Methods and systems for filling a gap

Abstract

A method and system for filling a gap are disclosed. An exemplary method includes the step of providing a substrate to a reaction chamber. The substrate includes a gap. The method includes the step of filling the gap with a metal-containing material.

Description

Technology Field

[0001] The present disclosure generally relates to the field of semiconductor processing methods and systems and the field of integrated circuit manufacturing. In particular, a method and system suitable for filling a gap are disclosed. Background Technology

[0002] For example, the scaling of semiconductor devices, such as logic and memory devices, has led to significant improvements in the speed and density of integrated circuits. However, conventional device scaling technology faces major challenges at the future technological crossroads.

[0003] For example, one challenge was to find a suitable method to fill gaps, such as depressions, trenches, and vias, with material without forming any gaps or voids. Seams or voids within the gaps can cause problems during subsequent etching or planarization steps, which are common in integrated circuit manufacturing.

[0004] Any discussion, including problems and solutions stated in this section, is incorporated into this disclosure solely for the purpose of providing context for the present disclosure. Any or all information in such discussion should not be construed as having been known at the time the present invention was made or otherwise constitutes the prior art.

[0005] The content of the present invention may introduce a selection of concepts in a simplified form, which may be explained in more detail below. The content of the present invention is not intended to necessarily distinguish the main or essential features of the claimed essence, nor is it intended to be used to limit the scope of the claimed essence.

[0006] Various embodiments of the present disclosure relate to a method for filling a gap, a structure and a device formed using said method, and an apparatus for performing said method and / or forming said structure and / or device. The layers can be used in various applications. For example, they can be used in the field of integrated circuit manufacturing.

[0007] Accordingly, a method for filling a gap is described herein. The method comprises the step of providing a substrate to a reaction chamber. The substrate comprises a gap. The substrate further comprises a proximal surface. The gap comprises a distal end and a sidewall. The method further comprises the step of executing a plurality of deposition cycles. A deposition cycle comprises a precursor pulse and a halogen reactant pulse.

[0008] The precursor pulse includes a step of exposing the substrate to the precursor. The precursor has the general chemical formula ML. n It includes compounds having M, L, and n is understood to be an integer from at least 1 to at most 6.

[0009] The halogen reactant pulse includes the step of exposing a substrate to a halogen reactant. The halogen reactant contains a halogen.

[0010] Therefore, the gap is at least partially filled by preferentially forming a metal-containing material on the distal end compared to the proximal surface and sidewall.

[0011] In some embodiments, both the distal end and the sidewall include a dielectric material.

[0012] In some embodiments, the distal end and the sidewall both comprise at least one of a metal material and a semiconductor material.

[0013] In some embodiments, the aromatic ligand is a substituted or unsubstituted benzene ring.

[0014] In some embodiments, the ligand is an alkylbenzene.

[0015] In some embodiments, the metal is molybdenum.

[0016] In some embodiments, the metal precursor includes bis(ethylbenzene)molybdenum.

[0017] In some embodiments, the halogen reactant includes an alkyl halide.

[0018] In some embodiments, the halogen reactant includes alkyl iodine.

[0019] In some embodiments, the halogen reactant is of the general formula X a R b C- CX a R' b It has, wherein X is a halogen, R and R' are independently H or alkyl groups, and a and b are independently 1 or 2, so a + b = 3 for each carbon atom.

[0020] In some embodiments, the halogen reactant may include a bond selected from XX bond, HX bond, CX bond, PX bond, NX bond, and SX bond, where X is a halogen.

[0021] In some embodiments, the deposition cycle further comprises a nitrogen reactant pulse, wherein the nitrogen reactant pulse includes the step of exposing the substrate to the nitrogen reactant.

[0022] In some embodiments, the nitrogen reactant includes NH3.

[0023] In some embodiments, the deposition cycle further includes an oxygen reactant pulse. The oxygen reactant pulse includes the step of exposing the substrate to the oxygen reactant.

[0024] In some embodiments, the deposition cycle further includes a carbon reactant pulse. The carbon reactant pulse includes the step of exposing the substrate to the carbon reactant.

[0025] In some embodiments, the method described herein includes the step of executing one or more supercycles. The step of executing a supercycle includes the step of executing a deposition cycle; and the step of exposing the substrate to a conversion process.

[0026] In some embodiments, the conversion process includes the step of exposing the substrate to thermal annealing.

[0027] In some embodiments, thermal annealing includes at least one step of exposing a substrate to an oxidizing agent, a nitrating agent, a reducing agent, and an inert gas.

[0028] An integrated circuit including a gap is further described herein. The gap is filled by a method as described herein.

[0029] A system is further described. The system includes a reaction chamber. The system further includes a metal precursor gas source. The metal precursor gas source includes a metal precursor. The system further includes a halogen reactant gas source. The halogen reactant gas source includes a halogen reactant. The system further includes a controller. The controller is configured to control the flow of gas into the reaction chamber to fill a gap contained in a substrate by a method as described herein.

[0030] These and other embodiments will be readily apparent to those skilled in the art from the following detailed description of specific embodiments with reference to the accompanying drawings. The present invention is not limited to any specific embodiments disclosed. Brief explanation of the drawing

[0031] A more complete understanding of the embodiments of the present disclosure can be obtained by referring to the detailed description of the invention and the claims in conjunction with the following exemplary drawings. FIG. 1 shows one embodiment of the method described herein. FIG. 2 shows one embodiment of the method described herein. FIG. 3 shows one embodiment of a system (300) according to an exemplary additional embodiment of the present disclosure. FIG. 4 illustrates another embodiment of the system (400) as described herein in a stylized manner. FIG. 5 shows a stylized method of a substrate (500) including a gap (510). FIGS. 6 to 8 show experimental data obtained for a gap filled with a metal-containing material according to an embodiment of the present disclosure. It will be understood that the elements of the drawings are depicted in a simplified and clear manner and are not necessarily drawn to scale. For example, to aid in understanding the embodiments illustrated in this disclosure, the dimensions of some components in the drawings may be exaggerated compared to other components. Specific details for implementing the invention

[0032] The description of exemplary embodiments of methods, structures, elements, and systems provided below is merely illustrative and intended only for illustrative purposes, and is not intended to limit the scope or claims of this disclosure. Furthermore, citing multiple embodiments describing features is not intended to exclude other embodiments having additional features or other embodiments including other combinations of specified features. For example, various embodiments are presented as exemplary embodiments and may be referenced in the dependent claims. Unless otherwise noted, exemplary embodiments or their components may be combined or applied separately.

[0033] In this disclosure, “gas” may include materials that are gas, vaporized solid, and / or vaporized liquid at normal temperature and pressure (NTP), and may consist of a single gas or a mixture of gases depending on the context. Gases other than process gases, i.e., gases introduced without passing through a gas distribution assembly, other gas distribution device, etc., may be used, for example, to seal the reaction space and may include seal gases such as rare gases. In some cases, the term “precursor” may refer to a compound that participates in a chemical reaction to produce another compound, and in particular, a compound comprising a membrane matrix or the main framework of a material formed by the method described herein, and the term “reactant” may be used interchangeably with the term precursor.

[0034] As used herein, the term “substrate” may refer to any underlying material or materials that can be used to form, or upon which an element, circuit, or film can be formed. The substrate may comprise a bulk material 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 Group III-V semiconductor materials, and may comprise one or more layers placed on or beneath the bulk material. Additionally, the substrate may comprise various features, such as indentations, protrusions, etc., formed within or on at least a portion of the layers of the substrate. For example, the substrate may comprise a bulk semiconductor material and at least one insulating or dielectric material layer placed on at least a portion of said bulk semiconductor material. A gap may be contained within the bulk of the substrate or in one or more layers placed on the bulk of the substrate.

[0035] As used herein, the term “deposition process” may refer to introducing a precursor (and / or reactant) into a reaction chamber to deposit a layer on a substrate. “Periodic deposition process” is an example of “deposition process”.

