Method and system for filling gaps

Abstract

Methods and systems for filling gaps are disclosed. The methods and systems are useful, for example, in the field of integrated circuit fabrication.

Description

Technical Field

[0001] This disclosure generally relates to the field of semiconductor processing methods and systems, and more specifically to the field of integrated circuit manufacturing. More specifically, methods and systems suitable for filling gaps are disclosed. Background Technology

[0002] The shrinking size of semiconductor devices (such as logic devices and memory devices) has led to significant increases in the speed and density of integrated circuits. However, traditional device scaling techniques face major challenges for future technology nodes.

[0003] For example, one challenge is to find a suitable way to fill gaps, such as recesses, grooves, and through holes, with a material without creating any gaps or voids.

[0004] Any discussion set forth in this section (including discussions of problems and solutions) has been included in this disclosure solely to provide background for this disclosure. Such discussion should not be construed as an admission that any or all information was known at the time this invention was made or otherwise constituted prior art. Summary of the Invention

[0005] This invention summary presents some concepts in a simplified form, which will be described in further detail below. This summary is not intended to identify, nor is it intended to limit, the scope of the claimed subject matter.

[0006] Various embodiments of this disclosure relate to methods for filling gaps, structures and devices formed using such methods, and apparatus for performing the method and / or for forming the structure and / or device. These layers can be used in a variety of applications. For example, they can be used in the field of integrated circuit manufacturing.

[0007] Therefore, this paper describes a method for filling gaps. The method includes providing a substrate to a reaction chamber. The substrate is provided with gaps. The method further includes depositing a convertible layer on the substrate and exposing the substrate to an active material. By exposing the substrate to the active material, at least a portion of the convertible layer is converted into a gap-filling fluid that at least partially fills the gaps.

[0008] In some embodiments, converting at least a portion of the convertible layer into a gap-filling fluid includes liquefying the convertible layer.

[0009] In some embodiments, the convertible layer includes a volatile element, and converting at least a portion of the convertible layer into a gap-filling fluid includes: evaporating the volatile element to form volatile vapor; and condensing the volatile vapor to form the gap-filling fluid.

[0010] In some embodiments, the method further includes curing a gap-filling fluid to fill the gap with a cured material.

[0011] In some embodiments, the active substance includes fluorine.

[0012] In some embodiments, the convertible layer is selected from metals, metal alloys, metal oxides, and metal nitrides.

[0013] In some embodiments, the convertible layer comprises a metal oxide containing metal and oxygen, and depositing the metal oxide on the substrate comprises one or more metal oxide deposition subcycles. The metal oxide deposition subcycle includes a metal precursor pulse, which includes exposing the substrate to a metal precursor containing metal; and an oxygen reactant pulse, which includes exposing the substrate to an oxygen reactant containing oxygen.

[0014] In some embodiments, the method further includes the step of converting the gap-filling fluid into a conversion material.

[0015] In some embodiments, the step of converting the gap-filling fluid into a conversion material includes exposing the substrate to direct plasma.

[0016] In some embodiments, the direct plasma is a direct oxygen plasma.

[0017] In some embodiments, the direct plasma is a direct nitrogen plasma.

[0018] In some embodiments, the method described herein includes performing multiple conversion cycles. The conversion cycle includes exposing a substrate to an active material and converting a gap-filling fluid into a conversion material.

[0019] In some embodiments, the methods described herein include performing multiple supercycles. Supercycles include depositing a convertible layer on a substrate; exposing the substrate to an active material; and converting a gap-filling fluid into a conversion material.

[0020] In some embodiments, the metal oxide includes titanium oxide, and the metal includes titanium.

[0021] In some embodiments, the metal precursor is selected from halides, halide oxides, and organometallic compounds.

[0022] In some embodiments, the metal precursor comprises titanium β-diketone.

[0023] A field-effect transistor is also described, which includes a gate contact, at least a portion of which is formed according to the method described herein.

[0024] A metal contact comprising a layer deposited by the method described herein is also described.

[0025] A system is also described, comprising a reaction chamber, a precursor gas source including a metal precursor, a deposition reactant gas source including a deposition reactant, an active material source arranged to provide an active material, a conversion reactant source arranged to provide a conversion reactant, and a controller. The controller is configured to control the gas flow into the reaction chamber to form a layer on a substrate by means of the methods described herein.

[0026] These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings. The invention is not limited to any of the specific embodiments disclosed. Attached Figure Description

[0027] A more complete understanding of embodiments of the present disclosure can be obtained by considering the following illustrative drawings, along with reference to the detailed description and claims.

[0028] Figure 1 An embodiment of the method disclosed herein is shown.

[0029] Figure 2 An embodiment of the method disclosed herein is shown.

[0030] Figure 3 A schematic diagram of an embodiment of the method described herein is shown.

[0031] Figure 4 Another embodiment of the method described herein is illustrated schematically.

[0032] Figure 5 The operation of the method described here is shown.

[0033] Figure 6 Micrographs of structures formed using embodiments of the methods described herein are shown.

[0034] Figure 7 A system 700 according to another exemplary embodiment of the present disclosure is shown.

[0035] Figure 8 Another embodiment of the system 800 described herein is illustrated in a stylized manner.

[0036] Figure 9 A stylized representation of a substrate 900 including a gap 910 is shown.

[0037] Figure 10-12 Schematic diagrams of embodiments of systems 1000, 1100, and 1200 as described herein are shown.

[0038] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to aid in understanding the embodiments illustrated in this disclosure. Detailed Implementation

[0039] The following description of exemplary embodiments of methods, structures, devices, and systems is merely illustrative and for purposes of explanation only; the following description is not intended to limit the scope of this disclosure or the claims. Furthermore, the description of multiple embodiments having the described features is not intended to exclude other embodiments having additional features or other embodiments combining different combinations of the described features. For example, various embodiments are set forth as exemplary embodiments and may be recited in the dependent claims. Unless otherwise stated, exemplary embodiments or their components may be combined or applied separately from each other.

[0040] In this disclosure, "gas" can include materials that are gaseous at ambient temperature and pressure (NTP), evaporated solids, and / or evaporated liquids, and may consist of a single gas or a mixture of gases, depending on the circumstances. Gases other than process gases, i.e., gases introduced without passing through gas distribution components, other gas distribution devices, etc., can be used, for example, to seal the reaction space, and may include sealing gases, such as rare gases. In some cases, the term "precursor" can refer to a compound that participates in a chemical reaction to produce another compound, particularly a compound constituting the membrane matrix or membrane backbone; the term "reactant" may be used interchangeably with the term "precursor."

[0041] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which devices, circuits, or films can be formed. A substrate can include bulk materials such as silicon (e.g., single-crystal silicon), other group IV materials such as germanium, or other semiconductor materials such as group II-VI or III-V semiconductor materials, and can include one or more layers covering or located beneath the bulk material. Furthermore, a substrate can include various features such as recesses, protrusions, etc., formed in or on at least a portion of the substrate layers. For example, a substrate can include at least one of a bulk semiconductor material and an insulating or dielectric material layer covering at least a portion of the bulk semiconductor material.

[0042] As used herein, the terms "film" and / or "layer" can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, partially or entirely molecular layers, partially or entirely atomic layers, or atomic and / or molecular clusters. A film or layer can consist partially or entirely of a plurality of dispersed atoms on a substrate surface and / or embedded in the substrate and / or embedded in a device fabricated on the substrate. A film or layer can include materials or layers having pinholes and / or islands. A film or layer can be at least partially continuous. A film or layer can be patterned, e.g., subdivided, and can be included in multiple semiconductor devices.

[0043] As used herein, "structure" may be or may include the substrate described herein. A structure may include one or more layers covering the substrate, such as one or more layers formed according to the methods described herein. A device portion may be or may include a structure.

[0044] The term “deposition process” as used herein can refer to the introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate. “Cyclic deposition process” is an example of a “deposition process”.

[0045] As used herein, the term "gap-filling fluid," also known as "flowable gap filler," can refer to a composition of substances that is liquid or capable of forming a liquid and having the ability to form a solid film under forming conditions. In some embodiments, the "gap-filling fluid" may only be temporarily in a flowable state, for example when the "gap-filling fluid" is temporarily formed by the formation of liquid oligomers from gaseous monomers during a polymerization reaction, and the liquid oligomers continue to polymerize to form a solid polymeric material. For ease of reference, in some embodiments, the solid material formed by the gap-filling fluid may be simply referred to as "gap-filling fluid."

[0046] The methods described herein may include depositing layers via a cyclic deposition process. The term “cyclic deposition process” or “cyclic deposition process” may refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD and cyclic CVD components.

[0047] The methods described herein can include depositing layers via atomic layer deposition processes. The term "atomic layer deposition" can refer to a vapor-phase deposition process performed in a processing chamber in a deposition cycle (typically multiple consecutive deposition cycles). As used herein, the term atomic layer deposition also means including processes specified by related terms, such as chemical vapor deposition (CVD), atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor / reactant gases and purge gases (e.g., inert carrier gases).

[0048] Typically, for an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other materials), forming a monolayer or sub-monolayer of material that is not readily reactive with the additional precursor (i.e., a self-limiting reaction). Subsequently, a reactant (e.g., another precursor or a reactive gas) may be introduced into the processing chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The reactant is capable of further reacting with the precursor. During one or more cycles, such as during each step of each cycle, a purging step may be utilized to remove any excess precursor from the processing chamber and / or any excess reactant and / or reaction byproducts from the reaction chamber.

[0049] As used herein, the term "purge" can refer to the process of supplying an inert or substantially inert gas to a reaction chamber between two gas pulses that react with each other. For example, purging can be provided between a precursor pulse and a reactant pulse, using an inert gas, to avoid or at least minimize gas-phase interactions between the precursor and reactant. It should be understood that purging can be performed temporally or spatially, or both. For example, in the case of temporal purging, the purging step can be used, for example, in the temporal sequence of supplying a first precursor to the reaction chamber, supplying a purge gas to the reaction chamber, and supplying a second precursor to the reaction chamber, wherein the substrate on which the deposited layer is located does not move. For example, in the case of spatial purging, the purging step can take the form of moving the substrate from a first position where the first precursor is continuously supplied through a purge gas curtain to a second position where the second precursor is continuously supplied.

