阅读说明：本技术 材料沉积系统以及相关方法和微电子装置 (Material deposition system and related method and microelectronic device ) 是由 J·A·斯迈思 G·S·桑胡 S·C·潘迪 M·E·科乌通斯基 于 2021-06-01 设计创作，主要内容包括：本专利申请涉及材料沉积系统,以及相关方法和微电子装置。一种材料沉积系统包括前体源以及与所述前体源选择性流体连通的化学气相沉积设备。所述前体源经配置以含有呈液态和固态中的一或多者的至少一种含金属前体材料。所述化学气相沉积设备包括壳体结构、分配歧管和衬底固持器。所述壳体结构经配置和定位以接收包括所述至少一种含金属前体材料的至少一个馈送流体流。所述分配歧管在所述壳体结构内,且与信号发生器电连通。所述衬底固持器在所述壳体结构内,与分配组件间隔开,且与额外信号发生器电连通。还描述了一种微电子装置和形成微电子装置的方法。(The present application relates to material deposition systems, and related methods and microelectronic devices. A material deposition system includes a precursor source and a chemical vapor deposition apparatus in selective fluid communication with the precursor source. The precursor source is configured to contain at least one metal-containing precursor material in one or more of a liquid state and a solid state. The chemical vapor deposition apparatus includes a housing structure, a distribution manifold, and a substrate holder. The housing structure is configured and positioned to receive at least one feed fluid stream comprising the at least one metal-containing precursor material. The distribution manifold is within the housing structure and is in electrical communication with a signal generator. The substrate holder is within the housing structure, spaced apart from the dispensing assembly, and in electrical communication with an additional signal generator. A microelectronic device and a method of forming a microelectronic device are also described.)

1. A material deposition system, comprising:

a precursor source configured to contain at least one metal-containing precursor material in one or more of a liquid state and a solid state; and

a chemical vapor deposition apparatus in selective fluid communication with the precursor source and comprising:

a housing structure configured and positioned to receive at least one feed fluid stream comprising the at least one metal-containing precursor material;

a distribution manifold within the housing structure and in electrical communication with a signal generator; and

a substrate holder within the housing structure and spaced apart from the distribution manifold, the substrate holder in electrical communication with an additional signal generator.

2. The material deposition system of claim 1, further comprising an ionization device downstream of the precursor source and upstream of the chemical vapor deposition apparatus, the ionization device configured to at least partially ionize the at least one metal-containing precursor material.

3. The material deposition system of claim 2, further comprising:

a chamber cleaning material source configured to contain at least one chamber cleaning material; and

an additional ionization device downstream of the chamber cleaning material source and upstream of the chemical vapor deposition apparatus, the additional ionization device configured to at least partially ionize the at least one chamber cleaning material.

4. The material deposition system of claim 3, wherein the ionization device and the additional ionization device are spaced apart from each other on a sealable cover of the containment structure.

5. The material deposition system of claim 1, wherein the precursor source is configured in a flowable solid form containing the at least one metal-containing precursor material and is positioned on or above a sealable lid of the containment structure.

6. The material deposition system of claim 1, wherein the precursor source is configured in a liquid form containing the at least one metal-containing precursor material and is in selective fluid communication with the chemical vapor deposition apparatus through an insulated wire.

7. The material deposition system of any one of claims 1-6, further comprising a heating apparatus configured and positioned to heat the precursor source.

8. The material deposition system of any one of claims 1-6, further comprising an effluent fluid treatment apparatus downstream of the chemical vapor deposition apparatus, the effluent fluid treatment apparatus configured to remove one or more materials from at least one effluent fluid stream exiting the housing structure of the chemical vapor deposition apparatus.

9. The material deposition system of claim 8, further comprising a bypass apparatus downstream of the chemical vapor deposition apparatus and upstream of the effluent fluid treatment apparatus.

10. The material deposition system of any one of claims 1-6, further comprising a carrier gas source in selective fluid communication with the precursor source.

11. The material deposition system of any one of claims 1-6, wherein the chemical vapor deposition apparatus further comprises a coil structure between the distribution manifold and the substrate holder and in electrical communication with another signal generator.

