas. In operation 1420, the generated fluorine-containing species may be introduced into the processing chamber and react with the carbon-containing and molybdenum-containing film, such as the carbon-containing MoO x , MoN containing carbon x or carbon-containing MoO x N y, to remove the carbon-containing and molybdenum-containing films from the inner surface of the processing chamber. The fluorine-containing substance may include a fluorine-containing source gas, a fluorine-containing plasma (e.g., free radicals, ions, charged neutral species), or a mixture thereof. Subsequently, in operation 1430, an oxygen-containing source gas (e.g., O 2 ) may be supplied to a plasma source according to the processing conditions selected for the fluorine-containing source gas in operation 1410 to generate oxygen-containing species in the plasma source. An appropriate portion of an inert gas may also be provided to mix with the oxygen-containing source gas. In operation 1440, the oxygen-containing species generated in operation 1430 may be introduced into the processing chamber to oxidize carbon or carbon-containing constituents in the carbon-containing and molybdenum-containing film. In some embodiments, the oxygen-containing species may include an oxygen-containing source gas, an oxygen-containing plasma (e.g., free radicals, ions, charged neutral species), or a mixture thereof.

[0270] The flow rates of the fluorine-containing source gas in operation 1410 and the oxygen-containing source gas in operation 1430 may be selected from any of the process conditions in Tables 1 and 2. The flow rates of operations 1410 and 1430 may be configured to be the same or may be different from each other. After operation 1440 is completed, in operation 1450, operations 1410-1440 may be optionally repeated one or more times as needed. Co-flow for removal of carbon and molybdenum containing films

[0271] Fig.15 15 is a flow chart of an exemplary method for cleaning the interior surface of a processing chamber on which a carbon-containing and molybdenum-containing film is deposited according to some embodiments. The operations in flow chart 1500 can be performed according to co-flow. The operations in flow chart 1500 can be performed in a different order and / or with fewer or additional operations. In operation 1510, a fluorine-containing source gas (e.g., NF 200) can be added according to one or more of the processing conditions A1-A3 and B1-B3 in Tables 1 and 2. 3 ), oxygen-containing source gas (e.g., O 2 ) is supplied to the plasma source as a co-flow with an inert gas to generate fluorine-containing species and oxygen-containing species in the plasma source. In operation 1520, the generated fluorine-containing species and oxygen-containing species may be introduced into the processing chamber to react with the carbon-containing and molybdenum-containing films.

[0272] In some embodiments, the processing condition may be one of the processing conditions described in A1-A3 and B1-B3, wherein the chamber pressure may not change before the chamber cleaning is completed. In some embodiments, the chamber cleaning may involve more than one processing condition, and the processing chamber pressure may be changed during the cleaning. For example, the chamber may be exposed to fluorine-containing substances and oxygen-containing substances at a first chamber pressure for a first duration, and then the chamber pressure may be changed to a second chamber pressure for a second duration. In some embodiments, the chamber pressure may be changed from a higher pressure to a lower pressure. For example, the first chamber pressure may be between about 2 Torr and about 6 Torr, between about 2.5 Torr and about 5.5 Torr, or between about 3 Torr and about 5 Torr, and the second chamber pressure may be between about 0.5 Torr and about 2 Torr, between about 0.5 Torr and about 1.8 Torr, or between about 0.5 Torr and about 1.6 Torr. In some embodiments, the chamber pressure may be changed from a lower pressure to a higher pressure. For example, the first chamber pressure may be between about 0.5 Torr and about 2 Torr, and the second chamber pressure may be between about 2 Torr and about 6 Torr.

[0273] In some embodiments, the fluorine-containing species may include a fluorine-containing source gas, a fluorine-containing plasma (e.g., free radicals, ions, charged neutral species), or a mixture thereof; and the oxygen-containing species may include an oxygen-containing source gas, an oxygen-containing plasma (e.g., free radicals, ions, charged neutral species), or a mixture thereof. For example, during a first duration, the chamber may be exposed to a fluorine-containing plasma and an oxygen-containing plasma, while during a second duration, the chamber may be exposed to a fluorine-containing plasma and an oxygen-containing species in a plasma-free environment (e.g., ozone or other oxygen-containing source gas). Alternatively, during a first duration, the chamber may be exposed to a fluorine-containing plasma and an oxygen-containing species in a plasma-free environment, while during a second duration, the chamber may be exposed to a fluorine-containing plasma and an oxygen-containing plasma. An optional sweep operation may be performed after operation 1520.

[0274] In optional operation 1530, operations 1510 and 1520 may be repeated once or more than once. The processing conditions in operation 1530 may be the same as or different from the flow conditions used in operation 1510 performed before operation 1530 is performed. Device

[0275] Fig.16 Schematic diagram of an exemplary processing apparatus with a remote plasma source according to some embodiments is shown. It should be understood that Fig.16The processing chamber in the process chamber can be used to deposit a silicon-containing layer or a molybdenum-containing layer according to some embodiments, and / or etch a silicon-containing layer or a molybdenum-containing layer formed in the processing chamber. In some embodiments, a silicon-containing layer or a molybdenum-containing layer can be formed in a processing chamber and then etched in the same processing chamber using a remote plasma source without exposing the silicon-containing layer or the molybdenum-containing layer to the ambient atmosphere.

[0276] The plasma processing apparatus 1600 includes a remote plasma source 1602 separated from a processing chamber 1604. The remote plasma source 1602 is fluidly coupled to the processing chamber 1604 through a gas distributor or showerhead 1606. In some embodiments, the showerhead 506 includes an ion filter for filtering ions to limit ion bombardment damage to the substrate 1612. Free radical species and / or ions are generated in the remote plasma source 1602, wherein the free radical species can be supplied to the processing chamber 1604. Precursors (e.g., one or more molybdenum-containing precursors) are supplied to the processing chamber 1604 through one or more precursor gas outlets 1608 (e.g., a manifold) disposed downstream of the remote plasma source 1602 and the showerhead 1606. A pressure gauge, a butterfly valve, or any other pressure monitoring device can be fluidly coupled to the processing chamber 1604 to maintain a certain pressure range of the processing chamber 1604 when the one or more molybdenum-containing precursors flow into the processing chamber.

[0277] The substrate 1612 is supported on a substrate support structure or wafer pedestal 1614. The wafer pedestal 1614 may be configured with lift pins or other movable support members to position the substrate 1612 within the processing region (i.e., deposition / etching region 1610). The substrate 1612 may be moved closer to or further away from the showerhead 1606. The wafer pedestal 1614 may be configured with lift pins or other movable support members to position the substrate 1612 within the processing region (i.e., deposition / etching region 1610). Fig.16 In FIG. 1 , the substrate 1612 is shown to have been raised into the deposition / etching zone 1610 .

[0278] In some embodiments, the wafer pedestal 1614 includes an electrostatic chuck 1616. The electrostatic chuck 1616 includes one or more electrostatic clamping electrodes 1618 embedded in the body of the electrostatic chuck 1616. In some embodiments, the one or more electrostatic clamping electrodes 1618 can be coplanar or substantially coplanar. The electrostatic clamping electrodes 1618 can be powered by a direct current (DC) power source or a DC clamping voltage (e.g., between about 200V and about 2000V) so that the substrate 512 can be held on the electrostatic chuck 1616 by electrostatic attraction. The electrostatic clamping electrodes 1618 can be powered by a first wire 1620. The electrostatic chuck 1616 can further include one or more heating elements 1622 embedded in the body of the electrostatic chuck 1616. The one or more heating elements 1622 can include a resistive heater. In some embodiments, the one or more heating elements 1622 are disposed below the one or more electrostatic clamping electrodes 1618. The one or more heating elements 1622 can be configured to heat the substrate 1612 to a temperature greater than about 450° C., greater than about 500° C., greater than about 550° C., greater than about 600° C., or greater than about 650° C. The one or more heating elements 1622 provide selective temperature control of the substrate 1612. The one or more heating elements 1622 can be powered by a second electrical wire 1624.

[0279] The coil 1628 is arranged around the remote plasma source 1602, wherein the remote plasma source 1602 includes an outer wall (e.g., a quartz dome). The coil 1628 is electrically coupled to a plasma generator controller 1632, which can be used to form and maintain a plasma in the plasma region 1634 through inductively coupled plasma generation. In some embodiments, the plasma generator controller 1632 may include a power supply source for supplying power to the coil 1628, wherein the power during plasma generation may be in the range of between about 300 W and about 15 kW per station, or in the range of between about 1 kW and about 10 kW per station. In some embodiments, an electrode or antenna for parallel plate or capacitively coupled plasma generation may be used to generate a continuous supply of free radicals through plasma excitation rather than inductively coupled plasma generation. Regardless of the mechanism used to ignite and maintain the plasma in the plasma region 1634, plasma excitation may be utilized to continuously generate free radical species during layer formation (e.g., film deposition) and / or remote plasma processing.

[0280] In some embodiments, fluorine-containing radicals including fluorine radicals (F*), hydrogen-containing radicals including hydrogen radicals (H*), nitrogen-containing radicals including nitrogen radicals (N*), oxygen-containing radicals including oxygen radicals (O*), carbon-containing radicals including carbon radicals (C*), amine-containing radicals including amine radicals (NH*, NH2*), or a combination thereof are generated in the plasma region 1634 under approximately steady-state conditions during steady-state film deposition or remote plasma processing controlled by the plasma generator controller 1632, but transients may occur at the beginning and end of film deposition and / or remote plasma etching. In one example, fluorine-containing radicals may be generated in the plasma region 1634. In another example, oxygen-containing radicals may be generated in the plasma region 1634. In yet another example, fluorine-containing radicals and oxygen-containing radicals may be generated in the plasma region 1634. Although Fig.16 Nitrogen (N*) and amine radicals (NH*) are shown, but it should be understood that the aforementioned radicals are merely illustrative. Fig.16 Other free radicals may be present in addition or in lieu of the free radicals depicted.

[0281] While one or more source gases are being supplied to the remote plasma source 1602, a supply of ions and radicals can be continuously generated within the plasma region 1634. Ions generated in the plasma region 1634 can be filtered out by an ion filter of the showerhead 1606. In this way, the radicals generated in the plasma region 1634 can be supplied to the substrate 1612 in the processing chamber 1604 and ion bombardment can be limited. The conditions in the remote plasma source 1602, including the composition of the source gas provided to the remote plasma source 1602 and the RF power supplied to the coil 1628, can be controlled to optimize the generation of desired radical species in the plasma region 1634. In some embodiments, the source gas can include an oxygen-containing reactant such as oxygen, ozone, carbon monoxide, carbon dioxide, nitrous oxide, nitrogen dioxide, or mixtures thereof, a fluorine-containing reactant such as nitrogen trifluoride, fluorine (F 2 ), molecular fluorine, carbon tetrafluoride, carbon hexafluoride, xenon difluoride, fluoromethane, difluoromethane, tetrafluoroethylene, hexafluoroethane, octafluoropropane, sulfur hexafluoride, or mixtures thereof. In some embodiments, the source gas may include nitrogen trifluoride, fluorine (F 2 ), oxygen or a combination thereof.

[0282] In some embodiments, the source gas may be mixed with one or more additional gases. The one or more additional gases may be supplied to the remote plasma source 1602. In some embodiments, the source gas is mixed with one or more additional gases to form a gas mixture, wherein the one or more additional gases may include a carrier gas. Non-limiting examples of additional gases may include helium, neon, argon, krypton, xenon, or mixtures thereof. The one or more additional gases may support or stabilize steady-state plasma conditions within the remote plasma source 1602 or assist in transient plasma ignition or extinguishing processes. Fig.16 16, a source gas supply 1636 is fluidly coupled to the remote plasma source 1602 to supply a source gas. Although not shown, another source gas supply can be fluidly coupled to the remote plasma source 1602 to supply another source gas. For some embodiments, about 5 sccm to about 4,000 sccm, or about 200 sccm to about 4,000 sccm, or about 500 sccm to about 3,000 sccm, or about 500 sccm to about 2,000 sccm, or about 500 sccm to about 1,500 sccm of source gas can be supplied from the source gas supply 1636. In addition, an additional gas supply 1638 is fluidly coupled to the remote plasma source 1602 to supply the one or more additional gases. For some embodiments, one or more carrier gases (inert gases) (e.g., helium, neon, argon, krypton, xenon, or mixtures thereof) can be supplied to the remote plasma source 1602. For some embodiments, about 1,000 sccm to about 9,000 sccm, or about 1,000 sccm to about 2,000 sccm, or about 6,000 sccm to about 9,000 sccm of the one or more carrier gases may be supplied from additional gas supply 1638. Although Fig.16 The embodiments in 1604 depict the gas mixture of the source gas and the one or more additional gases being introduced through separate gas outlets, but it should be understood that the gas mixture can be introduced directly into the remote plasma source 1602. That is, the premixed dilution gas mixture can be supplied to the remote plasma source 1602 through a single gas outlet.

[0283] Plasma activated species 1642 (e.g., excited nitrogen, hydrogen, carbon, oxygen, and / or fluorine radicals) flow out of the remote plasma source 1602 and enter the processing chamber 1604 through one or more gas outlets (e.g., showerhead 1606). The one or more gas outlets may include one or more manifolds. A pressure gauge, butterfly valve, or other pressure monitoring device may be fluidly coupled to the processing chamber 1604 to maintain a certain pressure range of the processing chamber 1604 when the fluorine-containing species and the oxygen-containing species flow into the processing chamber. In some embodiments, the processing chamber pressure may operate in a low pressure range between about 0.5 Torr and about 2 Torr or in a high pressure range between about 2 Torr and about 6 Torr. The plasma activated species 1642 within the showerhead 1606 and within the processing chamber 1604 are generally not subjected to sustained plasma excitation therein. The showerhead 1606 may have multiple gas ports to diffuse the plasma activated species 1642 stream into the processing chamber 1604. In some embodiments, the multiple gas ports may be spaced apart from each other. In some embodiments, the plurality of gas ports can be arranged in an array of regularly spaced channels or through-holes extending through a plate separating the remote plasma source 1602 from the processing chamber 1604. The plurality of gas ports can smoothly disperse and diffuse the radicals (including the plasma activated species 1642) exiting from the remote plasma source 1602 into the deposition / etching region 1610 of the processing chamber 1604 and filter out ions.