[0050] As used herein, “precursor” includes gases or materials that can be converted into a gaseous state, which may be represented by a chemical formula that includes elements that can be introduced into the deposition process described herein.

[0051] The term "oxygen reactant" can refer to a gas or a material that can be converted into a gaseous state, and can be represented by a chemical formula containing oxygen. In some cases, the chemical formula includes both oxygen and hydrogen.

[0052] The term "nitrogen reactant" can refer to a gas or a material that can be converted into a gaseous state, and can be represented by a chemical formula containing nitrogen. In some cases, the chemical formula includes both nitrogen and hydrogen.

[0053] Furthermore, in this disclosure, any two numbers of a variable may constitute a feasible range of that variable, and any range indicated may or may not include endpoints. Additionally, any variable value indicated may refer to an exact value or an approximate value, and includes equivalents, and may refer to an average, median, representative value, multi-value, etc. Furthermore, in some embodiments of this disclosure, the terms "comprising," "consisting of," and "having" independently mean "generally or broadly comprising," "including," "substantially constituted of," or "consisting of."

[0054] In this disclosure, in some embodiments, the meaning of any definition does not necessarily exclude the common and customary meaning.

[0055] This paper describes a method for filling a gap contained within a substrate. The method includes providing the substrate to a reaction chamber. A convertible layer is then deposited on the substrate. The convertible layer can be deposited using a conformal deposition technique, such as atomic layer deposition (ALD) or another cyclic deposition process. Alternatively, the convertible layer can be deposited using a deposition technique that produces a non-conformal layer, i.e., a non-uniform layer (e.g., a layer with a greater thickness on a flat surface of the substrate than inside the gap or trench; or a layer with a greater thickness inside the gap or trench than on a flat surface of the substrate). Examples of techniques that can produce non-conformal layers are chemical vapor deposition and plasma-enhanced chemical vapor deposition. The substrate is then exposed to an active material. Thus, at least a portion of the convertible layer is converted into a gap-filling fluid. The gap-filling fluid is then cured, such that the gap is filled with a cured material.

[0056] In some embodiments, the convertible layer is conformally deposited on the substrate. In other words, the convertible layer may have a constant thickness on the substrate surface, including in gaps, recesses, etc., for example within an error range of 50%, 20%, 10%, 5%, 2%, 1%, 0.5%, or 0.1%.

[0057] In some embodiments, the convertible layer is deposited by a deposition method that produces a higher growth rate at the distal surface of the gap than at the proximal surface of the gap. In some embodiments, the growth rate at the distal surface of the gap is at least 200% to at most 500%, or at least 100% to at most 200%, or at least 50% to at most 100%, or at least 20% to at most 50%, or at least 10% to at most 20%, or at least 5% to at most 10%, or at least 2% to at most 5%, or at least 1% to at most 2%.

[0058] In some embodiments, the convertible layer comprises a volatile compound, i.e., a compound that can vaporize when exposed to a suitable reactant. Thus, when the substrate is exposed to the active material, the volatile compound can volatilize and form vapor. The vapor can then be condensed to form a gap-filling fluid, i.e., a liquid phase, in the gap. The gap-filling fluid is then solidified, such that the gap is filled with a solidified material. Despite such embodiments, it should be understood that in some embodiments, the vapor formation step is omitted, and the convertible layer is directly converted into a gap-filling fluid. In other words, in some embodiments, the convertible layer may liquefy upon exposure to the active material. Optionally, the gap-filling fluid may then be solidified to form a solidified material in the gap.

[0059] In some embodiments, the gap-filling fluid is formed wherever the convertible layer is present on the substrate. When the substrate has a surface completely covered by the convertible layer, the gap-filling fluid can be formed across the entire substrate surface, including external and internal gaps contained within the substrate. When the substrate has a surface only partially covered by the convertible layer, the gap-filling fluid can preferentially be formed only in those locations where the convertible layer is present. When the gap-filling fluid is formed outside and inside the gap, in some exemplary modes of operation, the gap-filling fluid can be drawn into the gap by at least one of capillary force, surface tension, and gravity. It should be understood that the distal portion of a gap feature refers to the portion of the gap feature relatively far from the substrate surface, while the proximal portion of a gap feature refers to the portion of the gap feature closer to the substrate surface compared to the lower / deeper portion of the gap feature.

[0060] Furthermore, it should be understood that in some embodiments, the exposure of the substrate to the active material, the optional condensation of volatile vapors, and the curing of the gap-filling fluid occur at least partially simultaneously. In other words, the exposure of the substrate to the active material, the optional condensation of volatile vapors, and the curing of the gap-filling fluid may, but do not necessarily, occur simultaneously.

[0061] The materials formed according to this method are very advantageous, for example, in the field of integrated circuit manufacturing.

[0062] Suitable active substances include ions and free radicals. Suitable free radicals include halogen free radicals. In some embodiments, the active substance includes fluorine. Therefore, in such embodiments, volatile vapors, interstitial fluids, and curing materials include fluorides. Suitable fluorinated active substances include fluorine free radicals.

[0063] In some embodiments, exposing the substrate to the active material includes generating plasma in a remote plasma generator. The remote plasma generator is suitably located outside the reaction chamber and may be adjacent to or at a predetermined distance from the reaction chamber. The remote plasma generator can be operatively connected to the reaction chamber via a reactant conduit, such as a stainless steel tube. Thus, at least one of reactants, such as free radicals and ions, can be brought into the reaction chamber from the remote plasma generator. Optionally, the reactant conduit may include one or more mesh plates. The mesh plates can advantageously block charged substances, i.e., ions, while allowing uncharged active substances, such as free radicals, to pass through. Therefore, the substrate can advantageously be exposed only to free radicals.

[0064] In some embodiments, the active material includes fluorine radicals generated in a remote plasma source. For example, a plasma gas containing NF3 may be supplied to the remote plasma source. In some embodiments, the plasma gas includes nitrogen, fluorine, and a rare gas, such as argon (Ar). In some embodiments, the plasma gas includes NF3 and an inert gas, such as Ar. Such a remote plasma source can suitably generate fluorine radicals that can be used as the active material.

[0065] In some embodiments, NF3 is provided to a remote plasma source at a flow rate of at least 0.01 sccm to at most 1000 sccm, or at least 0.1 sccm to at most 100 sccm, or at least 1 sccm to at most 10 sccm.

[0066] In some embodiments, an inert gas, such as argon, is supplied to a remote plasma source at a flow rate of at least 0.001 slm to at most 100 slm, or at least 0.01 slm to at most 10 slm, or at least 0.1 slm to at most 1 slm.

[0067] In some embodiments, exposing the substrate to the active material includes generating plasma in a reaction chamber. In other words, exposing the substrate to the active material may include exposing the substrate to direct plasma.

[0068] In some embodiments, the remote plasma source is provided with an RF power source that generates a power of at least 0.1 kW to at most 10 kW, or at least 0.2 kW to at most 5 kW, or at least 0.5 kW to at most 2 kW.

[0069] In some embodiments, the reaction chamber is maintained at a pressure of at least 1 Pa to at most 1000 Pa, or at least 2 Pa to at most 500 Pa, or at least 5 Pa to at most 200 Pa, or at least 10 Pa to at most 100 Pa, while the substrate is exposed to the active material.

[0070] In some embodiments, when the substrate is exposed to the active material, the substrate is maintained at a temperature of at least -25°C to at most 400°C, or at least 0°C to at most 200°C, or at least 25°C to at most 150°C, or at least 50°C to at most 100°C.

[0071] In some embodiments, the duration of substrate exposure to the active material is at least 0.1 seconds to at most 1000 seconds, or at least 0.2 seconds to at most 500 seconds, or at least 0.5 seconds to at most 200 seconds, or at least 1.0 seconds to at most 100 seconds, or at least 2 seconds to at most 50 seconds, or at least 5 seconds to at most 20 seconds.

[0072] Depositing a convertible layer may include performing a cyclic deposition process. A cyclic deposition process may include cyclic CVD, ALD, or a hybrid cyclic CVD / ALD process. For example, in some embodiments, the growth rate of a particular ALD process may be lower compared to a CVD process. One way to increase the growth rate is to operate at a deposition temperature higher than that typically used in ALD processes, resulting in at least one portion of the chemical vapor deposition process, namely a non-self-limiting surface and a gas-phase reaction, but still utilizing the sequential introduction of reactants. This process may be referred to as cyclic CVD. In some embodiments, a cyclic CVD process may include introducing two or more precursors or reactants into a reaction chamber, wherein there may be an overlap time between the two or more precursors or reactants in the reaction chamber, resulting in a deposited ALD component and a deposited CVD component. This is referred to as a hybrid process. According to a further example, a cyclic deposition process may include a continuous flow of one reactant or precursor and a periodic pulse of the second reactant or precursor entering the reaction chamber.

[0073] In some embodiments, the convertible layer comprises a Group IIIA element. Suitable Group IIIA elements include B, Al, Ga, and In.

[0074] In some embodiments, the convertible layer includes a family IVA element. Suitable family IVA elements include C, Si, Ge, and Sn.

[0075] In some embodiments, the convertible layer includes VA family elements. Suitable VA family elements include N, P, As, and Sb.

[0076] In some embodiments, the convertible layer includes VIA family elements. Suitable VIA family elements include O, S, Se, and Te.

[0077] In some embodiments, the convertible layer comprises a transition metal. Suitable transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Cd, Hf, Ta, W, and Re.

[0078] In some embodiments, the convertible layer comprises a rare earth element. Suitable rare earth elements include lanthanides such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0079] In some embodiments, the convertible layer includes an elemental metal, such as an elemental metal with an impurity content of less than 10 atomic%, less than 5 atomic%, less than 2 atomic%, or less than 1 atomic%.