12. A method of forming a microelectronic device, comprising:

directing a feed fluid stream into a chemical vapor deposition apparatus containing a substrate structure, the feed fluid stream comprising at least one metal-containing precursor material in one or more of a liquid state and a solid state;

forming a plasma within the chemical vapor deposition apparatus using the at least one feed fluid stream; and

forming a metal-containing material on the base structure using the plasma.

13. The method of claim 12, further comprising selecting the at least one metal-containing precursor material to comprise one or more of a tantalum-containing precursor material, a hafnium-containing precursor material, a zinc-containing precursor material, a vanadium-containing precursor material, an iridium-containing precursor material, a zirconium-containing precursor material, a tungsten-containing precursor material, a niobium-containing precursor material, and a scandium-containing precursor material.

14. The method of claim 12, further comprising selecting the at least one metal-containing precursor material to comprise:

one or more of boron and carbon; and

one or more of tantalum, hafnium, zinc, vanadium, iridium, zirconium, tungsten, niobium, and scandium.

15. The method of any one of claims 12-14, further comprising forming the feed fluid stream to include one or more of droplets and solid particles of the at least one metal-containing precursor suspended in a carrier gas.

16. The method of any of claims 12 to 14, wherein forming a plasma within the chemical vapor deposition apparatus comprises applying a voltage to one or more of a distribution manifold, a substrate holder offset from the distribution manifold, and a coil structure between the distribution manifold and the substrate holder to form the plasma from a component of the at least one feed fluid stream.

17. The method of any of claims 12-14, further comprising ionizing at least a portion of the at least one metal-containing precursor material of the feed fluid stream prior to directing the feed fluid stream into the chemical vapor deposition apparatus.

18. The method of any one of claims 12 to 14, wherein forming a metal-containing material on the base structure using the plasma comprises forming one or more of a metal boride-containing material, a metal carbide-containing material, and a metal borocarbide-containing material on the base structure using the plasma.

19. The method of any one of claims 12-14, further comprising trapping one or more of unreacted precursors and reaction byproducts of the at least one metal-containing precursor material from the formation of the metal-containing material in at least one effluent fluid treatment apparatus downstream of the chemical vapor deposition apparatus.

20. A microelectronic device comprising a microelectronic device structure including a metal-containing material overlying a base structure formed by plasma-enhanced chemical vapor deposition, the metal-containing material comprising M on the base structure₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_yAnd M₁M₂B_xC_yWherein M is₁And M₂Are each a metal selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc.

21. The microelectronic device of claim 20, wherein the metal-containing material has a thickness in a range from about 2 microns to about 3 microns.

22. The microelectronic device of any of claims 20 and 21, wherein the metal-containing material has a non-uniform distribution of one or more elements thereof.

23. A method of forming a microelectronic device, comprising:

forming a metal-containing material on a base structure by plasma-enhanced chemical deposition, the metal-containing material comprising:

one or more of carbon and boron; and

one or more of tantalum, hafnium, zinc, vanadium, iridium, zirconium, tungsten, niobium, and scandium; and

etching the base structure using the metal-containing material as a hard mask.

24. The method of claim 23, wherein forming a metal-containing material on a base structure comprises forming a M on the base structure₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_yAnd M₁M₂B_xC_yWherein M is₁And M₂Are metals selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc, respectively.

25. The method of any one of claims 23 and 24, wherein etching the base structure using the metal-containing material as a hard mask comprises low temperature etching the base structure.

26. The method of any one of claims 23 and 24, wherein etching the base structure using the metal-containing material as a hard mask comprises forming high aspect ratio structures from portions of the base structure, the high aspect ratio structures each having an aspect ratio in a range from about 5:1 to about 100: 1.

Technical Field

In various embodiments, the present disclosure relates generally to the field of microelectronic device design and fabrication. More particularly, the present disclosure relates to material deposition systems, and to related methods and microelectronic devices.

Background

Microelectronic device designers often desire to increase the integration or density of features within a microelectronic device by reducing the size of individual features and by reducing the separation distance between adjacent features. In addition, microelectronic device designers often desire architectures that design not only be compact but also provide performance advantages and simplify the design.

