TW202108815A - Methods for depositing a molybdenum nitride film on a surface of a substrate by a cyclical deposition process and related semiconductor device structures including a molybdenum nitride film - Google Patents

Abstract

Methods for depositing a molybdenum nitride film on a surface of a substrate are disclosed. The methods may include: providing a substrate into a reaction chamber; and depositing a molybdenum nitride film directly on the surface of the substrate by performing one or more unit deposition cycles of cyclical deposition process, wherein a unit deposition cycle may include, contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor, and contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor. Semiconductor device structures including a molybdenum nitride film are also disclosed.

Description

Method for depositing molybdenum nitride film on substrate surface by cyclic deposition process and related semiconductor device structure including molybdenum nitride film

[ Cross reference of related applications ]

This application claims to be filed on August 23, 2019 and is titled ``Methods for depositing molybdenum nitride films on the surface of substrates by a cyclic deposition process and related semiconductor device structures including molybdenum nitride films (METHODS FOR DEPOSITING) A MOLYBDENUM NITRIDE FILM ON A SURFACE OF A SUBSTRATE BY A CYCLICAL DEPOSITION PROCESS AND RELATED SEMICONDUCTOR DEVICE STRUCTURES INCLUDING A MOLYBDENUM NITRIDE FILM), which is hereby incorporated by reference Incorporated into this article. This application is related to the application on August 23, 2019, titled ``Methods for forming polycrystalline molybdenum films on the surface of substrates and related structures including polycrystalline molybdenum films (METHODS FOR FORMING A POLYCRYSTALLINE MOLYBDENUM FILM OVER A SURFACE OF A SUBSTRATE AND RELATED STRUCTURES INCLUDING A POLYCRYSTALLINE MOLYBDENUM FILM)" US Provisional Patent Application No. 62/891,247, the entire content of which is incorporated herein by reference.

The present invention generally relates to a method for depositing a molybdenum nitride film on the surface of a substrate and a specific method for depositing a molybdenum nitride film by a cyclic deposition process. The present invention also generally relates to a semiconductor device structure including a molybdenum nitride film.

Complementary metal-oxide-semiconductor (CMOS) technology conventionally uses n-type and p-type polysilicon as gate electrode materials. However, doped polysilicon may not be an ideal gate electrode material for advanced technology nodes. For example, although doped polysilicon is conductive, there may still be surface areas that can be depleted of carriers under bias. This depletion region can appear as an additional gate insulator thickness, commonly referred to as gate depletion, and can increase the equivalent oxide thickness. Although the gate depletion region may be extremely thin, on the order of a few angstroms (Å), it may become significant when the gate oxide thickness is reduced in advanced technology nodes. In addition, for both NMOS and PMOS devices, polysilicon does not exhibit an ideal effective work function (eWF). In order to overcome the non-ideal effective work function of doped polysilicon, a threshold voltage can be used to adjust the implantation. However, as device geometries decrease in advanced technology nodes, the threshold voltage adjustment implantation process may become more and more complicated.

To overcome the problems associated with doped polysilicon gate electrodes, non-ideal doped polysilicon gate materials can be replaced with alternative materials, such as metals, metal nitrides, and metal carbides. For example, the characteristics of the metal nitride film can be used to provide a more ideal effective work function for both NMOS and PMOS devices. The effective work function of the gate electrode, that is, the energy required to extract electrons, can be compatible with the barrier height of semiconductor materials . For example, in the case of a PMOS device, the effective work function is about 5.0-5.2 eV, and in the case of an NMOS device, the effective work function is about 4.1-4.3 eV.

Therefore, there is a need for a method for forming low-resistivity gate electrodes for both NMOS devices and PMOS devices with better effective work functions.

The summary of the present invention is provided to introduce a series of concepts in a simplified form. These concepts are further detailed in the detailed description of illustrative specific examples of the following disclosure. This summary is not intended to identify the key features or basic features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

In some embodiments, a method for depositing a molybdenum nitride film on the surface of a substrate by a cyclic deposition process is provided. The method may include: providing the substrate into the reaction chamber; and directly depositing the molybdenum nitride film on the surface of the substrate by performing one or more unit deposition cycles of the cyclic deposition process, wherein the unit deposition cycle includes: The first gas phase reactant of the molybdenum halide precursor is contacted; and the substrate is contacted with the second gas phase reactant containing the nitrogen precursor.

In some embodiments of the present invention, a semiconductor device structure including a molybdenum nitride film is provided. The semiconductor device structure of the present invention may include: a semiconductor channel region; and a gate stack structure directly disposed on the semiconductor channel region, wherein the gate stack structure includes: a gate dielectric directly disposed on the semiconductor channel region; and directly Molybdenum nitride film placed on the gate dielectric.

For the purpose of summarizing the present invention and the advantages achieved over the prior art, certain objectives and advantages of the present invention have been described above. Of course, it should be understood that all such goals or advantages may not be achieved according to any specific embodiment of the present invention. Therefore, for example, those familiar with the art should realize that the present invention can achieve or optimize an advantage or a set of advantages as taught or suggested herein without the need to achieve other goals or advantages as might be taught or suggested herein. Implement or execute.

All these specific examples are intended to be within the scope of the invention disclosed herein. These and other specific examples will become apparent to those familiar with the art from the detailed description of some specific examples below with reference to the accompanying drawings, but the present invention is not limited to any one or more specific examples disclosed.

Although some specific examples and embodiments are disclosed below, those skilled in the art will understand that the present invention extends beyond the specific examples and/or uses specifically disclosed in the present invention, as well as obvious modifications and equivalents thereof. Therefore, it is hoped that the scope of the present invention disclosed should not be limited by the specific examples of the specific disclosure described below.

The illustrations presented herein are not intended to be actual views of any specific materials, structures or devices, but are merely idealized representations for describing specific examples of the present invention.

As used herein, the term "substrate" can refer to any underlying material or material on which a device, circuit, or film can be formed or used.

As used herein, the term "cyclical deposition" may refer to the sequential introduction of two or more precursors (reactants) into the reaction chamber to deposit a film on the substrate and includes such as atomic layer deposition (atomic layer deposition). , ALD) and cyclic chemical vapor deposition (cyclical chemical vapor deposition, cyclic CVD) deposition technology.

As used herein, the term "cyclical chemical vapor deposition" can refer to any process in which a substrate is sequentially exposed to two or more volatile precursors, which react on the substrate and/ Or decompose to deposit the film.

As used herein, the term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which a deposition cycle is performed in a reaction chamber, preferably a plurality of continuous deposition cycles. Generally, during the deposition cycle of each unit, the precursor is chemically adsorbed on the deposition surface (for example, the substrate surface or the previously deposited underlying surface, such as the material from the previous ALD cycle), and the formation is not easy to react with the additional precursor (that is, Self-limiting reaction (self-limiting reaction)) monolayer or sub-monolayer. Thereafter, if necessary, a reactant (for example, another precursor or reaction gas) can be subsequently introduced into the reaction chamber for conversion of the chemically adsorbed precursor to the desired material on the deposition surface. Generally, this reactant can further react with the precursor. In addition, during the deposition cycle of each unit, a purge step can also be used to remove excess precursors from the reaction chamber and/or remove excess reactants and/or reaction side effects from the reaction chamber after the chemical adsorption precursors are converted. product. In addition, when performed with alternating pulses of one or more precursor components, reactive gas, and purge gas (for example, inert carrier gas), the term "atomic layer deposition" as used herein also means to include those represented by related terms Processes such as "chemical vapor atomic layer deposition", "atomic layer epitaxy (ALE)", molecular beam epitaxy (MBE), gas source MBE, organic metal MBE, and chemical beam epitaxy crystal.

As used herein, the term "film" can refer to any physically continuous or physically discontinuous structure and material formed by the methods disclosed herein. For example, "film" may include 2D materials, nano laminates, nano rods, nano tubes, nanoparticles, or even part or all of molecular layers, or part or all of atomic layers or atoms and/or molecules Of clusters. A "film" can include a material or layer that has pinholes but is still at least partially physically continuous.

As used herein, the term "molybdenum nitride film" may refer to a film including at least a molybdenum component and a nitrogen component.

As used herein, the term "molybdenum halide precursor" may refer to a reactant comprising at least a molybdenum component and a halide component, wherein the halide component may include one of a chlorine component, an iodine component, or a bromine component or More.

As used herein, the term "molybdenum sulfide halide" may refer to a reactant containing at least a molybdenum component, a halide component, and a chalcogen component, where the chalcogen element is an element of group IV of the periodic table, including oxygen (O), sulfur (S), selenium (Se) and tellurium (Te).

As used herein, the term "molybdenum oxyhalide" may refer to a reactant containing at least a molybdenum component, an oxygen component, and a halide component.

As used herein, the term "reducing agent" can refer to a reactant that donates electrons to another species in a redox chemical reaction.

As used herein, the term "crystalline film" may refer to a film showing a crystalline structure of at least short-range order or even long-range order, and includes single crystal films and polycrystalline films.

As used herein, the term "amorphous film" may refer to a film that does not substantially show an ordered crystalline structure as observed in a crystalline film.

As used herein, the term "gas" may refer to vapor or vaporized solid and/or vaporized liquid, and may be composed of a single gas or a mixture of gases.

Specific examples of the present invention include methods that can be used to deposit molybdenum nitride films and related semiconductor device structures including molybdenum nitride films deposited according to specific examples of the present invention. In some embodiments of the present invention, for example, the molybdenum nitride film may form a part of the gate stack, such as at least a part of the gate electrode of the transistor device structure. Molybdenum nitride film-based gate electrodes can provide gate stacks with better effective work functions for both PMOS and NMOS devices.

Existing work function metals used to form gate electrodes have limitations due to their improper effective work function values. For example, the effective work function of a known material can vary with its thickness. Therefore, as the device geometry is reduced in advanced technology nodes, the thickness of the corresponding device film (such as the work function metal of the gate electrode) can also be reduced as the value of the effective work function of the overall gate stack changes. . Such changes in the effective work function of the gate stack can produce effective work functions that are not ideal for both NMOS and PMOS device structures.