[0080] In some embodiments, the convertible layer comprises a metal alloy.

[0081] In some embodiments, the convertible layer comprises a metal oxide.

[0082] In some embodiments, the convertible layer comprises a metal nitride.

[0083] According to some examples of the invention, the deposition of a convertible layer includes a thermal deposition process. In these cases, the deposition process does not include generating plasma to form an active material for the deposition process.

[0084] In some embodiments, depositing a convertible layer on a substrate includes performing multiple convertible layer deposition cycles. Therefore, a convertible layer with a desired thickness can be formed on the substrate. The convertible layer deposition cycle includes a convertible layer precursor pulse and a convertible layer reactant pulse. The convertible layer precursor pulse includes exposing the substrate to a convertible layer precursor. The convertible layer reactant pulse includes exposing the substrate to a convertible layer reactant.

[0085] Specifically, depositing a convertible layer may include performing a specific number of deposition cycles before exposing the substrate to the active material. Thus, a predetermined amount of convertible layer may be deposited on the substrate before exposure to the active material. It should be understood that the exact number of convertible layer deposition cycles performed until the substrate is exposed to the active material may depend on the specific material being deposited. In some embodiments, the method includes performing from at least 2 to at most 100 convertible layer deposition cycles for each exposure to the active material. In some embodiments, the method includes performing from at least 5 to at most 50 convertible layer deposition cycles for each exposure to the active material. In some embodiments, the method includes performing from at least 10 to at most 20 convertible layer deposition cycles for each exposure to the active material.

[0086] In some embodiments, the convertible layer precursor pulse lasts for at least 0.01 seconds to at most 100 seconds, or at least 0.1 seconds to at most 10 seconds, or at least 0.2 seconds to at most 5.0 seconds, or at least 0.5 seconds to at most 2.0 seconds.

[0087] In some embodiments, the convertible layer reactant pulse lasts for at least 0.01 seconds to at most 100 seconds, or at least 0.1 seconds to at most 10 seconds, or at least 0.2 seconds to at most 5.0 seconds, or at least 0.5 seconds to at most 2.0 seconds.

[0088] In some embodiments, subsequent convertible layer deposition cycles are separated by purging between convertible layer deposition cycles. In some embodiments, the duration of purging between convertible layer deposition cycles is at least 0.01 seconds to at most 100 seconds, or at least 0.1 seconds to at most 10 seconds, or at least 0.2 seconds to at most 5.0 seconds, or at least 0.5 seconds to at most 2.0 seconds.

[0089] In some embodiments, the convertible layer precursor pulse and the convertible layer reactant pulse are separated by a purge during the convertible layer deposition cycle. In some embodiments, the duration of the purge during the convertible layer deposition cycle is at least 0.025 seconds to at most 2.0 seconds, or at least 0.05 seconds to at most 0.8 seconds, or at least 0.1 seconds to at most 0.4 seconds, or at least 0.2 seconds to at most 0.3 seconds.

[0090] In some embodiments, the convertible layer comprises a metal oxide. The metal oxide comprises a metal and oxygen. In such embodiments, depositing a metal oxide on a substrate may include one or more metal oxide deposition sub-cycles. The metal oxide deposition sub-cycle includes a metal precursor pulse and an oxygen reactant pulse. The metal precursor pulse includes exposing the substrate to a metal precursor. The metal precursor comprises a metal. The oxygen reactant pulse includes exposing the substrate to an oxygen reactant. The oxygen reactant comprises oxygen. Suitable oxygen reactants include oxygen-containing gases or compounds, such as O2, H2O, O3, and H2O2. In some embodiments, the oxygen reactant comprises H2O.

[0091] In some embodiments, the metal oxide includes titanium oxide.

[0092] In some embodiments, the convertible layer comprises a metal nitride. In some embodiments, the metal nitride comprises a transition metal nitride. Alternatively or additionally, the metal nitride comprises a rare earth metal nitride. In some embodiments, the metal nitride comprises vanadium nitride. In some embodiments, the metal nitride comprises titanium nitride. In such embodiments, depositing a metal nitride on a substrate may include one or more metal nitride deposition sub-cycles. The metal nitride deposition sub-cycle includes a metal precursor pulse and a nitrogen reactant pulse. The metal precursor pulse includes exposing the substrate to a metal precursor. The metal precursor comprises a metal. The nitrogen reactant pulse includes exposing the substrate to a nitrogen reactant. The nitrogen reactant comprises nitrogen.

[0093] In some embodiments, the metal content of the convertible layer is at least 1.0 atomic% to at most 100.0 atomic%, or at least 3.0 atomic% to at most 97.0 atomic%, or at least 5.0 atomic% to at most 95.0 atomic%, or at least 10.0 atomic% to at most 90.0 atomic%, or at least 20.0 atomic% to at most 80.0 atomic%, or at least 30.0 atomic% to at most 70.0 atomic%, or at least 40.0 atomic% to at most 60.0 atomic%.

[0094] In some embodiments, the nitrogen content of the convertible layer is at least 1.0 atomic% to at most 99.0 atomic%, or at least 3.0 atomic% to at most 97.0 atomic%, or at least 5.0 atomic% to at most 95.0 atomic%, or at least 10.0 atomic% to at most 90.0 atomic%, or at least 20.0 atomic% to at most 80.0 atomic%, or at least 30.0 atomic% to at most 70.0 atomic%, or at least 40.0 atomic% to at most 60.0 atomic%.

[0095] In some embodiments, the oxygen content of the convertible layer is at least 1.0 atomic% to at most 99.0 atomic%, or at least 3.0 atomic% to at most 97.0 atomic%, or at least 5.0 atomic% to at most 95.0 atomic%, or at least 10.0 atomic% to at most 90.0 atomic%, or at least 20.0 atomic% to at most 80.0 atomic%, or at least 30.0 atomic% to at most 70.0 atomic%, or at least 40.0 atomic% to at most 60.0 atomic%.

[0096] In some embodiments, the convertible layer can be uniformly deposited on the substrate. For example, the thickness of the convertible layer can remain constant within an error range of 20%, 10%, 5%, 1%, or 0.1% on the substrate surface, regardless of whether the convertible layer is deposited on a generally flat portion of the substrate or in gaps such as recesses, trenches, or vias.

[0097] In some embodiments, a post-convertible layer deposition purge follows the deposition of the convertible layer on the substrate. In some embodiments, the duration of the post-convertible layer deposition purge is at least 0.025 seconds to at most 2.0 seconds, or at least 0.05 seconds to at most 0.8 seconds, or at least 0.1 seconds to at most 0.4 seconds, or at least 0.2 seconds to at most 0.3 seconds.

[0098] In some embodiments, the metal precursor is selected from halides, halide oxides, and organometallic compounds.

[0099] In some embodiments, the metal precursor includes a transition metal precursor. In some embodiments, the metal precursor includes a rare earth metal precursor. In some embodiments, the metal precursor includes a Group IIIA metal precursor.

[0100] In some embodiments, the metal precursor comprises an alkylamine ligand. In some embodiments, the metal precursor comprises an alkoxide ligand. In some embodiments, the metal precursor comprises an unsubstituted or alkyl-substituted cyclopentadienyl ligand. In some embodiments, the metal precursor comprises a metal-halide bond.

[0101] In some embodiments, the metal precursor includes a titanium precursor. Suitable titanium precursors include halides and organometallic titanium compounds. In some embodiments, the metal precursor includes titanium β-diketonate. In some embodiments, the titanium precursor is selected from tetrakis(dimethylamino)titanium, titanium isopropoxide (IV), trimethoxy(pentamethylcyclopentadienyl)titanium (IV), and titanium tetrachloride.

[0102] In some embodiments, the titanium precursor includes titanium halides, such as titanium chloride, titanium fluoride, titanium bromide, and titanium iodide.

[0103] After partially filling the gap with a gap-filling fluid, and optionally after solidifying the gap-filling fluid to form a solidified material in the gap, in some embodiments, the method further includes the step of converting the gap-filling fluid or solidified material into a conversion material. In some embodiments, converting the gap-filling fluid or solidified material includes exposing the substrate to a direct plasma. Suitable direct plasmas include direct oxygen plasmas. Therefore, in some embodiments, the method described herein includes exposing the substrate to a direct oxygen plasma. Suitably, the direct oxygen plasma employs a plasma gas comprising a gas selected from O2, H2O, H2O2, O3, and CO2. Therefore, a conversion material containing oxygen can be formed. In some embodiments, oxides can be formed in this manner.

[0104] Other suitable direct plasmas include direct nitrogen plasma. Direct nitrogen plasma refers to plasma generated in a reaction chamber positioned on a substrate. Therefore, in some embodiments, the method described herein includes exposing the substrate to direct nitrogen plasma. Suitably, the direct nitrogen plasma employs a plasma gas comprising gases selected from NH3, N2H2, N2, and gas mixtures comprising H2 and N2. Thus, a nitrogen-containing conversion material can be formed. The cured material can be further processed and can be further transformed into another suitable material. Therefore, in some embodiments, the method described herein also includes the step of converting a gap-filling fluid or cured material into a conversion material. For example, converting a gap-filling fluid or cured material into a conversion material may include the step of exposing the substrate to a direct plasma, such as direct nitrogen plasma. In some embodiments, nitrides may be formed in this manner.

[0105] In some embodiments, the conversion of the interstitial filling fluid to form a conversion material can occur at least partially simultaneously with the formation of the interstitial filling fluid. For example, when a plasma containing a plasma gas comprising halogens and conversion reactants is used, an interstitial filling fluid can be formed, which is readily converted to form a conversion material. Thus, a plasma containing a plasma gas comprising halogens and oxygen reactants, such as oxygen-containing substances like O2, can be used to fill the interstitial space with oxides. Alternatively, a plasma containing a plasma gas comprising halogens and a reducing agent, such as a hydrogen-containing substance like H2, can be used to fill the interstitial space with metals. Alternatively, a plasma containing a plasma gas comprising halogens and a nitriding agent, such as a nitrogen-containing substance like N2, can be used to fill the interstitial space with nitrides. Alternatively, a plasma containing a plasma gas comprising halogens and a carburizing agent, such as a carbonaceous substance like an alkane like CH4, can be used to fill the interstitial space with carbides.