[0284] In the case where the plasma activated species 1642 is delivered to the process chamber 1604 from the showerhead 1606, a precursor 1644 (or other process gas) may be introduced into the process chamber 1604. The precursor 1644 may include a molybdenum-containing precursor. The precursor 1644 may be introduced through a precursor gas outlet 1608, wherein the precursor gas outlet 1608 may be fluidly coupled to the precursor supply 1640. The precursor gas outlet 1608 may include openings spaced apart from one another so that the stream of precursor 1644 may be introduced in a direction parallel to the flow of the plasma activated species 1642 out of the showerhead. In some embodiments, the precursor gas outlet 1608 may be located downstream of the showerhead 1606. In some embodiments, the precursor gas outlet 1608 is part of the showerhead 1606, such as in a dual plenum showerhead. The dual plenum showerhead may provide separate outlets / channels for the plasma activated species 1642 and the precursor 1644 to avoid mixing in the showerhead 1606. In this way, the precursor 1644 can flow into the processing chamber 1604 through the showerhead 1606 without being exposed to the plasma in the remote plasma source 1602. The precursor gas outlet 1608 can be located upstream of the deposition / etching zone 1610 and the substrate 1612. The deposition / etching zone 1610 is located inside the processing chamber 1604 between the precursor gas outlet 1608 and the substrate 1612.

[0285] During the film deposition process, most of the precursor 1644 can be prevented from mixing with the plasma activated species 1642 in or near the showerhead 1606. In some embodiments, the precursor 1644 can be delivered to the substrate 1612 during the dosing phase of the ALD cycle, separate from the plasma activated species 1642 delivered to the substrate 1612 during the plasma exposure phase of the ALD cycle. The adsorbed precursor 1644 can react with radicals of the plasma activated species 1642 during the plasma exposure phase of the ALD cycle to deposit a film, such as a silicon-containing layer or a molybdenum-containing layer. In some embodiments, the precursor 1644 can be delivered to the substrate 1612 in a continuous manner to interact with the plasma activated species 1642 in the deposition / etching zone 1610 to deposit a film by CVD. In some embodiments, the plasma activated species 1642 can be delivered to the substrate 1612 without delivering the precursor 1644 to etch the silicon-containing layer or the molybdenum-containing layer deposited on the substrate or on the inner surface (e.g., inner wall) of the processing chamber.

[0286] The gas may be removed from the process chamber 1604 through an outlet 1648 that is fluidly coupled to a pump (not shown). Thus, the radical species or the purge gas may be removed from the process chamber 1604.

[0287] In some embodiments, a heat shield (not shown) may be disposed below the wafer pedestal 1614. The heat shield acts as a thermal insulator below the wafer pedestal 1614 to slow down heat loss through thermal radiation, thereby reducing the amount of power required to maintain the wafer pedestal 1614 at a particular elevated temperature and also preventing other components within the processing chamber 1604 from overheating due to excessive heat radiated from the wafer pedestal 1614. For example, the heat shield may be radially offset from the stem 1626 and may have a thin annular body with a high view factor relative to the underside of the electrostatic chuck 1616. Thus, the annular heat shield may reduce radiative heat loss from the wafer pedestal 1614.

[0288] In some embodiments, a controller 1650 (e.g., a system controller) is in operable communication with the plasma processing apparatus 1600. In some embodiments, the controller 1650 includes a processor system 1652 (e.g., a microprocessor) configured to execute instructions stored in a data system 1654 (e.g., a memory). In some embodiments, the controller 1650 can communicate with the plasma generator controller 1632 to control plasma parameters and / or conditions in the remote plasma source 1602. In some embodiments, the controller 1650 can communicate with the wafer pedestal 1614 to control pedestal elevation, electrostatic adsorption and desorption, and temperature. In some embodiments, the controller 1650 may control other processing conditions, such as RF power settings, frequency settings, duty cycles, pulse times, pressure within the processing chamber 1604, pressure within the remote plasma source 1602, gas flow rates from the source gas supply source 1636, gas flow rates from the additional gas supply source 1638 and other sources, the temperature of the wafer pedestal 1614, and the temperature of the processing chamber 1604, as well as other processing conditions.

[0289] The controller 1650 may contain instructions for controlling the processing conditions for the operation of the plasma processing device 1600. The controller 1650 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, a stepper motor controller board, etc. Instructions for implementing appropriate control operations are executed on the processor. These instructions may be stored on a memory device associated with the controller 1650 or it may be provided via a network.

[0290] In certain embodiments, the controller 1650 controls all or most of the activities of the plasma processing device 1600 described herein. For example, the controller 1650 may control all or most of the activities of the plasma processing device 1600 associated with film deposition and / or remote plasma etching. The controller 1650 may also control all or most of the activities of the plasma processing device 1600 associated with in-situ chamber cleaning. The controller 1650 may execute system control software, including instruction sets for controlling timing, gas composition, gas flow rate, chamber pressure, chamber temperature, RF power level, substrate position, substrate temperature, and / or other parameters. Other computer programs, scripts, or routines stored on a memory device associated with the controller 1650 may be used in some embodiments. In a multi-station reactor, the controller 1650 may include different or identical instructions for different device stations, thereby allowing the device stations to operate independently or synchronously.

[0291] In some embodiments, the controller 1650 may include instructions configured to perform operations such as depositing a molybdenum-containing layer on the substrate 1612 and exposing the interior surfaces of the processing chamber 1604 to the plasma-activated species 1642 generated in the remote plasma source 1602 to remove the molybdenum-containing film formed on the interior surfaces of the processing chamber 1604. In some embodiments, exposing the interior surfaces of the processing chamber 1604 to the plasma-activated species 1642 occurs by adjusting one or more of the following parameters: chamber pressure, substrate temperature, exposure time, and flow rate of one or more source gases or one or more carrier gases.

[0292] In some embodiments, plasma processing apparatus 1600 may include a user interface associated with controller 1650. The user interface may include a display screen, a graphical software display of plasma processing apparatus 1600 and / or processing conditions, and a user input device (e.g., a pointing device, a keyboard, a touch screen, a microphone, etc.). Computer program code for controlling the above operations may be written in a conventional computer-readable programming language. Fig.16 The controller 1650 is implemented by Fig. 9 The above description of the controller 929 is further described. Cleaning of High-K Dielectric Materials

[0293] In some embodiments, various films other than molybdenum may be deposited during semiconductor device manufacturing operations. Thin films used in integrated circuit (IC) manufacturing operations may include dielectric materials. Dielectric materials may include metal-containing oxides, nitrides, or carbides. For example, the gate dielectric of a transistor may be deposited by depositing various oxides or nitrides (e.g., silicon oxide (SiO 2 ), hafnium oxide (HfO 2 )、ZrO 2), silicon oxynitride (SiON), or a mixture thereof). In addition to gate dielectrics, dielectric materials may also be used in other elements of semiconductor devices, such as insulating features in metallization layers, isolation trenches, and memory cell structures. Some of the various thin films may include dielectric materials, such as high-k dielectric materials deposited on features or substrates. Metal-containing dielectric materials may be deposited using precursors by suitable deposition processes (e.g., ALD, PEALD, CVD, epitaxial growth, or PECVD). Precursors (e.g., gaseous precursors) may react on the substrate to form a metal-containing layer, but the precursors may also be transferred to another location within the processing chamber, where they may be deposited in a condensed form (e.g., a solid film, particles, or wall deposits). Depending on the deposition temperature and / or the sublimation temperature, the metal-containing dielectric material deposited on the chamber wall or other chamber components may sublimate, transfer, flake off, or otherwise be redeposited on other components or surfaces within the processing chamber. Re-deposition of metal-containing dielectric materials may occur on the substrate, thereby changing the composition of the thin film on the substrate, causing device reliability issues and adversely affecting manufacturing yields. The processing chamber may be periodically cleaned to remove metal-containing dielectric materials from the interior surfaces of the processing chamber.

[0294] Certain criteria may be considered when designing and performing a chamber cleaning process. First, during the chamber cleaning operation, the temperature of the process chamber wall or other components to be cleaned may be kept relatively low to reduce potential damage to the chamber components due to exposure to thermal energy and / or reduce energy consumption. For example, maintaining the temperature of the process chamber wall at a constant temperature above 200°C may require continuous operation of the heater and may increase the likelihood of oxidation of the aluminum or aluminum-containing alloy used to construct the process chamber. In some embodiments, during the chamber cleaning, the temperature of the process chamber wall may preferably be maintained at about 125°C to about 200°C, or less than about 200°C. Second, a moderate chamber pressure range may be maintained during the chamber cleaning. Achieving a low chamber pressure may require a powerful vacuum pump, so additional time may be required before starting the chamber cleaning operation, thereby increasing the overall chamber cleaning cycle. High chamber pressures (especially in non-inert environments) may form undesirable oxides or other films on the inner surfaces of the process chamber. In some embodiments, the chamber pressure may preferably be maintained at about 0.5 Torr to about 50 Torr. Third, the etching rate of the film of the chamber components may be high enough to have a shorter duration for the entire chamber cleaning cycle. In some embodiments, the etch rate may preferably be about 500 angstroms / minute to about 1,000 angstroms / minute. Fourth, the process chamber cleaning may be designed to produce volatile reaction products rather than non-volatile reaction products that may require additional cleaning operations. Fifth, the one or more chemicals used in the cleaning may be readily available and have a relatively low cost. In addition, the chemical may be a chemical that does not chemically react with the materials of the chamber walls or other components being cleaned.

[0295] Provided herein is a method for removing one or more dielectric materials from one or more components of a processing chamber. The one or more components may include surfaces of a processing chamber, a pedestal, a showerhead, a foreline, etc. A chamber cleaning operation may include a two-part cleaning operation, including (i) introducing a fluorine-containing substance (e.g., fluorine radicals generated by a remote plasma), and (ii) introducing one or more thermal etchants into the processing chamber. Thermal etching uses a gas phase reagent to react with a substrate surface and chemically and / or thermally etch materials from the substrate surface. As used herein, thermal etching may also be referred to as "chemical etching" and vice versa. Thermal etching can be applied to a variety of materials. It may be desirable to be selective in the thermal etching reaction to remove one of the materials in the presence of other materials. The selectivity of etching has many applications in semiconductor device manufacturing and surface cleaning. Compared to other conventional etching techniques (e.g., plasma etching or sputtering), the selectivity of thermal etching may be higher. Thermal etching generally involves solid etching materials and gaseous etching precursors. Etching precursor (for example, hot etchant) is any reactant gas in the hot etching reaction, which reacts with solid etching material to promote the removal of solid etching material from the substrate surface. In some implementations, the etching precursor can modify the surface layer of the substrate surface, and thermal energy can be applied to etch the modified surface layer. The one or more hot etchants may include halides, such as chlorides or bromides. In the first part, the fluorine-containing substance can react with the dielectric material to produce a fluorine-containing reaction product in the dielectric material, such as a fluoride of a metal. The fluorine-containing reaction product may be non-volatile. In the second part, the hot etchant can react with the fluorine-containing reaction product to produce a volatile reaction product, which may be a chloride or bromide of a metal in the dielectric material. The cleaning operation may also include removing the volatile reaction product from the processing chamber. In some embodiments, the metal fluoride reaction product reacts with the hot etchant through a ligand exchange reaction to produce a volatile chloride or bromide of the same metal. The ligand exchange reaction may refer to a reaction in which fluorine in a metal fluoride is replaced with a halogen element to form a metal halide. The halogen element may include Br or Cl.

[0296] The two-part cleaning process according to some embodiments may moderately meet some or all of the above-mentioned standards for the treatment chamber cleaning process. For example, the two-part cleaning process may involve maintaining the temperature of the treatment chamber at less than about 200°C, thereby preventing high energy consumption and potential oxidation of metal parts (such as aluminum-containing parts) or the inner wall of the treatment chamber. In some embodiments, the two-part cleaning process does not require a low chamber pressure during the cleaning operation, thereby reducing the time of the entire cleaning cycle. For example, the two-part cleaning process may require a chamber pressure of about 0.5 Torr to about 100 Torr. According to some embodiments, a high etching rate (about 500 to about 1,000 angstroms per minute) can be obtained by the two-part cleaning process. In addition, as described above, the two-part cleaning process may include generating volatile reaction products by the second part of the treatment (the chamber is exposed to the hot etchant). The volatile reaction products can be relatively easily removed from the treatment chamber using, for example, a vacuum pump. In addition, the hot etchant involved in the two-part cleaning process may include a halogen element that is non-reactive with the aluminum or aluminum-containing material constituting the one or more parts. Furthermore, according to some embodiments, when cleaning a process chamber via a two-part cleaning process, no major upgrades to a processing apparatus including the process chamber are required.

[0297] In summary, the methods disclosed herein are used to remove dielectric materials from the inner surface or other components of a processing chamber. The dielectric material may include a metal-containing oxide, such as hafnium oxide, zirconium oxide, aluminum oxide, tin oxide, yttrium oxide, lanthanum oxide, or a mixture thereof. The dielectric material may include a metal-containing nitride, such as hafnium nitride, zirconium nitride, aluminum nitride, or a mixture thereof. The dielectric material may be removed by exposing the dielectric material to a fluorine-containing substance and a non-fluorine-containing halogen substance. The halogen may include bromine (Br) or chlorine (Cl). The reaction according to some embodiments may produce only volatile products, which may be relatively easy to remove from the processing chamber. In some embodiments, the method is performed at a temperature of about 50 to about 650°C. Fig.17A flow chart of an example of removing dielectric materials according to some embodiments is shown. The operations of flow chart 100 may be performed in a different order and / or different, fewer or additional operations. In operation 110, a plurality of substrates may be processed in a processing chamber using production processing. The production processing may include depositing a dielectric film on one or more substrates in any suitable deposition pathway (e.g., ALD, PEALD, CVD, or PECVD) by flowing chemical precursors, one or more reactants, or one or more sweep gases. The dielectric film may include any of many possible metal-containing oxides. For example, it may include hafnium oxide, zirconium oxide, aluminum oxide, tin oxide, yttrium oxide, lanthanum oxide, or a mixture thereof. According to some embodiments, metal-containing nitrides, carbides, oxynitrides, oxycarbides, and the like may also be deposited. For example, metal-containing nitrides may include hafnium nitride, zirconium nitride, aluminum nitride, or a mixture thereof. During deposition on the substrate, the dielectric film may also be formed on the inner surface of the processing chamber or on the surface of other components disposed in the processing chamber. A dielectric film formed on a surface of a process chamber or other component may become thicker as a production process is repeated in the process chamber. Although much of the discussion herein focuses on production processes that are deposition processes, the invention is not limited to deposition processes. Any production process that produces a dielectric film on a process chamber component may employ a cleaning process as described herein. For example, a production process may include etching or otherwise removing a dielectric film from one or more substrates. The substrate being processed may include one or more features formed thereon.