In some specific examples of the present invention, the resistivity of the deposited molybdenum nitride film can be an important parameter for improving the efficiency of semiconductor devices, such as where the molybdenum nitride film can be used as a gate electrode, a liner (for example, in a memory In application), barrier layer material, capping material or part of the contact layer. As discussed above, next-generation technology nodes may require ever-decreasing film thicknesses. However, as the film thickness of the conductive film decreases, the resistivity of the conductive film may increase, resulting in loss of efficiency in the structure of the associated semiconductor device. As a non-limiting example, the molybdenum nitride film of the present invention can be used as a substitute for the common titanium nitride film currently used in semiconductor device structures. Therefore, the molybdenum nitride film of the present invention can have a lower resistivity than the resistivity usually achieved in a titanium nitride film of comparable thickness.

Therefore, specific examples of the present invention may include a method for depositing a molybdenum nitride film on the surface of a substrate by a cyclic deposition process. The method may include: providing the substrate into the reaction chamber; and directly depositing the molybdenum nitride film on the surface of the substrate by performing one or more unit deposition cycles of the cyclic deposition process, wherein the unit deposition cycle includes: The first gas phase reactant of the molybdenum halide precursor is contacted; and the substrate is contacted with the second gas phase reactant containing the nitrogen precursor.

The method of directly depositing a molybdenum nitride film on the surface of a substrate disclosed herein may include a cyclic deposition process, such as atomic layer deposition (ALD) or cyclic chemical vapor deposition (cyclic CVD).

Non-limiting illustrative examples of cyclic deposition methods may include atomic layer deposition (ALD), where ALD is usually based on a self-limiting reaction, whereby sequential and alternating reactant pulses are used to deposit about one atom (or Molecule) single layer of material. The deposition conditions and precursors are usually selected to provide a self-saturating reaction so that the absorber layer of one reactant leaves a surface termination that does not react with the gas phase reactant of the same reactant. The substrate is then brought into contact with a different reactant, which reacts with the previous termination to allow the deposition to continue. Therefore, each cycle of alternating pulses usually leaves no more than about one monolayer of the desired material. However, as mentioned above, those skilled in the art will recognize that in one or more ALD cycles, more than one single layer of material can be deposited, for example, in the case of unregulated alternate nature of how certain gas phase reactions occur .

In an exemplary ALD process for directly depositing a molybdenum nitride film on the surface of a substrate, the unit deposition cycle may include exposing the substrate to the first gas phase reactant, and removing any unreacted first reactant from the reaction chamber And reaction by-products, and exposing the substrate to the second gas phase reactant, followed by a second removal step. In some embodiments of the present invention, the first gas phase reactant may include a molybdenum halide precursor and the second gas phase reactant may include a nitrogen precursor.

The precursor can be separated by an inert gas (such as argon (Ar) or nitrogen (N ₂ )) to prevent gas phase reactions between the reactants and enable self-saturating surface reactions. However, in some embodiments, the substrate can be moved to contact the first gas phase reactant and the second gas phase reactant respectively. Due to the self-saturation of the reaction, there may be no need for strict temperature control of the substrate and precise dose control of the precursor. However, the substrate temperature is preferably such that the gas species introduced will not condense into a single layer, nor decompose on the surface. Before contacting the substrate with the next reactive chemical species, such as by purging the reaction space or by moving the substrate, the excess chemical species and reaction byproducts (if any) are removed from the substrate surface. With the help of inert purge gas, undesired gaseous molecules can be effectively discharged from the reaction space. A vacuum pump can be used to assist in purging.

A reactor capable of a cyclic deposition process can be used to deposit the molybdenum nitride film as described herein. Such reactors include ALD reactors and CVD reactors configured to provide precursors. According to some specific examples, a showerhead reactor can be used. According to some specific examples, cross-flow, batch, small batch, or space ALD reactors can be used.

In some embodiments of the present invention, a batch reactor can be used. In some specific examples, a vertical batch reactor can be used. For example, a vertical batch reactor may include a reaction chamber and an elevator that is constructed and arranged to move boats configured to support batches of between 10 and 200 substrates into or out of the reaction chamber. In other specific examples, the batch reactor includes configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers. Wafers or small batch reactors with 2 or less wafers. In some specific examples using batch reactors, the inconsistency between wafers is less than 3% (1σ), less than 2%, less than 1%, or even less than 0.5%.

The exemplary cyclic deposition process described herein can optionally be performed in one or more related reaction chambers in the reactor and connected to the cluster tool. In the cluster tool, because each reaction chamber is dedicated to one type of process, the temperature of the reaction chamber in each module can be kept constant, which is higher than that of a reactor that heats the substrate to the process temperature before each round Processing capacity. In addition, in the cluster tool, the process pressure time required to pump the reaction chamber to the substrate can be reduced. In some specific examples of the present invention, the exemplary cyclic deposition process for depositing molybdenum nitride films disclosed herein can be performed in a cluster tool containing multiple reaction chambers, wherein each individual reaction chamber can be used to expose the substrate to Individual precursor gases and substrates can be transferred between different reaction chambers for exposure to multiple precursors. The substrate transfer is performed in a controlled environment to prevent substrate contamination. In some embodiments of the present invention, the cyclic deposition process described herein can be performed in a cluster tool containing multiple reaction chambers, where each individual reaction chamber can be configured to heat the substrate to different temperatures.

The free-standing reactor may be equipped with a load-lock. In that case, there is no need to cool the reaction chamber between rounds.

According to some non-limiting examples of the present invention, the ALD process can be used to directly deposit the molybdenum nitride film on the surface of the substrate. In some embodiments of the present invention, each ALD unit deposition cycle may include two different deposition steps or stages. In the first stage of the unit deposition cycle (the "molybdenum stage"), the surface of the substrate to be deposited can be brought into contact with the first gas phase reactant containing the molybdenum precursor chemically adsorbed on the surface of the substrate, thereby forming on the surface of the substrate No more than about one reactant species monolayer. In the second stage ("nitrogen stage") of the unit deposition cycle, the surface of the substrate to be deposited can be brought into contact with a second gas phase reactant containing a nitrogen precursor.

Referring to FIG. 1, an exemplary cyclic deposition process for directly depositing a molybdenum nitride film on the surface of a substrate can be understood, which illustrates an exemplary atomic layer deposition process 100 for depositing a molybdenum nitride film on the surface of a substrate.

In more detail, FIG. 1 shows an exemplary molybdenum nitride deposition process 100 including a cyclic deposition stage 105. The exemplary atomic layer deposition process 100 may begin at process block 110, which includes providing a substrate into a reaction chamber and heating the substrate to a desired deposition temperature.

In some embodiments of the present invention, the substrate may include a planar substrate or a patterned substrate, which includes high aspect ratio features, such as vertical trenches, horizontal trenches, vertical gap features, horizontal gap features, and/or fin structures. The substrate may include one or more materials, including but not limited to semiconductor materials, dielectric materials, and metal materials. The substrate may also include one or more exposed surfaces, including but not limited to semiconductor surfaces, dielectric surfaces, and metal surfaces.

In some specific examples, the substrate may include semiconductor materials, such as but not limited to silicon (Si), germanium (Ge), germanium tin (GeSn), silicon germanium (SiGe), silicon germanium tin (SiGeSn), silicon carbide (SiC) Or group III-V semiconductor materials.

In some embodiments, the substrate may include dielectric materials, such as but not limited to silicon-containing dielectric materials and metal oxide dielectric materials. In some embodiments, the substrate may include one or more silicon-containing dielectric materials/surfaces, such as, but not limited to _{, silicon dioxide (SiO 2} ), silicon suboxide, silicon nitride (Si ₃ N ₄ ), silicon oxynitride ( SiON), silicon carbide (SiOC), silicon carbide nitride (SiOCN), silicon carbide nitride (SiCN). In some specific examples, the substrate may be one or more metal oxide materials/surfaces, such as but not limited to aluminum oxide (Al ₂ O ₃ ), hafnium oxide (HfO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), hafnium silicate (HfSiO _x ), and lanthanum oxide (La ₂ O ₃ ).

In some embodiments, the substrate may include an engineered substrate, in which a surface semiconductor layer is disposed above the body support, with an intermediate buried oxide (BOX) disposed therebetween.

The patterned substrate may include a substrate that may include semiconductor device structures formed in or onto the surface of the substrate. For example, the semiconductor device structure may include a partially manufactured semiconductor device structure, such as a transistor and/or a memory device. In some embodiments, the substrate may include a single crystal surface and/or may include one or more sub-surfaces of a non-single crystal surface, such as a polycrystalline surface and/or an amorphous surface.

The reaction chamber used for deposition can be an atomic layer deposition reaction chamber, or a chemical vapor deposition reaction chamber, or any of the reaction chambers as previously described herein.

In some specific examples of the process block 110 (FIG. 1 ), the substrate may be heated to the deposition temperature for the subsequent cycle deposition stage 105. For example, the substrate can be heated to temperatures below about 700°C, or below about 600°C, or below about 500°C, or below about 400°C, or below about 300°C, or even below about 200°C. Substrate temperature. In some embodiments, the substrate temperature during the cyclic deposition process 100 may be between about 200°C and 700°C, or between about 350°C and 600°C, or between about 450°C and 550°C.

In addition to achieving the desired deposition temperature, that is, the desired substrate temperature, the exemplary cyclic deposition process 100 can also adjust the pressure in the reaction chamber during film deposition. For example, in some specific examples, the exemplary cyclic deposition process 100 can be adjusted to less than 300 Torr, or less than 200 Torr, or less than 100 Torr, or less than 50 Torr, or less than 30 Torr, or It is carried out in a reaction chamber with a pressure of less than 10 Torr, or less than 5 Torr, or even less than 2 Torr. In some embodiments, the pressure in the reaction chamber during deposition can be adjusted between about 2 Torr and 300 Torr, or between about 30 Torr and 80 Torr.

Once the substrate is heated to the desired deposition temperature and the pressure in the reaction chamber is adjusted, the exemplary cyclic deposition process 100 (for example, an ALD process) can be continued with the cyclic deposition stage 105 by means of a process block 120, which includes making the substrate and containing The first gas phase reactant of the molybdenum halide precursor (ie, the molybdenum precursor) contacts.