One approach for achieving increased integration density involves reducing the lateral footprint of individual features by increasing the aspect ratio (i.e., the ratio of vertical height to horizontal width or diameter) of the individual features and the proximity of adjacent features. Unfortunately, conventional methods and systems to form relatively high aspect ratio features require relatively thick deposition of conventional hard mask materials to retain them during the completion of the etch action, which can negatively impact the etch rate (e.g., at the bottom of the structure) and limit the feature height that can be implemented. In addition, conventional hardmask materials that facilitate relatively reduced thicknesses may be difficult to form and/or process (e.g., require complex and costly processing methods).

Accordingly, new methods and systems are needed for forming microelectronic devices, such as microelectronic devices containing high aspect ratio features, and new microelectronic devices formed using the same.

Disclosure of Invention

In some embodiments, a material deposition system includes a precursor source and a chemical vapor deposition apparatus in selective fluid communication with the precursor source. The precursor source is configured to contain at least one metal-containing precursor material in one or more of a liquid state and a solid state. The chemical vapor deposition apparatus includes a housing structure, a distribution manifold, and a substrate holder. The housing structure is configured and positioned to receive at least one feed fluid stream comprising the at least one metal-containing precursor material. The distribution manifold is within the housing structure and is in electrical communication with a signal generator. The substrate holder is within the housing structure, spaced apart from the dispensing assembly, and in electrical communication with an additional signal generator.

In additional embodiments, a method of forming a microelectronic device includes directing a feed fluid stream into a chemical vapor deposition apparatus containing a substrate structure. The feed fluid stream includes at least one metal-containing precursor material in one or more of a liquid state and a solid state. Forming a plasma within the chemical vapor deposition apparatus using the at least one feed fluid stream. Forming a metal-containing material on the base structure using the plasma.

In further embodiments, a microelectronic device includes a microelectronic device structure including a metal-containing material formed by plasma-enhanced chemical vapor deposition overlying a base structure. The metal-containing material comprises M on the base structure₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_yAnd M₁M₂B_xC_yWherein M is₁And M₂Are metals selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc, respectively.

In yet other embodiments, a method of forming a microelectronic device includes forming a metal-containing material on a base structure by plasma-enhanced chemical deposition. The metal-containing material comprises one or more of carbon and boron; and one or more of tantalum, hafnium, zinc, vanadium, iridium, zirconium, tungsten, niobium, and scandium. Etching the base structure using the metal-containing material as a hard mask.

Drawings

Fig. 1 is a simplified schematic diagram of a material deposition system according to an embodiment of the present disclosure.

Fig. 2 is a simplified partial cross-sectional view of a microelectronic device structure formed using the material deposition system shown in fig. 1, in accordance with an embodiment of the present disclosure.

Detailed Description

The following description provides specific details such as material compositions and processing conditions (e.g., temperature, pressure, flow rates, etc.) in order to provide a thorough description of embodiments of the present disclosure. However, it will be understood by those of ordinary skill in the art that the embodiments of the present disclosure may be practiced without necessarily using these specific details. Indeed, embodiments of the disclosure may be practiced in conjunction with conventional systems and methods used in the industry. Additionally, only those process components and acts necessary to understand the embodiments of the present disclosure are described in detail below. It will be understood by those of ordinary skill in the art that some process components (e.g., piping, line filters, valves, temperature detectors, flow detectors, pressure detectors, etc.) are inherently disclosed herein, and that the addition of various conventional process components and actions will be consistent with the present disclosure. Moreover, the description provided below does not form a complete process flow for manufacturing microelectronic devices. The structures described below do not form complete microelectronic devices. Additional acts to form a complete microelectronic device according to the structure may be performed by conventional fabrication techniques.

The figures presented herein are for illustrative purposes only and are not intended to be actual views of any particular material, component, structure, device, or system. It is contemplated that the shapes depicted in the drawings will vary, due to, for example, manufacturing techniques and/or tolerances. Thus, embodiments described herein should not be construed as limited to the particular shapes or regions as illustrated, but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as box-shaped may have coarse and/or non-linear features, and a region illustrated or described as circular may include some coarse and/or linear features. Furthermore, the illustrated acute angles may be rounded, and vice versa. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims. The figures are not necessarily to scale. Additionally, common elements between the figures may retain the same numerical designation.