[0106] In some embodiments, the method described herein includes exposing the substrate to a reducing agent after at least a portion of the convertible layer has been converted into a gap-filling fluid and before converting the gap-filling fluid into a conversion material. Suitable reducing agents include hydrogen-containing gases, hydrogen radicals, and direct hydrogen plasma.

[0107] In some embodiments, the conversion gap-filling fluid or cured material includes exposing the gap-filling fluid or conversion material to both the reduction and oxidation steps. In some embodiments, the reduction step precedes the oxidation step. Alternatively, the oxidation step may precede the reduction step. In some embodiments, the reduction step includes exposing the substrate to a hydrogen plasma. In some embodiments, the oxidation step includes exposing the substrate to an oxygen plasma.

[0108] In some embodiments, the conversion gap-filling fluid or curing material includes exposing the gap-filling fluid or conversion material to a reduction step and a nitriding step. It should be understood that the nitriding step refers to the step of converting the material into a nitride. In some embodiments, the reduction step precedes the nitriding step. Alternatively, the nitriding step may precede the reduction step. In some embodiments, the reduction step includes exposing the substrate to a hydrogen plasma. In some embodiments, the nitriding step includes exposing the substrate to a nitrogen plasma. Suitable nitrogen plasmas include plasmas in which the plasma gas includes at least one of N2, NH3, and N2H2.

[0109] In some embodiments, the methods described herein include multiple redeposition cycles. For example, the methods described herein may include at least 2 to at most 5, or at least 5 to at most 10, or at least 10 to at most 20, or at least 20 to at most 50, or at least 50 to at most 100 redeposition cycles. A redeposition cycle includes the steps of: depositing a convertible layer on a substrate, exposing the substrate to an active material, condensing volatile vapors, and curing gap-filling fluid to form a cured material. Optionally, one or more subsequent steps in a redeposition cycle are separated by intra-cycle purging. Optionally, subsequent redeposition cycles are separated by inter-cycle purging.

[0110] In some embodiments, the methods described herein include multiple conversion cycles. For example, the methods described herein may include at least 2 to at most 5, or at least 5 to at most 10, or at least 10 to at most 20, or at least 20 to at most 50, or at least 50 to at most 100 conversion cycles. A conversion cycle includes exposing a substrate to an active material; optionally condensing volatile vapors; optionally curing a gap-filling fluid; and converting the gap-filling fluid or cured material into a conversion material. Optionally, one or more subsequent steps in a conversion cycle are separated by purges within the conversion cycle. Optionally, subsequent conversion cycles are separated by purges between conversion cycles.

[0111] In some embodiments, the methods described herein include multiple supercycles. For example, the methods described herein may include at least 2 to at most 5, or at least 5 to at most 10, or at least 10 to at most 20, or at least 20 to at most 50, or at least 50 to at most 100 supercycles. A supercycle includes depositing a convertible layer on a substrate; exposing the substrate to an active material; optionally condensing volatile vapors; optionally curing a gap-filling fluid; and optionally converting the gap-filling fluid or cured material into a convertible material.

[0112] When the method includes alternatingly depositing a convertible layer, exposing the substrate to an active material, optionally condensing volatile vapors, optionally curing a gap-filling fluid, converting the gap-filling fluid or cured material into a convertible material, and repeating the sequence, a convertible material can be effectively formed.

[0113] The total number of supercycles included in the method described herein depends in particular on the desired total layer thickness. In some embodiments, the method includes from at least 1 supercycle to at most 100 supercycles, or from at least 2 supercycles to at most 80 supercycles, or from at least 3 supercycles to at most 70 supercycles, or from at least 4 supercycles to at most 60 supercycles, or from at least 5 supercycles to at most 50 supercycles, or from at least 10 supercycles to at most 40 supercycles, or from at least 20 supercycles to at most 30 supercycles. In some embodiments, the method includes up to 100 superloops, or up to 90 superloops, or up to 80 superloops, or up to 70 superloops, or up to 60 superloops, or up to 50 superloops, or up to 40 superloops, or up to 30 superloops, or up to 20 superloops, or up to 10 superloops, or up to 5 superloops, or up to 4 superloops, or up to 3 superloops, or up to 2 superloops, or a single superloop.

[0114] It should be understood that providing a purging step between different method steps appropriately allows for the minimization of parasitic reactions between different precursors and reactants. It should be understood that no plasma is generated in the reaction chamber during purging.

[0115] In some embodiments, the convertible layer and interstitial filling fluid comprise molybdenum (Mo), such as molybdenum deposited via physical vapor deposition. The convertible layer may be exposed to chlorine radicals generated in an indirect or remote plasma to form a molybdenum-containing interstitial filling fluid. The molybdenum-containing interstitial filling fluid can be converted into a conversion material using, for example, a hydrogen plasma to create interstitials at least partially filled with metallic molybdenum. The hydrogen plasma can use pure hydrogen as the plasma gas. Alternatively, a mixture of hydrogen and argon can be used as the plasma gas for the hydrogen plasma.

[0116] In some embodiments, the convertible layer comprises molybdenum oxide. This convertible layer can be exposed to a remote plasma, wherein the plasma gas includes HCl, to form a molybdenum-containing interstitial fluid. The molybdenum-containing interstitial fluid can then be thermally annealed in an oxidant such as H₂O₂ to produce interstitials at least partially filled with molybdenum oxide.

[0117] In some embodiments, the convertible layer comprises molybdenum nitride. This convertible layer can be exposed to a remote plasma, wherein the plasma gas includes Cl2, to form a molybdenum-containing interstitial filling fluid. The molybdenum-containing interstitial filling fluid can then be exposed to a direct nitrogen plasma to create interstitials at least partially filled with molybdenum nitride.

[0118] In some embodiments, the convertible layer comprises molybdenum nitride. This convertible layer can be exposed to a remote plasma, wherein the plasma gas comprises N2 and Cl2. Therefore, a molybdenum-containing interstitial fluid can be formed, which is subsequently converted to molybdenum nitride in the same process step. Therefore, it should be understood that in some embodiments, the formation of the interstitial fluid and the conversion of the interstitial fluid to form the conversion material can occur in the same process step and can occur simultaneously.

[0119] It should be understood that the techniques used to form convertible layers (such as convertible layers containing molybdenum) are known in the art.

[0120] Exemplary gaps include recesses, contact holes, through holes, trenches, etc. In some embodiments, the depth of the gap is at least 5 nm to at most 500 nm, or at least 10 nm to at most 250 nm, or at least 20 nm to at most 200 nm, or at least 50 nm to at most 150 nm, or at least 100 nm to at most 150 nm.

[0121] In some embodiments, the width of the gap is at least 10 nm to at most 10,000 nm, or at least 20 nm to at most 5,000 nm, or at least 40 nm to at most 2,500 nm, or at least 80 nm to at most 1,000 nm, or at least 100 nm to at most 500 nm, or at least 150 nm to at most 400 nm, or at least 200 nm to at most 300 nm.

[0122] In some embodiments, the length of the gap is at least 10 nm to at most 10,000 nm, or at least 20 nm to at most 5,000 nm, or at least 40 nm to at most 2,500 nm, or at least 80 nm to at most 1,000 nm, or at least 100 nm to at most 500 nm, or at least 150 nm to at most 400 nm, or at least 200 nm to at most 300 nm.

[0123] In some embodiments, the convertible layer is deposited at a substrate temperature below 800°C or at least 50°C to at most 500°C or at least 100°C to at most 300°C. In some embodiments, the convertible layer is deposited at temperatures of at least -25°C to at most 300°C, or at least 0°C to at most 250°C, or at least 25°C to at most 200°C, or at least 50°C to at most 150°C, or at least 75°C to at most 125°C.

[0124] In some embodiments, when the substrate is exposed to the active material, the substrate is maintained at the following temperatures: below 800°C, or at least -25°C to at most 800°C, or at least 0°C to at most 700°C, or at least 25°C to at most 600°C, or at least 50°C to at most 400°C, or at least 75°C to at most 200°C, or at least 100°C to at most 150°C.

[0125] In some embodiments, when the gap-filling fluid or cured material is converted into a conversion material, the substrate is maintained at the following temperatures: below 800°C, or at least -25°C to at most 800°C, or at least 0°C to at most 700°C, or at least 25°C to at most 600°C, or at least 50°C to at most 400°C, or at least 75°C to at most 200°C, or at least 100°C to at most 150°C. In some embodiments, the substrate is maintained at a temperature equal to the temperature maintained when the gap-filling fluid or cured material is converted into a conversion material when exposed to the active material. In some embodiments, the substrate is maintained at a temperature equal to at least one of the temperature maintained when the substrate is exposed to the active material and the temperature at which the gap-filling fluid or cured material is converted into a conversion material when depositing the convertible layer.

[0126] In some embodiments, at least one of the condensed vapor and the cured gap-filling fluid is carried out at the same temperature at which the substrate is exposed to the active material. In some embodiments, the conversion of the gap-filling fluid or the cured material into a conversion material is carried out at the same temperature at which the substrate is exposed to the active material.

[0127] In some embodiments, the currently described method is performed at pressures of less than 760 Torr, or at least 0.2 Torr to at most 760 Torr, at least 1 Torr to at most 100 Torr, or at least 1 Torr to at most 10 Torr. In some embodiments, the convertible layer is deposited at pressures of at most 10.0 Torr, or at most 5.0 Torr, or at most 3.0 Torr, or at most 2.0 Torr, or at most 1.0 Torr, or at most 0.1 Torr, or at most 10 Torr. -2 The pressure of the torrent, or at most 10 -3 The pressure of the torrent, or at most 10 -4 The pressure of the torrent, or at most 10 -5 The pressure is specified as follows: a pressure of at least 0.1 Torr to at most 10 Torr, or at least 0.2 Torr to at most 5 Torr, or at least 0.5 Torr to at most 2.0 Torr. In some embodiments, at least one of the condensed volatile vapor and the cured gap-filling fluid is carried out at the same pressure as the deposition of the convertible layer. In some embodiments, the conversion of the gap-filling fluid or cured material into a conversion material is carried out at the same pressure as the pressure at which the substrate is exposed to the active material.