In some embodiments of the present invention, the molybdenum halide precursor may include a molybdenum chloride precursor, a molybdenum bromide precursor, or a molybdenum iodide precursor. For example, as a non-limiting embodiment, molybdenum chloride may include one or more of the following: molybdenum pentachloride (MoCl ₅ ) or molybdenum hexachloride (MoCl ₆ ).

In some embodiments, the molybdenum halide precursor may include a molybdenum sulfide halide precursor, such as a molybdenum oxyhalide precursor selected from the group consisting of molybdenum oxychloride, molybdenum oxyiodide, and/or molybdenum oxybromide. In some specific examples, the molybdenum precursor may include molybdenum oxychloride, which includes one or more of the following: molybdenum trichloride (V) (MoOCl ₃ ), molybdenum tetrachloride (VI) (MoOCl ₄ ), or two Chlorinated molybdenum (IV) dioxide (MoO ₂ Cl ₂ ).

In an alternative embodiment, the first gas phase reactant, that is, the molybdenum precursor may include a metal organic molybdenum precursor, such as Mo(NMe ₂ ) ₄ , Mo(NEt ₂ ) ₄ , Mo ₂ (NMe ₂ ) ₆ , Mo(tBuN) ₂ (NMe ₂ ) ₂ , Mo(tBuN) ₂ (NEt ₂ ) ₂ , Mo(NEtMe) ₄ , Mo(NtBu) ₂ (StBu) ₂ , Mo(NtBu) ₂ (iPr ₂ AMD) ₂ Mo (thd) ₃ , MoO ₂ (acac), MoO ₂ (thd) ₂ and/or MoO ₂ (iPr ₂ AMD) _{2 The} first gas phase reactant may include an organometallic molybdenum compound, including (but not limited to) containing ring Pentadienyl (Cp) ligands, η ⁶ -arene ligands and carbonyl ligands, such as Mo(CO) _{6 ,} Mo(Cp) ₂ H ₂ , Mo(iPrCp) ₂ H ₂ , Mo(η ⁶ -Ethylbenzene) ₂ , MoCp(CO) ₂ (η ³ -allyl), MoCp(CO) ₂ (NO), Mo(benzene) ₂ , MoCp ₂ Cl ₂ and NMe) ₃ , and variants thereof.

In at least one embodiment of the present invention, the first gas phase reactant may include bis(tertiary butylimino) bis(dimethylamino) molybdenum (VI). The first gas phase reactant may react with the second gas phase reactant, where the second gas phase reactant may include ammonia gas. The resulting molybdenum nitride film can have work function values, resistivity and flatband shift suitable for pMOS work function metal applications. For example, this can be partly attributed to the higher electronegativity of molybdenum compared to titanium or vanadium. In addition, the lower resistivity of molybdenum nitride makes the effective work function higher.

In some embodiments of the present invention, contacting the substrate with the molybdenum halide precursor may comprise between about 0.1 seconds and about 60 seconds, or between about 0.1 seconds and about 10 seconds, or even between about 0.5 seconds and about 0.5 seconds. The contact period between 5.0 seconds. In addition, during the contact between the substrate and the molybdenum halide precursor, the flow rate of the molybdenum halide precursor may be less than 1000 sccm, or less than 500 sccm, or less than 100 sccm, or less than 10 sccm, or even less than 1 sccm. In addition, during the contact between the substrate and the molybdenum halide precursor, the flow rate of the molybdenum precursor may be in the range of about 1 sccm to 2000 sccm, about 5 sccm to 1000 sccm, or about 10 sccm to about 500 sccm.

An exemplary cyclic deposition process for depositing a molybdenum nitride film as by process 100 of FIG. 1 can be continued by purging the reaction chamber. For example, excess molybdenum halide precursors and reaction byproducts (if present) can be removed from the substrate surface, for example, by pumping with an inert gas. In some embodiments of the present invention, the purge process may include a purge cycle, wherein the substrate surface is purged for less than about 5 seconds, or less than about 3 seconds, or less than about 2 seconds, between about 2 to 5 seconds Time period. The excess molybdenum halide precursor and any possible reaction by-products can be removed by means of a vacuum created by a pumping system in fluid communication with the reaction chamber. In some embodiments of the present invention, the purge cycle after contacting the substrate with the first gas phase reactant may be omitted.

The exemplary cyclic deposition process 100 can be continued with the second stage of the cyclic deposition stage 105 by means of a process block 130, which includes contacting a substrate with a second gas phase reactant, and in particular, contacting the substrate with a nitrogen precursor. The second gas phase reactant contact ("nitrogen stage").

In some embodiments of the present invention, the nitrogen precursor may include at least one of the following: molecular nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), hydrazine derivatives, or nitrogen-based electricity Pulp. In some specific examples, the hydrazine derivative may include an alkyl-hydrazine, which includes at least one of the following: tertiary butylhydrazine (C ₄ H ₉ N ₂ H ₃ ), methylhydrazine (CH ₃ NHNH ₂ ), 1 ,1-Dimethylhydrazine ((CH ₃ ) ₂ N ₂ H ₂ ), 1,2-Dimethylhydrazine, ethylhydrazine, 1,1-diethylhydrazine, 1-ethyl-1-methylhydrazine, isopropylhydrazine , Phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, N-aminopiperidine, N-aminopyrrole, N-aminopyrrolidine, N-methyl-N-phenylhydrazine, 1-amino-1,2,3,4-tetrahydroquinoline, N-aminopiper, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, 1-ethyl-1-phenylhydrazine , 1-amino acridine, 1-methyl-1-(m-tolyl)hydrazine, 1-ethyl-1-(p-tolyl)hydrazine, 1-aminoimidazole, 1-amino-2,6 -Dimethylpiperidine, N-aminoaziridine or azo-tert-butane. In some embodiments, the nitrogen-based plasma can be generated by applying RF power to a nitrogen-containing gas, and the nitrogen-based plasma can include atomic nitrogen (N), nitrogen ions, nitrogen radicals, and nitrogen excited species. In some embodiments, the nitrogen-based plasma may further include additional reactive species, such as by adding another gas.

In some embodiments of the present invention, contacting the substrate with the nitrogen precursor may be comprised between about 0.01 second and about 180 seconds, or between about 0.05 second and about 60 seconds, or even between about 0.1 second and about 10.0 seconds. The contact period between seconds. In some embodiments, the substrate can be exposed to the nitrogen precursor for a period of less than 60 seconds, or less than 30 seconds, or less than 15 seconds, or even less than 5 seconds. In some embodiments, the substrate may be exposed to the nitrogen precursor for a period of between 5 seconds and 60 seconds or between 5 seconds and 30 seconds. In addition, during the contact between the substrate and the nitrogen precursor, the flow rate of the nitrogen precursor may be less than 30 slm, or less than 15 slm, or less than 10 slm, or less than 5 slm, or less than 2 slm, or even less than 1 slm. In addition, during the contact between the substrate and the nitrogen precursor, the flow rate of the nitrogen precursor may be in the range of about 0.1 slm to 30 slm, about 2 slm to 15 slm, or equal to or greater than 2 slm.

Once the substrate is brought into contact with the nitrogen precursor, the exemplary cyclic deposition process 100 can be performed by purging the reaction chamber, as previously described herein. In some embodiments of the present invention, the purge cycle after contacting the substrate with the nitrogen precursor can be omitted.

The cyclic deposition stage 105 of the exemplary cyclic deposition process 100 can be continued with the decision gate 140, wherein the decision gate 140 depends on the average film thickness of the deposited molybdenum nitride film. For example, if the average film thickness of the deposited molybdenum nitride film is not sufficient for the desired device application, the cyclic deposition stage 105 can be repeated by returning to the process block 120 and continuing through another unit deposition cycle, where The unit deposition cycle may include contacting the substrate with the molybdenum halide precursor (process block 120), purging the reaction chamber, contacting the substrate with the nitrogen precursor (process block 130), and purging the reaction chamber again. In some embodiments, the unit deposition cycle of the cyclic deposition stage 105 can omit the purge cycle after introducing the precursor.

The unit deposition cycle of the cyclic deposition stage 105 can be repeated one or more times until the molybdenum nitride film with the desired average film thickness is deposited on the substrate. Once the molybdenum nitride film has been deposited to the desired average film thickness, the exemplary cyclic deposition process 100 can be completed via process block 150, and the substrate with the molybdenum nitride film deposited thereon can undergo further processing for forming, for example, Semiconductor device structure.

It should be understood that, in some embodiments of the present invention, the order of contacting the substrate with the first gas phase reactant (for example, a molybdenum precursor) and the second gas phase reactant (for example, a nitrogen precursor) may be such that the substrate first contacts with the second gas phase reactant. The two gas phase reactants are contacted, followed by contact with the first gas phase reactant. In addition, in some embodiments, the cyclic deposition stage 105 of the exemplary cyclic deposition process 100 may include contacting the substrate with the first gas phase reactant one or more times before contacting the substrate with the second gas phase reactant one or more times. Times. In addition, in some embodiments, the cyclic deposition stage 105 of the exemplary cyclic deposition process 100 may include contacting the substrate with the second gas phase reactant one or more times before contacting the substrate with the first gas phase reactant one or more times. Times.

In some specific examples, the cyclic deposition process described herein may include a hybrid ALD/CVD or cyclic CVD process. For example, in some embodiments, the growth rate of the ALD process may be lower than that of the CVD process. One way to increase the growth rate can be to operate at a higher substrate temperature than the ALD process is usually used to produce some parts of the chemical vapor deposition process, but still use the sequential introduction of precursors. This type of process can be called It is cyclic CVD. In some specific examples, the cyclic CVD process may include introducing two or more precursors into the reaction chamber, where there may be a certain overlap period between the two or more precursors in the reaction chamber, resulting in deposition. ALD composition and deposited CVD composition. For example, the cyclic CVD process may include the continuous flow of the first precursor into the reaction chamber and the periodic pulse of the second precursor into the reaction chamber.