[0298] Operation 1710 involves processing a plurality of substrates. After processing each of these substrates, it is removed from the processing chamber. For example, a transfer tool can be used to move the substrate out of the processing chamber without breaking the vacuum.

[0299] In operation 1720, the production process may be stopped. In some embodiments, the semiconductor device manufacturing process may be stopped. In some embodiments, when the process is stopped, the production process is no longer used to process the wafer. Instead, the process chamber or components therein are cleaned to remove films formed thereon.

[0300] In operation 1730, a remote plasma with a fluorine-containing species and a thermal etchant containing Br or Cl may be introduced into the processing chamber to remove dielectric material from the interior surface. Although much of the discussion herein focuses on the use of fluorine-containing species generated by a remote plasma, the disclosed cleaning process is not limited to a remote plasma source. For example, fluorine radicals generated by any method may be used.

[0301] The process gas may flow into a remote plasma source, wherein RF power is applied to the remote plasma source to generate plasma activated species (e.g., free radicals / ions) of the process gas. The process gas may include a fluorine-containing chemical. In some embodiments, the source gas used to generate the plasma may include nitrogen fluoride (NF 3 ), tetrafluoromethane (CF 4 ), trifluoromethane (CHF 3 ), difluoromethane (CH 2 F 2 ), fluoromethane (CH 3 F), sulfur hexafluoride (SF 6 ), octafluoropropane (C 3 F 8 ), octafluorocyclobutane (C 4 F 8 ), hexafluorocyclobutene (C 4 F 6 )、1,2,3,3,4-pentafluorocyclobutene-4-yl (C 4 F 5 ), fluorine (F 2 ) or a mixture thereof.

[0302] In some embodiments, the thermal etchant may include hydrogen bromide (HBr), hydrogen chloride (HCl), boron trichloride (BCl 3 ), or a mixture thereof, or boron bromide (BBr 3 ), phosphorus trichloride (PCl 3 ), carbon tetrachloride (CCl 4 ), nitrogen trichloride (NCl 3 ), or a mixture thereof.

[0303] In some embodiments, remote plasma may be generated in a remote plasma source that can be fluidically coupled to a processing chamber. The remote plasma may include plasma-activated substances. The plasma-activated substances may include fluorine-containing substances. The remote plasma source for generating remote plasma may include inductively coupled plasma (ICP), transformer coupled plasma (TCP), capacitively coupled plasma (CCP), microwave plasma, direct current (DC) plasma, laser-generated plasma, or other plasma technologies known in the art. Plasma may be delivered to the processing chamber from the remote plasma source so that the plasma-activated substances are distributed toward one or more inner surfaces of the processing chamber. In some embodiments, plasma is delivered to the processing chamber from the remote plasma source through a showerhead. Additionally or alternatively, plasma is delivered to the processing chamber from the remote plasma source by a distributor that preferentially directs plasma to the one or more inner surfaces of the processing chamber.

[0304] In some embodiments, the fluorine-containing substance and the thermal etchant containing Br or Cl may flow into the processing chamber together for a predetermined time to react with the dielectric material on the inner surface of the processing chamber and remove the dielectric material. In some embodiments, one or more fluorine-containing processing gases may flow into a remote plasma source from a processing gas supply source (e.g., a first processing gas supply source), wherein RF power is applied to the remote plasma source to generate a remote plasma of a plasma-activated substance (e.g., free radicals / ions) including a fluorine-containing processing gas. The plasma-activated substance may include a fluorine-containing substance. In some embodiments, a thermal etchant containing Br or Cl may be supplied to a remote plasma source from a processing gas supply source (e.g., a second processing gas supply source), wherein the remote plasma including the fluorine-containing substance and the thermal etchant containing Br or Cl may be pre-mixed and co-flowed in the processing chamber. In another example, the remote plasma including the fluorine-containing substance and the thermal etchant containing Br or Cl may be separately supplied to the inlet of the processing chamber, and they may be mixed in the processing chamber. In some embodiments, the fluorine-containing substance and the thermal etchant flow cyclically. Each cycle may include a first stage for flowing the fluorine-containing substance and a second stage for flowing the thermal etchant.

[0305] In some embodiments, the remote plasma (which may produce fluorine-containing species) may not electronically activate the Br or Cl-containing thermal etchant. For example, the Br or Cl-containing thermal etchant may not mix with or may not react with the fluorine-containing species in the remote plasma. Once introduced into the processing chamber, the plasma-activated fluorine-containing species may react with the dielectric material to form a fluorine-containing reaction product. For example, a metal oxide may be converted into a non-volatile metal fluoride. Substantially simultaneously (in a co-current embodiment), the non-volatile metal fluoride may react with the Br or Cl-containing thermal etchant to produce a volatile Br or Cl-containing product (e.g., a metal bromide or a metal chloride). The reaction of the metal fluoride with the thermal etchant may be a ligand exchange reaction. In HfO 2 In the case of HfO 2 Can react with fluorinated species to form non-volatile HfF 4 .Hf 4 It is non-volatile and can react with BCl 3 (a thermal etchant containing Br or Cl) to produce a volatile reaction product (e.g. HfCl 4 During or after operation 1730, the volatile reaction products may be removed from the interior surfaces of the processing chamber, leaving the interior surfaces free of dielectric material.

[0306] In some embodiments, a remote plasma with a fluorine-containing substance and a thermal etchant containing Br or Cl can be introduced cyclically. The remote plasma including the fluorine-containing substance can be first introduced into the processing chamber for a predetermined time. Subsequently, the thermal etchant containing Br or Cl can be introduced into the processing chamber for a predetermined time. Although the fluorine-containing substance is introduced before the thermal etchant containing Br or Cl is introduced, the dielectric material (e.g., a metal-containing oxide) can be removed from the inner surface of the processing chamber according to a reaction sequence substantially similar to the above-mentioned co-flow embodiment.

[0307] In some embodiments, the cyclic introduction of the remote plasma including the fluorine-containing species and the thermal etchant containing Br or Cl can be optionally repeated depending on the process recipe. For example, the cyclic introduction can be repeated more than once.

[0308] In some embodiments, the chamber pressure in operation 1730 may be about 0.5 Torr to about 100 Torr, or about 1 Torr to about 80 Torr. The chamber temperature may be about 50° C. to about 650° C., or about 50° C. to about 450° C. The etching rate of the dielectric material may be about 500 angstroms / minute to about 1,000 angstroms / minute.

[0309] In some embodiments, water and / or alcohol, such as methanol, ethanol, or propanol, are added in operation 1730. For cyclic introduction, water or alcohol can be introduced into the processing chamber, which is separate from the introduction of remote plasma or thermal etchant containing Br or Cl. For co-flow, water or alcohol, remote plasma, and thermal etchant containing Br or Cl can flow into the processing chamber together. In some cases, the addition of water and / or alcohol increases the etching rate of the dielectric material.

[0310] In operation 1740, the one or more volatile reaction products may be removed from the processing chamber by a vacuum pump fluidly coupled to the processing chamber, thereby freeing the interior surfaces of the processing chamber from dielectric materials. For example, the one or more volatile reaction products may also include: 2 、F 2 or Cl 2 .

[0311] In operation 1750, one or more substrates may be optionally provided in the process chamber to restart the production process. The substrate may be transferred to the process chamber by a transfer tool to deposit dielectric material on the feature or substrate. The deposition process may be repeated until the thickness of the film, wall deposits, or particles on the inner surface of the process chamber exceeds a predetermined threshold.

[0312] Fig.18 An example flowchart of removing dielectric material according to some embodiments is shown. The operations of flowchart 1800 may be performed in a different order and / or with different, fewer, or additional operations. Flowchart 1800 may involve a circulating flow of a fluorine-containing species and a thermal etchant containing Br or Cl.

[0313] In operation 1810, a remote plasma including a fluorine-containing species is introduced into a processing chamber, and a dielectric material deposited on surfaces within the processing chamber reacts with the fluorine-containing species to produce a fluorine-containing non-volatile reaction product.

[0314] In some embodiments, the time for which the dielectric material is exposed to the fluorine-containing substance may depend on the diffusion of fluorine in the dielectric material and the chamber temperature. It should be understood that the time for introducing the fluorine-containing substance or the thermal etchant may be the same or substantially the same as the time for which the dielectric material on or at the inner surface is exposed to the fluorine-containing substance or the thermal etchant. In some embodiments, the reaction between the fluorine-containing substance and the dielectric material may be carried out in the presence of a fluorine-containing non-volatile reaction product (e.g., HfF 4 ) is formed in the entire dielectric material to be removed. For example, for dielectric materials in which fluorine diffuses slowly, a longer exposure time to the fluorine-containing substance may be required. For dielectric materials in which fluorine diffuses rapidly, less exposure time may be required when the fluorine-containing substance is introduced into the processing chamber. During the introduction of the fluorine-containing substance, the exposure time may be inversely proportional to the chamber temperature. For example, when the chamber temperature is relatively low, a longer exposure time may be required. In some embodiments, the dielectric material may be exposed to the fluorine-containing substance for about 30 seconds to about 300 seconds. For example, the fluorine-containing substance (i.e., fluorine substance) is introduced into the processing chamber for about 30 seconds to about 300 seconds.

[0315] In operation 1820, thermal etching may be performed by introducing a thermal etchant containing Br or Cl into the process chamber, and the dielectric material deposited on the inner surface of the process chamber reacts with the fluorine-containing species to produce a fluorine-containing non-volatile reaction product. The thermal etchant (e.g., Br or Cl) may be introduced into the process chamber to form a dielectric material. 3 ) is provided to the processing chamber to react with the fluorine-containing non-volatile reaction product (e.g., HfF 4 ) reaction, so that the fluorine-containing non-volatile reaction product is converted into a volatile reaction product (HfCl 4 In some embodiments, the non-volatile reaction product may be exposed for about 30 to about 300 seconds. For example, the thermal etchant may be introduced into the processing chamber for about 30 to about 300 seconds.

[0316] The two-step etching reaction including operations 1810 and 1820 may involve converting the non-volatile reaction product formed in operation 1810 into a volatile reaction product in operation 1820. The dielectric material (e.g., a metal-containing oxide or a metal-containing nitride) may be converted into a metal-containing fluoride (e.g., a non-volatile reaction product) by exposing it to a fluorine-containing substance in operation 1810. In operation 1820, the fluorine ligand in the metal-containing fluoride may be replaced by another non-fluorine halogen ligand (e.g., Br or Cl) in the thermal etchant to form a reaction product that is more volatile than the metal-containing fluoride. The metal element in the metal-containing oxide (or nitride) may include hafnium, zirconium, tin, aluminum, or a mixture thereof.

[0317] In some embodiments, only a single cycle (including complete conversion of the dielectric coating and thermal etching) is required to remove the dielectric material. The fluorine-containing species can diffuse into the entire thickness of the dielectric material to be removed and convert the entire or substantially the entire thickness into metal fluoride. Subsequently, the fluorine ligands throughout the coating can be replaced by Br or Cl ligands to form volatile reaction products to complete the etching process.

[0318] In operation 1830, operations 1810-1820 may be optionally repeated more than once depending on the process recipe. In some embodiments, the cycle including partial diffusion / conversion and thermal etching may be repeated more than once to remove the dielectric material. Instead of allowing the fluorine-containing substance to completely penetrate through the entire dielectric material to be removed, in the first cycle, the dielectric material may be exposed to the fluorine-containing substance for a predetermined period of time and converted to a fluoride for subsequent thermal etching. In the one or more subsequent cycles, the remaining dielectric material may be subjected to the same treatment as the first cycle until the entire dielectric material is removed from the inner surface of the processing chamber. In one example, the etching rate of the dielectric material may be about 500 angstroms / minute to about 1,000 angstroms / minute.

[0319] Fig.19 A flow chart of an example of removing dielectric materials according to some embodiments is shown. Flowchart 1900 may involve the co-flow of fluorine-containing substances and thermal etchants containing Br or Cl. In operation 1910, a remote plasma including a fluorine-containing substance and a thermal etchant containing Br or Cl may flow into a processing chamber together. In some embodiments, the remote plasma and the thermal etchant may be introduced for about 0.1 seconds to about 600 seconds. Compared to a circulating flow, the co-flow according to operation 1910 may reduce the total etching cycle time. In the 1910 operation, the formation of metal fluoride (i.e., non-volatile reaction products) by the fluorine-containing substance and the formation of volatile reaction products by reacting with the thermal etchant may occur substantially simultaneously. Water vapor and / or alcohol (e.g., methanol, ethanol, or propanol) may be mixed with the fluorine-containing substance and the thermal etchant containing Br or Cl to accelerate the etching of the dielectric material. In operation 1920, more than one operation 1910 may be performed according to a processing recipe.

[0320] Hafnium Oxide (HfO x ) is an example of a metal-containing dielectric material that can be deposited on a substrate, for example, by ALD, PEALD, CVD, or PECVD using one or more hafnium-containing precursors. Hafnium oxide is sometimes used to form a gate dielectric stack. During deposition of hafnium oxide on a substrate, hafnium oxide may also form as a film, wall deposits, or particles on the surface of a processing chamber interior or one or more components in the processing chamber. Cleaning hafnium oxide deposits from walls or components is a challenging problem.

[0321] According to some embodiments, hafnium oxide formed on the interior surfaces or components of the processing chamber may react with a fluorine-containing species (e.g., NF 3 plasma) to form hafnium tetrafluoride (HfF 4 ) and oxygen: 4F*+HfO 2 →HfF 4 (Non-volatile)+O 2 (1) Reaction product HfF 4 It is not very volatile and may form solid particles in the process chamber or remain on the surface of the process chamber and become a source of contamination. Additional operations may be required to remove non-volatile HfF from the process chamber. 4 .