As used herein, the term "substrate" means and includes a base material or construction on which additional material is formed. The substrate may be a semiconductor substrate, a base semiconductor layer on a support structure, a metal electrode, or a semiconductor substrate having one or more layers, structures, or regions formed thereon. The substrate may be a conventional silicon substrate, or other bulk substrate comprising a layer of semiconductive material. As used herein, the term "bulk substrate" means and includes not only silicon wafers, but also silicon-on-insulator (SOI) substrates, such as silicon-on-sapphire (SOS) substrates and silicon-on-glass (SOG) substrates, epitaxial layers of silicon on a base semiconductor basis, and other semiconductor or optoelectronic materials, such as silicon germanium, gallium arsenide, gallium nitride, and indium phosphide. The substrate may be doped or undoped. By way of non-limiting example, the substrate may comprise at least one of: silicon, silicon dioxide, silicon with native oxide, silicon nitride, silicon carbonitride, glass, semiconductor, metal oxide, metal, titanium nitride, titanium carbonitride, tantalum nitride, tantalum carbonitride containing carbon, niobium nitride, niobium carbonitride containing carbon, molybdenum nitride, molybdenum carbonitride containing carbon, tungsten nitride, tungsten carbonitride containing carbon, copper, cobalt, nickel, iron, aluminum, and noble metals.

As used herein, "memory device" means and includes a microelectronic device that exhibits, but is not limited to, memory functionality.

As used herein, the term "configured" refers to the size, shape, material composition, orientation, and arrangement of one or more of at least one structure and at least one device that facilitates the operation of the one or more of the structure and the device in a predetermined manner.

As used herein, the terms "vertical", "longitudinal", "horizontal" and "transverse" refer to the major plane of a structure and are not necessarily defined by the earth's gravitational field. A "horizontal" or "transverse" direction is a direction substantially parallel to the major plane of the structure, while a "vertical" or "longitudinal" direction is a direction substantially perpendicular to the major plane of the structure. The main plane of the structure is defined by the surface of the structure having a relatively large area compared to the other surfaces of the structure.

As used herein, spatially relative terms, such as "under," "lower," "bottom," "above," "upper," "top," "front," "back," "left," "right," and the like, may be used for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Unless otherwise specified, spatially relative terms are intended to encompass different orientations of the material in addition to the orientation depicted in the figures. For example, if the materials in the figures are inverted, elements described as "under" or "beneath" or "bottom" other elements or features would then be oriented "over" or "top" the other elements or features. Thus, the term "lower" can encompass both an orientation of above and below, depending on the context in which the term is used, as will be apparent to those of ordinary skill in the art. The materials may be otherwise oriented (e.g., rotated 90 degrees, inverted, or flipped) and the spatially relative descriptors used herein interpreted accordingly.

As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

As used herein, "and/or" includes any and all combinations of one or more of the associated listed items.

As used herein, the term "substantially" with respect to a given parameter, property, or condition means and includes the degree to which the given parameter, property, or condition meets the variation (e.g., within an acceptable tolerance) as would be understood by one of ordinary skill in the art. For example, depending on the particular parameter, property, or condition being substantially met, the parameter, property, or condition may meet at least 90.0%, meet at least 95.0%, meet at least 99.0%, meet at least 99.9%, or even meet 100.0%.

As used herein, "about" or "approximately" with respect to a value of a particular parameter includes the value and the degree of variation of the value within an acceptable tolerance for the particular parameter as would be understood by one of ordinary skill in the art. For example, "about" or "approximately" with respect to a value may include an additional value that is within 90.0% to 110.0% of the value, such as within 95.0% to 105.0% of the value, within 97.5% to 102.5% of the value, within 99.0% to 101.0% of the value, within 99.5% to 100.5% of the value, or within 99.9% to 100.1% of the value.