In some embodiments, the cyclic deposition process for depositing the molybdenum nitride film may include unit deposition, which further includes contacting the substrate with a third gas phase reactant containing a reducing agent. As a non-limiting example, in some specific examples, the nitrogen precursor and the reducing agent can be co-flowed into the reaction chamber, that is, the substrate is brought into contact with the nitrogen precursor and the reducing agent at the same time. As another non-limiting example, in some specific examples, the nitrogen precursor and the reducing agent can be introduced into the reaction chamber by separate gas pulses. For example, the substrate can be contacted with the nitrogen precursor and the substrate can be contacted with the reducing agent. Perform a purge cycle between the processes.

In more detail, FIG. 2 shows an exemplary cyclic deposition process 200 for molybdenum nitride deposition. The exemplary process 200 may include a cyclic deposition stage 205 including a process block 230 in which the substrate is contacted with a gas including a nitrogen precursor and a reducing agent precursor, that is, the nitrogen precursor and the reducing agent precursor are exposed at the same time于substrate.

The exemplary cyclic deposition process 200 may begin at process block 210, which includes providing a substrate into a reaction chamber and heating the substrate to a desired deposition temperature. The process block 210 may be substantially the same as the process block 110 of FIG. 1, and therefore, for the sake of brevity, the description of the process block 210 is not repeated.

The exemplary cyclic deposition process 200 can be continued by the cyclic deposition stage 205, which can begin with a process block 220, which includes contacting a substrate with a molybdenum halide precursor. The process block 220 may be substantially the same as the process block 120 of FIG. 1, and therefore, for the sake of brevity, the description of the process block 220 is not repeated.

The exemplary cyclic deposition process 200 (FIG. 2) can be continued by purging the reaction chamber as previously discussed with respect to the exemplary process 100 of FIG. 1. In some embodiments of the present invention, the purge cycle after contacting the substrate with the molybdenum halide precursor can be omitted.

The exemplary cyclic deposition process 200 can be continued with the second stage of the cyclic deposition stage 205 by means of a process block 230, which includes contacting a substrate with a gas containing a nitrogen precursor and a reducing agent. In other words, the substrate can be in contact with a gas including both the nitrogen precursor and the reducing agent. In at least one embodiment of the present invention, the single gas contacting the substrate can be both the nitrogen precursor and the reducing agent.

In some embodiments, the nitrogen precursor may include one or more of the nitrogen precursors previously described with respect to the process block 130 of FIG. 1, and therefore, for the sake of brevity, may be used in one of the exemplary process 200 Or more nitrogen precursors are not described a second time.

In some embodiments of the present invention, the substrate can be contacted with a gas containing a nitrogen precursor and a reducing agent for between about 0.01 seconds and about 180 seconds, between about 0.05 seconds and about 60 seconds, or between about 0.1 seconds and about 10.0 seconds The period between, or lasts less than 60 seconds, or less than 30 seconds, or less than 15 seconds, or even less than 5 seconds. In some embodiments, the substrate may be exposed to the gas including the nitrogen precursor and the reducing agent for a period of between about 5 seconds and 60 seconds or between about 5 seconds and 30 seconds. In addition, during the contact between the substrate and the gas containing both the nitrogen precursor and the reducing agent, the flow rate of the nitrogen precursor can be less than 30 slm, or less than 15 slm, or less than 10 slm, or less than 5 slm, or less than 2 slm , Or less than 1 slm, or even between about 1 slm and 30 slm. In addition, the flow rate of the reducing agent can be less than 30 slm, or less than 15 slm, or less than 10 slm, or less than 5 slm, or less than 2 slm, or even between about 2 slm and 30 slm.

The exemplary cyclic deposition process 200 can be performed by purging the reaction chamber, as previously described herein. In some embodiments of the present invention, the purge cycle after contacting the substrate with the nitrogen precursor/reducing agent can be omitted.

The cyclic deposition stage 205 of the exemplary cyclic deposition process 200 can be continued with a decision gate 240, wherein the decision gate 240 depends on the average film thickness of the deposited molybdenum nitride film. For example, if the average film thickness of the deposited molybdenum nitride film is not sufficient for a specific device application, the cyclic deposition stage 205 can be repeated by returning to the process block 220 and continuing through another unit deposition cycle, where the unit The deposition cycle may include contacting the substrate with a molybdenum halide precursor (process block 220), purging the reaction chamber, contacting the substrate with a gas containing a nitrogen precursor and a reducing agent (process block 230), and purging the reaction chamber again. In some embodiments, the unit deposition cycle of the cyclic deposition stage 205 can omit the purge cycle after introducing the precursor.

The unit deposition cycle of the cyclic deposition stage 205 can be repeated one or more times until a molybdenum nitride film with a desired average film thickness is deposited on the substrate. Once the molybdenum nitride film has been deposited to the desired average film thickness, the exemplary cyclic deposition process 200 may end through process block 250, and the substrate with the molybdenum nitride film deposited thereon may undergo further processing for forming, for example,装置结构。 Device structure.

It should be understood that, in some embodiments of the present invention, the sequence of contacting the substrate with the molybdenum halide precursor and the gas containing the nitrogen precursor and reducing agent can be such that the substrate is first contacted with the gas containing the nitrogen precursor and reducing agent, and then with the halogenated gas. Molybdenum precursor contact. Additionally, in some embodiments, the cyclic deposition stage 205 of the exemplary process 200 may include contacting the substrate with the molybdenum halide precursor one or more times before contacting the substrate with the gas containing both the nitrogen precursor and the reducing agent. In addition, in some embodiments, the cyclic deposition stage 205 of the exemplary process 200 may include contacting the substrate with a gas containing a nitrogen precursor and a reducing agent one or more times before contacting the substrate with the molybdenum halide precursor one or more times. .

In some embodiments, the exemplary cyclic deposition process for depositing molybdenum nitride films may include separate pulses of the nitrogen precursor and the reducing agent. For example, the purge cycle may be used to contact the substrate with the nitrogen precursor and the substrate with the reducing agent. Between contacts.

In more detail, FIG. 3 shows an exemplary cyclic deposition process 300 including a cyclic deposition stage 305. In some embodiments, the cyclic deposition stage 305 may include a process block 330 for contacting the substrate with a nitrogen precursor, and a process block 340 for contacting the substrate with a reducing agent, that is, the substrate may be exposed to the nitrogen precursor, respectively. Material and reducing agent.

The exemplary cyclic deposition process 300 may begin at process block 310, which includes providing a substrate into a reaction chamber and heating the substrate to a desired deposition temperature. The process block 310 may be substantially the same as the process block 110 of FIG. 1, and therefore, for the sake of brevity, the description of the process block 310 is not repeated.

The exemplary cyclic deposition process 300 can be continued by the cyclic deposition stage 305, which can begin with a process block 320, which includes contacting a substrate with a molybdenum halide precursor. The process block 320 may be substantially the same as the process block 120 of FIG. 1, and therefore, for the sake of brevity, the description of the process block 320 is not repeated.

The exemplary cyclic deposition stage 305 of the exemplary cyclic deposition process 300 (FIG. 3) can be continued by purging the reaction chamber as previously discussed with respect to the exemplary process 100 of FIG. 1. In some embodiments of the present invention, the purge cycle after contacting the substrate with the molybdenum halide precursor can be omitted.

The exemplary cyclic deposition process 300 (FIG. 3) can be continued with the second stage of the cyclic deposition stage 305 by means of a process block 330, which includes contacting a substrate with a nitrogen precursor. The process block 330 may be substantially the same as the process block 130 of FIG. 1, and therefore, for the sake of brevity, the description of the process block 330 is not repeated.

The exemplary cyclic deposition stage 305 of process 300 (FIG. 3) can be continued by purging the reaction chamber as previously discussed with respect to exemplary process 100 of FIG. 1. In some embodiments of the present invention, the purge cycle after contacting the substrate with the nitrogen precursor can be omitted.

The exemplary cyclic deposition process 300 may continue with the third stage of the cyclic deposition stage 305 by means of a process block 340, which includes contacting a substrate with a reducing agent. In some embodiments of the present invention, the reducing agent precursor may be selected from those previously described with respect to the process block 230, and therefore, for the sake of brevity, one or more reducing agents used in the process 220 are not repeated.

In some embodiments of the present invention, the substrate can be contacted with the reducing agent for a period of time between about 0.01 second and about 180 seconds, between about 0.05 second and about 60 seconds, or between about 0.1 second and about 10.0 seconds, or less than A period of 60 seconds, or less than 30 seconds, or less than 15 seconds, or even less than 5 seconds. In some embodiments, the substrate may be exposed to the reducing agent precursor for a period of between 5 seconds and 60 seconds or between 5 seconds and 30 seconds. In addition, during the contact between the substrate and the reducing agent, the flow rate of the reducing agent precursor can be less than 100 slm, or less than 50 slm, or less than 25 slm, or less than 10 slm, or less than 5 slm, or even between about 5 slm and 100 slm. between slm.

The exemplary cyclic deposition process 300 (FIG. 3) can be continued by purging the reaction chamber as previously discussed with respect to the exemplary process 100 of FIG. 1. In some specific examples of the present invention, the purge cycle after contacting the substrate with the reducing agent may be omitted.

The cyclic deposition stage 305 of the exemplary process 300 (FIG. 3) can be continued by the decision gate 350, where the decision gate 350 depends on the average film thickness of the deposited molybdenum nitride film. For example, if the average film thickness of the deposited molybdenum nitride film is not sufficient for the desired device application, the cyclic deposition stage 305 can be repeated by returning to the process block 320 and continuing through another unit deposition cycle, where The unit deposition cycle may include contacting the substrate with the molybdenum halide precursor (process block 320), purging the reaction chamber, contacting the substrate nitrogen precursor (process block 330), purging the reaction chamber, and contacting the substrate with the reducing agent (process block 340) and purge the reaction chamber again. In some embodiments, the unit deposition cycle of the cyclic deposition stage 305 can omit the purge cycle after introducing the precursor.