[0036] The method described herein may include the step of forming a material by a periodic deposition process. The term “periodic deposition process” or “cyclic deposition process” may refer to forming a material within a gap by sequentially introducing precursors (and / or reactants) into a reaction chamber and includes processing techniques such as atomic layer deposition (ALD) and periodic chemical vapor deposition (periodic CVD), and hybrid periodic deposition processes including ALD components and CVD components.

[0037] The method described herein may include the step of filling a gap by an atomic layer deposition process. The term “atomic layer deposition” may refer to a vapor deposition process, wherein deposition cycles, typically a plurality of consecutive deposition cycles, are performed in a process chamber. As used herein, the term atomic layer deposition also means including processes designated by related terms such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy, when performed with alternating pulses of precursor(s) / reaction gas(s) and purge (e.g., inert carrier) gas(s).

[0038] Generally, in the case of an ALD process, during each cycle, a precursor is introduced into a reaction chamber and chemisorbed onto a deposition surface (e.g., a substrate surface that may contain a material previously deposited from a previous ALD cycle or other materials), forming a monolayer or sub-monolayer that does not readily react with additional precursors (i.e., a self-limiting reaction). The substrate surface may contain a physisorption or chemisorption catalyst, such as a halogen-containing catalyst. After introducing the precursor into the reaction chamber, a reactant (e.g., another precursor or reaction gas) may subsequently be introduced into the process chamber to convert the precursor chemisorbed on the deposition surface into the desired material. The halogen reactant may further react with the precursor. During one or more cycles, for example, by using a purge step during each step of each cycle, excess precursor may be removed from the process chamber, and / or excess reactant and / or reaction byproducts may be removed from the process chamber.

[0039] As used herein, the term "purge" may refer to a procedure in which a purge gas is supplied to a reaction chamber between two pulses of gases that react with each other. For example, a purge, or a purge using, for example, an inert gas, may be supplied between a precursor pulse and a reactant pulse so as to avoid or at least minimize gas-phase interactions between the precursor and the halogen reactant. It should be understood that the purge may affect time or space, or both. For example, in the case of a temporal purge, the purge step may be used in the temporal sequence of, for example, a step of supplying a first precursor to the reaction chamber, a step of supplying a purge gas to the reaction chamber, and a step of supplying a second precursor to the reaction chamber, wherein the substrate on which the layer is deposited does not move. For example, in the case of a spatial purge, the purge step may take the following form: a step of moving the substrate from a first position where the first precursor is continuously supplied to a second position where the second precursor is continuously supplied through a purge gas curtain.

[0040] As used herein, "metal precursor" includes a gas or material that can be represented by a chemical formula containing a metal that may be a gas and may be incorporated into the deposition process described herein.

[0041] The term "oxygen reactant" may refer to a gas or material that can be a gas and can be represented by a chemical formula containing oxygen. In some cases, the chemical formula includes oxygen and hydrogen.

[0042] The term "nitrogen reactant" may refer to a gas or material that can be a gas and can be represented by a chemical formula containing nitrogen. In some cases, the chemical formula includes nitrogen and hydrogen.

[0043] The term "carbon reactant" may refer to a gas or material that can be a gas and can be represented by a chemical formula containing carbon. In some embodiments, the chemical formula includes carbon and hydrogen.

[0044] The term "halogen reactant" may refer to a gas or material that can be a gas and can be represented by a chemical formula containing a halogen. In some embodiments, the chemical formula further includes one or more of carbon and hydrogen.

[0045] Additionally, in the present disclosure, any two values ​​of a variable may constitute an executable range of said variable, and any indicated range may include or exclude endpoints. Additionally, any value of the indicated variable may refer to an exact value or an approximate value, may include an equivalent, and may refer to an average, median, representative, majority, etc.

[0046] Furthermore, in this disclosure, the term "comprising" indicates that, when referring to a specific feature, such feature is included but does not exclude the existence of other feature, provided that such feature is not prevented from being executed. The meaning of the term "comprising" should be understood to include the meaning of the term "constituting." The term "constituting" indicates that no further feature exists in the corresponding embodiment other than that which follows the above expression. The term "comprising" includes the meaning of "substantially constituting." The term "substantially constituting" indicates that no additional feature exists in the embodiment other than that which follows the above expression, except where such additional feature does not have any significant effect on the characteristics or functions of the embodiment.

[0047] It will be understood that the distal portion of the gap refers to a part of the gap feature removed relatively far from the surface of the substrate, and the proximal portion of the gap feature refers to a part of the gap feature closer to the surface of the substrate compared to the lower / deeper / further removed portion of the gap feature. It should be understood that the gap is not necessarily oriented in a direction substantially perpendicular to the surface of the substrate. Conversely, an obliquely oriented gap is possible. Additionally, in some embodiments, the gap may be or include a portion substantially parallel to the surface of the substrate.

[0048] In the present disclosure, any defined meaning does not necessarily exclude the ordinary and conventional meaning in some embodiments.

[0049] A method for filling a gap is described herein. The method can be appropriately characterized as a vapor deposition method. The method comprises the step of providing a substrate to a reaction chamber. The substrate further comprises a proximal surface. The gap comprises a distal end and a sidewall. A single-crystal silicon wafer may be a suitable substrate. Other substrates, for example, a single-crystal germanium wafer, a gallium arsenide wafer, quartz, sapphire, glass, steel, aluminum, a silicon-on-insulator substrate, plastic, etc. may be suitable.

[0050] The substrate will be understood to include a gap. The method comprises the step of executing a plurality of deposition cycles. The deposition cycles include precursor pulses and halogen reactant pulses.

[0051] The precursor pulse includes a step of exposing the substrate to the precursor. The precursor has the general chemical formula ML. n It includes compounds having M, L, and n is understood to be an integer from at least 1 to at most 6.

[0052] The halogen reactant pulse includes the step of exposing a substrate to a halogen reactant. The halogen reactant contains a halogen.

[0053] Therefore, the gap is at least partially filled. During the filling of the gap, the metal-containing material is preferentially formed on the distal end of the gap compared to the proximal surface of the substrate and the sidewall of the gap. That is, the metal-containing material is formed on the distal end at a relatively higher growth rate compared to the growth rate at which the metal-containing material is formed on the sidewall and the proximal surface. For example, the growth rate at which the material is formed on the distal end of the gap may be 10 times, 5 times, 2 times, 1.5 times, 1.2 times, or 1.1 times the growth rate at which the material is formed on at least one of the sidewall of the gap and the proximal surface of the substrate.

[0054] The material formed according to this method can be advantageously used in the field of integrated circuit manufacturing.

[0055] In some embodiments, the metal-containing material comprises an alkali metal. In some embodiments, the precursor appropriately comprises an alkali metal. That is, in some embodiments, M is an alkali metal. Suitable alkali metals include Li, Na, K, Rb, and Cs.

[0056] In some embodiments, the metal-containing material comprises an alkaline earth metal. In these embodiments, the precursor appropriately comprises an alkaline earth metal. That is, in some embodiments, M is an alkaline earth metal. Suitable alkaline earth metals include Be, Mg, Ca, Sr, and Ba.

[0057] In some embodiments, the metal-containing material comprises a transition metal. In some embodiments, the precursor appropriately comprises a transition metal. That is, in some embodiments, M is a transition metal. Suitable transition metals include Sc, Y, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, and Hg.

[0058] In some embodiments, the metal-containing material comprises a lanthanide. In some embodiments, the precursor appropriately comprises a lanthanide. That is, in some embodiments, M is a lanthanide. Suitable lanthanides include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0059] In some embodiments, the metal-containing material comprises a post-transition metal. In some embodiments, the precursor appropriately comprises a post-transition metal. That is, in some embodiments, M is a post-transition metal. Suitable post-transition metals include Ga, In, Sn, Tl, Pb, and Bi.

[0060] In some embodiments, the metal precursor may be pulsed more than once, e.g., two, three, or four times, before the halogen reactant is pulsed into the reaction chamber. Similarly, before the metal precursor is pulsed into the reaction chamber (i.e., before it is provided), there may be more than one pulse, such as two, three, or four halogen reactant pulses.