An embodiment of the present disclosure will now be described with reference to fig. 1, which schematically illustrates a material deposition system 100 (e.g., a Plasma Enhanced Chemical Vapor Deposition (PECVD) system). The material deposition system 100 can be used to produce microelectronic device structures comprising metal-containing materials (e.g., metal-containing carbon materials, metal-boron-containing carbon materials) by PECVD, as described in further detail below. As shown in fig. 1, the material deposition system 100 may include at least one precursor source 102, and at least one PECVD apparatus 104 in selective (i.e., operator or system controlled) fluid communication with the precursor source 102. The material deposition system 100 may further include additional equipment operatively associated with one or more of the precursor source 102 and the PECVD apparatus 104, as described in further detail below.

Precursor source 102 includes at least one apparatus (e.g., a containment vessel) configured and operable to contain (e.g., store) and/or generate at least one precursor material to be used by PECVD apparatus 104 to generate a metal-containing material (e.g., a metal-containing carbon material, a metal-containing boron-carbon material). For example, the resulting metal-containing material may be used as a hard mask material to form a microelectronic device, as described in further detail below. In some embodiments, the precursor materials of precursor source 102 include at least one metal-containing precursor material, such as one or more of a tantalum (Ta) -containing precursor material, a hafnium (Hf) -containing precursor material, a zinc (Zn) -containing precursor material, a vanadium (V) -containing precursor material, an iridium (Ir) -containing precursor material, a zirconium (Zr) -containing precursor material, a tungsten (W) -containing precursor material, a niobium (Nb) -containing precursor material, and a scandium (Sc) -containing precursor material.

The precursor source 102 can be configured and operated to contain one or more of at least one liquid precursor material (e.g., at least one liquid metal-containing precursor material) and at least one flowable solid precursor material (e.g., at least one flowable solid metal-containing precursor material). In some embodiments, the precursor source 102 is configured and operated to contain one or more liquid metal-containing precursor materials. In further embodiments, the precursor source 102 is configured and operated to contain one or more flowable solid metal-containing precursor materials.