The unit deposition cycle of the cyclic deposition stage 305 can be repeated one or more times until the molybdenum nitride film with the desired average film thickness is deposited on the substrate. Once the molybdenum nitride film has been deposited to the desired average film thickness, the exemplary cyclic deposition process 300 may end through process block 360, and the substrate with the molybdenum nitride film deposited thereon may undergo further processing for forming, for example,装置结构。 Device structure.

It should be understood that, in some specific examples of the present invention, the contact sequence of the substrate and the molybdenum halide precursor, the nitrogen precursor, and the reducing agent can be performed in any conceivable sequence and is not limited by the sequence shown in FIG. 3. In addition, the contact of the substrate with a specific precursor (such as a molybdenum halide precursor, a nitrogen precursor, or a reducing agent) can be repeated one or more times before the subsequent process blocks of the cyclic deposition stage 305 are performed.

The exemplary deposition process disclosed herein can be about 0.05 Å/cycle to about 10 Å/cycle, about 0.5 Å/cycle to about 5 Å/cycle, or even about 0.5 Å/cycle to about 2 Å/cycle growth rate The molybdenum nitride film is deposited directly on the surface of the substrate. In some embodiments, the growth rate of the molybdenum nitride film directly deposited on the surface of the substrate is greater than about 0.5 Å/cycle, greater than about 1 Å/cycle, or even greater than about 2 Å/cycle. In some specific examples of the present invention, the molybdenum nitride film can be deposited at a temperature, that is, the substrate temperature, between 300°C and 700°C, or between 400°C and 500°C, or even lower than 450°C, Deposit at a growth rate between 0.5 Å/cycle and 1 Å/cycle, or between 0.8 Å/cycle and 1 Å/cycle.

The molybdenum nitride film deposited by the method disclosed herein may be a physically continuous film. In some specific examples, the molybdenum nitride film may be less than about 100 Å, or less than about 60 Å, or less than about 50 Å, or less than about 40 Å, or less than about 30 Å, or about 20 Å. , It is physically continuous even at an average film thickness between about 20 Å and 100 Å.

In some embodiments, the average film thickness of the film that can be physically continuous may not be the same as the average film thickness of the film that is electrically continuous, and vice versa.

In some specific examples, the molybdenum nitride film deposited according to the method disclosed herein can be below 40 Å, or below 30 Å, or below 20 Å, or below 10 Å, or even at about 10 Å to The average film thickness between 40 Å is physically continuous. In other words, the molybdenum nitride film may have an average film closure thickness of less than 40 Å, or less than 30 Å, or less than 20 Å, less than 10 Å, or even between about 10 Å and 40 Å. The thickness at which the film becomes physically continuous can be determined using low-energy ion scattering (LEIS).

In some specific examples, the molybdenum nitride film of the present invention may have an average film thickness of about 20 Å to 250 Å, or about 50 Å to 200 Å, or even about 100 Å to 150 Å. In some specific examples, the molybdenum nitride film of the present invention may have a thickness greater than about 20 Å, or greater than about 30 Å, or greater than about 40 Å, or greater than about 50 Å, or greater than about 60 Å, or greater than about 100 Å, Or greater than about 250 Å, or greater than about 500 Å, or even an average film thickness between about 20 Å and 500 Å. In some specific examples, the molybdenum nitride film of the present invention may have a thickness of less than about 250 Å, or less than about 100 Å, or less than about 50 Å, or less than about 25 Å, or less than about 10 Å, or less than about 5 Å, Or even an average film thickness of about 5 Å and 250 Å.

In some embodiments, the molybdenum nitride film deposited according to the process disclosed herein may include a low-resistivity molybdenum nitride film. In more detail, FIG. 4 shows the resistivity of a plurality of molybdenum nitride films of various thicknesses deposited according to a specific example of the present invention, wherein the data marked 400 includes those deposited by the cyclic deposition process 100 (FIG. 1) Molybdenum nitride film, the data labeled 410 includes the molybdenum nitride film deposited by the cyclic deposition process 200 (FIG. 2), and the data labeled 420 includes the molybdenum nitride deposited by the cyclic deposition process 300 (FIG. 3) membrane. The inspection of the resistivity data in FIG. 4 clearly shows that the reducing agent added in both process 200 (data marked 410) and process 300 (data marked 420) reduces the resistivity of the molybdenum nitride film. In addition, the further inspection of Fig. 4 clearly shows that compared to the molybdenum nitride film deposited by the co-flow of nitrogen precursor and reducing agent (process 200/data marked as 410), the introduction of nitrogen precursor and reducing agent respectively The pulse (process 300/data labeled 420) further reduces the resistivity of the deposited molybdenum nitride film.

As a non-limiting example, the molybdenum nitride film deposited according to a specific example of the present invention may have a resistivity of less than 750 μΩ-cm at an average film thickness of less than 200 Å, or an average film thickness of less than 100 Å It can have a resistivity of less than 750 μΩ-cm, or can have a resistivity of less than 1300 μΩ-cm with an average film thickness of less than 25 Å.

As another non-limiting example, the molybdenum nitride film deposited according to a specific example of the present invention may have a resistivity of less than 550 μΩ-cm at an average film thickness of less than 200 Å or an average film thickness of less than 100 Å It can have a resistivity of less than 550 μΩ-cm, or can have a resistivity of less than 950 μΩ-cm with an average film thickness of less than 25 Å.

As another non-limiting example, the molybdenum nitride film deposited according to a specific example of the present invention may have a resistivity of less than 250 μΩ-cm at an average film thickness of less than 200 Å, or an average film thickness of less than 100 Å It can have a resistivity of less than 250 μΩ-cm, or can have a resistivity of less than 600 μΩ-cm with an average film thickness of less than 25 Å.

In some specific examples, for a molybdenum nitride film having an average film thickness between about 10 Å and 200 Å, or between about 20 Å and 100 Å, or even between about 20 Å and 50 Å, according to the present invention The deposited molybdenum nitride film may have a thickness between 250 μΩ-cm and 1000 μΩ-cm, or between 250 μΩ-cm and 750 μΩ-cm, or even between 250 μΩ-cm and 500 μΩ-cm. Resistivity.

The excellent resistivity of the molybdenum nitride film deposited by the specific example of the present invention is further shown in FIG. 5, which shows the various thicknesses of the molybdenum nitride film deposited on the dielectric substrate according to the specific example of the present invention. Resistivity. In addition, FIG. 5 also compares the resistivity molybdenum film of the present invention and the prior art titanium nitride film of different thicknesses deposited using the titanium tetrachloride precursor. The data marked 500 corresponds to a titanium _{nitride film deposited using titanium tetrachloride (TiCl 4} ) as the metal precursor. All the films depicted in Figure 5 are deposited on the exposed surface of the dielectric material.

In more detail, the data labeled 510 corresponds to the molybdenum nitride film deposited on the silicon oxide substrate, and the data labeled 520 corresponds to the molybdenum nitride film deposited on the hafnium oxide (HfO ₂ ) substrate. The exemplary molybdenum nitride film depicted in FIG. 5 uses molybdenum (IV) chloride (MoO ₂ Cl ₂ ) as a molybdenum halide precursor at a deposition temperature (ie, substrate temperature) of less than about 500°C , Ammonia (NH ₃ ) is used as the nitrogen precursor and hydrogen (H ₂ ) is deposited as a reducing agent.

The inspection of the resistivity data in FIG. 5 clearly shows that when compared with the resistivity of the titanium nitride film of comparable thickness in the prior art, the molybdenum nitride film of the present invention has a reduced resistance at a reduced average film thickness. rate.

As a non-limiting example, the molybdenum nitride film of the present invention may have a resistivity of less than 250 μΩ-cm at an average film thickness of less than 50 Å, or may have a resistivity of less than 300 μΩ at an average film thickness of less than 40 Å. -cm resistivity, or 400 μΩ-cm resistivity at an average film thickness of less than 25 Å. In some specific examples, the molybdenum nitride film of the present invention may have a resistivity between about 250 μΩ-cm and 400 μΩ-cm at an average film thickness of less than 50 Å.

In some specific examples, the molybdenum nitride film deposited according to the specific examples disclosed herein may include a crystalline film or an amorphous film. In a specific example, where the molybdenum nitride film is crystalline, the molybdenum nitride film may include a MoN phase or a Mo ₂ N phase. In some specific examples, the molybdenum nitride film may include a MoN phase and a Mo ₂ N phase.

In more detail, FIG. 6 shows x-ray diffraction (XRD) data obtained from an exemplary molybdenum nitride film deposited according to a specific example of the present invention, wherein the XRD data marked as 600 includes a cyclic deposition process 100 ( Figure 1) The deposited molybdenum nitride film, the XRD data labeled 610 include the molybdenum nitride film deposited by the cyclic deposition method 200 (Figure 2) and the XRD data labeled 620 include the XRD data of the cyclic deposition process 300 (Figure 3). ) Deposited molybdenum nitride film. The inspection of the XRD data of FIG. 6 shows that there is no significant difference between the XRD data of the molybdenum nitride film deposited by the process 100, 200, or 300. However, further examination of the XRD data in Figure 6 shows the four main peaks marked 630, 640, 650, and 660 in the XRD data. The XRD peak labeled 630 corresponds to the MoN phase with (200) crystal orientation and the Mo ₂ N phase (200) with (111) crystal orientation. The XRD peak labeled 640 corresponds to the Mo ₂ N phase with (200) crystal orientation. The XRD peak labeled 650 corresponds to the MoN phase with (220) crystal orientation and the Mo ₂ N phase with (200) crystal orientation. The XRD peak labeled 660 corresponds to the MoN phase with (222) crystal orientation and the Mo2N phase with (311) crystal orientation.

In a specific example, the composition of the deposited molybdenum nitride film includes at least MoN phase and Mo ₂ N phase, and the MoN phase existing in the molybdenum nitride film is compared with the Mo ₂ N phase existing in the molybdenum nitride film. The ratio (MoN:Mo ₂ N) can be controlled during the cyclic deposition process of the present invention. For example, the MoN:Mo ₂ N ratio can be changed by changing the cyclic deposition parameters for molybdenum nitride deposition, including (but not limited to) deposition temperature, reaction chamber pressure, precursor concentration or addition of another gas species .