[0128] In some embodiments, the method further includes a step of curing the gap-filling fluid or curing material. In some embodiments, curing may be performed after all the gap-filling fluid or curing material has been deposited. Alternatively, curing may be cyclical. For example, the method described herein may include a curing step after each step of exposing the substrate to the active material. Alternatively, the method described herein may include a curing step after every other step of exposing the substrate to the active material. Alternatively, the method described herein may include a curing step after a step in which at least 1% to at most 2%, or at least 2% to at most 5%, or at least 5% to at most 10%, or at least 10% to at most 20%, or at least 20% to at most 50%, or at least 50% to at most 100% of the condensed vapors have been condensed.

[0129] The curing step suitably includes subjecting the substrate to some form of energy, such as at least one of heat, radiation, and particles. An exemplary curing step includes exposing the substrate to UV radiation. Alternatively, the curing step may include exposing the substrate to a direct plasma, such as an inert gas plasma, like argon plasma. Alternatively, the curing step may include exposing the substrate to one or more active substances, such as ions and / or free radicals generated in a remote plasma, such as a remote inert gas plasma, like a remote argon plasma. Alternatively, the curing step may include exposing the substrate to photons, such as at least one of UV photons, photons in the visible spectrum, IR photons, and photons in the microwave spectrum. Alternatively, the curing step may include heating the substrate.

[0130] Single-crystal silicon wafers can be a suitable substrate. Other substrates may also be suitable, such as single-crystal germanium wafers, gallium arsenide wafers, quartz, sapphire, glass, steel, aluminum, silicon-on-insulator substrates, plastics, etc.

[0131] In some embodiments, the convertible layer includes elements selected from Ge, Sb, and Te.

[0132] Suitably, when the convertible layer comprises Ge, the active material may contain fluorine. For example, the active material may contain at least one of fluorine radicals and fluoride ions. Thus, an interstitial filling fluid comprising at least one of GeF2 and GeF4 can be formed.

[0133] Suitablely, when the convertible layer contains Sb, the active material may contain fluorine. For example, the active material may contain at least one of fluorine radicals and fluoride ions. Thus, an interstitial filling fluid containing at least one of SbF3 and SbF5 can be formed.

[0134] Suitablely, when the convertible layer comprises Te, the active material may contain bromine. For example, the active material may contain at least one of bromine radicals and bromide ions. Thus, an interstitial filling fluid comprising Te2Br can be formed.

[0135] In some embodiments, the convertible layer may include elements selected from Nb, Ta, V, Ti, Zr, and Hf.

[0136] In some embodiments, the convertible layer may include niobium (Nb). In such embodiments, the active material may suitably include at least one of chlorine and iodine. For example, the active material may contain at least one of chlorine radicals, chloride ions, iodine radicals, and iodide ions. Thus, an interstitial filling fluid comprising at least one of NbCl4 and NbI5 can be formed.

[0137] In some embodiments, the convertible layer may include tantalum (Ta). In such embodiments, the active material may suitably include one or more of fluorine, chlorine, bromine, and iodine. For example, the active material may include free radicals or ions containing fluorine, chlorine, bromine, or iodine. Thus, an interstitial filling fluid comprising at least one of TaCl5, TaI5, TaF5, and TaBr5 can be formed.

[0138] In some embodiments, the convertible layer may include vanadium (V). In such embodiments, the active material may suitably include at least one of fluorine and bromine. For example, the active material may include fluorine- or bromine-containing ions or radicals. Thus, an interstitial filling fluid comprising at least one of VF4, VF5, and VBr3 can be formed.

[0139] In some embodiments, the convertible layer may include V and O. In such embodiments, the active material may suitably include at least one of F and Cl. For example, the active material may contain at least one of chloride ions, chlorine radicals, fluoride ions, and fluorine radicals. Thus, interstitial filling fluids comprising vanadium, oxygen, and one of fluorine and chlorine can be obtained. Examples of such interstitial filling fluids include VOCl2, V2O2F4, VOCl3, and VOF3.

[0140] In some embodiments, the convertible layer may comprise titanium (Ti). In such embodiments, the active material may suitably comprise fluorine. For example, the active material may comprise at least one of fluoride ions and free radicals. Thus, an interstitial filling fluid comprising TiF4 can be formed.

[0141] In some embodiments, the convertible layer may include zirconium (Zr). In such embodiments, the active material may suitably include one of chlorine, bromine, and iodine. For example, the active material may contain one or more ions and radicals, including at least one of chlorine, bromine, and iodine. Thus, an interstitial filling fluid comprising at least one of ZrI4, ZrCl4, and ZrBr4 can be formed.

[0142] In some embodiments, the convertible layer may include Zr and O. In such embodiments, the active material suitably includes H and F. For example, the active material may contain at least one of H and F ions and H and F radicals. In such embodiments, an interstitial filling fluid comprising ZrF6(H2O)2 can be obtained.

[0143] In some embodiments, the convertible layer may include hafnium (Hf). In such embodiments, the active material may suitably include one of chlorine and iodine. For example, the active material may include at least one of chlorine radicals, chloride ions, iodine radicals, and iodide ions. Thus, an interstitial filling fluid comprising at least one of HfCl4 and HfI4 can be formed.

[0144] In some embodiments, the convertible layer may include rhodium (Rh). In such embodiments, the active material may suitably include bromine. For example, the active material may contain at least one of bromine-containing atoms and free radicals. Thus, an interstitial filling fluid comprising RhBr3 can be formed.

[0145] In some embodiments, the convertible layer may include iron (Fe). In such embodiments, the active material may suitably include bromine. For example, the active material may contain at least one of bromine-containing atoms and free radicals. Thus, an interstitial filling fluid containing at least one of FeBr3 and FeBr2 can be formed.

[0146] In some embodiments, the convertible layer may include chromium (Cr). In such embodiments, the active material may suitably contain fluorine. For example, the active material may contain at least one of fluorine-containing atoms and free radicals. Thus, an interstitial filling fluid comprising CrF5 can be formed.

[0147] In some embodiments, the convertible layer may include molybdenum (Mo). In such embodiments, the active material may suitably include at least one of chlorine, bromine, or iodine. For example, the active material may contain at least one of chlorine, bromine, or iodine atoms and a free radical. Thus, a layer comprising Mo6Cl can be formed. 12 Interstitial filling fluid of at least one of MoCl4, MoI3 and MoBr3.

[0148] In some embodiments, the convertible layer comprises gold (Au). In such embodiments, the active material may suitably comprise fluorine or bromine. For example, the active material may contain at least one of fluorine or bromine atoms and free radicals. Thus, an interstitial filling fluid comprising at least one of AuF3 and AuBr can be formed.

[0149] In some embodiments, the convertible layer comprises silver (Ag). In such embodiments, the active material may suitably contain fluorine. For example, the active material may contain at least one of fluorine-containing atoms and free radicals. Thus, an interstitial filling fluid comprising AgF3 can be formed.

[0150] In some embodiments, the convertible layer comprises platinum (Pt). In such embodiments, the active material may suitably comprise bromine. For example, the active material may contain at least one of bromine-containing atoms and free radicals. Thus, an interstitial filling fluid comprising PtBr4 can be formed.

[0151] In some embodiments, the convertible layer comprises nickel (Ni). In such embodiments, the active material may suitably comprise bromine. For example, the active material may contain at least one of bromine-containing atoms and free radicals. Thus, an interstitial filling fluid comprising NiBr2 can be formed.

[0152] In some embodiments, the convertible layer comprises copper (Cu). In such embodiments, the active material may suitably comprise bromine. For example, the active material may contain at least one of bromine-containing atoms and free radicals. Thus, an interstitial filling fluid comprising CuBr2 can be formed.

[0153] In some embodiments, the convertible layer comprises cobalt (Co). In such embodiments, the active material may suitably comprise iodine. For example, the active material may contain at least one of iodine atoms and free radicals. Thus, an interstitial filling fluid comprising CoI can be formed.

[0154] In some embodiments, the convertible layer may include Co and O, and the active material may include H and Cl, which contain free radicals or ions. In such embodiments, an interstitial filling fluid comprising CoCl2(H2O)2 may be formed.

[0155] In some embodiments, the convertible layer comprises zinc (Zn), such as metallic Zn or inorganic Zn compounds. In such embodiments, the active material may suitably comprise at least one of chlorine or iodine radicals and ions. Thus, an interstitial filling fluid comprising at least one of ZnCl2 and ZnI2 can be formed.

[0156] In some embodiments, the convertible layer may include aluminum (Al). In such embodiments, the active material may suitably include at least one of chlorine and iodine, which contain free radicals or ions. Thus, an interstitial filling fluid comprising at least one of AlCl3 and AlI3 can be formed.

[0157] In some embodiments, the convertible layer may include indium (In). In such embodiments, the active material may suitably include at least one of bromine radicals and ions. Thus, an interstitial filling fluid comprising InBr3 can be formed.

[0158] In some embodiments, the convertible layer comprises tin (Sn). In such embodiments, the active material may suitably comprise at least one ion and radical containing chlorine and bromine. Thus, an interstitial filling fluid comprising at least one of SnCl2 and SnBr2 can be formed.

[0159] In some embodiments, the convertible layer may include bismuth (Bi). In such embodiments, the active material may suitably include at least one of fluorine-containing atoms and free radicals. Thus, an interstitial filling fluid comprising BiF5 can be formed.

[0160] According to other embodiments of this disclosure, a device or a portion thereof may be formed using the methods and / or structures described herein. The device may include a substrate, one or more insulating layers, one or more metal layers, and one or more semiconductor layers. The device may also include gaps filled according to the methods disclosed herein.