[0061] In some embodiments, a purge follows at least one of the metal precursor pulse and the halogen reactant pulse. Thus, in some embodiments, a purge follows the metal precursor pulse; a purge follows the halogen reactant pulse; or a purge follows both the metal precursor pulse and the halogen reactant pulse.

[0062] Exemplary gaps include recesses, contact holes, vias, trenches, etc. In some embodiments, the gap has a depth of at least 5 nm to a maximum of 500 nm, or at least 10 nm to a maximum of 250 nm, or at least 20 nm to a maximum of 200 nm, or at least 50 nm to a maximum of 150 nm, or at least 100 nm to a maximum of 150 nm.

[0063] In some embodiments, the gap may have a width of at least 10 nm to a maximum of 10,000 nm, or at least 20 nm to a maximum of 5,000 nm, or at least 40 nm to a maximum of 2,500 nm, or at least 80 nm to a maximum of 1,000 nm, or at least 100 nm to a maximum of 500 nm, at least 150 nm to a maximum of 400 nm, or at least 200 nm to a maximum of 300 nm.

[0064] In some embodiments, the gap may have a length of at least 10 nm to a maximum of 10,000 nm, or at least 20 nm to a maximum of 5,000 nm, or at least 40 nm to a maximum of 2,500 nm, or at least 80 nm to a maximum of 1,000 nm, or at least 100 nm to a maximum of 500 nm, at least 150 nm to a maximum of 400 nm, or at least 200 nm to a maximum of 300 nm.

[0065] In some embodiments, the gap comprises both a distal end and a sidewall containing a dielectric material. In some embodiments, the gap has a surface that is entirely or substantially composed of a dielectric material. In some embodiments, the gap comprising the distal end and the sidewall is lined with a dielectric liner having a thickness of, for example, at least 1 nm to a maximum of 50 nm, or at least 1 nm to a maximum of 5 nm, or at least 5 nm to a maximum of 20 nm, or at least 20 nm to a maximum of 50 nm. Exemplary dielectric materials include silicon-containing materials, such as silicon oxide, silicon nitride, carbide, silicon oxynitride, silicon oxycarbide, and silicon oxynitride. Other suitable dielectric materials may include metal oxides such as aluminum oxide, hafnium oxide, or zirconium oxide.

[0066] In some embodiments, the gap includes both the distal end and the sidewall, which are made of semiconductor material. In some embodiments, the gap has a surface that is entirely or substantially made of semiconductor material.

[0067] In some embodiments, the gap includes both a distal end and a sidewall comprising at least one of a metal and a semiconductor material. In some embodiments, the gap has a surface that is entirely or substantially composed of at least one of a metal and a semiconductor material.

[0068] In some embodiments, the gap includes both a distal end and a sidewall comprising at least one of a metal material and a semiconductor material. In some embodiments, the gap has a surface that is entirely or substantially composed of at least one of a metal material and a semiconductor material.

[0069] Suitable semiconductor materials include elemental semiconductors such as silicon, germanium, and alloys thereof. Suitable semiconductor materials further include compound semiconductors such as tin oxide, indium oxide, copper oxide, and alloys thereof. Suitable metal materials include one or more metals and alloys. Suitable metals include transition metals, refractory metals, and post-transition metals. Exemplary metals include Mo, W, Ru, Cu, Co, and Al.

[0070] In some embodiments, the gap includes both the distal end and the sidewall, which are made of metal. In some embodiments, the gap has a surface that is entirely or substantially made of metal. In some embodiments, the gap, including its distal end and the sidewall, is lined with a metal liner having a thickness of, for example, at least 1 nm to a maximum of 50 nm, or at least 1 nm to a maximum of 5 nm, or at least 5 nm to a maximum of 20 nm, or at least 20 nm to a maximum of 50 nm.

[0071] In some embodiments, the distal end of the gap comprises a metal and the sidewalls of the gap comprise a dielectric. In some embodiments, the distal end of the gap comprises a dielectric and the sidewalls of the gap comprise a metal.

[0072] In some embodiments, the method described herein is a thermal deposition process. That is, in some embodiments, the method as described herein may involve a thermal reaction between a metal precursor and a halogen reactant. A thermal process will be understood to refer to a process in which the activation energy for the thermal reaction is substantially provided by thermal energy. Thus, no additional energy source, such as plasma or energy radiation, such as ultraviolet light, is required to allow the reaction to proceed.

[0073] The precursor includes metal and aromatic ligands. In some embodiments, the aromatic ligand is a substituted or unsubstituted benzene ring.

[0074] In some embodiments, the ligand is an alkylbenzene. Thus, in some embodiments, the precursor comprises a ligand containing an alkyl-substituted benzene ring in turn. Examples of such precursors include a precursor containing a metal center and one or more methylbenzene ligands, ethylbenzene ligands, or propylbenzene ligands. An exemplary precursor of this type is bis(ethylbenzene)molybdenum. A precursor containing an alkyl-substituted benzene ring, such as bis(ethylbenzene)molybdenum, can be advantageously used to fill the gap with a haloalkane reactant such as 1,2-diiodoethane. Thus, in some embodiments, the precursor comprises bis(ethylbenzene)molybdenum, and the halogen reactant comprises 1,2-diiodoethane.

[0075] In some embodiments, the aromatic ligand included in the precursor has a general structure according to Formula 1:

[0076] (1)

[0077] It will be understood that each of R1 to R6 can be independently selected from H and C1 to C6 hydrocarbyl, such as aliphatic hydrocarbyl, such as linear alkyl or cyclic alkyl, such as C1 to C6 linear alkyl.

[0078] In some embodiments, R1 is a C1 to C6 alkyl such as CH3, and R2 to R6 are H. In some embodiments, R1 and R3 are C1 to C6 alkyl such as CH3, and R2, R4, R5, and R6 are H. In some embodiments, R1 and R4 are C1 to C6 alkyl such as CH3, and R2, R3, R5, and R6 are H. In some embodiments, R1 is CH2CH3, and R2 to R6 are H.

[0079] In some embodiments, the metal is molybdenum.

[0080] In some embodiments, the precursor includes bis(ethylbenzene)molybdenum.

[0081] In some embodiments, the precursor may include one or more metals. In some embodiments, the precursor includes two or more metals.

[0082] Unless the present invention is limited to any particular theory or mode of operation, in some embodiments, it is believed that the halogen reactant can preferentially catalyze metal growth at the distal end of the gap compared to the proximal surface of the substrate, including the gap and the sidewalls of the gap.

[0083] The halogen reactant may include a bond selected from, for example, XX bond, HX bond, CX bond, PX bond, NX bond, and SX bond, where X is a halogen.

[0084] In some embodiments, the halogen reactant comprises at least one of a halogen element and a hydrogen halide. Suitable halogen elements include F2, Cl2, Br2, and I2. Suitable hydrogen halides include HF, HCl, HBr, and HI.

[0085] In some embodiments, the halogen reactant comprises a halogenated hydrocarbon containing two halogen atoms. In some embodiments, at least two halogen atoms of the halogen reactant are attached to different carbon atoms. In some embodiments, the halogen reactant comprises a hydrocarbon containing at least two carbon atoms attached to each other. The halogen reactant may comprise three carbon atoms. Additionally, the halogen reactant may comprise four, five, or six carbon atoms. The halogen reactant may comprise linear, branched, cyclic, and / or aromatic carbon chains. For example, the halogen reactant may comprise an alkyl halide.