In some specific examples, the MoN phase of molybdenum nitride may be better than the Mo ₂ N phase of molybdenum nitride, that is, the _{ratio of MoN:Mo 2} N increases. As a non-limiting example, compared to the Mo ₂ N phase, the MoN phase can be deposited preferably by adding a reducing agent to the deposition process.

The exemplary cyclic deposition method disclosed herein can also deposit molybdenum nitride films with improved average rms surface roughness. For example, in some specific examples, the molybdenum nitride film may have a thickness of less than 0.30 nanometers, or less than 0.25 nanometers, or less than 0.20 nanometers, or less than 0.10 nanometers, or even between 0.10 nanometers and 0.30 nanometers. Average rms surface roughness (R _a ) between (after deposition). The average rms surface roughness (R _a ) of the deposited molybdenum nitride film can be measured by atomic force microscopy (AFM), for example, by scanning a surface area of about 100 μm×100 μm.

In some specific examples, the surface roughness of the molybdenum nitride film can be expressed as the percentage roughness of the average total thickness of the molybdenum nitride film. For example, the percentage surface roughness of the molybdenum nitride film of the present invention can be less than 10%, or less than 5%, or less than 3%, or less than 2%, or less than 1.5%, or even less than 1%. As a non-limiting example, the molybdenum nitride film deposited according to a specific example of the present invention may have an average film thickness of about 100 Å, wherein the molybdenum nitride film has an rms surface roughness (R _a ) less than 4 Å and less than 4% corresponds to the percentage surface roughness.

In some embodiments, the substrate may include at least one of a dielectric surface, a semiconductor surface, or a metal surface. As used herein, the term "dielectric surface" can refer to the surface of a dielectric material, including (but not limited to) silicon-containing dielectric materials such as silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, and mixtures thereof ) And, for example, metal oxides. As used herein, the term "metal surface" may refer to a surface including a metal component, including but not limited to a metal surface, a metal oxide surface, a metal silicide surface, a metal nitride surface, and a metal carbide surface. In some embodiments, the substrate may include both a dielectric surface and a metal surface, and the cyclic deposition process of the present invention can be used to directly deposit a molybdenum nitride film on both the dielectric surface and the metal surface. Without using the intervening nucleus layer.

The molybdenum nitride film deposited according to specific examples of the present invention can be used in a variety of applications. For example, the molybdenum nitride film can be used as a barrier layer material to prevent metal species from diffusing into the interlayer dielectric, or as a liner, or as a part of a gate stack formed on a semiconductor device structure.

As a non-limiting illustrative specific example, the molybdenum nitride film deposited according to the specific example of the present invention can be used as a barrier layer in back-end-of-line (BEOL) metallization applications, as shown in FIG. 7 Shown. In more detail, FIG. 7 shows a partially manufactured semiconductor device structure 700, which includes a substrate 702, which may include partially manufactured and/or manufactured semiconductor device structures, such as transistors and memory devices (not shown). The partially manufactured semiconductor device structure 700 may include a dielectric material 704 formed on the substrate 702. The material may include a low-k dielectric material, such as a silicon-containing dielectric material or a metal oxide dielectric material. . The trench may be formed in the dielectric material 704 and the barrier layer 706 may be disposed on the surface of the trench, which prevents or substantially prevents the metal interconnect material 708 from diffusing into the surrounding dielectric material 704. In some embodiments of the present invention, the barrier layer 706 may include a molybdenum nitride film deposited by the deposition process described herein.

The partially fabricated semiconductor structure 700 may also include a metal interconnection material 708 for electrically interconnecting a plurality of device structures disposed in/on the substrate 702. In some embodiments, the metal interconnect material 708 may include copper or cobalt. In addition, the capping layer 710 may be disposed on the upper surface of the metal interconnect material 708. Therefore, referring to FIG. 7, the semiconductor device structure 700 may also include a cap layer 710 directly disposed on the upper surface of the metal interconnect material 708. The capping layer 710 can be used to prevent the metal interconnect material 708 from oxidizing, and it is important to prevent the metal interconnect material 708 from diffusing to be formed on the partially manufactured semiconductor structure 700 in the subsequent manufacturing process (ie, for the multilayer interconnect structure) The additional dielectric materials. In some embodiments, the metal interconnection material 708, the molybdenum nitride barrier layer 706, and the cap layer 710 can collectively form electrodes for electrical interconnection of a plurality of semiconductor devices disposed in/on the substrate 702. In some embodiments, the capping layer 710 may include a molybdenum nitride film deposited according to embodiments of the present invention.

As another non-limiting embodiment, the molybdenum nitride film of the present invention may include at least a part of the gate electrode in the gate stack formed on the semiconductor channel region. In more detail, FIG. 8 shows a schematic cross-sectional view of a semiconductor device structure including a molybdenum nitride film deposited according to a specific example of the present invention. The semiconductor device structure 800 may include a transistor structure including a semiconductor body 816 that includes a source region 802, a drain region 804, and a semiconductor channel region 806 disposed between the source region 802 and the drain region 804.

In some embodiments, the semiconductor device structure 800 may include an NMOS device, and the semiconductor body 816 and the semiconductor channel region 806 may both be doped p-type, and both the source region 802 and the drain region 804 may be doped n type. In an alternative embodiment, the semiconductor device structure 800 may include a PMOS device, and both the semiconductor body 816 and the semiconductor channel region 806 may be doped n-type, and both the source region 802 and the drain region 804 may be doped p-type. In some embodiments, the semiconductor body 816 may include substantially single crystal silicon.

Disposed above the semiconductor channel region 806 is a gate stack 808, which may include a gate dielectric 809 and a gate electrode 811. In some embodiments, the gate dielectric may include a silicon oxide intermediate layer 816 directly disposed on the semiconductor channel region 806 and a high-k dielectric layer 812 directly disposed on the intermediate layer 816. In some embodiments of the present invention, the high-k dielectric layer 812 may include at least one of the following: hafnium oxide (HfO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), hafnium silicate (HfSiO _x ), lanthanum oxide (La ₂ O ₃ ) or a mixture/laminate thereof.

The gate electrode 811 is arranged above the gate dielectric 809 and in some embodiments, the gate electrode 811 is arranged directly above the gate dielectric 809. The gate electrode may include a molybdenum nitride film 810 deposited according to an embodiment of the present invention. Directly disposed above the molybdenum nitride film 810 may be another metal film 814 to complete the gate electrode 811. For example, the other metal film 814 may include a transition carbide (e.g., titanium carbide) or a transition nitride (e.g., titanium carbide). , Titanium nitride).

In some embodiments of the present invention, the effective work function of the gate stack 808 disposed above the semiconductor channel region 806 can be determined by the deposition method used to deposit the molybdenum nitride film 810 and the average film thickness of the molybdenum nitride film 810 Adjustment. For example, for an average molybdenum nitride film thickness of less than 50 Å, less than 40 Å, less than 30 Å, or less than 20 Å, or less than 15 Å, or between 15 Å and 50 Å, the molybdenum nitride film is included The effective work function of the gate stack 808 can be in the range of about 4 eV to about 5 eV, or greater than 4 eV, or greater than 4.5 eV, or greater than 4.75 eV.

Therefore, in some specific examples, the molybdenum nitride film includes a portion of the gate stack formed in the semiconductor channel region, wherein the average thickness of the molybdenum nitride film is less than 50 Å, or less than 40 Å, or less than 30 Å, or less than 20 Å. Å, or less than 20 Å, or less than 15 Å, or between 15 Å and 50 Å, the gate stack has greater than 4.0 eV, or greater than 4.5 eV, or greater than 4.75 eV, or even greater than 4.9 eV, or less than 4 Effective work function between eV and 5 eV.

As a non-limiting example, FIG. 9 illustrates the effective work function of a gate stack (disposed above the semiconductor channel region) of a molybdenum nitride film of various average film thicknesses deposited according to a specific example of the present invention. The inspection of Figure 9 shows that as the average film thickness of the molybdenum nitride layer decreases from about 50 Å to 15 Å, the corresponding effective work function of the gate stack including the molybdenum nitride film only slightly decreases from about 4.75 eV to about 4.6 eV. Therefore, in some specific examples of the present invention, the average molybdenum nitride film thickness is less than 50 Å, or less than 40 Å, or less than 30 Å, or less than 20 Å, or less than 15 Å, or between 15 Å and 50 Å. From time to time, the molybdenum nitride film of the present invention may include a molybdenum nitride film having a temperature greater than 4 eV, or greater than 4.25 eV, or greater than 4.5 eV, or greater than 4.75 eV, or greater than 4.8 eV, or between 4 eV and 4.8 eV, or within 4.6 Part of the gate stack with an effective work function between eV and 4.75 eV. In some specific examples, when the average molybdenum nitride film thickness is equal to or less than 50 Å, the gate stack containing the molybdenum nitride film disposed above the semiconductor channel region has an effective work function greater than 4.75 eV.

As another non-limiting example, FIG. 10 illustrates the effective work function of a gate stack including molybdenum nitride films of different average film thicknesses deposited using an exemplary cyclic deposition process 300 (FIG. 3 ). The review of Figure 10 shows that as the average film thickness of the molybdenum nitride film decreases from about 45 Å to 15 Å, the corresponding effective work function of the gate stack including the molybdenum nitride film remains substantially at a value of about 4.75 eV constant. Therefore, in some specific examples, the average molybdenum nitride film thickness is less than 50 Å, or less than 40 Å, or less than 30 Å, or less than 20 Å, or less than 15 Å, or even between about 15 Å and 50 Å. Next, the molybdenum nitride of the present invention may include a molybdenum nitride having a value greater than 4.6 eV, or greater than 4.75 eV, or greater than 4.8 eV, or greater than 4.9 eV, or greater than 5.0 eV, or between 4.6 eV and 4.9 eV, or even 4.75 eV Part of the gate stack between 4.8 eV and 4.8 eV.

In some device applications, such as PMOS device structures, the ability to form gate stacks containing molybdenum nitride films may be desirable, where the effective work function of the gate stacks is substantially independent of the average film thickness of the molybdenum nitride film .