[0161] A field-effect transistor including a gate contact comprising a layer formed according to the method described herein is also described.

[0162] A metal contact comprising a layer deposited by the method described herein is also described.

[0163] This document also provides a metal-insulator-metal (MIM) metal electrode comprising a layer formed by the method described herein.

[0164] This document also describes a system comprising a reaction chamber, a precursor gas source, a deposition reactant gas source, an active material source, a conversion reactant source, and a controller. The precursor gas source comprises a metal precursor. The deposition reactant gas source comprises a deposition reactant. The active material source is arranged to provide the active material. The conversion reactant source is arranged to provide the conversion reactant. The controller is configured to control the gas flow into the reaction chamber to form a layer on a substrate using the methods described herein.

[0165] In some embodiments, the system includes two distinct, separate reaction chambers: a first reaction chamber and a second reaction chamber. The first reaction chamber is configured to deposit a conversion layer. The second reaction chamber is configured to expose a substrate to an active material for converting a gap-filling fluid or curing material into a conversion material, or both. In some embodiments, the first reaction chamber is maintained at a first reaction chamber temperature, and the second reaction chamber is maintained at a second reaction chamber temperature. In some embodiments, the first reaction chamber temperature is lower than the second reaction chamber temperature, for example, at least 10°C to at most 100°C lower. In some embodiments, the first reaction chamber temperature is higher than the second reaction chamber temperature, for example, at least 10°C to at most 100°C higher. In some embodiments, the first reaction chamber temperature is equal to the second reaction chamber temperature, for example, within the range of 10°C, 20°C, 30°C, or 40°C.

[0166] Figure 1 A schematic diagram of an embodiment of the method described herein is shown. This method can be used to fill gaps, for example, to form electrodes in semiconductor devices. However, unless otherwise stated, the method described herein is not limited to these applications. The method includes step 111 of positioning a substrate on a substrate support. The substrate support is located in a reaction chamber. Suitable substrate supports include bases, pedestals, etc. The method also includes depositing a convertible layer 112 on the substrate. The convertible layer comprises a volatile element. Optionally, the reaction chamber is then purged. The method then includes exposing the substrate to an active material 115. As a result, the volatile element evaporates and forms a vapor. The invention is not limited to any particular theory or mode of operation, and it is believed that under the correct conditions that can be determined by a person skilled in the art based on this disclosure, the vapor pressure of the vapor in the gap is sufficiently high such that the vapor condenses in the gap and forms a flowable phase. Therefore, the vapor condenses in the gap 116 to form a gap-filling fluid in the gap. The gap-filling fluid 117 can then be solidified, for example by cooling the substrate, or by another means, such as by exposing the substrate to radiation. Optionally, the steps of depositing a convertible layer 112 on the substrate, exposing the substrate to the active material 115, condensing the volatile vapor 116, and solidifying the gap-filling fluid 117 can be repeated 119 once or multiple times. Thus, the gaps can be effectively filled. The method ends 118 when the gaps have been filled to the desired extent.

[0167] Optionally, purging is performed after depositing the convertible layer 112 on the substrate via post-deposition purging. It should be understood that purging may partially or completely overlap with the steps of condensing volatile vapors and solidifying gap-filling fluid. Optionally, purging is performed after exposing the substrate to the active material 115. Purging can be accomplished by exposing the substrate to a purge gas, which in turn can be accomplished by, for example, supplying a purge gas to the reaction chamber. Exemplary purge gases include rare gases. Exemplary rare gases include He, Ne, Ar, Xe, and Kr. Alternatively, purging may include conveying the substrate through a purge gas curtain. During purging, excess chemicals and reaction byproducts (if any) can be removed from the substrate surface or the reaction chamber, such as by purging the reaction space or by moving the substrate, before the substrate proceeds to the next step.

[0168] Figure 2 Another embodiment of the method described herein is illustrated schematically. Figure 2 The method is similar in some ways to Figure 1 The method also includes positioning the substrate on a substrate support 211, depositing a convertible layer 212 on the substrate, exposing the substrate to an active material 213, condensing volatile vapors 214, and curing a gap-filling fluid 215. As previously described, the steps from depositing the convertible layer 212 on the substrate to curing the gap-filling fluid 215 can be repeated 219 once or multiple times.

[0169] Figure 2 Methods and Figure 1 The method differs in that it further includes a step of converting the cured phase 216 to form a conversion material. Optionally, purging is performed after the step of converting the cured phase 216. For example, the step of converting the cured phase 216 may include exposing the substrate to a direct plasma, such as a direct oxygen plasma or a direct nitrogen plasma. Optionally, Figure 2 The method includes multiple supercycles, wherein the steps from depositing a convertible layer 212 on a substrate to converting the solidified phase 216 are repeated once or multiple times. By selecting a predetermined number of supercycles, a predetermined amount of conversion material can be formed on the substrate. Alternatively or additionally, Figure 2 The method may include multiple conversion cycles, wherein the steps of exposing the substrate to the active material 213, condensing the volatile vapor 214, curing the interstitial filling fluid 215, and converting the solidified phase 216 are repeated 220 one or more times. This can advantageously increase yield. After a predetermined amount of conversion material has been formed on the substrate, Figure 2 The method ends at 217.

[0170] Figure 3A schematic diagram of an embodiment of the method described herein is shown. This method can be used to fill gaps, for example, to form electrodes in semiconductor devices. However, unless otherwise stated, the method described herein is not limited to these applications. The method includes step 311 of positioning a substrate on a substrate support. The substrate support is located in a reaction chamber. Suitable substrate supports include bases, pedestals, etc. The method also includes depositing a convertible layer 312 on the substrate. Optionally, the reaction chamber is then purged. The method then includes exposing the substrate to an active material 315. As a result, the convertible layer is converted into a gap-filling fluid. The invention is not limited to any particular theory or mode of operation, and it is believed that under suitable conditions that can be determined by a person skilled in the art based on this disclosure, the convertible layer forms a flowable phase when exposed to a predetermined active material. Optionally, the steps of depositing the convertible layer 312 on the substrate and exposing the substrate to the active material 315 can be repeated 319 once or multiple times. Thus, gaps can be effectively filled. When the gap has been filled to the desired extent, the method ends 318.

[0171] Optionally, purging is performed after depositing the convertible layer 312 on the substrate via post-deposition purging. Optionally, purging is performed after exposing the substrate to the active material 315.

[0172] Figure 4 Another embodiment of the method described herein is illustrated schematically. Figure 4 The method is similar in some ways to Figure 3 The method also includes positioning the substrate on a substrate support 411, depositing a convertible layer 412 on the substrate, and exposing the substrate to an active material 413. As previously described, the steps of depositing the convertible layer 412 on the substrate and exposing the gap-filling fluid to the active material 413 can be repeated 419 once or multiple times.

[0173] Figure 4 Methods and Figure 3 The method differs in that it further includes the step of converting the interstitial fluid 416 to form the conversion material. Optionally, the step of converting the interstitial fluid 416 is performed after the interstitial fluid has solidified. Optionally, purging is performed after the step of converting the interstitial fluid 416. For example, the step of converting the interstitial fluid 416 may include exposing the substrate to direct plasma, such as direct oxygen plasma or direct nitrogen plasma. Optionally, Figure 2 The method includes multiple supercycles, wherein the steps from depositing a convertible layer 412 on the substrate to filling the conversion gap with fluid 416 are repeated once or multiple times. By selecting a predetermined amount of supercycles, a predetermined amount of conversion material can be formed on the substrate. Alternatively or additionally, Figure 4The method may include multiple conversion cycles, wherein the steps of exposing the substrate to the active material 413 and the conversion gap filling fluid 416 are repeated 420 once or multiple times. This can advantageously increase yield. After a predetermined amount of conversion material has been formed on the substrate, Figure 4 The method ends at 417.

[0174] According to Figure 4 In an exemplary embodiment of the method, the convertible layer includes titanium oxide, exposing the substrate to the active material includes exposing the substrate to fluorine radicals, and the conversion gap filling fluid includes a reduction step and an oxidation step. Specifically, the reduction step includes exposing the substrate to H2 plasma, i.e., to a plasma employing a plasma gas containing H2. The oxidation step includes exposing the substrate to O2 plasma, i.e., to a plasma employing a plasma gas containing O2.

[0175] Figure 5 The operation of the method described herein is shown. In particular, Figure 5 A substrate 510 comprising multiple gaps 540 is shown. Figure a) shows a convertible layer 520 conformally deposited on the substrate 510. Figure b) shows the same substrate 510 after exposure to an active material. Exposure to the active material can convert at least a portion of the convertible layer 520 into volatile vapor, which can be condensed to form a gap-filling fluid in the gaps. Optionally, the gap-filling fluid can then be cured to form a cured material 530. In another mode of operation, exposure to the active material can result in the direct formation of a liquid phase without intermediate vapor formation. Optionally, the liquid phase can then be cured to form a cured material 530. Optionally, the cured material 530 or the gap-filling fluid can be converted into a convertible material, as described elsewhere herein.

[0176] Figure 6 Figure a) shows a transmission electron microscope (TEM) image of a substrate 610 on which a TiO2 layer 620 is deposited. The TiO2 layer 620 is an example of a convertible layer. Figure 6 Figure b) illustrates how a portion of the TiO2 layer transforms into a layer 630 containing titanium, oxygen, and fluorine upon exposure to fluorine radicals. The layer 630 containing titanium, oxygen, and fluorine partially fills the gaps 640 disposed in the substrate. Another portion of the TiO2 layer 625 remains untransformed. This other portion 625 of the TiO2 layer may be further transformed, at least partially, into another layer 630 containing titanium, oxygen, and fluorine upon further exposure to fluorine radicals.

[0177] Figure 7 A system 700 according to another exemplary embodiment of the present disclosure is illustrated. System 700 can be used to perform the methods described herein and / or form structural or device portions as described herein, such as in an integrated circuit.