[0086] In some embodiments, the halogen reactant comprises two or more halogen atoms, and at least two halogen atoms are attached to different carbon atoms. The halogen atoms may be the same halogen, e.g., bromine, iodine, fluorine, or chlorine. Alternatively, the halogen may be different halogens, e.g., iodine and bromine, bromine and chlorine, or chlorine and iodine. The halogen reactant may comprise two halogen atoms attached to different carbon atoms. The halogen reactant may comprise three halogen atoms, each attached to a different carbon atom. The halogen reactant may comprise four halogen atoms, each attached to a different carbon atom. Alternatively, in an embodiment in which the halogen reactant comprises three, four, or more halogen atoms, some carbon atoms may be attached to two or three halogen atoms. In some embodiments, two halogen atoms within the halogen reactant are attached to carbon, hydrogen, and adjacent carbon atoms of the halogen-containing compound. Accordingly, the halogen reactant may comprise two adjacent carbon atoms, each having at least one halogen substituent. In some embodiments, each adjacent carbon atom has only one halogen substituent. Alternatively, one or both of the carbon atoms attached to the halogen may have two halogen atoms attached. An embodiment in which one or both of the carbon atoms attached to the halogen have three halogen atoms attached thereto may be considered. The positions of the two carbon atoms in the carbon chain may vary. In some embodiments, they are at the ends of the carbon chain, but in some embodiments, they are located far from the ends of the carbon chain. As is obvious to those skilled in the art, the positions of the given carbon atoms in the carbon chain limit the number of available potential substituents.

[0087] For example, in an embodiment, if the halogen reactant comprises two carbon atoms, at least one halogen atom is attached to each carbon. If the two carbon reactant comprises two halogen atoms, each of them is attached to a different carbon atom. In an embodiment where the halogen reactant comprises two carbon atoms and three halogens, one of the carbon atoms is double-substituted with a halogen. In an embodiment where the halogen reactant comprises two carbon atoms and four halogens, two carbon atoms are double-substituted with halogens. Alternatively, one carbon atom may have one halogen substituent, while the second carbon atom may have three.

[0088] In some embodiments, the halogen reactant comprises three carbon atoms and two halogen atoms, each halogen atom is attached to a different carbon atom. Thus, in some embodiments, one carbon atom does not have a halogen atom attached thereto. Two halogen atoms may be attached to neighboring carbon atoms (i.e., carbon atoms adjacent to each other in a carbon chain). Alternatively, one carbon atom may exist between the halogenated carbon atoms. For example, the halogen reactant may comprise, be essentially composed of, or be composed of 1,2-dihalopropane or 1,3-dihalopropane, such as 1,2-dichloropropane, 1,3-dichloropropane, 1,2-diiodopropane or 1,3-diiodopropane, 1,2-difluoropropane or 1,3-difluoropropane.

[0089] In an embodiment in which the halogen reactant comprises three carbon atoms and three halogen atoms, each carbon atom may have a halogen atom attached thereto. Alternatively, any one of the three carbon atoms may have two halogen atoms attached thereto, and one carbon atom at the end or in the middle of the carbon chain may be halogen-free. The double-substituted carbon atom may be at the end or in the middle of the carbon chain. As another alternative, in some embodiments, the three-carbon halogen reactant may contain four halogen atoms. In such embodiments, each carbon may have a halogen atom attached thereto, and one carbon at the end or in the middle of the carbon chain may have an additional halogen atom attached thereto. As yet another alternative, two of the carbons may have two halogen atoms attached thereto, while one carbon atom at the end or in the middle of the carbon chain may be halogen-free. In some embodiments, the halogen reactant comprises a 1,2-dihaloalkane or a 1,2-dihaloalkene or a 1,2-dihaloalkyne or a 1,2-dihaloarene, wherein the halogen is attached to an adjacent carbon atom.

[0090] In an embodiment in which the halogen reactant comprises four carbons, there may be two, three, four, five, or six halogen substituents attached to the carbons. For example, the halogen reactant may have the chemical formula CH3-CXH-CH2-CXH2, CH3-CH2-CXH-CXH2, CH3-CXH-CXH-CH3, or H2CX-CH2-CH2-CXH2. In an embodiment in which the four-carbon halogen comprises three carbons, the halogen reactant may have a chemical formula such as H2CX-CXH-CH2-CXH2, H2CX-CXH-CXH-CH3, HCX2-CXH-CH2-CH3, HCX2-CH2-CXH-CH3, or HCX2-CH2-CH2-CXH2 or CH3-CXH-CX2-CH3. In the chemical formula, X represents a halogen such as F, Cl, Br, or I. Examples of such reactants are 1,2-dihalobutane, 1,3-dihalobutane, and 1,4-dihalobutane.

[0091] In some embodiments, a cyclic or aromatic halogen reactant may be used. In some embodiments, the halogen reactant comprises a cyclic or aromatic compound. The halogen reactant may comprise a dihalogenated benzene ring. The benzene ring may comprise two or more halogens. The benzene ring may additionally contain substituents, such as one or more alkyl groups. The halogen reactant may comprise, essentially consist of, or be composed of dihalogenated benzenes, such as 1,2-dibromobenzene, 1,2-diiodobenzene, or 1,2-dichlorobenzene. The dihalogenated benzene may also be 1,3-dihalogenated or 1,4-dihalogenated benzene. Additionally, trihalogenated benzenes, such as 1,2,3- or 1,2,4-halogenated benzene, are possible. Aromatic halogen reactants may contain four, five, or six halogens. Cyclic halogen reactants may include, for example, cyclopentane halogenated or cyclohexane halogenated. Cyclic halogen reactants may contain two or more halogens. For example, cyclohexane halogenated may contain up to twelve halogens, which may be the same or different. Halogens may be located in a cis- or trans- configuration. Halogens in cyclohexane halogenated may be located at carbon positions 1 and 2, 1 and 3, 1 and 4, or 1,2,3 or 1,2,4. Examples of cyclic reactants are 1,2-diiodocyclohexane, 1,3-diiodocyclohexane, 1,4-diiodocyclohexane, 1,2-dibromocyclohexane, 1,3-dibromocyclohexane, 1,4-dibromocyclohexane, 1,2-difluorocyclohexane, 1,3-difluorocyclohexane, and 1,4-difluorocyclohexane.

[0092] In some embodiments, the halogen reactant is of the general formula X a R b C―CX a R' bIt has, wherein X is a halogen, R and R' are independently H or an alkyl group, and a and b are independently 1 or 2, so a + b = 3 for each carbon atom. In some embodiments, X is iodine. In some embodiments, X is bromine. In some embodiments, X is chlorine. In some embodiments, a is 1 for two carbon atoms. In some embodiments, a is 1 for one carbon atom and 2 for the other carbon atom. In some embodiments, R and R' are both H.

[0093] In some embodiments, the halogen reactant comprises an alkyl halide. Suitable alkyl halides are C n H 2n+2-m X m It can have the chemical formula, where n and m are integers from 1 to 4, and X is a halogen such as F, Cl, Br, and I. An exemplary alkyl halide is 1,2-diiodoethane.

[0094] In some embodiments, the halogen reactant comprises two or more halogen atoms attached to a carbon skeleton.

[0095] In some embodiments, the halogen reactant is of the general formula X a R b C―(CX c R'' d ) n -CX a R' b It has. X is a halogen, and R, R', and R'' will be understood as independently being H or alkyl groups. Also, since a and b are independently 1 or 2, a + b = 3 for each carbon atom. Also, n is 0, 1, 2, 3, 4, or 5. Also, c and d are independently 0, 1, or 2, and therefore c + d = 2 for each carbon atom.

[0096] In some embodiments, the halogen reactant is of the general formula X a R b C- CX aR' b It has, wherein X is a halogen, R and R' are independently H or alkyl groups, and a and b are independently 1 or 2, so a + b = 3 for each carbon atom.

[0097] In some embodiments, the halogen reactant includes alkyl iodine.

[0098] In some embodiments, the halogen reactant comprises 1,2-diiodoethane.

[0099] In some embodiments, the halogen reactant may include a bond selected from XX bonds, HX bonds, CX bonds, PX bonds, NX bonds, and SX bonds. It should be understood that X is a halogen.

[0100] In some embodiments, the halogen reactant comprises 1,2-dihaloalkanes or 1,2-dihaloalkenes or 1,2-dihaloalkynes or 1,2-dihaloarenes.