[0322] In some embodiments, hafnium oxide can be prepared by reacting with boron trichloride (BCl 3 ) to remove from the interior surface of the processing chamber: 4BCl 3 +3HfO 2 →3HfCl 4 (Volatility)+2B 2 O 3 (2)

[0323] Involving BCl 3 The reaction can produce a volatile reaction product HfCl 4 , which can be removed from the process chamber relatively easily by a vacuum pump, unlike non-volatile B 2 O 3 may remain in the process chamber. Therefore, additional reactions may be required to avoid the formation of non-volatile B 2 O 3 and / or convert it into volatile products.

[0324] In some embodiments, HfO 2 Can be exposed to fluorinated species (i.e., fluorinated species or fluorinated free radicals) and BCl 3 , and the following reactions (3) and (4) can occur. 4F*+HfO 2 →HfF 4 +O 2 (3a) 3F 4 +4BCl 3 →3HfCl 4 (Volatile)+4BF 3 (3b) 12F*+3HfO 2 +4BCl 3 →3HfCl 4(Volatile)+4BF 3 +3O 2 (4)

[0325] In reactions (3a) and (3b), the fluorine substance is first introduced into the processing chamber, and after the fluorine substance is introduced into the processing chamber, BCl 3 In the first step of reaction (3a), HfO 2 Can react with fluorine substances to produce non-volatile HfF 4 In the second stage of the reaction (3b), BCl is provided 3 With HfF 4 The reaction produces volatile HfCl 4 , which can be combined with BF 3 In reaction (4), the fluorine species reacts with BCl 3 Fluorine and BCl 3 The co-flow may still undergo a reaction sequence similar to reaction (3) and produce volatile products such as HfCl 4 , O 2 and BF 3 Whether the fluorine substance is introduced or BCl 3 What is the order of HfO 2 It can react with fluorine species first, and then produce HfF 4 With BCl 3 Ligand exchange reaction to generate volatile HfCl 4 The above reaction can be generalized to any reaction in which a metal-containing dielectric is first reacted with a fluorine species (eg, fluorine radicals) and then the resulting metal fluoride is reacted with a chlorine- or bromine-containing species via a ligand exchange reaction to produce a volatile metal chloride or metal bromide. application

[0326] According to some embodiments, the inner surface of a processing chamber on which a dielectric material is deposited or the surface of a component disposed in the processing chamber may be cleaned. The inner surface may include the inner wall of the processing chamber, the base, the showerhead, the foreline, or other components that may be in contact with the precursor and other reactants, thereby forming a film, wall deposits or particles on the inner surface. The dielectric material may include a metal-containing oxide or a metal-containing nitride with a metal element (e.g., hafnium, zirconium, tin, aluminum, or a mixture thereof), and may include hafnium oxide, zirconium oxide, tin oxide, yttrium oxide, lanthanum oxide, aluminum oxide, hafnium nitride, zirconium nitride, aluminum nitride, or a mixture thereof. According to some embodiments, removing a dielectric material may involve removing a dielectric material that may produce a non-volatile reaction product by reacting with a fluorine-containing substance, and a ligand (e.g., fluorine) in the non-volatile reaction product may be replaced by another ligand to produce a metal compound that is more volatile than the non-volatile reaction product. Device

[0327] The apparatus of the present invention is configured for chamber cleaning, such as plasma cleaning followed by thermal etching. The apparatus may be configured for other processing operations, such as deposition, development and etching operations. In some embodiments, the apparatus is configured to perform all wet etching and dry etching operations. The apparatus may include multiple stations in a single wafer chamber or the same processing chamber. For multiple stations in the same processing chamber, various processing operations, such as those described in the present invention, may be performed in different stations in the same processing chamber.

[0328] The apparatus may be configured to include a remote plasma source separate from the processing chamber. In some embodiments, the remote plasma source may be disposed upstream of the processing chamber. The remote plasma source may be fluidically coupled to the processing chamber via a showerhead of the processing chamber. The remote plasma source may also be fluidically coupled to one or more gas supply sources to receive one or more processing gases (including fluorine) to produce fluorine-containing species.

[0329] The apparatus may include a process gas supply source to supply the thermal etchant to the processing chamber via a gas line. In some embodiments, the process gas supply source may be fluidly coupled to a remote plasma source, wherein the thermal etchant may be mixed with a remote plasma generated in the remote plasma source, and the mixture may be delivered to the processing chamber. In some embodiments, the process gas supply source may provide the thermal etchant directly from the process gas supply source to the processing chamber without mixing with the remote plasma until the thermal etchant is introduced into the processing chamber. The additional gas supply source may be equipped with a heater to control the temperature of the thermal etchant in the processing chamber.

[0330] The apparatus may also be configured to include an evacuation system (eg, a vacuum pump) to remove any fluorine-containing species, thermal etchants, and any reaction products from the processing chamber during or after chamber cleaning.

[0331] Fig. 20 A cross section of an example remote plasma system fluidly coupled to an example process chamber according to some embodiments is shown. The process chamber 2010 may include a showerhead 2020, a pedestal 2030 for supporting a substrate (including one or more features formed on the substrate). The pedestal 2030 may be coupled to a gate valve 2040, which may be opened to exhaust the process gas and any reaction products from the process chamber 2010. The remote plasma system 2050 may include a remote plasma source 2060, wherein a process gas 2070 may flow from a first process gas source (not shown here), and RF power is applied to the remote plasma source 2060 to generate plasma-activated species of the process gas (e.g., radicals / ions of a fluorine-containing species). The process gas may include nitrogen fluoride (NF 3 ), tetrafluoromethane (CF4 ), trifluoromethane (CHF 3 ), difluoromethane (CH 2 F 2 ), fluoromethane (CH 3 F), sulfur hexafluoride (SF 6 ), octafluoropropane (C 3 F 8 ), octafluorocyclobutane (C 4 F 8 ), hexafluorocyclobutene (C 4 F 6 )、1,2,3,3,4-pentafluorocyclobutene-4-yl (C 4 F 5 ), fluorine (F 2 ) or a mixture thereof. The remote plasma source 2060 may include an ICP, a TCP, a CCP, a microwave plasma, a DC plasma, or a laser-generated plasma. The plasma-activated species generated in the remote plasma source 2060 may be supplied to the processing chamber 2010 via a gas inlet 2080 fluidly coupled to the showerhead 202. The thermal etchant described herein may be supplied from a second processing gas supply source (not shown here), which is fluidly coupled to the processing chamber 2010 to deliver the thermal etchant to the processing chamber. In some embodiments, the second processing gas supply source may be fluidly coupled to the remote plasma source 2050. The processing chamber 2010 may also include a vacuum pump 2090 for removing processing gases and reaction products from the processing chamber 2010.

[0332] Fig.21 21 shows a cross-section of a station in a multi-station processing tool using an exemplary remote plasma device according to some embodiments. A station in a multi-station substrate processing tool 2100 may include a remote plasma cleaning device 2111 and a processing chamber 2103 that may be fluidly coupled to a remote plasma source (not shown here). Each station may also include a showerhead 2105 and a remote plasma cleaning device configured to support a substrate ( Fig.21 The remote plasma cleaning device 2111 may be configured to direct plasma-activated species (e.g., fluorine-containing species or fluorine species) into a volume (e.g., a microvolume) between the showerhead 2105 and the pedestal 2107. The plasma-activated species may be generated in the remote plasma source by receiving a process gas as described herein from a first process gas supply (not shown here) and igniting a plasma. In some embodiments, the remote plasma cleaning device 2111 may be disposed above the showerhead 2105 to deliver the fluorine-containing species in a downward direction. In some embodiments, the fluorine-containing species may be configured to deliver the fluorine-containing species in an upward direction.

[0333] In some embodiments, the fluorine-containing species can be supplied from a remote plasma source disposed upstream of the remote plasma cleaning apparatus 2111. The fluorine-containing species can enter the process chamber 2103 of the multi-station processing tool 2100 through a process gas inlet 2109 fluidly coupled to the remote plasma source (not shown here). The fluorine-containing species can then be divided into substantially uniform streams 2113 on either side of the remote plasma cleaning apparatus 2111 and delivered to various locations within the process chamber 2103.

[0334] In some embodiments, the thermal etchant described herein can be provided from a second process gas supply (not shown here) that is fluidly coupled to the processing chamber 2103 to deliver the thermal etchant into the processing chamber 2103. In some embodiments, the second process gas supply can be fluidly coupled to a remote plasma source.

[0335] Return to reference Figure 7 , a schematic diagram of an exemplary processing station suitable for depositing dielectric materials (e.g., hafnium oxide) using ALD and / or CVD is shown. In some embodiments, either of ALD and / or CVD can be plasma enhanced. Processing station 700 can remove dielectric materials, such as metal oxides or metal nitrides, deposited on the inner surface of the processing chamber using the methods provided herein. For simplicity, processing station 700 is drawn as an independent processing station having a processing chamber 702 for maintaining a low pressure environment. However, it should be understood that multiple processing stations 700 may be included in a common processing tool environment. Further, it should be understood that in some embodiments, one or more hardware parameters of processing station 700 (including those discussed in detail below) can be adjusted in a programmatic manner by one or more computer controllers.

[0336] As previously described herein, the processing station 700 is in fluid communication with a reactant delivery system 701 for delivering a process gas to the showerhead 706. The reactant delivery system 701 optionally includes a mixing vessel 704 for mixing and / or conditioning the process gas for delivery to the showerhead 706. One or more mixing vessel inlet valves 720 can control the introduction of the process gas into the mixing vessel 704. Similarly, the showerhead inlet valve 705 can control the introduction of the process gas into the showerhead 706. In the case of using plasma exposure, the plasma can also be delivered to the showerhead 706 or can be generated in the processing station 700. In some embodiments, the remote plasma can be generated from a remote plasma source external to the processing station 700. The remote plasma including the fluorine species can be delivered from the remote plasma source (not shown) to the mixing vessel 704 through a gas line (not shown) to mix with other process gases (e.g., thermal etchants described herein) or other reactants (e.g., water vapor, methanol, ethanol, or propanol). The mixture can be introduced into the processing chamber 702. In some embodiments, the remote plasma can be delivered to the processing chamber 702 via a separate gas line without mixing with the thermal etchant or other reactants. Fig. 20 Remote plasma source or Fig.21 A portion or all of the remote plasma cleaning apparatus in may be fluidly coupled to the processing chamber 702 to provide a remote plasma.

[0337] Figure 7 Further included is a vaporization point 703 for vaporizing a liquid reactant to be supplied to a mixing container 704 fluidically coupled to the processing chamber 702. For example, a thermal etchant (e.g., boron bromide (BBr 3 ), phosphorus trichloride (PCl 3 ), carbon tetrachloride (CCl 4 ), nitrogen trichloride (NCl 3 ) or a mixture thereof) can be vaporized at an optional vaporization point 703 before being mixed with the remote plasma or provided separately to the processing chamber. The optional vaporization point 703 can also be configured to vaporize alcohols, such as methanol, ethanol, or propanol. In some embodiments, a liquid flow controller (LFC) upstream of the vaporization point 703 can be provided to control the mass flow rate of the liquid to be vaporized and delivered to the processing station 700. For example, the LFC can include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC can then be adjusted in response to a feedback control signal provided by a proportional integral derivative (PID) controller electrically connected to the MFM.

[0338] Showerhead 706 distributes processing gas to substrate 712. Figure 7In the illustrated embodiment, substrate 712 is positioned below showerhead 706 and is shown resting on pedestal 708. Showerhead 706 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to substrate 712.

[0339] In some embodiments, microvolume 707 is located below showerhead 706. Performing ALD and / or CVD processing in a microvolume rather than in the entire volume of a process station can reduce reactant exposure and sweep time, can reduce the time to change process conditions (e.g., pressure, temperature, etc.), can limit the exposure of the process station robot to process gases, etc. Exemplary microvolume sizes include, but are not limited to, volumes between 0.1 liters and 2 liters. The microvolume also affects production yields. Using a microvolume significantly reduces cycle time due to faster sweeps and higher precursor partial pressures in the microvolume.

[0340] In some embodiments, the pedestal 708 may be raised or lowered to expose the substrate 712 to the volume between the substrate 712 and the showerhead 706. It should be appreciated that in some embodiments, the pedestal height may be programmatically adjusted by an appropriate computer controller 750. In some embodiments, the showerhead 706 may have multiple plenum volumes with multiple temperature control devices.

[0341] In some embodiments, the susceptor 708 can be temperature controlled by a heater 710. In some embodiments, during the non-plasma thermal exposure, the susceptor 708 can be heated to a temperature of about 50° C. to about 650° C. or about 50° C. to about 450° C., as described in the disclosed embodiments. In some embodiments, the heater 710 of the susceptor 708 can include a plurality of independently controllable temperature control zones.

[0342] Further, in some embodiments, pressure control of the processing station 700 may be provided by a butterfly valve (or gate valve) 718. Figure 7 In the embodiment shown in FIG. 7 , butterfly valve 718 regulates the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 700 can also be adjusted by changing the flow rate of one or more gases introduced into process station 700.

[0343] In some embodiments, the position of the showerhead 706 can be adjusted relative to the pedestal 708 to change the volume between the substrate 712 and the showerhead 706. Further, it should be understood that the vertical position of the pedestal 708 and / or the showerhead 706 can be changed within the scope of the present invention by any suitable mechanism. In some embodiments, the pedestal 708 may include a rotating shaft for rotating the orientation of the substrate 712. It should be understood that in some embodiments, one or more of these exemplary adjustments can be performed in a programmatic manner by one or more appropriate computer controllers.

[0344] In an operation where plasma may be used, such as in an operation where a dielectric material is deposited on a substrate, the showerhead 706 and / or the pedestal 708 are electrically connected to a radio frequency (RF) power supply 714 and a matching network 716 to power the plasma. Thus, one or both of the showerhead 706 and the pedestal 708 may be powered to generate the plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of the processing station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power supply 714 and the matching network 716 may be operated at any suitable power to form a plasma having a desired radical species composition. Examples of suitable powers are up to about 1000 W.

[0345] In some embodiments, instructions for the controller may be provided via input / output control (IOC) sequencing instructions. In one example, instructions for setting conditions for a processing stage may be included in a corresponding recipe stage of a processing recipe. In some cases, the processing recipe stages may be arranged in sequence so that all instructions for a processing stage are executed simultaneously with the processing stage. In some embodiments, instructions for setting one or more processing station parameters may be included in a recipe stage. For example, a recipe stage may include instructions for setting one or more fluorine-containing processing gases or Br or Cl-containing thermal etchants (e.g., HCl, HBr, or BCl). 3 ) flow rate instructions, and time delay instructions for the recipe phase. In some embodiments, the controller may include the following about Figure 8 Any features described by the system controller 850.