As a non-limiting example, the precursor source 102 can include a storage vessel configured and operated to hold liquid materials including one or more of liquid Ta-containing precursor materials, liquid Hf-containing precursor materials, liquid Zn-containing precursor materials, liquid V-containing precursor materials, liquid Ir-containing precursor materials, liquid Zr-containing precursor materials, liquid W-containing precursor materials, liquid Nb-containing precursor materials, and liquid Sc-containing precursor materials. For example, the precursor source 102 can include a storage vessel configured and operated to hold a liquid Ta-containing precursor material, including liquid tantalum (V) ethoxide (Ta (OC)₂H₅)₅Melting point (mp) ═ 21 ℃), tris (diethylamino) (tert-butylimino) tantalum (V) ((CH)₃)₃CNTa(N(C₂H₅)₂)₃) Tris (ethylmethylamino) (tert-butylimino) tantalum (V) (C)₁₃H₃₃N₄Ta), tantalum pentafluoride (TaF)₅Mp 96.8 ℃), tantalum pentachloride (TaCl)₅Mp 216 deg.c) and pentakis (dimethylamino) tantalum (V) (Ta (N (CH)₃)₂)₅Mp ═ 100 ℃ C.). As another example, the precursor source 102 may include storageA vessel configured and operated to hold a liquid Hf containing precursor material comprising hafnium (IV) tert-butoxide (Hf [ OC (CH) in a liquid state₃)₃]₄) Tetrakis (diethylamino) hafnium (IV) ([ (CH)₂CH₃)₂N]₄Hf), tetrakis (ethylmethylamino) hafnium (IV) ([ (CH)₃)(C₂H₅)N]₄Hf), bis (trimethylsilyl) amino hafnium (IV) chloride ([ [ (CH)₃)₃Si]₂N]₂HfCl₂Mp 44 deg.C and dimethyl bis (cyclopentadienyl) hafnium (IV) ((C)₅H₅)₂Hf(CH₃)₂Mp ═ 118 ℃ C.). As another example, the precursor source 102 can include a storage vessel configured and operated to hold a liquid Zn-containing precursor material, including diethyl zinc in a liquid state ((C)₂H₅)₂Zn) and bis (pentafluorophenyl) zinc ((C)₆F₅)₂Zn, mp ═ 105 ℃ C.). As another example, the precursor source 102 can include a storage vessel configured and operated to contain a liquid V-containing precursor material, including liquid vanadium (V) triisopropoxide (OV) (OCH (CH)₃)₂)₃) Vanadium pentafluoride (VF)₅Mp 19.5 deg.C), vanadium tetrachloride (VCl)₄Mp ═ 20.5 ℃ C.) and bis (cyclopentadienyl) vanadium (II) (V (C)₅H₅)₂Mp ═ 167 ℃), in a controlled manner. As another example, the precursor source 102 can include a storage vessel configured and operated to hold a liquid Zr-containing precursor material, including tetrakis (ethylmethylamino) zirconium (IV) (Zr (NCH) in a liquid state₃C₂H₅)₄) Bis (cyclopentadienyl) zirconium (IV) dihydride (C)₁₀H₁₂Zr, mp 300 ℃), dimethyl bis (pentamethylcyclopentadienyl) zirconium (IV) (C)₂₂H₃₆Zr, mp ═ 206 ℃ and tetrakis (dimethylamino) zirconium (IV) ([ (C)₂H₅)₂N]₄Zr, mp ═ 60 ℃). As another example, the precursor source 102 can include a storage vessel configured and operated to hold a liquid W-containing precursor material, including bis (t-butylimino) bis (dimethylamino) in a liquid state) Tungsten (VI) (((CH)₃)₃CN)₂W(N(CH₃)₂)₂) Tetracarbonyl (1, 5-cyclooctadiene) tungsten (0) (C)₁₂H₁₂O₄W, mp ═ 158 ℃ C., and tungsten hexacarbonyl (0) (W (CO))₆Mp 150 deg.c). As another example, precursor source 102 can include a storage vessel configured and operated to hold a liquid Nb-containing precursor material, including a liquid tris (diethylamino) (tert-butylimino) niobium (Nb-TBTDEN),^tBuN═Nb(NEt₂)₃、^tBuN═Nb(NMeEt)₃、^tamylN＝Nb(OtBu)₃Niobium (V) ethoxide (Nb (OCH)₂CH₃)₅Mp 6 ℃), niobium pentafluoride (NbF)₅Mp 73 deg.C), niobium pentachloride (NbCl)₅Mp 205 deg.C and niobium (V) ethoxide (Nb (OCH)₂CH₃)₅Mp ═ 6 ℃ C.). As another example, the precursor source 102 can comprise a storage vessel configured and operated to hold liquid Sc-containing precursor material, including Sc (thd) in a liquid state₃(thd ═ 2,2,6, 6-tetramethyl-3, 5-heptanedione) ((C)₅H₅)₃Sc，mp＝240℃)、Sc(MeCp)₂(Me2pz) (MeCp-methylcyclopentadienyl, Me2 pz-3, 5-dimethylpyrazole ester) and one or more of tris (N, N-diisopropylacetamido) scandium.