[0101] In some embodiments, the deposition cycle further includes a nitrogen reactant pulse. The nitrogen reactant pulse includes the step of exposing the substrate to the nitrogen reactant.

[0102] In some embodiments, the nitrogen reactant comprises NH3. Other suitable nitrogen reactants comprise N2H2, N2, and a gas mixture comprising N2 and H2.

[0103] The nitrogen reactant pulse can be executed, for example, after the precursor pulse, after the halogen reactant pulse, or after the purge step following the precursor pulse or the halogen reactant pulse.

[0104] In some embodiments, the deposition cycle includes the step of sequentially executing a plurality of subsequent precursor pulses and nitrogen reactant pulses before and after executing a halogen reactant pulse. Accordingly, in some embodiments, the sequence of the Y deposition cycle can be expressed by the following formula: ((P + N)*X + R)*Y, where P represents the precursor pulse, N represents the nitrogen reactant pulse, X is an integer, R represents the halogen reactant pulse, and Y is another integer. In some embodiments, X is equal to Y. In some embodiments, X and Y are different. Accordingly, the deposition cycle may include the step of executing a sequence X including a precursor pulse, a nitrogen reactant pulse, and then a halogen reactant pulse. In some embodiments, X is at least 1 to at most 20, or at least 2 to at most 10. In some embodiments, Y is at least 1 to a maximum of 1000, or at least 5 to a maximum of 2000, or at least 25 to a maximum of 400, or at least 100 to a maximum of 200.

[0105] In some embodiments, the deposition cycle further includes an oxygen reactant pulse. The oxygen reactant pulse includes the step of exposing the substrate to the oxygen reactant. It should be understood that an oxygen reactant refers to a gaseous compound containing oxygen. Exemplary oxygen reactants include O2, H2O, O3, and H2O2.

[0106] The oxygen reactant pulse can be executed, for example, after the precursor pulse, after the halogen reactant pulse, or after the purge step following the precursor pulse or the halogen reactant pulse.

[0107] In some embodiments, the deposition cycle includes the step of sequentially executing a plurality of subsequent precursor pulses and oxygen reactant pulses before and after executing a halogen reactant pulse. Accordingly, in some embodiments, the sequence of the Y deposition cycle can be represented by the following formula: ((P + O)*X + R)*Y, where P represents the precursor pulse, O represents the nitrogen reactant pulse, X is an integer, R represents the halogen reactant pulse, and Y is another integer. In some embodiments, X is equal to Y. In some embodiments, X and Y are different. Accordingly, the deposition cycle may include the step of executing a sequence X including a precursor pulse, an oxygen reactant pulse, and then a reactant pulse. In some embodiments, X is at least 1 to at most 20, or at least 2 to at most 10. In some embodiments, Y is at least 1 to a maximum of 1000, or at least 5 to a maximum of 2000, or at least 25 to a maximum of 400, or at least 100 to a maximum of 200.

[0108] In some embodiments, the deposition cycle further includes a carbon reactant pulse. The carbon reactant pulse includes the step of exposing the substrate to the carbon reactant. It should be understood that carbon reactant refers to a gaseous compound containing carbon. Exemplary carbon reactants include hydrocarbons, such as aromatic or aliphatic hydrocarbons, such as alkanes and alkenes. Exemplary carbon reactants include CH4. In some embodiments, the carbon reactant includes CO2.

[0109] The carbon reactant pulse can be executed, for example, after the precursor pulse, after the halogen reactant pulse, or after the purging step following the precursor pulse or the halogen reactant pulse.

[0110] In some embodiments, the deposition cycle includes the step of sequentially executing a plurality of subsequent precursor pulses and carbon reactant pulses before and after executing a halogen reactant pulse. Accordingly, in some embodiments, the sequence of the Y deposition cycle can be expressed by the following formula: ((P + C)*X + R)*Y, where P represents the precursor pulse, C represents the carbon reactant pulse, X is an integer, R represents the halogen reactant pulse, and Y is another integer. In some embodiments, X is equal to Y. In some embodiments, X and Y are different. Accordingly, the deposition cycle may include the step of executing a sequence X including a precursor pulse, a carbon reactant pulse, and then a reactant pulse. In some embodiments, X is at least 1 to at most 20, or at least 2 to at most 10. In some embodiments, Y is at least 1 to a maximum of 1000, or at least 5 to a maximum of 2000, or at least 25 to a maximum of 400, or at least 100 to a maximum of 200.

[0111] In some embodiments, the metal included in the precursor includes molybdenum. Accordingly, the gap may be filled with a molybdenum-containing material. The molybdenum included in the material deposited according to the present disclosure may include molybdenum element and other forms of molybdenum. For example, the molybdenum deposited according to the present disclosure may partially have oxidation states of 0, +2, +3, +4, +5, and / or +6. In some embodiments, at least 60% of the molybdenum is deposited as a metal element. In some embodiments, at least 80% or at least 90% of the molybdenum is deposited as a metal element. In some embodiments, at least 93% or at least 95% of the molybdenum is deposited as a metal element.

[0112] It will be understood that the precursor comprises an aromatic ligand. For example, the precursor may comprise one or more benzene rings. In some embodiments, the precursor comprises two benzene rings. One or both of the benzene rings may comprise hydrocarbon substituents. In some embodiments, each benzene ring of the precursor comprises an alkyl substituent. The alkyl substituent may be a methyl group, an ethyl group, or a linear or branched alkyl group comprising three, four, five, or six carbon atoms. For example, the alkyl substituent of the benzene ring may be an n-propyl group or an iso-propyl group. Additionally, the alkyl substituent may be a butyl, pentyl, or hexyl moiety in the n-, iso-, tert-, or sec- form. In some embodiments, the molybdenum precursor comprises, is essentially composed of, or is composed of bis(ethylbenzene)molybdenum.

[0113] In an exemplary embodiment, the precursor comprises a molybdenum-containing precursor such as bis(ethylbenzene)molybdenum, the halogen reactant comprises a halogen-containing reactant such as CH2I-CH2I, and the nitrogen reactant comprises a nitrogen and hydrogen-containing compound such as NH3.

[0114] In some embodiments, a molybdenum-containing material, e.g., a metallic molybdenum material, may have a resistivity of at least 5 μΩ cm to a maximum of 300 μΩ cm, or at least 10 μΩ cm to about 100 μΩ cm, or at least 20 μΩ cm to a maximum of 50 μΩ cm, e.g., 10 μΩ cm, 15 μΩ cm, 20 μΩ cm, or 30 μΩ cm.

[0115] The molybdenum contained in the material formed according to the method described herein may be at least partially in elemental form. Thus, the oxidation state of the molybdenum may be zero. The molybdenum-containing material may contain additional elements such as nitrogen, carbon and / or oxygen. Other additional or alternative elements are possible. In some embodiments, the molybdenum-containing material may contain a significant proportion of elements other than molybdenum. However, in some embodiments, the molybdenum-containing material may contain substantially only molybdenum. Thus, the molybdenum-containing material may contain molybdenum, be essentially composed of molybdenum, or be composed of molybdenum.

[0116] In some embodiments, the molybdenum-containing material may comprise, for example, about 60 to about 99 atomic percent (atomic %) of molybdenum, or about 75 to about 99 atomic percent of molybdenum, or about 75 to about 95 atomic percent of molybdenum, or about 80 to about 95 atomic percent of molybdenum. The molybdenum-containing material formed by the method according to the present disclosure may comprise, for example, about 80 atomic percent, about 83 atomic percent, about 85 atomic percent, about 87 atomic percent, about 90 atomic percent, about 95 atomic percent, about 97 atomic percent, or about 99 atomic percent of molybdenum.