[0346] Return to reference Figure 8 , shows a schematic diagram of an exemplary multi-station processing tool suitable for depositing and removing dielectric films according to some embodiments. In some embodiments, one or more hardware parameters of the processing tool 800 (including those parameters discussed in detail below) can be adjusted in a programmatic manner by one or more computer controllers 850.

[0347] The processing stations may be configured as modules in a cluster tool. Figure 8 A semiconductor processing cluster tool architecture having a vacuum integrated deposition module suitable for performing deposition and etching operations described herein is depicted. Such a cluster processing tool architecture may include a remote plasma as described herein.

[0348] Figure 8Also shown is a schematic diagram of an embodiment of a multi-station processing tool 800, which has an inbound loading lock 802 and an outbound loading lock 804, one or both of which may include a remote plasma source. A robot 806 at atmospheric pressure is configured to move a wafer through a pod 808 loaded box to the inbound loading lock 802 through an atmospheric port 810. The wafer is placed on a pedestal 812 in the inbound loading lock 802 by the robot 806, the atmospheric port 810 is closed, and the loading lock is pumped. In the case where the inbound loading lock 802 includes a remote plasma source, the wafer may be exposed to a remote plasma treatment to treat the substrate surface in the loading lock before being introduced into the processing chamber 814. The remote plasma generated from the remote plasma source may be supplied to each processing station (as described below) to clean the internal surface according to the method described herein. In some embodiments, the remote plasma may be fluidly coupled to a first processing gas supply source (not shown here) to receive a processing gas from the first processing gas supply source, and a second processing gas supply source (not shown here) to receive a thermal etchant from the second processing gas supply source. A second process gas supply may also be fluidly coupled to each process chamber 814. Further, the wafer may also be heated in the inbound load lock 802, for example to remove moisture and adsorbed gases. Next, a chamber transfer port 816 leading to the process chamber 814 is opened, and another robot (not shown) places the wafer onto a pedestal in the first station of the process station (shown in the process station) for processing. Although depicted in Figure 8 The embodiments in the present invention include a load lock, but it should be understood that in some embodiments, the wafer can be directly fed into the processing station.

[0349] The depicted processing chamber 814 includes four processing stations, Figure 8 In the illustrated embodiment, the stations are numbered from 1 to 4. Each station has a heating base (shown as 818 in station 1) and a gas line inlet. It should be understood that in some embodiments, each processing station may have different or multiple purposes. For example, in some embodiments, the processing station may switch between heat and plasma processing modes. Additionally or alternatively, in some embodiments, the processing chamber 814 may include one or more pairs of matching heat and plasma processing stations. Although the depicted processing chamber 814 includes four stations, it should be understood that the processing chamber according to the present invention may have any suitable number of stations. For example, in some embodiments, the processing chamber may have five or more stations, while in other embodiments, the processing chamber may have three or less stations.

[0350] Figure 8An embodiment of a wafer handling system 890 for transferring wafers within the processing chamber 814 is depicted. In some embodiments, the wafer handling system 890 can transfer wafers between various processing stations and / or between a processing station and a load lock. It should be understood that any suitable wafer handling system can be used. Non-limiting examples include a wafer turntable and a wafer handling robot. Figure 8 Also depicted is an embodiment of a system controller 850 for controlling processing conditions and hardware states of the processing tool 800. The system controller 850 may include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. The processor 852 may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, a stepper motor controller board, and the like.

[0351] In some embodiments, the system controller 850 controls all activities of the processing tool 800. In some embodiments, the parameters adjusted by the system controller 850 may be related to processing conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF bias power level), etc. These parameters may be provided to the user in the form of a recipe (which may be input using a user interface).

[0352] In some embodiments, the system controller 850 may be configured with instructions to: provide a semiconductor substrate in the process chamber 814 to form a dielectric material on the one or more features on the substrate; remove the dielectric material formed on the substrate; remove the semiconductor substrate from the process chamber 814, wherein the dielectric material is formed on one or more interior surfaces of the process chamber 814; in the absence of the semiconductor substrate in the process chamber 814, expose the one or more interior surfaces of the process chamber 814 to a fluorine-containing species to form a non-volatile reaction product; and in the absence of the semiconductor substrate in the process chamber 814, expose the one or more interior surfaces of the process chamber 814 to a thermal etchant to convert the non-volatile reaction product into a volatile reaction product. In some embodiments, the system controller 850 may be further configured with instructions to introduce the fluorine-containing species and the thermal etchant into the process chamber as a co-flow or circulating flow. Figure 8 Additional aspects of the system controller 850 have been described above and will not be repeated here. Figure 7 , 8 , 20 or 21. The controller described in any one of Figure 8 The tool implementation in . Prevents aluminum fluoride from redepositing on the printhead during cleaning

[0353] In some embodiments, semiconductor device manufacturing generally involves various deposition processes to deposit one or more silicon-containing films to form integrated circuits and related devices by various methods including CVD, PECVD, ALD or PEALD. The result of the deposition process is that one or more silicon-containing materials are not only deposited on the substrate to be deposited with various materials, but also deposited on the inner surface of the processing chamber where the deposition process occurs. Therefore, the film formed by the various materials is formed on the inner surface of the processing chamber, and the material may accumulate over time to form deposition byproducts. The deposition byproducts may include silicon-based materials, such as silicon oxide, silicon carbide or silicon nitride. The deposition byproducts may be dissolved, separated, thermally desorbed or evaporated by subsequent processing in the processing chamber, causing the substrate or the features formed on the substrate to be contaminated. This contamination is a cause of low production yield / output or equipment reliability problems. The deposition byproducts accumulated on the inner surface of the processing chamber are regularly removed to avoid contaminating the processing chamber.

[0354] One method of removing contaminants from a processing chamber is to introduce a plasma stream that includes fluorine (F)-containing species. For this type of cleaning, one or more source gases (e.g., cleaning gases) may be used, including nitrogen trifluoride (NF 3 ), carbon tetrafluoride (CF 4 ), carbon hexafluoride (C 2 F 6 ), octafluoropropane (C 3 F 8 ), other fluorine-containing compounds (i.e., fluorine-containing reactants). One or more source gases may be supplied to the plasma source. The plasma source may be an inductively coupled plasma reactor, a capacitively coupled plasma reactor, a microwave plasma reactor, a DC plasma reactor, or a laser-generated plasma reactor. The plasma stream generated from the plasma source may flow into the processing chamber to clean the inner surface of the processing chamber. The plasma stream may include fluorine-containing substances (including fluorine-based free radicals), oxygen-containing substances (including oxygen-based free radicals), and an inert gas. The above reference Figure 12-21 An example of such F-containing cleaning treatment is described.

[0355] Aluminum fluoride can be formed on the surface area or inner wall of internal parts made of aluminum or aluminum-containing materials by the reaction between aluminum and fluorine-containing species introduced for plasma cleaning. Aluminum fluoride can be deposited on the wall at low temperatures and can be thermally desorbed above about 450°C. Aluminum fluoride can be aluminum trifluoride (AlF 3 ), and may contaminate the substrate or features of the substrate in subsequent processing. In some cases, aluminum trifluoride is a gaseous contaminant that diffuses into the showerhead and may be deposited / adsorbed on the showerhead, thereby contaminating the substrate or features of the substrate in subsequent processing.

[0356] One aspect of the embodiment relates to a method for cleaning a processing chamber by providing a plasma flow into the processing chamber at a predetermined temperature as described herein. A plasma source is coupled to the processing chamber via a showerhead fluid. The plasma flow may have a sufficient flow rate to prevent gaseous contaminants from diffusing to one or more locations in the processing chamber. The plasma flow from the plasma source may include a fluorine-containing substance. The fluorine-containing substance in the plasma flow may react with the deposition byproducts, thereby removing the deposition byproducts from the inner surface of the processing chamber. Gaseous byproducts may be generated by the reaction between the fluorine-containing substance and the deposition byproducts. The gaseous byproducts may be removed from the processing chamber.

[0357] Another aspect of the embodiment relates to a method for preventing showerhead contamination in a processing chamber by introducing a plasma stream including a fluorine-containing species. Although the fluorine-containing species removes silicon-based deposition products from the inner surfaces of the processing chamber, the fluorine-containing species may react with aluminum in aluminum-containing parts and form aluminum fluoride, such as aluminum trifluoride (AlF 3 ). By maintaining the processing chamber temperature at a predetermined temperature, aluminum fluoride can be thermally desorbed from the surface and be in the gas phase. A plasma flow with a sufficient flow rate can prevent gaseous aluminum fluoride from reaching the surface of the showerhead, thereby keeping the showerhead surface substantially free of aluminum fluoride. According to some embodiments, chamber cleaning and prevention of showerhead contamination can be achieved by providing a plasma flow. This can occur at a predetermined temperature. The substrate can be transferred to the chamber to deposit a film at a predetermined temperature without changing the processing chamber temperature.

[0358] Return to reference Fig.16 , shows a schematic diagram of an exemplary plasma processing apparatus according to some embodiments. It should be understood that according to some embodiments, Fig.16 The plasma processing device in the present invention can be used to deposit films by ALD, PEALD, CVD or PECVD, and / or to clean the processing chamber by delivering a plasma stream. The processing chamber (or "chamber") cleaning of the present invention can include delivering a plasma stream containing a fluorine-containing species to remove deposition byproducts from one or more surface areas or internal surfaces of internal components of the plasma processing device and to limit the diffusion of gaseous contaminants from specific locations within the processing chamber. In some embodiments, Fig.16 The apparatus may be used to deposit films by remote plasma CVD, and may also be used to clean a process chamber by providing a plasma flow containing fluorine-containing species.

[0359] According to some embodiments, after the substrate is removed from the processing chamber, the plasma flow generated from the remote plasma source can be supplied to the processing chamber. The processing chamber can be maintained at a predetermined temperature. The plasma flow including the fluorine-containing substance can be transported at a sufficient flow rate to clean the inner surface of the processing chamber by reacting with the deposition byproducts, and substantially prevent the gaseous pollutants (e.g., gaseous aluminum fluoride) in the processing chamber from being deposited on the surface of the shower head in the processing chamber. Therefore, the shower head surface can remain substantially free of aluminum fluoride. The substrate can be transferred to the processing chamber to deposit a film on the substrate. The deposition of the film on the substrate can occur before or after the chamber cleaning. Chamber cleaning (including preventing the shower head from being contaminated) and film deposition can be performed sequentially without changing the processing chamber temperature and / or without exposing the substrate to the ambient atmosphere. In some embodiments, chamber cleaning and film deposition can be repeated without changing the processing chamber temperature. The processing chamber temperature can be the temperature in the environment adjacent to the substrate. In some cases, the processing chamber temperature corresponds to the susceptor temperature.

[0360] Fig.16The plasma processing apparatus 1600 in the embodiment includes a remote plasma source 1602 separated from a processing chamber 1604. The remote plasma source 1602 is fluidly coupled to the processing chamber 1604 through a gas distributor or showerhead 1606. A coil 1628 may be arranged around the remote plasma source 1602, wherein the remote plasma source 1602 includes an outer wall (e.g., a ceramic dome). In some embodiments, the remote plasma source 1602 includes an outer wall that includes a ceramic material resistant to fluorine-containing substances. The outer wall may be semicircular or elliptical. In some embodiments, the outer wall may be made of a ceramic material. The coil 1628 is electrically connected to a plasma generator controller 1632, which may be used to form and maintain plasma in a plasma region 1634 by inductively coupled plasma generation, capacitively coupled plasma generation, microwave plasma generation, DC plasma generation, or laser-generated plasma generation. In some embodiments, the plasma generator controller 1632 may include a power supply for powering the coil 1628, wherein during plasma generation, the power may be in a range between about 500 watts (W) and about 15 kilowatts (kW) per station, or in a range between about 2 kW and about 10 kW per station. In some embodiments, electrodes or antennas for parallel plate plasma generation, inductively coupled plasma generation, capacitively coupled plasma generation, microwave plasma generation, DC plasma generation, or laser generated plasma generation may be used to generate a continuous supply of free radicals by plasma excitation. In some embodiments, free radicals and / or ions may be generated by inductively coupled plasma generation. In some embodiments, free radicals and / or ions may be generated by microwave plasma, direct current (DC) plasma, or laser generated plasma. Regardless of the mechanism used to ignite and maintain the plasma in the plasma region 1634, plasma excitation may be utilized to continuously generate free radical species.

[0361] While one or more source gases are being supplied to the remote plasma source 1602, a supply of ions and radicals may be continuously generated within the plasma region 1634. Ions generated in the plasma region 1634 may be filtered out by an ion filter of the showerhead 1606. In this way, radicals generated in the plasma region 1634 may be supplied to the substrate 1612 in the processing chamber 1604 and ion bombardment may be limited. Conditions in the remote plasma source 1602, including the composition of the source gas supplied to the remote plasma source 1602 and the RF power supplied to the coil 1628, may be controlled to optimize the generation of desired radical species in the plasma region 1634.

[0362] exist Fig.16In the embodiment, source gas supply source 1636 is fluidly coupled to remote plasma source 1602 to supply source gas. In some embodiments, one or more source gases may include an oxygen-containing reactant (e.g., oxygen (O 2 ), carbon dioxide (CO 2 ), or nitrogen dioxide (NO 2 )), fluorine-containing reactants (e.g. nitrogen trifluoride (NF 3 ), fluorine (F 2 ), carbon tetrafluoride (CF 4 ), or carbon hexafluoride (C 2 F 6 )), hydrogen-containing reactants (e.g. hydrogen (H 2 ) or methane (CH 4 )), inert gases such as argon (Ar), or nitrogen-containing reactants such as nitrogen (N 2 ), ammonia (NH 3 ), diazene (N 2 H 2 ), or hydrazine (N 2 H 4 )), carbon-containing reactants (e.g. acetylene (C 2 H 2 ), or propylene (C 3 H 6 ), or a mixture thereof).