[0178] In the illustrated example, system 700 includes one or more reaction chambers 702, precursor gas source 704, reactant gas source 706, purge gas source 708, exhaust device 710, and controller 712.

[0179] Reaction chamber 702 can include any suitable reaction chamber, such as an ALD or CVD reaction chamber. In some embodiments, the reaction chamber includes a spray head injector, a substrate support, and a direct plasma source (all not shown). In an exemplary mode of operation, an RF bias can be applied to the spray head injector via the direct plasma source, and the substrate support can be grounded. Therefore, the substrate can be effectively exposed to direct plasma, which is useful, for example, when converting gap-filling fluids or cured materials into conversion materials.

[0180] Precursor gas source 704 may include a container and one or more precursors as described herein—alone or mixed with one or more carrier gases (e.g., inert gases). Reactant gas source 706 may include a container and one or more reactants as described herein—alone or mixed with one or more carrier gases. Purge gas source 708 may include one or more inert gases as described herein. Although four gas sources 704-708 are shown, system 700 may include any suitable number of gas sources. Gas sources 704-708 may be coupled to reaction chamber 702 via lines 714-718, each of which may include a flow controller, valve, heater, etc. Exhaust device 710 may include one or more vacuum pumps.

[0181] Figure 7 System 700 includes a remote plasma source 720 operatively coupled to reaction chamber 702. Suitable remote plasma sources 720 are known in the art and include inductively coupled plasma sources, microwave plasma sources, and capacitive plasma sources. The remote plasma source may be located near the reaction chamber or at a distance from the reaction chamber, for example, at a distance of at least 1.0 m to at most 10.0 m. When the remote plasma source 720 is located at a distance from reaction chamber 702, the remote plasma source 720 can be operatively connected to reaction chamber 702 via an active material conduit 730. The active material conduit may include a pipe. Optionally, the pipe may include one or more mesh plates. The mesh plates may at least partially block some active materials, such as ions and electromagnetic radiation, while allowing other active materials, such as free radicals, to pass through.

[0182] Controller 712 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in system 700. This circuitry and components are used to introduce precursors, reactants, and purge gases from corresponding sources 704-708. Controller 712 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to ensure proper operation of system 700. Controller 712 may include control software to electrically or pneumatically control valves to control the inflow and outflow of precursors, reactants, and purge gases from reaction chamber 702. Controller 712 may include modules, such as software or hardware components like FPGAs or ASICs, to perform certain tasks. Modules may advantageously be configured to reside on addressable storage media of the control system and configured to perform one or more processes.

[0183] Other configurations of system 700 are possible, including different numbers and types of precursor and reactant sources, as well as purge gas sources. Furthermore, it should be understood that numerous arrangements with valves, conduits, precursor sources, and purge gas sources can be used to achieve the objective of selectively supplying gas to reaction chamber 502. Additionally, for the sake of illustrative purposes and for simplicity, many components have been omitted, and these components may include, for example, various valves, manifolds, purgers, heaters, containers, vents, and / or bypasses.

[0184] During operation of system 700, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate processing system to reaction chamber 702. Once such a substrate is transferred to reaction chamber 702, one or more gases, such as precursors, reactants, carrier gases, and / or purge gases, from gas sources 704-708 are introduced into reaction chamber 702.

[0185] Figure 8 Another embodiment of the system 800 described herein is illustrated in a stylized manner. Figure 8 System 800 is similar to Figure 7 The system comprises two distinct reaction chambers: a first reaction chamber 810 and a second reaction chamber 820. The first reaction chamber 810 is arranged for depositing a convertible layer. The second reaction chamber 820 is arranged for exposing a substrate to an active material and converting a gap-filling fluid or curing material into a conversion material, at least one of these.

[0186] Figure 9 A schematic diagram of a substrate 900 including a gap 910 is shown. The gap 910 includes a proximal portion 911 and a distal portion 912. The proximal portion 911 includes a proximal surface, and the distal portion 912 includes a distal surface. Compared to the proximal surface, this method results in the formation of at least one of a gap-filling fluid, a curing material, and a conversion material on the distal surface, thereby causing bottom-up filling of the gap 910.

[0187] Furthermore, exemplary methods for filling gaps according to embodiments of the methods described herein are discussed. As known in the art, a convertible layer comprising TiO2 is deposited on a substrate using a common atomic layer deposition process. The substrate is then exposed to an active material comprising fluorine radicals. The active material is generated using a remote plasma source. A plasma gas comprising NF3 and Ar is supplied to the remote plasma source. Specifically, NF3 is supplied to the remote plasma source at a flow rate of 2.8 sccm, and Ar is supplied at a flow rate of 0.2 slm. The remote plasma is powered by a plasma power of 0.8 kW. When the substrate is exposed to the active material, the substrate is positioned in a reaction chamber maintaining a pressure of 60 Pa and is maintained at a temperature of at least 100°C to at most 150°C. The substrate is exposed to the active material for at least 20 seconds to at most 40 seconds. It should be noted that in this example, the processing conditions are given for a 1-liter reaction chamber volume and a 300 mm wafer. Those skilled in the art will understand that these values ​​can be readily extended to other reaction chamber volumes and wafer sizes.

[0188] Figure 10 A schematic diagram of an embodiment of the system 1000 as described herein is shown. The system 1000 includes a reaction chamber 1010 in which plasma 1020 is generated. Specifically, plasma 1020 is generated between a spray head injector 1030 and a substrate support 1040.

[0189] In the illustrated configuration, system 1000 includes two alternating current (AC) power supplies: a high-frequency power supply 1021 and a low-frequency power supply 1022. In this configuration, the high-frequency power supply 1021 provides radio frequency (RF) power to the spray head injector, and the low-frequency power supply 1022 provides an AC signal to the substrate support 1040. The RF power can be provided, for example, at frequencies of 13.56 MHz or higher, such as at least 20 MHz to at most 50 MHz, or at least 50 MHz to at most 100 MHz, or at least 100 MHz to at most 200 MHz, or at least 200 MHz to at most 500 MHz, or at least 500 MHz to at most 1000 MHz, or at least 1000 MHz to at most 2000 MHz, or at least 2000 MHz to at most 5000 MHz. For example, low-frequency AC signals can be provided at frequencies of 2 MHz or lower, such as at least 100 kHz to at most 200 kHz, or at least 200 kHz to at most 500 kHz, or at least 500 kHz to at most 1000 kHz, or at least 1000 kHz to at most 2000 kHz.

[0190] Process gas, comprising precursors, reactants, or both, is supplied to the conical gas distributor 1050 via gas line 1060. The process gas then reaches the reaction chamber 1010 through orifice 1031 in the spray head injector 1030.

[0191] Although the high-frequency power supply 1021 is shown as electrically connected to the spray head injector and the low-frequency power supply 1022 is shown as electrically connected to the substrate support 1040, other configurations are possible. For example, in some embodiments (not shown), both the high-frequency and low-frequency power supplies may be electrically connected to the spray head injector; or both the high-frequency and low-frequency power supplies may be electrically connected to the substrate support; or the high-frequency power supply may be electrically connected to the substrate support and the low-frequency power supply may be electrically connected to the spray head injector.

[0192] In some embodiments, such as Figure 10 The direct plasma system of System 1000 can be advantageously used to fill gaps with titanium-containing materials. For example, a substrate containing a convertible layer of titanium can be provided. The convertible layer can contain any titanium-containing material, such as elemental titanium, titanium oxide, titanium carbide, titanium nitride, or mixtures thereof. The substrate can then be exposed to a fluorine-containing plasma, such as a plasma in which the plasma gas includes a fluorocarbon, such as a fluorinated alkane, such as perfluorooctane. Any fluorocarbon can be used, but liquid fluorocarbons such as perfluorooctane are particularly advantageous due to their ease of use. Thus, the convertible layer can be converted to form a titanium- and fluorine-containing gap-filling fluid. The fluorine-containing gap-filling fluid can then be converted to form another titanium-containing material in the gap, such as elemental titanium, titanium oxide, titanium carbide, titanium nitride, or mixtures thereof. This can be achieved, for example, by exposing the substrate to thermal direct plasma or remote plasma processing using one or more inert gases, reducing agents such as H2, oxidizing agents such as O2, nitriding agents such as NH3, and carburizing agents such as CH4.

[0193] Figure 11 A schematic diagram of another embodiment of the system 1100 as described herein is shown. The system 1100 includes a reaction chamber 1110, which is separated from a plasma generation space 1125 that generates plasma 1120. Specifically, the reaction chamber 1110 is separated from the plasma generation space 1125 by a spray head injector 1130, and the plasma 1120 is generated between the spray head injector 1130 and the top plate 1126 of the plasma generation space.

[0194] In the configuration shown, system 1100 includes three AC power sources: a first power source 1121, a second power source 1122, and a third power source 1123.

[0195] In some embodiments, the first power supply 1121 is a high-frequency power supply, and the second power supply 1122 is a low-frequency power supply. In such an embodiment, the first power supply 1121 provides radio frequency (RF) power to the top plate of the plasma generation space, and the second power supply 1122 provides an AC signal to the spray head injector 1130. Therefore, plasma can be generated in the plasma generation space 1125. In such an embodiment, the third power supply 1123 may be omitted or may be turned off.

[0196] Alternatively, in some embodiments, the first power supply 1121 is a low-frequency power supply, the second power supply 1122 is a high-frequency power supply, and the third power supply 1123 is another low-frequency power supply. In such an embodiment, the first power supply 1121 provides an AC signal to the top plate of the plasma generation space, the second power supply 1122 provides RF power to the spray head injector 1130, and the third power supply 1123 provides an AC signal to the substrate support 1140. In such an embodiment, plasma can be suitably generated in the plasma generation space 1125 and in the reaction chamber 1130 between the substrate support 1140 and the spray head injector 1130.

[0197] For example, radio frequency power can be provided at a frequency of 13.56 MHz or higher. For example, low-frequency AC signals of the first and second low-frequency power supplies 1122, 1123 can be provided at a frequency of 2 MHz or lower.