[0117] The resistivity of the molybdenum-containing material can be reduced by using post-deposition annealing. Annealing can be performed immediately after the deposition of the molybdenum-containing material, that is, before any additional layers are deposited. Alternatively, annealing can be performed after additional layers are deposited. The molybdenum-containing material can be capped prior to annealing. The cap layer may comprise, essentially constitute, or be composed of silicon nitride. An annealing temperature of about 320°C to about 470°C may be used. For example, the annealing temperature may be 330°C, 350°C, 380°C, 400°C, 430°C, or 450°C. Annealing may be performed in a gas atmosphere comprising, essentially consisting of, or composed of argon, an argon-hydrogen mixture, hydrogen, nitrogen, or a nitrogen-hydrogen mixture. The duration of the annealing may be about 1 minute to about 60 minutes, for example, 5 minutes, 20 minutes, 30 minutes, or 45 minutes. The annealing may be performed at a pressure of 0.05 to 760 Torr. For example, the pressure during annealing may be about 1 Torr, about 10 Torr, about 100 Torr, or about 500 Torr.

[0118] In some embodiments, the method as described herein includes the step of exposing a substrate to a conversion process. In some embodiments, the conversion process may be performed after the gap is filled with material. Alternatively, the conversion process may be performed periodically. If the conversion process is performed periodically, the conversion process may be performed after the gap is partially filled, then the conversion process may be performed, then the gap is filled slightly more, then another conversion process may be performed, etc...

[0119] Accordingly, in some embodiments, the method as described herein may include the step of executing one or more supercycles. The supercycle includes the step of executing a supercycle that executes a deposition cycle; and the step of exposing the substrate to a conversion process.

[0120] That is, the conversion process may be performed once after the gap is filled, or may be performed multiple times, that is, the gap filling step and the conversion step may be performed alternately and periodically to fill the gap with the converted material. Accordingly, in some embodiments, the method as described herein comprises a plurality of supercycles. A supercycle comprises the step of at least partially filling a gap contained in a substrate with a metal-containing material and the step of exposing the substrate to the conversion process. In some embodiments, the method described herein comprises at least 2 supercycles to a maximum of 5 supercycles, or at least 5 supercycles to a maximum of 10 supercycles, or at least 10 supercycles to a maximum of 20 supercycles, or at least 20 supercycles to a maximum of 50 supercycles, or at least 50 supercycles to a maximum of 100 supercycles, or at least 100 supercycles to a maximum of 200 supercycles, or at least 200 supercycles to a maximum of 500 supercycles, or at least 500 supercycles to a maximum of 1000 supercycles.

[0121] The total number of supercycles included in the method described herein depends, in particular, on the total amount of material required to fill a specific gap. In some embodiments, the method comprises at least 1 supercycle to a maximum of 100 supercycles, or at least 2 supercycles to a maximum of 80 supercycles, or at least 3 supercycles to a maximum of 70 supercycles, or at least 4 supercycles to a maximum of 60 supercycles, or at least 5 supercycles to a maximum of 50 supercycles, or at least 10 supercycles to a maximum of 40 supercycles, or at least 20 supercycles to a maximum of 30 supercycles. In some embodiments, the method comprises up to 100 supercycles, or up to 90 supercycles, or up to 80 supercycles, or up to 70 supercycles, or up to 60 supercycles, or up to 50 supercycles, or up to 40 supercycles, or up to 30 supercycles, or up to 20 supercycles, or up to 10 supercycles, or up to 5 supercycles, or up to 4 supercycles, or up to 3 supercycles, or up to 2 supercycles, or a single supercycle.

[0122] Any material formed by the method described herein may appropriately undergo a conversion treatment. In some embodiments, a molybdenum-containing material undergoes a conversion treatment.

[0123] The transformation process appropriately includes a step of treating the substrate with at least one of a form of energy, e.g., thermal energy, radiation, and particles. An exemplary process includes a step of exposing the substrate to UV rays. Additionally or alternatively, the transformation process may include a step of exposing the substrate to a direct plasma, such as an inert gas plasma, e.g., an argon plasma. Additionally or alternatively, the transformation process may include a step of exposing the substrate to one or more reactive species, such as ions and / or radicals generated in a remote plasma, such as a remote inert gas plasma, e.g., a remote argon plasma. Additionally or alternatively, the transformation process may include a step of exposing the substrate to at least one of photons, e.g., UV photons, photons of the visible spectrum, IR photons, and photons of the microwave spectrum. Additionally or alternatively, the transformation process may include a step of heating the substrate.

[0124] In some embodiments, the conversion treatment includes the step of exposing the substrate to thermal annealing. Suitable annealing is so known in the art and includes spike annealing, microwave annealing, rapid thermal annealing (RTA), and immersion annealing. Thermal annealing may be appropriately performed in a cyclic manner, for example, after a deposition step in a supercycle. Additionally or alternatively, annealing may be performed as a post-deposition treatment.

[0125] In some embodiments, the conversion process includes the step of exposing the substrate to thermal annealing.

[0126] In some embodiments, thermal annealing comprises at least one step of exposing a substrate to an oxidizing agent such as O2, a nitrating agent such as NH3, a reducing agent such as H2, and an inert gas such as Ar.

[0127] In some embodiments, the substrate is exposed to a conversion process for a duration of at least 0.1 seconds to a maximum of 1000 seconds, or at least 0.2 seconds to a maximum of 500 seconds, or at least 0.5 seconds to a maximum of 200 seconds, or at least 1.0 seconds to a maximum of 100 seconds, or at least 2 seconds to a maximum of 50 seconds, or at least 5 seconds to a maximum of 20 seconds.

[0128] In some embodiments, the deposition cycle in the method described herein is performed at a temperature of at least 300°C to a maximum of 400°C, or at least 200°C to a maximum of 600°C.

[0129] In some embodiments, and during the conversion process, the substrate is maintained at a temperature of less than 800°C, or at least -25°C to a maximum of 800°C, or at least 0°C to a maximum of 700°C, or at least 25°C to a maximum of 600°C, or at least 50°C to a maximum of 400°C, or at least 75°C to a maximum of 200°C, or at least 100°C to a maximum of 150°C, or at least 150°C to a maximum of 300°C, or at least 300°C to a maximum of 500°C, or at least 500°C to a maximum of 800°C. In some embodiments, the temperature at which the substrate is maintained while the metal-containing material is formed is the same as the temperature at which the substrate is maintained while the metal-containing material is converted into a conversion material.

[0130] In some embodiments, the method currently described is performed at a pressure of less than 760 Torr or at least 0.2 Torr to a maximum of 760 Torr, at least 1 Torr to a maximum of 100 Torr, or at least 1 Torr to a maximum of 10 Torr. In some embodiments, the switchable layer is at a pressure of up to 10.0 Torr, or up to 5.0 Torr, or up to 3.0 Torr, or up to 2.0 Torr, or up to 1.0 Torr, or up to 0.1 Torr, or up to 10 -2 Tor's pressure, or up to 10 -3 Tor's pressure, or up to 10 -4Tor's pressure, or up to 10 -5 It is deposited at a pressure of at least 0.1 Torr to a maximum of 10 Torr, at least 0.2 Torr to a maximum of 5 Torr, or at least 0.5 Torr to a maximum of 2.0 Torr.

[0131] An integrated circuit is further described herein. The integrated circuit includes a gap. The gap is filled by a method as described herein. The filled gap may serve as, for example, a via, a contact, a wiring, or part thereof.

[0132] A system is further described herein. The system comprises a reaction chamber. The system further comprises a precursor gas source. The precursor gas source comprises a metal precursor. The system further comprises a halogen reactant gas source comprising a halogen reactant. The system further comprises a controller. The controller is configured to control the flow of gas into the reaction chamber to fill a gap contained in a substrate by a method as described herein.

[0133] Optionally, the system further includes a conversion reactant source. The conversion reactant source, if present, can be arranged to provide conversion reactants to the reaction chamber.