[0363] It should be understood that the mixture of source gases used for film deposition may be different from the mixture of source gases used for chamber cleaning. The film to be deposited may be a silicon-based film including doped or undoped silicon carbide, for example, oxygen-doped silicon carbide (SiCO), nitrogen-doped silicon carbide (SiCN), and nitrogen and oxygen-doped silicon carbide (SiOCN). For many, the doped silicon carbide has up to about 50% atoms of dopant atoms, whether these atoms are atoms of oxygen, nitrogen, or another element. The amount of doping provides the desired film properties. Silicon-based films may also include silicon oxide (SiOx), silicon nitride (SixNy), or oxygen-doped silicon nitride (SiON). The gas mixture supplied to the remote plasma source for film deposition processing may include, but is not limited to, oxygen (O 2 ), carbon dioxide (CO 2 ), nitrogen dioxide (NO 2 ), hydrogen (H 2 ), methane (CH 4 ), argon (Ar), nitrogen (N 2 ), ammonia (NH 3 ), diazene (N 2 H 2 ), hydrazine (N 2 H 4 ), acetylene (C 2 H2 ), propylene (C 3 H 6 ), or a mixture thereof.

[0364] The gas mixture used for chamber cleaning may include a fluorine-containing gas such as nitrogen trifluoride (NF 3 ), fluorine (F 2 ), carbon tetrafluoride (CF 4 ) or carbon hexafluoride (C 2 F 6 For example, the gas mixture may include, but is not limited to, trifluorinated (NF 3 ), fluorine (F 2 ), oxygen (O 2 ), carbon dioxide (CO 2 ), nitrogen dioxide (NO 2 ), hydrogen (H 2 ), argon (Ar), nitrogen (N 2 ), or a mixture thereof.

[0365] The type of radical species generated in the remote plasma source 1602 may be determined by the source gas supplied to the remote plasma source 1602. In some embodiments, depending on the nature of the source gas, a mixture of radical species (including hydrogen radicals (H*), nitrogen radicals (N*), oxygen radicals (O*), fluorine radicals (F*), amine radicals (NH*, NH 2 *), carbon radicals (C*), or mixtures thereof) can be generated in the plasma region 1634 under approximately steady-state conditions during steady-state film deposition or chamber cleaning controlled by the plasma generator controller 1632, but transients may occur at the beginning and end of film deposition and / or chamber cleaning.

[0366] The additional gas supply source 1638 is fluidly coupled to the remote plasma source 1602 for supplying the one or more additional gases. Fig.16 The embodiments in the drawings depict that the gas mixture of the source gas and the one or more additional gases are introduced through separate gas outlets, but it should be understood that the gas mixture can be introduced directly into the remote plasma source 1602. That is, the premixed dilution gas mixture can be supplied to the remote plasma source 1602 through a single gas outlet. The one or more additional gases may include a carrier gas. Non-limiting examples of additional gases may include helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and nitrogen (N 2 ). The one or more additional gases may support or stabilize steady-state plasma conditions within the remote plasma source 1602 or assist in transient plasma ignition or extinguishing processes.

[0367] In some embodiments, a gas conduit from a gas source (not shown) through a source gas supply 1636 into a remote plasma source 1602 and / or a gas conduit from a gas source (not shown) through an additional source gas supply 1638 into a remote plasma source 1602 may be designed to withstand high gas flow rates according to some embodiments.

[0368] In some embodiments, a co-reactant is introduced during the deposition reaction that is not a primary silicon-containing precursor or hydrogen radicals. In some embodiments, the plasma processing apparatus is configured to introduce a co-reactant via source gas supply 1636 or additional gas supply 1638, in which case the co-reactant is at least partially converted to plasma. Examples of such co-reactants include carbon dioxide (CO 2 ), carbon monoxide (CO), water (H 2 O), methanol (CH 3 OH), oxygen (O 2 ), ozone (O 3 ), nitrogen (N 2 ), nitrous oxide (N 2 O), ammonia (NH 3 ), diazene (N 2 H 2 ), methane (CH 4 ), ethane (C 2 H 6 ), acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), diborane (B 2 H 6 ), and mixtures thereof. This material can be used as a nitriding agent, an oxidizing agent, a reducing agent, etc.

[0369] Plasma activated species 1642 (e.g., excited nitrogen, hydrogen, carbon, oxygen, fluorine, and / or amine radicals) flow out of the remote plasma source 1602 and into the processing chamber 1604 through the showerhead 1606. In some embodiments, the plasma activated species 1642 can be a plasma stream. The plasma activated species 1642 within the showerhead 1606 and within the processing chamber 1604 generally do not undergo sustained plasma excitation therein. The showerhead 1606 can have a plurality of gas ports to diffuse the stream of plasma activated species 1642 into the processing chamber 1604. In some embodiments, the plurality of gas ports can be spaced apart from each other. In some embodiments, the plurality of gas ports can be arranged as a regularly spaced array of channels or through holes extending through a plate separating the remote plasma source 1602 from the processing chamber 1604. The plurality of gas ports can allow the free radicals (including the plasma activated species 1642) exiting the remote plasma source 1602 to be dispersed and diffused smoothly into the deposition region 1610 of the processing chamber 1604 and filter out ions. The plasma activated species 1642 (ie, plasma stream) can further flow in a downward direction or substantially downward direction once passing through the plurality of gas ports in the showerhead 1606. In some embodiments, the plasma stream can include fluorine-containing species and other plasma activated species.

[0370] With the plasma activated species 1642 delivered to the process chamber 1604 from the showerhead 1606, one or more silicon-containing precursors 1644 (or other process gases) may be introduced into the process chamber 1604 to deposit a silicon-based film. The silicon-containing precursor 1644 may be introduced through a gas outlet 1608, which may be fluidly coupled to a silicon-containing precursor supply 1640. The gas outlet 1608 may include openings spaced apart from one another so that a stream of the silicon-containing precursor 1644 may be introduced in a direction parallel to the flow of the plasma activated species 1642 out of the showerhead 1606. In some embodiments, the gas outlet 1608 may be located downstream of the showerhead 1606. In some embodiments, the gas outlet 1608 is part of the showerhead 1606, such as in a dual plenum showerhead. The dual plenum showerhead may provide separate outlets / channels for the plasma activated species 1642 and the silicon-containing precursor 1644 to avoid mixing in the showerhead 1606. In this way, the silicon-containing precursor 1644 can flow into the processing chamber 1604 through the showerhead 1606 without being exposed to the plasma in the remote plasma source 1602. The gas outlet 1608 can be located upstream of the deposition zone 1610 and the substrate 1612. The deposition zone 1610 is located inside the processing chamber 1604 between the gas outlet 1608 and the substrate 1612. In some embodiments, a direct plasma can be formed in the processing chamber. To generate the direct plasma, in some embodiments, a plasma processing apparatus can be provided or modified to include an upper electrode, a lower electrode, and a radio frequency (RF) generation system, the RF generation system can generate an RF voltage and output it to one of the upper electrode and the lower electrode, and the other of the upper electrode and the lower electrode can be grounded or floating. In some embodiments, the RF generation system can include an RF voltage generator and a matching network. The direct plasma can include fluorine-containing substances and other plasma-activated substances. In some embodiments, the direct plasma can be formed at a location near the showerhead.

[0371] In some embodiments, the silicon-containing precursor may include at least one or more Si-Si bonds and / or at least one or more Si-H bonds. Silicon-containing precursors suitable for use according to the disclosed embodiments may include: silane (SiH 4 ), disilane (Si 2 H 6 ), and organosilanes such as methylsilane, ethylsilane, isopropylsilane, tert-butylsilane, dimethylsilane, diethylsilane, di-tert-butylsilane, allylsilane, sec-butylsilane, tert-hexylsilane, isopentylsilane, tert-butyldisilane, di-tert-butyldisilane, and the like.

[0372] In some embodiments, the silicon-containing precursor may also include halosilanes. Halosilanes include at least one halogen group and may or may not include hydrogen and / or carbon groups. Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes. Specific chlorosilanes are tetrachlorosilane, trichlorosilane, dichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, tert-butylchlorosilane, di-tert-butylchlorosilane, chloroisopropylsilane, chlorosec-butylsilane, tert-butyldimethylchlorosilane, tert-hexyldimethylchlorosilane (thexyl dimethylchlorosilane) and the like.

[0373] In some embodiments, the silicon-containing precursor may also include aminosilanes. Aminosilanes include at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogen, oxygen, halogens, and carbon. Examples of aminosilanes are mono-, di-, tri-, and tetra-aminosilanes (H, 3 Si(NH 2 ), H 2 Si(NH 2 ) 2 、HSi(NH 2 ) 3 and Si(NH 2 ) 4 ), and substituted mono-, di-, tri- and tetraaminosilanes, such as tert-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tert-butylamino)silane (SiH 2 (NHC(CH 3 ) 3 ) 2 (BTBAS), diisopropylaminosilane (DIPAS), tert-butyl silylcarbamate, SiH(CH 3 )-(N(CH 3 ) 2 ) 2 、SiHCl-(N(CH 3 ) 2 ) 2 、(Si(CH 3 ) 2 NH) 3 and the like. Further examples of aminosilanes are trisilylamine (N(SiH 3 ) 3 In some embodiments, aminosilanes with two or more amine groups attached to the central Si atom may be used. These may cause less damage than aminosilanes with only a single amine group attached.

[0374] Further examples of silicon-containing precursors include trimethylsilane (3MS); ethylsilane; butosilane; pentasilane; octylsilane; heptylsilane; hexasilane; cyclotetrasilane; cycloheptylsilane; cyclohexasilane; cyclooctylsilane; cyclopentasilane; 1,4-dioxa-2,3,5,6-tetrasilacyclohexane; diethoxymethylsilane (DEMS); diethoxysilane (DES ), dimethoxymethylsilane, dimethoxysilane (DMOS), methyldiethoxysilane (MDES), methyldimethoxysilane (MDMS), octamethoxydodecyloxane (OMODDS), tert-butyloxydisilane, tetramethylcyclotetrasiloxane (TMCTS), tetraoxymethylcyclotetrasiloxane (TOMCTS), triethoxysilane (TES), triethoxysiloxane (TRIES), and trimethoxysilane (TMS or TriMOS).

[0375] In addition to the silicon-containing precursor, the environment adjacent to the substrate may also include one or more free radical substances, preferably in a substantially low energy state. The free radical may include a hydrogen radical, a nitrogen radical, an oxygen radical, an amine radical, a carbon radical, or a mixture thereof. In some embodiments, all or substantially all or a considerable portion of the hydrogen atom radicals may be in a ground state, for example, at least about 90% or about 95% of the hydrogen atom radicals adjacent to the substrate may be in a ground state. In some implementations, when the excited hydrogen atom radical loses its energy or relaxes, the excited hydrogen atom radical may become a substantially low energy state hydrogen atom radical or a ground state hydrogen atom radical. The hydrogen atom radical in a substantially low energy state or ground state can selectively destroy Si-H and Si-Si bonds, and substantially retain Si-O, Si-N and / or Si-C bonds. In some implementations, the processing conditions may be provided so that the excited hydrogen atom radical loses energy or relaxes to form a substantially low energy state or ground state hydrogen atom radical.

[0376] During the film deposition process, a majority of the silicon-containing precursor 1644 may be prevented from mixing with the plasma-activated species 1642 in or adjacent to the showerhead 1606. In some embodiments, the silicon-containing precursor 1644 may be delivered to the substrate 1612 during the dosing phase of the ALD cycle, separate from the plasma-activated species 1642 delivered to the substrate 1612 during the plasma exposure phase of the ALD cycle. The adsorbed silicon-containing precursor 1644 may react with radicals of the plasma-activated species 1642 during the plasma exposure phase of the ALD cycle to deposit a film. In some embodiments, the silicon-containing precursor 1644 may be delivered to the substrate 1612 in a continuous manner to interact with the plasma-activated species 1642 in the deposition region 1610 to deposit a film by CVD. During CVD film formation, radicals of the plasma-activated species 1642 may mix with the silicon-containing precursor 1644 in the gas phase.

[0377] Gas may be removed from the process chamber 1604 through an outlet 1648 that is fluidly coupled to a pump (not shown). Thus, radical species or purge gas may be removed from the process chamber 1604.

[0378] The substrate 1612 is supported on a substrate support structure or wafer pedestal (i.e., pedestal) 1614. The pedestal 1614 can be configured with lift pins or other movable support members to position the substrate 1612 within the deposition zone 1610. The substrate 1612 can be moved closer to or further away from the showerhead 1606. The pedestal 1614 can also adjust the temperature of the substrate 1612 in some embodiments, which can provide some selective control over thermally activated surface reactions on the substrate 1612.

[0379] The susceptor 1614 may be made of a ceramic material. In one embodiment, the susceptor 1614 may be made of aluminum nitride suitable for high temperature processing (e.g., a plasma processing environment that does not cause any thermal damage to the susceptor 1614). Other surfaces of the processing chamber 1604 may be formed of a ceramic material (e.g., aluminum nitride).

[0380] In some embodiments, the base 1614 includes an electrostatic chuck 1616. The electrostatic chuck 1616 may include one or more electrostatic clamping electrodes 1618 embedded in the body of the electrostatic chuck 1616. In some embodiments, the one or more electrostatic clamping electrodes 1618 may be coplanar or substantially coplanar. The electrostatic clamping electrodes 1618 may be powered by a direct current (DC) power source or a DC clamping voltage (e.g., between about 200V and about 2000V) so that the substrate 1612 can be held on the electrostatic chuck 1616 by electrostatic attraction. The electrostatic clamping electrodes 1618 may be powered by a first wire 1620. The electrostatic chuck 1616 may further include one or more heating elements 1622 embedded in the body of the electrostatic chuck 1616. The one or more heating elements 1622 may include a resistive heater. In some embodiments, the one or more heating elements 1622 are disposed below the one or more electrostatic clamping electrodes 1618. The one or more heating elements 1622 can be configured to heat the substrate 1612 to a temperature greater than about 450° C., greater than about 500° C., greater than about 550° C., greater than about 600° C., or greater than about 650° C. The one or more heating elements 1622 provide selective temperature control of the substrate 1612. The one or more heating elements 1622 can be powered by a second electrical wire 1624.