Therefore, in some specific examples, the gate stack may include a molybdenum nitride film with an average film thickness between about 15 Å and 45 Å, and the effective work function of the gate stack may be substantially equal to that of the molybdenum nitride film. Effective work function independent of film thickness. In addition, for an average film thickness between about 15 Å and 45 Å, the gate stack including the molybdenum nitride film may include a substantially constant effective work function of about 4.8 eV. In addition, the gate stack may include a molybdenum nitride film deposited by a cyclic deposition process including the following: contacting the substrate with a molybdenum halide precursor, a nitrogen precursor, and a reducing agent in sequence, wherein the average thickness of the molybdenum nitride film is about Between 15 Å and 45 Å, the gate stack contains a substantially constant effective work function of approximately 4.8 eV.

As another non-limiting application of the molybdenum nitride film of the present invention, FIG. 11 is another cross-sectional schematic diagram of an exemplary semiconductor device structure. The semiconductor device structure includes a molybdenum nitride film deposited according to a specific example of the present invention, and In particular, the structure of the FinFet semiconductor device is shown.

In more detail, FIG. 11 illustrates a non-limiting embodiment of a semiconductor device structure 1100 including an exemplary FinFET device structure. The semiconductor device structure 1100 may include a substrate 1102, and the substrate may include a bulk silicon (Si) substrate. The substrate 1102 may be doped with p-type dopants (for NMOS-type FinFET devices) and/or with n-type dopants (for PMOS-type FinFET devices).

The semiconductor device structure 1100 may also include an isolation region 1104, and the isolation region may include a shallow trench isolation (STI) region. The semiconductor device structure 1100 may also include a fin structure 1106 extending above the top surface of the isolation region 1104, and a portion of the fin structure 1106 is buried under the gate stack 1108 including the semiconductor channel region. The gate dielectric 1110 may be disposed above the sidewall of the fin structure 1106 and the gate dielectric 1110 may include silicon oxide and/or high-k dielectric materials.

The gate electrode may be disposed on the gate dielectric 1110 to provide electrical contact with the semiconductor channel region, and the gate electrode may include the molybdenum nitride film 1112 deposited according to the embodiment of the present invention, and may include transition metal carbide or transition metal carbide. Additional metal film 1114 of metal nitride. In some embodiments of the present invention, the semiconductor device structure 1100 may further include a source/drain region 1116 adjacent to the semiconductor channel region.

As another non-limiting application of the molybdenum nitride film of the present invention, FIG. 12 shows another schematic diagram of an exemplary semiconductor device structure. The semiconductor device structure includes a molybdenum nitride film deposited according to a specific example of the present invention, and particularly depicts Shows the structure of a surround gate (GAA) semiconductor device.

In more detail, the semiconductor device structure 1200 may include a semiconductor substrate 1202 and a dielectric film 1204 disposed on the substrate 1202. In addition, the GAA device structure may include a semiconductor line 1206 (doped p-type or n-type), in which a gate dielectric 1208 is arranged around and surrounding the semiconductor line 1206. The gate electrode may be disposed around the area of the semiconductor wire 1206, and may include a molybdenum nitride film 1210 deposited according to an embodiment of the present invention. In addition, the gate electrode may include another metal film 1212, such as transition metal carbide or transition metal nitride.

A specific example of the present invention also provides a semiconductor device structure including a molybdenum nitride film. In some specific examples, the semiconductor device structure may include: a semiconductor channel region; and a gate stack directly disposed on the semiconductor channel region, wherein the gate stack includes: a gate dielectric directly disposed on the semiconductor channel region and including The gate electrode of the molybdenum nitride film directly placed on the gate dielectric.

In some specific examples, when the average molybdenum nitride film thickness is less than 100 Å, or less than 50 Å, or less than 20 Å, or less than 10 Å, or between 10 Å and 50 Å, the semiconductor device structure may include A molybdenum nitride film with a resistivity of less than 1000 μΩ-cm, or less than 500 μΩ-cm, or less than 250 μΩ-cm, or between 250 μΩ-cm and 1000 μΩ-cm. In some specific examples, with an average film thickness of less than 100 Å, the semiconductor device structure may include a molybdenum nitride film that may have a resistivity of less than 250 μΩ-cm. In some embodiments, with an average film thickness of less than 25 Å, the semiconductor device structure may include a molybdenum nitride film that may have a resistivity of less than 500 μΩ-cm.

In some embodiments, the semiconductor device structure including the molybdenum nitride film may include both the MoN phase and the Mo ₂ N phase. In some specific examples, the semiconductor device structure includes a physically continuous molybdenum nitride film with an average film thickness of less than 40 Å, or less than 30 Å, or less than 20 Å, or less than 15 Å, or between 15 Å and 40 Å . In some embodiments, the semiconductor device structure may include a molybdenum nitride film that may be amorphous or crystalline.

In some embodiments, the semiconductor device structure including the molybdenum nitride film may include a PMOS work function metal device structure, a FinFET semiconductor device structure, or a wrap-around gate semiconductor device structure.

Specific examples of the present invention may also include a reaction system configured to deposit the molybdenum nitride film of the present invention. In more detail, FIG. 13 schematically illustrates a reaction system 1300, which includes a reaction chamber 1302, and the reaction chamber further includes a substrate for holding a substrate (not shown) under predetermined pressure, temperature and environmental conditions and for selecting a substrate Mechanisms that are sexually exposed to various gases. The precursor reactant source 1304 can be coupled to the reaction chamber 1302 by pipes or other suitable components 1304A, and can be further coupled to a manifold, a valve control system, a mass flow control system, or used to control the source of the precursor reactant 1304. Gaseous precursors. The precursor (not shown) is supplied by the precursor reactant source 1304, and the reactant (not shown) can be liquid or solid at room temperature and standard atmospheric pressure. Such precursors can be vaporized in the reactant source vacuum container, and the reactant source vacuum container can be maintained at or higher than the vaporization temperature in the precursor source chamber. In such a specific example, the vaporized precursor can be transported with a carrier gas (eg, inactive or inert gas), and then fed into the reaction chamber 1302 via the pipe 1304A. In other specific examples, the precursor may be vapor under standard conditions. In such specific cases, the precursor does not need to be vaporized and may not require a carrier gas. For example, in one specific example, the precursor can be stored in a storage cylinder. The reaction system 1300 may also include additional precursor reactant sources, such as precursor reactant sources 1306 and 1308, which may also be coupled to the reaction chamber through the pipes 1306A and 1308A as described above. In some embodiments, the precursor reactant source 1304 may include molybdenum halide, the precursor reactant source 1306 may include a nitrogen precursor, and the precursor reactant source 1308 may include a reducing agent.

The purge gas source 1310 can also be coupled to the reaction chamber 1302 via a pipe 1310A, and can selectively supply various inert or rare gases to the reaction chamber 1302 to assist in removing the precursor gas or exhaust gas from the reaction chamber. Various inert or rare gases can be supplied from solid, liquid or stored gaseous forms.

The reaction system 1300 of FIG. 13 may also include a system operation and control mechanism 1312 that provides electronic circuits and mechanical components to selectively operate valves, manifolds, pumps, and other equipment included in the reaction system 1300. Such circuits and components operate to introduce precursors and purge gas from respective precursor sources 1304, 1306, 1308 and purge gas source 1310. The system operation and control mechanism 1312 also controls the timing of the gas pulse sequence, the temperature of the substrate and the reaction chamber, the pressure of the reaction chamber, and provides various other operations required for the proper operation of the reaction system 1300. The operation and control mechanism 1312 may include control software and electrical or pneumatic control valves to control the flow of precursors, reactants, and purge gas into and out of the reaction chamber 1302. The control system may include modules that perform certain tasks, such as software or hardware components, for example, FPGA or ASIC. The module can advantageously be configured to reside on the addressable storage medium of the control system and configured to execute one or more programs.

Those familiar with the relevant technology will understand that other configurations of the reaction system of the present invention are possible, including different numbers and types of precursor reactant sources and purge gas sources. In addition, such persons will also understand that there are many configurations of valves, pipes, precursor sources, and purge gas sources that can be used to achieve the goal of selectively feeding gas into the reaction chamber 1302. In addition, as a schematic representation of the reaction system, in order to simplify the illustration, many components have been omitted, and such components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and/or bypasses. .

The illustrative specific examples of the present invention described above do not limit the scope of the present invention, because these specific examples are only examples of specific embodiments of the present invention, and the scope of the present invention is determined by the scope of the attached patent application and its statutory, etc. Definition of effect. Any equivalent specific examples are intended to be within the scope of the present invention. In fact, in addition to those shown and described herein, various modifications of the present invention (such as alternative applicable combinations of the described elements) may become apparent to those skilled in the art based on the description. Such modifications and specific examples are also intended to fall within the scope of the attached patent application.