[0134] In some embodiments, the system comprises two separate, i.e., separate reaction chambers: a first reaction chamber and a second reaction chamber. The first reaction chamber is configured to form a material within a gap contained in a substrate. The second reaction chamber is configured to convert the material into a conversion material. In some embodiments, the first reaction chamber is maintained at the first reaction chamber temperature, and the second reaction chamber is maintained at the second reaction chamber temperature. In some embodiments, the first reaction chamber temperature is lower than the second reaction chamber temperature, for example, by at least 10°C to a maximum of 100°C. In some embodiments, the first reaction chamber temperature is higher than the second reaction chamber temperature, for example, by at least 10°C to a maximum of 100°C. In some embodiments, the first reaction chamber temperature is the same as the second reaction chamber temperature, for example, within an allowable limit of 10°C, 20°C, 30°C, or 40°C.

[0135] According to additional embodiments of the present disclosure, an element or a part thereof may be formed using the method and / or structure described herein. The element may comprise a substrate, one or more insulating layers, one or more metal layers, and one or more semiconductor layers. The element further comprises a gap filled using the method disclosed herein.

[0136] An integrated circuit comprising a gap filled using a method as described herein is further described herein. In some embodiments, the integrated circuit comprises a buried power line comprising a metal formed using a method as described herein, such as a buried power line comprising molybdenum.

[0137] A field-effect transistor comprising a gate contact including a material formed according to the method described herein is further described.

[0138] A metal contact comprising a material deposited by a method as described herein is further described.

[0139] A metal-insulator-metal (MIM) capacitor comprising an electrode including a material formed by the method described herein is further provided in the present invention.

[0140] FIG. 1 shows a schematic diagram of one embodiment of the method as described herein. The method may be used, for example, to form electrodes in a semiconductor device. However, unless otherwise stated, the method described herein is not limited to such applications. The method comprises the step (111) of positioning a substrate on a substrate support. The substrate support is located within a reaction chamber. Suitable substrate supports include a pedestal, a susceptor, etc. The method further comprises the step (112) of filling a gap contained in the substrate with a metal-containing material. Suitable metal-containing materials and methods for forming them are described elsewhere in the present invention. Optionally, the reaction chamber is then purged. When a sufficient amount of metal-containing material is formed within the gap, the method is terminated (113).

[0141] Purging can be performed by exposing the substrate to a purge gas, and the purge gas can be performed in turn, for example, by supplying the purge gas to the reaction chamber. Exemplary purge gases include inert gases. Exemplary inert gases include He, Ne, Ar, Xe, and Kr. Alternatively, purging may include the step of transporting the substrate through a purge gas curtain. During purging, if excess chemicals and reaction byproducts are present, they may be removed from the substrate surface or the reaction chamber before the substrate undergoes the next step, for example, by purging the reaction space or moving the substrate.

[0142] FIG. 2 schematically illustrates another embodiment of the method described herein. The method of FIG. 2 is similar to the method of FIG. 1 in that it also includes the step of positioning a substrate on a substrate support (211) and the step of filling a gap with a metal-containing material (212). The method of FIG. 2 differs from the method of FIG. 1 in that it further includes the step of converting the metal-containing material (213) to form a conversion material. Optionally, spreading is performed after the step of converting the metal-containing material (213). The step of converting the metal-containing material (213) may include the step of exposing the substrate to a direct plasma, such as a direct oxygen plasma, a direct nitrogen plasma, a direct carbon plasma, or a direct inert gas plasma. Optionally, the method of FIG. 2 includes a plurality of supercycles (214) in which the step of filling a gap with a metal-containing material (212) and the step of converting the metal-containing material (213) are repeated one or more times. After a predetermined amount of conversion material is formed on the substrate, the method of FIG. 2 is terminated (215).

[0143] FIG. 3 illustrates a system (300) according to an exemplary additional embodiment of the present disclosure. The system (300) may be used to perform and / or perform a method as described herein, or to form a structure or component as described herein, for example, in an integrated circuit.

[0144] In the illustrated example, the system (300) includes one or more reaction chambers (302), a metal precursor gas source (304), a halogen reactant gas source (306), a purge gas source (308), an exhaust (310), and a controller (312).

[0145] The reaction chamber (302) may include any suitable reaction chamber, such as an ALD or CVD reaction chamber. In some embodiments, the reaction chamber includes a showerhead injector and a substrate support (not shown).

[0146] The metal precursor gas source (304) may include a vessel and one or more metal precursors as described herein. The metal precursor may be provided to the reaction chamber (302) alone or mixed with one or more carrier gases (e.g., inert gases). The halogen reactant gas source (306) may include one or more reactants and a vessel as described herein. The halogen reactant may be provided to the reaction chamber alone or mixed with one or more carrier gases. The purge gas source (308) may include one or more purge gases, e.g. inert gases, nitrogen, or a mixture thereof, as described herein. Although shown as four gas sources (304-308), the system (300) may include any suitable number of gas sources, e.g., additional oxygen reactant sources, nitrogen reactant sources, carbon reactant sources, and inert gas sources. Gas supply sources (304-308) can be connected to the reaction chamber (302) via lines (314-318), each of which may include a flow controller, valve, heater, etc. The exhaust (310) may include one or more vacuum pumps.

[0147] The controller (312) includes electronic circuits and software for selectively operating valves, manifolds, heaters, pumps, and other components included in the system (300). These circuits and components operate to introduce metal precursors, one or more reactants, and purge gas from their respective sources (304-308). The controller (312) may control the timing of the gas pulse sequence, the temperature of the substrate and / or reaction chamber, the pressure of the reaction chamber, and various other operations to provide proper operation of the system (300). The controller (312) may include control software that electrically or pneumatically controls valves to control the flow of metal precursors, one or more reactants, and purge gas into and from the reaction chamber (302). The controller (312) may include software or hardware components, such as modules like FPGAs or ASICs, that perform specific tasks. The modules are configured to be mounted on an addressable storage medium of the control system and may be advantageously configured to execute one or more processes.

[0148] Other configurations of the system (300) are possible, including different numbers and types of precursor and reactant sources and purge gas sources. Additionally, it will be understood that there are multiple arrangements of valves, conduits, precursor sources, and purge gas sources that can be used to achieve the purpose of selectively supplying gas into the reaction chamber (402). Furthermore, while the system is schematically depicted, many components have been omitted for the sake of simplification of the example, and these components may include, for example, various valves, manifolds, purifiers, heaters, vessels, vents, and / or bypasses.

[0149] During the operation of the system (300), a substrate, such as a semiconductor wafer (not shown), is transferred, for example, from a substrate handling system to a reaction chamber (302). Once the substrate(s) are transferred to the reaction chamber (302), one or more gases from a gas source (304-308), such as a precursor, a reactant, a carrier gas, and / or a purge gas, are introduced into the reaction chamber (302).

[0150] FIG. 4 illustrates another embodiment of the system (400) as described herein in a stylized manner. The system (400) of FIG. 4 is similar to that of FIG. 3. It comprises two separate reaction chambers: a first reaction chamber (410) and a second reaction chamber (420). The first reaction chamber (410) is arranged to fill a gap with a metal-containing material. The second reaction chamber (420) is arranged to convert the metal-containing material into a conversion material.

[0151] FIG. 5 shows a schematic diagram of a substrate (500) including a gap (510). The gap (510) includes a sidewall (511) and a distal end (512). The substrate further includes a proximal surface (520) located, for example, outside the gap, for example, adjacent thereto. In some embodiments, the sidewall (511) and the distal end (512) are made of the same material. In some embodiments, at least one of the sidewall (511) and the distal end is made of a dielectric such as a silicon-containing dielectric such as silicon oxide, silicon nitride, silicon carbide, and mixtures thereof. In some embodiments, the dielectric is made of hydrogen. In some embodiments, at least one of the sidewall (511) and the distal end (512) is made of a metal such as a transition metal, a post-transition metal, and a rare earth metal. In some embodiments, the metal is made of Cu, Co, W, Ru, Mo, Al, or an alloy thereof.