[0381] In some embodiments, a thermal shield (not shown) can be disposed below the pedestal 1614. The thermal shield acts as a thermal insulator below the pedestal 1614 to slow down heat loss through thermal radiation, thereby reducing the amount of power required to maintain the pedestal 1614 at a particular elevated temperature and also preventing other components within the processing chamber 1604 from overheating due to excessive heat radiated from the pedestal 1614. For example, the thermal shield can be radially offset from the stem 1626 and can have a thin annular body with a high view factor relative to the underside of the electrostatic chuck 1616. Thus, the annular thermal shield can reduce radiative heat loss from the pedestal 1614.

[0382] The controller 1650 may contain instructions for controlling the processing conditions of the operating plasma processing device 1600. The controller 1650 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, a stepper motor controller board, etc. Instructions for implementing appropriate control operations are executed on the processor. These instructions may be stored on a memory device associated with the controller 1650 or it may be provided via a network.

[0383] In certain embodiments, the controller 1650 controls all or most of the activities of the plasma processing apparatus 1600 described herein. For example, the controller 1650 may control all or most of the activities of the plasma processing apparatus 1600 associated with film deposition and / or chamber cleaning. In some embodiments, the controller 1650 includes a processor system 1652 (e.g., a microprocessor) configured to execute instructions stored in a data system 1654 (e.g., a memory). In some embodiments, the controller 1650 may communicate with the plasma generator controller 1632 to control plasma parameters and / or conditions in the remote plasma source 1602. In some embodiments, the controller 1650 may communicate with the pedestal 1614 to control pedestal elevation (substrate position), electrostatic adsorption and desorption, and temperature. In some embodiments, the controller 1650 may control other processing conditions, such as RF power settings, frequency settings, duty cycle, pulse time, pressure within the processing chamber 1604, pressure within the remote plasma source 1602, gas composition, gas flow rate from the source gas supply source 1636, gas composition, gas flow rate from the additional gas supply source 1638 and other sources, temperature of the pedestal 1614, and temperature of the processing chamber 1604, as well as other processing conditions.

[0384] In some embodiments, the controller 1650 may include instructions configured to perform operations such as heating the processing chamber 1604 to a predetermined temperature, delivering a plasma stream from the remote plasma source 1602 through the showerhead 1606 to the processing chamber 1604, and limiting gaseous contaminants from the showerhead 1606. In some embodiments, the plasma stream includes a fluorine-containing reactant, such as nitrogen trifluoride. For example, the plasma stream includes an oxygen-containing species (including oxygen-based free radicals), a fluorine-containing species (e.g., fluorine-based free radicals), and an inert gas. The inert gas may include nitrogen, argon, helium, neon, krypton, or a mixture thereof. In some embodiments, the predetermined temperature may range from about 450° C. to about 650° C.

[0385] In some embodiments, the controller 1650 may include instructions configured to perform operations such as introducing a first dose of a silicon-containing precursor 1644 in a gas phase to adsorb on the substrate 1612, and exposing the substrate 1612 to the plasma-activated species 1642 of the source gas generated in the remote plasma source 1602, wherein the adsorbed silicon-containing precursor 1644 reacts with the plasma-activated species 1642 to deposit a silicon-containing film. In some embodiments, the controller 1650 may include instructions configured to perform operations such as setting the chamber pressure in the process chamber 1604 to between 0.6 Torr and about 30 Torr, or between about 1 Torr and about 30 Torr, and setting the substrate temperature to an elevated temperature between about 200° C. and about 700° C. In some embodiments, the controller 1650 may include instructions configured to perform operations such as applying a first voltage to an electrostatic chuck 1616 of a pedestal 1614 to electrostatically clamp a substrate 1612 in the processing chamber 1604, reversing the polarity of the first voltage applied to the electrostatic chuck 1616, applying a second voltage less than the first voltage to the electrostatic chuck 1616, reversing the polarity of the second voltage applied to the electrostatic chuck 1616, and removing the substrate 1612 from the electrostatic chuck 1616. In some embodiments, the controller 1650 may include instructions configured to perform chamber cleaning using a plasma flow containing a fluorine-containing reactant and film deposition on the substrate 1612 using a silicon-containing precursor 1644 and a plasma-activated species 1642.

[0386] In some embodiments, plasma processing apparatus 1600 may include a user interface associated with controller 1650. The user interface may include a display screen, a graphical software display of plasma processing apparatus 1600 and / or processing conditions, and a user input device (e.g., a pointing device, a keyboard, a touch screen, a microphone, etc.). Computer program code for controlling the above operations may be written in a conventional computer-readable programming language. Additional aspects of the controller have been described above and will not be repeated here.

[0387] In some embodiments, a processing chamber of an exemplary plasma processing apparatus can be used (depending on the processing recipe) to deposit thin layers by any suitable deposition method (e.g., ALD, PEALD, CVD, or PECVD), and / or to clean interior surfaces of the processing chamber according to embodiments herein.

[0388] In some embodiments, the processing chamber may include a remote plasma source disposed on a top portion of the processing chamber. The remote plasma source may be a dome and include a coil surrounding the remote plasma source. The remote plasma source may include a plasma region within the remote plasma source. The remote plasma source may be fluidically coupled to the processing chamber via a showerhead.

[0389] In some embodiments, the source gas inlet may be disposed on the top of the remote plasma source, but the source gas inlet may be disposed at other locations of the remote plasma source. The source gas inlet may be fluidically coupled to the remote plasma source to supply one or more source gases from one or more gas sources to the remote plasma source. Radical species (e.g., nitrogen radicals, fluorine radicals, hydrogen radicals, oxygen radicals, argon radicals, carbon radicals, or mixtures thereof) may be generated in the plasma region to form a plasma stream. In some embodiments, a plasma stream including fluorine radicals may be generated when chamber cleaning is required. The plasma stream may flow through a plurality of gas ports in the showerhead in a downward direction or substantially downward direction. As used herein, a downward direction or substantially downward direction may refer to a direction perpendicular or substantially perpendicular to the main plane of the showerhead. The plasma stream may further flow downward to a base spaced a predetermined distance from the showerhead.

[0390] In some embodiments, the susceptor may include one or more heating elements embedded in or thermally connected to the susceptor. The heating element may be connected to a controller and may be configured to heat a substrate supported on the susceptor to a temperature suitable for processing (e.g., film deposition). The heating element may also operate in the absence of a substrate in the processing chamber. The processing chamber may further include an outlet for exhausting any gas from the processing chamber.

[0391] In some embodiments, the controller may be coupled to one or more gas sources to control the flow rate of one or more source gases entering the remote plasma source. In some embodiments, the flow rate of the plasma flow flowing through the showerhead may be proportional to the flow rate of the source gas. As the flow rate of the source gas increases, the flow rate of the plasma flow may also increase. In some embodiments, the plasma flow flowing through the showerhead may form a plasma volume extending from the showerhead to the base. Depending on the surface area of ​​the showerhead and the base, the entire surface of the base may be exposed to the plasma volume. In the case where the plasma flow includes fluorine-containing substances, the material deposited on the base may react with the incoming fluorine-containing substance flow. In some embodiments, depending on the flow rate of the source gas (and the corresponding plasma flow), the plasma flow contacting the surface of the base can move the gas flow adjacent to the base to other locations in the processing chamber.

[0392] Fig. 22A process flow chart 2200 for cleaning a process chamber according to some embodiments is presented. Process flow chart 2200 describes some embodiments of cleaning the interior surfaces of a process chamber to remove chamber contaminants and subsequently depositing a substantially contaminant-free film (e.g., a silicon-based film). Process chamber cleaning may include delivering a high-velocity plasma flow containing a fluorine-containing substance into the process chamber and limiting contaminant flow away from a specific location in the process chamber. For example, a high-velocity plasma flow containing a fluorine-containing substance limits contaminant flow away from a showerhead. The two process steps of cleaning the process chamber and depositing a silicon-based film may be performed without substantially changing the process chamber temperature and / or the process chamber pressure. In this way, chamber cleaning and deposition may be performed without introducing an air break between operations. In some embodiments, process chamber cleaning and film deposition are performed when the process chamber temperature is maintained at a predetermined temperature.

[0393] Semiconductor manufacturing processes include cleaning processes in which, after a predetermined number of depositions, films deposited on the surface areas of the interior surfaces or internal components of the processing chamber are removed by supplying one or more etching compositions to the interior of the processing chamber. The etching composition may contain fluorine-containing substances that may react with, for example, silicon-containing films on the walls to dissociate into gaseous etching byproducts. The processing chamber includes internal components or inner surfaces made of aluminum, anodized aluminum, and aluminum including alloys or ceramic materials. In some embodiments, the fluorine-containing substances in the etching composition may also react with aluminum to form aluminum fluoride on the surface of the aluminum-containing components.

[0394] Aluminum fluoride can be gaseous or condensed, depending on the temperature at which it is formed. Aluminum fluoride can be thermally desorbed from the susceptor at temperatures above about 450°C and transferred to another location in the process chamber and can be redeposited in a condensed form (e.g., a solid film or particles) at a different location, creating another source of contamination. Redeposition can occur on surface areas of internal components or on interior surfaces of the process chamber. An internal component can be a showerhead. Aluminum fluoride can migrate toward the showerhead and be redeposited on the showerhead surface. For example, needle-shaped aluminum fluoride flakes can form on the showerhead.

[0395] Re-deposited aluminum fluoride is undesirable because it may be unexpectedly deposited on one or more features of the semiconductor substrate during subsequent processing. During subsequent deposition or other substrate processing, gaseous aluminum fluoride or a mixture of gaseous aluminum fluoride and other reactants may adsorb on features on the substrate. This may change, for example, the electrical properties or chemical composition of the film deposited in subsequent depositions. As a result, semiconductor devices may have reliability issues due to undesirable impurities or may not function properly as designed. Aluminum fluoride that is redeposited on the walls of the processing chamber may flake off and land on the floor or other components of the processing chamber, thereby potentially becoming a source of chamber contamination.

[0396] Removing aluminum fluoride from the surface of the process chamber may require additional steps, including but not limited to cooling the process chamber, disassembly and cleaning. In addition, aluminum fluoride deposits are relatively difficult to remove. These additional steps may cause processing time delays and corresponding reductions in yield.

[0397] Prior to operation 2202, the substrate may be transferred out of the processing chamber. Prior to removing the substrate, one or more films may be deposited on the substrate at a predetermined temperature. The processing chamber temperature may be controlled by operating one or more heating elements in a pedestal or electrostatic chuck supporting the substrate. In some embodiments, the processing chamber temperature may be substantially the same as the substrate temperature. In some embodiments, the processing chamber temperature may be between about 450°C and about 650°C, or between about 500°C and about 600°C, or between about 530°C and about 570°C. The processing chamber temperature may be maintained until the chamber cleaning is completed. The one or more films may be silicon-based layers. For example, the silicon-based layer may include silicon oxide, silicon carbide, silicon oxycarbide, silicon carbonitride, or silicon oxycarbonitride. During the deposition of the one or more films, a film may also be formed on the inner surface of the processing chamber. For example, a film may be formed on the inner wall to form a deposition byproduct that may accumulate over the deposition time. For example, the deposition byproduct may include silicon, such as silicon oxide, silicon carbide, or silicon nitride.

[0398] In the case where the processing chamber temperature is below the predetermined temperature (e.g., the processing chamber is not in operation, etc.), the processing chamber temperature may be increased to the predetermined temperature in operation 2202. In some embodiments, the predetermined temperature may be determined based on the temperature of thermal desorption of the metal fluoride. For example, aluminum fluoride may evaporate at a temperature above about 450°C, and the predetermined temperature may range between about 450°C and about 650°C, or between about 500°C and about 600°C, or between about 530°C and about 570°C. In some embodiments, when depositing a film on a substrate, the processing chamber temperature may be increased to the predetermined temperature. Before performing chamber cleaning in operation 2204, the temperature of the processing chamber may be increased.

[0399] In operation 2204, the plasma flow can be delivered to the processing chamber. To this end, one or more source gases are supplied to the remote plasma source to generate the plasma flow. As described herein, in some embodiments, the one or more source gases may include: an oxygen-containing reactant, such as oxygen (O 2 ), carbon dioxide (CO 2 ), or nitrogen dioxide (NO 2 ); fluorine-containing reactants, such as nitrogen trifluoride (NF 3 ), fluorine (F 2 ), carbon tetrafluoride (CF 4 ), or carbon hexafluoride (C 2 F 6 ); hydrogen-containing reactants, such as hydrogen (H 2) or methane (CH 4 ); an inert gas such as argon (Ar); or a nitrogen-containing reactant such as nitrogen (N 2 ), ammonia (NH 3 ), diazene (N 2 H 2 ), or hydrazine (N 2 H 4 ); or a mixture thereof. In some embodiments, the source gas may include an oxygen-containing reactant, a fluorine-containing reactant, and an inert gas. The source gas may be supplied to the remote plasma source as a gas mixture, and separate gases may be provided to the remote plasma source. In some embodiments, the flow rate of the source gas to the remote plasma source ranges from about 1 to about 50 liters per minute (lpm), from about 1 to about 30 lpm, or from about 1 to about 20 lpm. In some embodiments, the processing chamber temperature at operation 2204 may be configured to be the same as the temperature at operation 2202.

[0400] In some embodiments, plasma is generated in a remote plasma source. Plasma may include ions, free radicals, and charged neutral species of one or more source gases. Plasma can be generated using an inductively coupled plasma (ICP) reactor, a capacitively coupled plasma (CCP) reactor, a microwave plasma reactor, a DC plasma reactor, or a laser generated plasma reactor. For example, plasma can be generated using an ICP reactor. The plasma generated in the remote plasma source can be delivered to the processing chamber as a plasma stream through a showerhead.

[0401] The plasma stream generated from the remote plasma source may include hydrogen radicals, nitrogen radicals, oxygen radicals, fluorine radicals, amine radicals, argon radicals or mixtures thereof. In some cases, the plasma stream includes at least fluorine radicals. In some embodiments, the processing chamber pressure during the chamber cleaning by conveying the plasma stream may be between about 0.6 Torr and about 30 Torr or between about 1 Torr and about 30 Torr. After the processing chamber temperature reaches a predetermined temperature, the plasma stream may be supplied to the inside of the processing chamber. In some embodiments, heating the processing chamber and conveying the plasma stream may occur substantially simultaneously.