[0198] A process gas, including precursors, reactants, or both, is supplied to the plasma generation space 1125 via a gas line 1160 passing through the top plate 1126 of the plasma generation space. Active substances, such as ions and free radicals, generated from the process gas by the plasma 1125, reach the reaction chamber 1110 through orifices 1131 in a spray head injector 1130. Alternatively, one or more precursors and reactants may be supplied directly to the reaction chamber 1130.

[0199] In some embodiments, such as Figure 11 The system 1100 shown can be used to convert a convertible layer, such as a titanium-containing convertible layer, into an interstitial filling fluid. For example, the convertible layer may contain at least one of titanium oxide, titanium nitride, and titanium oxynitride. For example, a fluorine-containing gas may be supplied to the plasma generation space 1125 to form fluorine-containing radicals. For example, a fluorocarbon compound such as perfluorooctane or CF4 mixed with an inert gas such as Ar can be used to generate F radicals and CF4 radicals. x At least one of the free radicals. It should be understood that x can be an integer from at least 1 to at most 3. Alternatively, x can be a non-integer positive number, in which case the symbol "CF" is used. x"This can refer to a mixture of various carbon- and fluorine-containing free radicals. These free radicals are generated together with ions in the plasma generation space 1125. Suitablely, the spray head injector 1130 blocks the ions and allows the free radicals to pass through. As an alternative to the spray head injector 1130, a mesh plate can be used. It should be understood that such mesh plates are known in the art."

[0200] In another alternative configuration, a mesh plate (not shown), such as a grounded mesh plate, can be mounted between the spray head injector 1130 and the substrate support 1140. Therefore, plasma can be generated in the reaction chamber between the mesh plate and the spray head injector 1130, in which case it is not necessary to generate plasma in the plasma generation space 1125. This configuration also advantageously blocks ions while allowing free radicals to pass through.

[0201] Therefore, a substrate containing a convertible layer (e.g., a convertible layer comprising at least one of titanium oxide, titanium nitride, and titanium oxynitride) can be exposed to free radicals, such as fluorine radicals, such as the aforementioned F radicals and CF radicals. x Free radicals. Therefore, interstitial fluids containing titanium and fluorine can be formed. It should be understood that various processing parameters, such as flow rate, plasma power, plasma frequency, and temperature, can be adjusted to control the aforementioned fluorination process, for example, by influencing the CF reaching the substrate surface. x The amount of F free radicals.

[0202] Figure 12 A schematic diagram of another embodiment of the system 1200 as described herein is shown. System 1200 includes a reaction chamber 1210 operatively connected to a remote plasma source 1225 in which plasma 1220 is generated. Any type of plasma source can be used as the remote plasma source 1225, such as inductively coupled plasma, capacitively coupled plasma, or microwave plasma.

[0203] Specifically, the active material is supplied from the plasma source 1225 to the reaction chamber 1210 via the active material conduit 1260 and the conical dispenser 1250, and is also supplied to the reaction chamber 1210 through the orifice 1231 in the spray plate injector 1230. Therefore, the active material can be supplied to the reaction chamber in a uniform manner.

[0204] In the configuration shown, system 1200 includes three power supplies: a first power supply 1221, a second power supply 1222, and a third power supply 1223.

[0205] The first power supply 1223 is a high-frequency power supply. It provides RF power to the remote plasma source 1225.

[0206] In some embodiments, the second power source 1222 is a high-frequency power source, and the third power source 1223 is also a high-frequency power source. In such embodiments, plasma can be appropriately generated in the remote plasma source 1225, above the spray plate injector 1230, and in the reaction chamber 1210.

[0207] In some embodiments, the second power source 1222 is a low-frequency power source, and the third power source 1223 is another low-frequency power source. In such embodiments, plasma can be appropriately generated only in the remote plasma source 1225.

[0208] In some embodiments, the second power supply 1222 is a low-frequency power supply, and the third power supply 1223 is a high-frequency power supply. In such embodiments, plasma can be appropriately generated in the remote plasma source 1225 and the reaction chamber 1210.

[0209] In some embodiments, the second power supply 1222 and the third power supply 1223 may be omitted or turned off. In such embodiments, plasma may be appropriately generated only in the remote plasma source 1225.

[0210] In the illustrated configuration, a first power supply 1221 provides radio frequency (RF) power to a remote plasma source, a second power supply 1222 provides AC power to a spray plate injector 1230, and a third power supply 1223 provides an AC signal to a substrate support 1240. The substrate 1241 is provided on the substrate support 1240. For example, RF power can be provided at a frequency of 13.56 MHz or higher. For example, a low-frequency AC signal can be provided at a frequency of 2 MHz or lower. For example, if the remote plasma source 1225 employs capacitively coupled plasma, RF power can be provided to the remote plasma source 1225 at a frequency of 13.56 MHz, or if the remote plasma source 1225 employs microwave plasma, RF power can be provided at a frequency of 2.45 GHz.

[0211] Processing gases, including precursors, reactants, or both, are supplied to plasma source 1225 via gas line 1260. Active substances, such as ions and free radicals, generated from the processing gases by plasma 1225 are directed to reaction chamber 1210.

[0212] In another exemplary embodiment, a method for filling gaps with a molybdenum-containing material is disclosed. First, a conversion layer is formed on a substrate including the gaps using any suitable deposition technique, such as physical vapor deposition, chemical vapor deposition, plasma-enhanced atomic layer deposition, atomic layer deposition, plasma-enhanced chemical vapor deposition, etc. The conversion layer includes molybdenum, such as metallic molybdenum, molybdenum oxide, molybdenum nitride, molybdenum oxynitride, or mixtures thereof. Then, the substrate is exposed to a chlorine-containing active material. The chlorine-containing active material may, for example, include chlorine-containing ions and free radicals, and can be obtained using a direct plasma system, such as... Figure 10 The system 1000 is formed. Alternatively, the chlorine-containing active substance can be composed of chlorine-containing free radicals, which can be generated by an indirect plasma system, such as... Figure 11 System 1100 or remote plasma system such as Figure 12 System 1200 is formed. Therefore, chlorine- and molybdenum-containing interstitial fluids can be suitably formed, which can fill the interstitial spaces under the influence of surface tension and capillary forces. The substrate can then be exposed to a conversion process to convert the interstitial fluid or the cured material formed during the solidification of the interstitial fluid, thereby forming a conversion material. Suitable conversion processes are disclosed herein. For example, exposing the substrate to a reducing agent such as H2 leads to the formation of metallic Mo; exposing the substrate to an oxidizing agent such as O2 leads to the formation of molybdenum oxide; and exposing the substrate to a nitriding agent such as NH3 leads to the formation of molybdenum nitride.

Claims

1. A method for filling a gap, the method comprising: - A substrate, including gaps, is provided to the reaction chamber; - Deposit a convertible layer on the substrate; as well as - Expose the substrate to the active material, thereby converting at least a portion of the convertible layer into a gap-filling fluid; The gap-filling fluid at least partially fills the gap. The convertible layer includes volatile elements, and converting at least a portion of the convertible layer into a gap-filling fluid comprises: - To cause volatile elements to evaporate and form vapors; and - Condensation of volatile vapors creates gap-filling fluid.

2. The method according to claim 1, wherein, Converting at least a portion of the convertible layer into a gap-filling fluid includes liquefying the convertible layer.

3. The method according to claim 1 or 2, wherein, The method further includes curing the gap-filling fluid, thereby filling the gap with a cured material.

4. The method according to claim 1 or 2, wherein, The active substance includes fluorine.

5. The method according to claim 1 or 2, wherein, The convertible layer is selected from metals, metal alloys, metal oxides, and metal nitrides.

6. The method according to claim 1 or 2, wherein, The convertible layer comprises a metal oxide, the metal oxide comprising a metal and oxygen, and wherein depositing the metal oxide on the substrate comprises one or more metal oxide deposition sub-cycles, the metal oxide deposition sub-cycles comprising: - A metal precursor pulse, comprising exposing a substrate to a metal precursor comprising the metal; and - An oxygen reactant pulse, which includes exposing a substrate to an oxygen reactant comprising the oxygen.

7. The method of claim 1 or 2, comprising a plurality of redeposition cycles, each redeposition cycle including the steps of depositing a convertible layer on a substrate and exposing the substrate to the active material.

8. The method according to claim 1 or 2, wherein, The method further includes the step of converting the gap-filling fluid into a conversion material.

9. The method according to claim 8, wherein, The step of converting the gap-filling fluid into the conversion material includes exposing the substrate to direct plasma.

10. The method according to claim 9, wherein, The direct plasma is direct oxygen plasma.

11. The method according to claim 9, wherein, The direct plasma is a direct nitrogen plasma.

12. The method according to claim 8, comprising a plurality of conversion cycles, wherein the conversion cycle includes: - Expose the substrate to the active material; as well as - Convert the gap-filling fluid into a conversion material.

13. The method of claim 8, further comprising a plurality of superloops, wherein the superloops include: - Deposit a convertible layer on the substrate; - Expose the substrate to the active material; as well as - Convert the gap-filling fluid into a conversion material.

14. The method according to claim 6, wherein, The metal oxide includes titanium oxide, and the metal includes titanium.

15. The method according to claim 6, wherein, The metal precursor is selected from halides, halide oxides, and organometallic compounds.

16. The method according to claim 15, wherein, The metal precursor includes titanium β-diketone.

17. A field-effect transistor including a gate contact comprising a layer formed by the method according to any one of claims 1 to 16.

18. A metal contact comprising a layer deposited by any one of claims 1 to 16.

19. A semiconductor processing system, comprising: Reaction chamber; Including precursor gas sources for metal precursors; Including the deposition reactant gas source; Arrange an active substance source to provide the active substance; Arrange a source of conversion reactants to provide conversion reactants; as well as A controller, wherein the controller is configured to control the airflow into the reaction chamber to form a layer on the substrate by the method according to any one of claims 1 to 16.

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