[0152] In some embodiments, the sidewall (511) and the distal end (512) have the same or substantially the same composition. In some embodiments, the sidewall (511) and the distal end (512) have different compositions. In some embodiments, the sidewall and the distal end (512) comprise a dielectric. In some embodiments, the sidewall (511) and the distal end (512) comprise a metal. In some embodiments, the sidewall (511) comprises a metal and the distal end (512) comprises a dielectric. In some embodiments, the sidewall (511) comprises a dielectric and the distal end comprises a metal.

[0153] In some embodiments, the proximal surface (520) has the same composition as the sidewall (511). In some embodiments, the proximal surface (520) has a different composition from the sidewall (511). In some embodiments, the proximal surface (520) has a different composition from the distal end (512). In some embodiments, the proximal surface (520) has the same composition as the distal end (512).

[0154] In some embodiments, the proximal surface (520), the sidewall (511), and the distal end (512) comprise the same material. In some embodiments, the proximal surface (520), the sidewall (511), and the distal end (512) comprise a dielectric. In some embodiments, the proximal surface (520), the sidewall (511), and the distal end (512) comprise a metal. In some embodiments, the proximal surface (520), the sidewall (511), and the distal end (512) comprise a semiconductor.

[0155] For additional examples, refer to FIG. 6. FIG. 6 shows experimental data, in particular scanning transmission electron microscope (STEM) images, obtained on a structure containing a gap that was at least partially filled by the method described herein. In particular, bis(ethylbenzene)molybdenum, Mo(EtBz)2 is used as a metal precursor, and 1,2-diiodoethane is used as a halogen reactant. The substrate is sequentially exposed to the metal precursor in precursor pulses and sequentially exposed to the halogen reactant in halogen reactant pulses. This process forms a metallic molybdenum film on a planar substrate. Surprisingly, the same process forms a molybdenum-containing material (620) containing metallic molybdenum. The metallic properties of the molybdenum-containing material (620) were confirmed by X-ray photoelectron spectroscopy (XPS) measurements.

[0156] The samples shown in FIG. 6, panels a) and b) were subjected to a periodic deposition process at a substrate temperature of at least 280°C to a maximum of 325°C and a pressure of 2 Torr. A precursor pulse time of 12 seconds was used. After the precursor pulse, a purge time of 10 seconds was used. A halogen reactant pulse time of 10 seconds was used. After the halogen reactant pulse, a purge time of 10 seconds was used. The sample in panel a) underwent 75 deposition cycles, which forms a molybdenum-containing material (620). The sample in panel b) underwent 110 deposition cycles. This surprisingly results in the complete filling of the gap with the molybdenum-containing material without the formation of seams.

[0157] The sample shown in panel c) of FIG. 6 underwent a periodic deposition process at a substrate temperature of at least 325°C to a maximum of 350°C. The pulse and purge times were the same as those of the samples shown in panels a) and b) of FIG. 6. The sample in panel c) underwent 55 deposition cycles, which form a molybdenum-containing material (620).

[0158] For additional exemplary implementations, refer to FIGS. 7 and FIGS. 8.

[0159] FIG. 7 shows a gap (710) having a critical dimension of 30 nm partially filled by an embodiment of the method described herein. The process having the result shown in FIG. 7 formed a molybdenum-containing material (720) within the gap. In particular, FIG. 7 shows a gap filled using a thermal ALD process comprising 78 deposition cycles. The deposition cycles include, in a given order, a precursor pulse, a reactant pulse, and a nitrogen reactant pulse. The precursor used was bis(ethylbenzene)molybdenum, the halogen reactant was 1,2-diiodoethane, and the nitrogen reactant was ammonia. The precursor pulse lasted for 10 seconds, followed by a 5-second purge. The halogen reactant pulse lasted for 0.5 seconds, followed by a 5-second purge. The nitrogen reactant pulse lasted for 8 seconds, followed by a 5-second purge. The process was performed at a susceptor temperature of 350°C and a pressure of 5 Torr.

[0160] FIG. 8 shows a gap having a critical dimension of 20 nm and thus smaller than the gap shown in FIG. 7. In particular, FIG. 8 shows a gap (810) filled using the same process used to fill the gap (710) shown in FIG. 7. Because the size of the gap (810) in FIG. 8 is smaller, these gaps (810) are completely filled with a molybdenum-containing material (820). Surprisingly and advantageously, no substantial seams or voids are formed.

[0161] Advantageously, some embodiments of the method enable filling the gap with metallic molybdenum or other molybdenum-containing compounds without forming any voids or seams. The method may also be applied to high aspect ratio gaps and / or capillary gaps having small critical dimensions, for example, gaps having critical dimensions of 10 to 20 nm or less.

Claims

Claim 1 A method for filling a gap, the method comprises the step of providing a substrate to a reaction chamber, wherein the substrate comprises the gap, the substrate further comprises a proximal surface, and the gap comprises a distal end and a sidewall; the method comprises the step of executing a plurality of supercycles, wherein each supercycle comprises: a deposition cycle comprising a precursor pulse and a halogen reactant pulse; and the step of exposing the substrate to a conversion treatment; wherein the precursor pulse comprises the step of exposing the substrate to a precursor, wherein the precursor is of the general chemical formula ML n A method comprising a compound having, wherein M is a metal, L is an aromatic ligand, and n is an integer from at least 1 to at most 6, wherein the halogen reactant pulse comprises the step of exposing the substrate to the halogen reactant, wherein the halogen reactant comprises a halogen, thereby preferentially forming a metal-containing material on the distal end relative to the proximal surface and the sidewall, thereby at least partially filling the gap. Claim 2 A method according to claim 1, wherein both the distal end and the sidewall comprise a dielectric material. Claim 3 A method according to claim 1 or 2, wherein both the distal end and the sidewall comprise at least one of a metal material and a semiconductor material. Claim 4 A method according to claim 1 or 2, wherein the aromatic ligand is a substituted or unsubstituted benzene ring. Claim 5 In paragraph 4, the method wherein the ligand is an alkylbenzene. Claim 6 A method according to claim 1 or 2, wherein the metal is molybdenum. Claim 7 In claim 6, the method wherein the precursor comprises bis(ethylbenzene)molybdenum. Claim 8 A method according to claim 1 or 2, wherein the halogen reactant comprises an alkyl halide. Claim 9 In claim 8, the method wherein the halogen reactant comprises alkyl iodine. Claim 10 In claim 8, the halogen reactant is of the general chemical formula X a R b C―CX a R' b A method having, wherein X is a halogen, R and R' are independently H or alkyl groups, and a and b are independently 1 or 2 such that for each carbon atom, a + b = 3. Claim 11 A method according to claim 1 or 2, wherein the halogen reactant comprises a bond selected from XX bond, HX bond, CX bond, PX bond, NX bond, and SX bond, wherein X is a halogen. Claim 12 A method according to claim 1 or 2, wherein the deposition cycle further comprises a nitrogen reactant pulse, the nitrogen reactant pulse comprising the step of exposing the substrate to the nitrogen reactant. Claim 13 In paragraph 12, the method wherein the nitrogen reactant comprises NH3. Claim 14 A method according to claim 1 or 2, wherein the deposition cycle further comprises an oxygen reactant pulse, the oxygen reactant pulse comprising the step of exposing the substrate to the oxygen reactant. Claim 15 A method according to claim 1 or 2, wherein the deposition cycle further comprises a carbon reactant pulse, the carbon reactant pulse comprising the step of exposing the substrate to the carbon reactant. Claim 16 delete Claim 17 A method according to claim 1, wherein the conversion process includes the step of exposing the substrate to thermal annealing. Claim 18 A method according to claim 17, wherein the thermal annealing comprises at least one step of exposing the substrate to an oxidizing agent, a nitrating agent, a reducing agent, and an inert gas. Claim 19 An integrated circuit comprising a gap, wherein the gap is filled by a method according to claim 1 or 2. Claim 20 A system comprising: a reaction chamber; a metal precursor gas source including a metal precursor; a halogen reactant gas source including a halogen reactant; and a controller configured to control the gas flow into the reaction chamber to fill a gap contained in a substrate by a method according to claim 1 or 2.

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