[0402] In some embodiments, the remote plasma source may be disposed above the processing chamber. The plasma flow generated above the processing chamber may pass through the showerhead in a downward direction or substantially downward direction toward the base. In other embodiments, the remote plasma source may be disposed at other locations of the plasma processing device. For example, the remote plasma source may be a subunit that is removably bolted to the side of the plasma processing device. The remote plasma source may be configured so that the plasma flow from the remote plasma source may flow to the showerhead in a horizontal direction or a diagonal direction depending on the position of the remote plasma source relative to the showerhead. In one example, the plasma flow may be supplied to the showerhead laterally from a remote plasma source disposed on one side of the processing chamber.

[0403] Once the plasma stream including fluorine radicals is delivered to the processing chamber, the fluorine radicals in the plasma stream can contact the surface area of ​​the internal components or the deposition byproducts on the inner surface of the processing chamber. After contacting the fluorine-containing substance, the deposition byproducts can dissociate into gaseous byproducts. The gaseous byproducts may be transferred within the processing chamber until they are removed from the processing chamber via the outlet coupled to the pump by the fluid.

[0404] In operation 2206, the deposition byproducts in the process chamber are etched away and the gaseous pollutants are prevented from being transferred to the showerhead surface. In some embodiments, the gaseous pollutants include metal fluorides. In some embodiments, the gaseous pollutants include aluminum fluoride. It should be understood that in some embodiments, the process chamber temperature in operation 2206 can be maintained at substantially the same temperature as in operations 2202 and 2204. For example, the process chamber temperature between about 450°C and about 650°C, between about 500°C and about 600°C, or between about 530°C and about 570°C can be maintained substantially the same from the start of operation 2202 until the completion of operation 2206.

[0405] The plasma stream having a sufficient flow rate can contact the deposition byproducts on the inner surface of the processing chamber when introduced into the processing chamber through the showerhead. The fluorine-containing species can react with the deposition byproducts and can produce gaseous byproducts, such as silicon tetrafluoride (SiF 4 ).

[0406] The plasma stream may also react with aluminum in aluminum-containing components to form aluminum fluoride. For example, a fluorine-containing substance may react with a susceptor made of aluminum nitride to form aluminum fluoride on the surface of the susceptor. Depending on the processing chamber temperature (or substrate temperature), condensed or gaseous aluminum fluoride may be formed. In some embodiments, condensed aluminum fluoride may be converted into a gas phase above a certain temperature. For example, aluminum fluoride may be thermally desorbed at a temperature above about 450°C. The plasma stream may limit the diffusion of gaseous contaminants (e.g., aluminum fluoride) outside the showerhead. The plasma stream may prevent gaseous aluminum fluoride from contaminating the surface of the showerhead, making the showerhead surface essentially contaminant-free.

[0407] In some embodiments, the flow rate of the plasma stream can be proportional to the flow rate of the one or more source gases supplied to the remote plasma source. For example, the flow rate of the plasma stream can be increased by increasing the flow rate of the source gas entering the remote plasma source. The velocity of the plasma stream can be configured to be greater than the velocity of the gaseous aluminum fluoride, which may be non-directional and random. In the case where a high-flow plasma stream containing a fluorine-containing substance is supplied from the showerhead toward the base at a predetermined temperature, the diffusion of the gaseous aluminum fluoride will be restricted and cannot enter the plasma volume, and the showerhead will not be substantially exposed to the gaseous aluminum fluoride.

[0408] In some embodiments, the flow rate of the one or more source gases may be at least 10 lpm, or at least 13 lpm, or at least 16 lpm. In some embodiments, the flow rate of the one or more source gases may be less than about 22 lpm, or less than about 25 lpm, or less than about 28 lpm. In some embodiments, the source gas may include nitrogen trifluoride at a flow rate of about 1-about 5 lpm, or about 1.5-about 4 lpm, or about 1.8-about 4 lpm; oxygen at a flow rate of about 3-10 lpm, or about 3.5-about 8 lpm, or about 4-about 7 lpm; argon at a flow rate of about 0-about 16 lpm, or about 0.01-about 10 lpm, or about 0.1-about 7 lpm; or a mixture thereof. In some embodiments, the flow rate of the source gas may be 1-about 50 lpm, or 1-about 30 lpm, or 1-about 20 lpm.

[0409] Since the volume of gaseous aluminum fluoride entering the plasma stream can be limited, the lower surface of the showerhead facing the susceptor can be substantially not exposed to gaseous aluminum fluoride, and the showerhead surface can remain substantially free of contamination after cleaning the chamber for more than 20 minutes, or 25 minutes, or 30 minutes, or 40 minutes, or 60 minutes according to some embodiments. In some embodiments, cleaning the chamber according to some embodiments can substantially eliminate the need for additional steps of chamber disassembly, cleaning, and chamber assembly to remove aluminum fluoride from the showerhead.

[0410] It should be understood that the above flow rate range of the source gas can be varied according to the design of the plasma processing device to achieve a substantially contamination-free showerhead surface. For example, the flow rate of the source gas can be varied according to the processing chamber size, processing chamber pressure and / or processing chamber temperature, etc.

[0411] In operation 2208, after preventing the showerhead from being contaminated by gaseous pollutants (e.g., aluminum fluoride), the substrate may be provided from another chamber or another station to the processing chamber for film deposition. The substrate may be supported on a susceptor for film deposition, and the silicon-based film described herein may be deposited on the substrate. In some embodiments, the processing chamber temperature in operation 2208 is set to be substantially the same as the temperature in operations 2202, 2204, and 2206. For example, the processing chamber temperature may be between about 450°C and about 650°C, or between about 500°C and about 600°C, or between about 530°C and about 570°C. In the case where film deposition is performed before operation 2202, the processing chamber temperature in operations 2202, 2204, 2206, and 2208 may be substantially the same as the temperature at the time of film deposition before operation 2202.

[0412] At operation 2210, a film may be deposited on a substrate in a process chamber. The film, such as doped or undoped silicon carbide and other films described herein, may be deposited by ALD, PEALD, CVD, PECVD, or any suitable deposition process. The film to be deposited may be a silicon-based film, including doped or undoped silicon carbide, such as oxygen-doped silicon carbide (SiCO), nitrogen-doped silicon carbide (SiCN), and nitrogen and oxygen-doped silicon carbide (SiOCN). Silicon-based films may also include silicon oxide (SiOx), silicon nitride (Si x N y ) or oxygen-doped silicon nitride (SiON). During the deposition process of operation 2210, a silicon-containing precursor may be flowed to the substrate. The silicon-containing precursor may react with the remote plasma provided from the remote plasma source, wherein Si-H bonds and / or Si-Si bonds in the silicon-containing precursor may be broken and serve as reaction sites to form bonds between the silicon-containing precursors in the deposited silicon-based film. The broken bonds may also serve as crosslinking sites during thermal treatment performed during or after deposition. The bonding and crosslinking of the reaction sites may together form a main skeleton or matrix in the resulting silicon carbide film.

[0413] The temperature in the environment adjacent to the substrate may be a deposition temperature that promotes the deposition reaction. The deposition temperature is sometimes limited by the application of the device containing the silicon-based film. In some embodiments, the processing chamber temperature in operation 2210 may be set to be substantially the same as the temperature in operations 2202, 2204, 2206, and 2208, and may be between about 450°C and about 650°C, or between about 500°C and about 600°C, or between about 530°C and about 570°C. In the case where film deposition is performed before operation 2202, the processing chamber temperature in operations 2202, 2204, 2206, 2208, and 2210 may be substantially the same as the temperature during film deposition before operation 2202. The processing chamber pressure may be any suitable pressure to generate reactive free radicals in the processing chamber. For example, the pressure may be between about 0.6 Torr and about 30 Torr, or between about 1 Torr and about 30 Torr, such as in an embodiment in which an inductively coupled plasma is implemented.

[0414] Before cleaning the interior of the processing chamber with the plasma flow, one or more film depositions in operation 2210 may be performed. For example, a film may be deposited on a substrate in the processing chamber. The substrate may be exposed to a silicon-containing precursor, a radical species, a co-reactant, and / or a carrier gas until a film having a certain thickness range is obtained. In some embodiments, the processing chamber temperature during operation 2210 may be set to be the same as the predetermined temperature in operations 2202, 2204, 2206, and 2208. Therefore, from the start of heating the processing chamber in operation 2202 until the completion of film deposition in operation 2210, the processing chamber temperature may not change, but may be maintained at a predetermined temperature.

[0415] After the film deposition of operation 2210, the substrate can be transferred from the processing chamber to another processing chamber or another station module for the next processing step. Another substrate can be transferred to the processing chamber for more film deposition. After performing a predetermined number of depositions, the processing chamber can be cleaned according to some embodiments described herein. In one example, after one or more films are deposited in operation 2210, the processing chamber temperature can be maintained at a predetermined temperature. The processing chamber cleaning process can be started by delivering a high-flow plasma flow containing fluorine to the processing chamber (operation 2204). As described in operation 2204 above, a high-flow plasma flow containing a fluorine-containing substance can be introduced into the processing chamber from a remote plasma source through a nozzle to remove deposition byproducts and prevent gaseous pollutants (e.g., aluminum fluoride) from contaminating the nozzle. The processing chamber temperature in operation 2204 can be maintained at the same or substantially the same temperature as in operation 2210. As described herein, the gaseous aluminum fluoride generated during the chamber cleaning is confined outside the nozzle by the high-flow plasma flow, so that the nozzle surface is substantially free of fluoride contamination.

[0416] Fig.23The present invention is a scanning electron micrograph (SEM) image of a ceramic sample (disposed on the lower surface of the showerhead) after passing through a plasma flow cleaning chamber according to some embodiments. The sample is located in the center of the lower surface of the showerhead and is separated from the base by a predetermined distance. The plasma flow is generated by a remote plasma source, which is coupled to the processing chamber fluid through the showerhead and is located upstream of the processing chamber relative to the inductively coupled plasma generator, so that the remote plasma source delivers the plasma flow to the processing chamber. The flow rate of the source gas including fluorine to the remote plasma source is set to about 15-about 22 lpm. The base temperature is set between about 500°C and about 600°C. The sample is exposed to the plasma flow for about 10 hours before removing the sample to identify the presence of aluminum fluoride. As Fig.23 As shown, only grains were shown in the ceramic sample. Substantially no evidence of aluminum fluoride flakes or particles was observed. This indicates that providing a high velocity plasma stream according to some embodiments is effective in substantially preventing aluminum fluoride from redepositing on the showerhead.

[0417] There are multiple advantages to cleaning the surface area of ​​internal components and the inner wall of the processing chamber by plasma flow according to some embodiments. At a suitable temperature between about 450°C and about 650°C, or between about 500°C and about 600°C, or between about 530°C and about 570°C, a high-flow plasma flow including a fluorine-containing substance generated from a remote plasma source can effectively limit the diffusion of gaseous aluminum fluoride outside the showerhead, thereby obtaining a substantially contamination-free showerhead. In addition, the cleaning of the processing chamber and subsequent deposition by plasma flow can be performed at substantially the same temperature without cooling the processing chamber for chamber cleaning. In addition, the cleaning of the processing chamber and subsequent film deposition can be performed using the same hardware without introducing new hardware components and without disassembling hardware components. Accordingly, increased production and reduced manufacturing time are achieved.

[0418] In the above description, numerous specific details are set forth to provide a thorough understanding of the embodiments presented. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known processing operations are not described in detail to avoid unnecessarily obscuring the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific embodiments, it should be understood that they are not intended to limit the disclosed embodiments.

[0419] Although the foregoing embodiments have been described in detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be made within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems and devices of the present embodiments. Accordingly, the present embodiments should be considered illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

Claims

1. A method for forming a metal-containing layer on a semiconductor substrate, the method comprising: Do at least one of the following: (a) co-flowing a metal-containing precursor and a reactant into a processing chamber containing the semiconductor substrate; as well as (b) After (a), flowing the reactant into a processing chamber containing the semiconductor substrate, wherein the reactant does not react with the metal-containing precursor in the gas phase.

2. The method of claim 1, wherein (b) comprises reacting the surface-bound metal-containing precursor with the reactant in the absence of a plasma to form a metal-containing layer on the semiconductor substrate.

3. The method according to claim 2, wherein the metal-containing layer formed is a substantially carbon-free molybdenum-containing or tungsten-containing layer having a carbon content of less than about 5 atomic %, wherein the layer is selected from the group consisting of a molybdenum (Mo) layer, a tungsten (W) layer, a molybdenum nitride (MoN) layer, a tungsten nitride (WN) layer, a molybdenum oxynitride (MoON) layer, a tungsten oxynitride (WON) layer, a molybdenum boride (MoB) layer, a tungsten boride (WB) layer, a molybdenum silicide (MoSi) layer, a tungsten silicide (WSi) layer and combinations thereof.

4. The method of claim 1, wherein the metal-containing precursor is a halogen-free, carbonyl-free compound comprising at least one ligand, wherein the at least one ligand is bound to a metal selected from the group consisting of molybdenum and tungsten.

5. The method of claim 4, wherein the halogen-free, carbonyl-free compound does not include metal-carbon bonds and metal-oxygen double bonds.

6. The method of claim 2, wherein the metal-containing layer is formed to have a carbon content of less than about 2 atomic %.

7. The method of claim 1, wherein the metal-containing layer formed is selected from the group consisting of Mo, MoN, and MoON.

8. A method for cleaning a process chamber, the method comprising: flowing a fluorine-containing substance into the process chamber, wherein the process chamber includes a molybdenum-containing film formed on an inner surface of the process chamber; as well as An oxygen-containing species is cyclically or simultaneously flowed into the process chamber with the fluorine-containing species to clean the process chamber, wherein the molybdenum-containing film is removed from the inner surface of the process chamber.

9. A method of removing dielectric material from one or more components of a processing chamber, the method comprising: (a) introducing (i) a remote plasma containing a fluorine species and (ii) a thermal etchant into the processing chamber, wherein the thermal etchant undergoes a ligand exchange reaction with a fluorine-containing reaction product of the dielectric material to produce a volatile reaction product; as well as (b) removing the volatile reaction products from the process chamber.

10. A method for cleaning a process chamber, the method comprising: heating the processing chamber to a predetermined temperature; as well as A plasma flow is delivered from a remote plasma source through a showerhead into the process chamber to clean the process chamber, wherein the remote plasma source is fluidly coupled to the process chamber through the showerhead and is located upstream of the process chamber, wherein the plasma flow limits diffusion of gaseous contaminants outside the showerhead.

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