100: Exemplary Atomic Layer Deposition Process / Exemplary Molybdenum Nitride Deposition Process / Exemplary Cyclic Deposition Process / Cyclic Deposition Process / Exemplary Process / Process 105: cyclic deposition stage 110, 120, 130, 150: process frame 140: Decision Gate 200: Exemplary Cyclic Deposition Process/Exemplary Process/Cyclic Deposition Process/Process 205: Cyclic Deposition Stage 210, 220, 230, 250: process frame 240: Decision Gate 300: Exemplary Cyclic Deposition Process / Exemplary Process / Cyclic Deposition Process / Process 305: Cyclic Deposition Stage 310, 320, 330, 340, 360: process frame 350: Decision Gate 400, 410, 420, 500, 510, 520: data 600, 610, 620: XRD data 630, 640, 650, 660: main peak/XRD peak 700: semiconductor device structure/semiconductor structure 702: Substrate 704: Dielectric material/surrounding dielectric material 706: barrier layer/molybdenum nitride barrier layer 708: Metal Interconnect Materials 710: cover layer 800: Semiconductor device structure 802: Source Region 804: Drain Area 806: semiconductor channel area 808: gate stack 809: gate dielectric 810: Molybdenum Nitride Film 811: gate electrode 812: High-k dielectric layer 814: another metal film 816: semiconductor body/silicon oxide interface layer/interface layer 1100: Semiconductor device structure 1102: substrate 1104: Quarantine 1106: Fin structure 1108: gate stack 1110: gate dielectric 1112: Molybdenum nitride film 1114: Extra metal film 1116: source/drain region 1200: Semiconductor device structure 1202: Semiconductor substrate/substrate 1204: Dielectric film 1206: Semiconductor wire 1208: gate dielectric 1210: Molybdenum nitride film 1212: another metal film 1300: reaction system 1302: reaction chamber 1304, 1306, 1308: precursor source/precursor source 1304A, 1306A, 1308A, 1310A: pipeline 1310: purge gas source 1312: System operation and control mechanism/operation and control mechanism

Although this specification ends with the scope of the patent application that specifically points out and clearly claims to be regarded as specific examples of the present invention, the present invention can be more easily determined from the description of certain embodiments of the specific examples of the present invention when understood in conjunction with the accompanying drawings. The advantages of the specific examples are shown in the drawings:

Figure 1 depicts an exemplary flow chart showing a cyclic deposition process for depositing a molybdenum nitride film according to a specific example of the present invention;

FIG. 2 is an exemplary flow chart showing an additional cyclic deposition process for depositing a molybdenum nitride film according to a specific example of the present invention;

FIG. 3 is an exemplary flow chart showing another cyclic deposition process for depositing a molybdenum nitride film according to a specific example of the present invention;

4 shows the resistivity of a plurality of molybdenum nitride films of various thicknesses deposited according to a specific example of the present invention;

FIG. 5 shows the resistivity of multiple molybdenum nitride films of different thicknesses deposited directly on the dielectric compared with the resistivities of titanium nitride films of different thicknesses deposited using a titanium tetrachloride precursor;

Figure 6 shows x-ray diffraction (XRD) data obtained from an exemplary molybdenum nitride film deposited according to a specific example of the present invention;

7 is a schematic cross-sectional view of an exemplary semiconductor device structure including a molybdenum nitride film deposited according to a specific example of the present invention;

8 shows a schematic cross-sectional view of an additional semiconductor device structure including a molybdenum nitride film according to a specific example of the present invention;

9 illustrates the effective work functions of various gate stacks including various thicknesses of molybdenum nitride films deposited according to a specific example of the present invention;

FIG. 10 illustrates the effective work function of other molybdenum nitride films of various thicknesses deposited according to specific examples of the present invention;

11 is a schematic diagram showing the structure of an exemplary semiconductor device including a molybdenum nitride film according to a specific example of the present invention;

FIG. 12 shows another schematic diagram of an exemplary semiconductor device structure including a molybdenum nitride film according to a specific example of the present invention; and

FIG. 13 shows a schematic diagram of a reaction system configured for depositing a molybdenum nitride film according to a specific example of the present invention.

100: Process

105: cyclic deposition stage

110, 120, 130, 150: process frame

140: Decision Gate

Claims (39)

A method for depositing a molybdenum nitride film on the surface of a substrate by a cyclic deposition process, the method comprising: Providing a substrate into a reaction chamber; and A molybdenum nitride film is deposited directly on the surface of the substrate by performing one or more unit deposition cycles of a cyclic deposition process, wherein a unit deposition cycle includes: Contacting the substrate with a first gas phase reactant containing a molybdenum precursor; and The substrate is contacted with a second gas phase reactant containing a nitrogen precursor. The method of claim 1, wherein the unit deposition cycle further comprises contacting the substrate with a third gas phase reactant containing a reducing agent. The method of claim 2, wherein the substrate is in contact with the nitrogen precursor and the reducing agent at the same time. The method of claim 2, wherein a purge cycle is performed between the processes of contacting the substrate with the nitrogen precursor and contacting the substrate with the reducing agent. The method of claim 2, wherein the reducing agent includes at least one of the following: molecular hydrogen (H ₂ ), atomic hydrogen (H), synthesis gas (H ₂ +N ₂ ), ammonia (NH ₃ ), Hydrazine (N ₂ H ₄ ), hydrazine derivatives, hydrogen-based plasma, alcohol, aldehyde, carboxylic acid, borane, amine or silane. The method of claim 1, wherein the nitrogen precursor comprises at least one of the following: molecular nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), hydrazine derivatives, or nitrogen-based electricity Pulp. The method of claim 1, further comprising heating the substrate to a deposition temperature of less than 450°C. The method of claim 1, wherein the molybdenum precursor comprises a molybdenum oxyhalide precursor. The method of claim 8, wherein the molybdenum oxychloride precursor comprises at least one of the following: molybdenum trichloride (V) (MoOCl ₃ ), molybdenum tetrachloride (VI) (MoOCl ₄ ), or dichlorodichloride Molybdenum (IV) oxide (MoO ₂ Cl ₂ ). The method of claim 1, wherein the molybdenum precursor comprises at least one of the following: molybdenum pentachloride (MoCl ₅ ) or molybdenum hexachloride (MoCl ₆ ). Such as the method of claim 1, wherein the molybdenum precursor contains at least one of the following: Mo(NMe ₂ ) ₄ , Mo(NEt ₂ ) ₄ , Mo ₂ (NMe ₂ ) ₆ , Mo(tBuN) ₂ (NMe ₂ ) ₂ , Mo(tBuN) ₂ (NEt ₂ ) ₂ , Mo(NEtMe) ₄ , Mo(NtBu) ₂ (StBu) ₂ , Mo(NtBu) ₂ (iPr ₂ AMD) ₂ Mo(thd) ₃ , MoO ₂ (acac), MoO ₂ (thd) ₂ , MoO ₂ (iPr ₂ AMD) ₂ Mo(CO) _{6 ,} Mo(Cp) ₂ H ₂ , Mo(iPrCp) ₂ H ₂ , Mo(η ⁶ -ethylbenzene) ₂ , MoCp(CO) ₂ (η ³ -allyl) and MoCp(CO) ₂ (NO). The method of claim 1, wherein the molybdenum nitride film has a resistivity of less than 750 μΩ-cm at an average molybdenum nitride film thickness of less than 50 Å. The method of claim 1, wherein the molybdenum nitride film has a resistivity of less than 250 μΩ-cm at an average molybdenum nitride film thickness of less than 100 Å. The method of claim 1, wherein the molybdenum nitride film has a resistivity of less than 400 μΩ-cm at an average molybdenum nitride film thickness of less than 25 Å. The method of claim 1, wherein the molybdenum nitride film has a percentage roughness of less than 1.5%. The method of claim 1, wherein the composition of the molybdenum nitride film includes both a MoN phase and a Mo ₂ N phase. The method of claim 1, wherein the molybdenum nitride film is directly deposited on a dielectric surface. The method of claim 1, wherein the molybdenum nitride film is physically continuous at an average film thickness of less than 40 Å. The method of claim 1, wherein the molybdenum nitride film includes a portion of a gate stack disposed above a semiconductor channel region, wherein at an average molybdenum nitride film thickness of less than 50 Å, the gate stack has a thickness greater than Effective work function of 4.6 eV. The method of claim 1, wherein the molybdenum nitride film includes a portion of a gate stack disposed above a semiconductor channel region, wherein at an average molybdenum nitride film thickness of less than 50 Å, the gate stack has a thickness greater than Effective work function of 4.75 eV. The method of claim 1, wherein the molybdenum nitride film includes a portion of a gate stack disposed above a semiconductor channel region, wherein at an average thickness of the molybdenum nitride film between about 15 Å and 50 Å, the molybdenum nitride film The gate stack has an effective work function between about 4.6 eV and 4.75 eV. The method of claim 2, wherein the molybdenum nitride film includes a portion of a gate stack disposed above a semiconductor channel region, wherein at an average thickness of the molybdenum nitride film between about 15 Å and 50 Å, the molybdenum nitride film The gate stack has a substantially constant effective work function of about 4.75 eV. A structure of a semiconductor device, including: A semiconductor channel area; and A gate stack directly arranged on the semiconductor channel region, wherein the gate stack includes: A gate dielectric is arranged on the semiconductor channel region; and A gate electrode includes a molybdenum nitride film arranged on the gate dielectric. The semiconductor device structure of claim 23, wherein the gate dielectric is directly disposed on the semiconductor channel region. The semiconductor device structure of claim 23, wherein the molybdenum nitride film is directly disposed on the gate dielectric. The semiconductor device structure of claim 23, wherein the molybdenum nitride film has a resistivity of less than 750 μΩ-cm at an average molybdenum nitride film thickness of less than 100 Å. The semiconductor device structure of claim 23, wherein the molybdenum nitride film has a resistivity of less than 250 μΩ-cm at an average molybdenum nitride film thickness of less than 100 Å. The semiconductor device structure of claim 23, wherein the molybdenum nitride film has a resistivity of less than 500 μΩ-cm at an average molybdenum nitride film thickness of less than 25 Å. The semiconductor device structure of claim 23, wherein the molybdenum nitride film has a composition including a MoN phase and a Mo ₂ N phase. The semiconductor device structure of claim 23, wherein the molybdenum nitride film is a physically continuous molybdenum nitride film having an average film thickness of less than 40 Å. The semiconductor device structure of claim 23, wherein the molybdenum nitride film is amorphous. The semiconductor device structure of claim 23, wherein the molybdenum nitride film is crystalline. Such as the semiconductor device structure of claim 23, wherein the gate stack has an effective work function greater than 4.6 eV at an average molybdenum nitride film thickness of less than 50 Å. Such as the semiconductor device structure of claim 23, wherein the gate stack has an effective work function greater than 4.75 eV at an average molybdenum nitride film thickness equal to or less than 50 Å. Such as the semiconductor device structure of claim 23, wherein, at an average molybdenum nitride film thickness between 15 Å and 50 Å, the gate stack has a substantially constant effective work function of about 4.75 eV. The semiconductor device structure of claim 23, wherein the semiconductor channel region includes a part of a FinFET semiconductor device structure. The semiconductor device structure of claim 23, wherein the semiconductor channel region includes a part of a wrap-around gate semiconductor device structure. A reaction system configured to perform the method of request 1. A semiconductor device structure including a molybdenum nitride film deposited by the method of claim 1.

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