As another non-limiting example, precursor source 102 can comprise a storage vessel configured and operated to hold a powder comprising solid particles of one or more metal-containing precursor materials, such as particles of one or more of a solid Ta-containing precursor material, a solid Hf-containing precursor material, a solid Zn-containing precursor material, a solid V-containing precursor material, a solid Ir-containing precursor material, a solid Zr-containing precursor material, a solid W-containing precursor material, a solid Nb-containing precursor material, and a solid Sc-containing precursor material. For example, the precursor source 102 can comprise a storage vessel configured and operated to hold a Ta-containing precursor material, including TaF₅、TaCl₅And (Ta (N (CH)₃)₂)₅Solid particles of one or more of (a). As another example, the precursor source 102 may comprise a storage vessel, whichThe storage container is configured and operated to hold a Hf-containing precursor material comprising [ [ (CH)₃)₃Si]₂N]₂HfCl₂And (C)₅H₅)₂Hf(CH₃)₂Solid particles of one or more of (a). As another example, the precursor source 102 can comprise a storage vessel configured and operated to hold a Zn-containing precursor material, including (C)₆F₅)₂Solid particles of Zn. As another example, the precursor source 102 can include a storage vessel configured and operated to hold a V-containing precursor material, including V (C)₅H₅)₂The solid particles of (1). As another example, the precursor source 102 can include a storage vessel configured and operated to hold a Zr-containing precursor material, including C₁₀H₁₂Zr、C₂₂H₃₆Zr and [ (C)₂H₅)₂N]₄Solid particles of one or more of Zr. As another example, the precursor source 102 can comprise a storage vessel configured and operated to hold W-containing precursor material, including C₁₂H₁₂O₄W and W (CO)₆Solid particles of one or more of (a). As another example, the precursor source 102 may include a storage vessel configured and operated to hold Nb-containing precursor material, including NbF₅And NbCl₅Solid particles of one or more of (a). As another example, the precursor source 102 can comprise a storage vessel configured and operated to hold Sc-containing precursor material, including Sc (thd)₃、(C₅H₅)₃Sc、Sc(MeCp)₂Solid particles of one or more of (Me2pz) and tris (N, N-diisopropylacetamido) scandium.

Material deposition system 100 may include a single (i.e., only one) precursor source 102, or may include multiple (i.e., more than one) precursor sources 102. If the material deposition system 100 includes multiple precursor sources 102, the precursor sources 102 may be substantially similar to each other (e.g., may exhibit substantially similar components, component sizes, component shapes, component material compositions, component material distributions, component positions, component orientations) and may be operated under substantially similar conditions (e.g., substantially similar temperatures, pressures, flow rates), or at least one of the precursor sources 102 may be different from (e.g., exhibit different components, different component sizes, different component shapes, different component material compositions, different component material distributions, different component positions, different component orientations) and/or may be operated under different conditions (e.g., different temperatures, different pressures, different flow rates, etc.) than at least one other of the precursor sources 102. For example, the material deposition system 100 can include at least two (2) precursor sources 102, wherein one of the precursor sources 102 is configured to contain a first metal-containing precursor material (e.g., a first liquid metal-containing precursor material, a first flowable solid metal-containing precursor material), and another of the precursor sources 102 is configured to contain a second, different metal-containing precursor material (e.g., a second liquid metal-containing precursor material, a second flowable solid metal-containing precursor material). In some embodiments, two or more precursor sources 102 are provided in parallel with each other within the material deposition system 100. In additional embodiments, two or more precursor sources 102 are provided in series with each other within the material deposition system 100.

With continued reference to fig. 1, the material deposition system 100 may optionally further include at least one heating apparatus 106 operatively associated with the precursor source 102. If present, heating device 106 may include at least one device (e.g., one or more of a heat exchanger, such as a tube-in-tube (Tube) heat exchanger and/or a shell-and-tube (Shell-and-tube) heat exchanger, a combustion heater, a nuclear heater, a sonication heater, a resistive heater, an inductive heater, an electromagnetic heater, such as an infrared heater and/or a microwave heater) configured and operated to heat at least a portion of precursor source 102. The heating apparatus 106 may be used to heat or maintain the precursor material of the precursor source 102 at a desired temperature, such as a temperature that promotes flowability of the precursor material. In some embodiments, such as some embodiments in which the precursor materials of the precursor source 102 include liquid precursor materials and solid (e.g., powdered) precursor materials, the heating apparatus 106 is included in the material deposition system 100 and is configured and positioned to heat the precursor source 102. In some such embodiments, lines (e.g., tubing, pipes) running from and between the precursor source 102 and the PECVD apparatus 104 are thermally isolated to maintain a desired temperature of at least one feed fluid stream directed from the precursor source 102 to the PECVD apparatus 104. In additional embodiments, such as some embodiments in which the precursor material of the precursor source 102 does not require supplemental heating, the heating apparatus 106 is omitted from the material deposition system 100.

Still referring to fig. 1, the material deposition system 100 may further include at least one carrier gas source 108 in selective fluid communication with the precursor source 102. The carrier gas source 108 may include at least one apparatus (e.g., at least one pressure vessel) configured and operable to hold (e.g., contain, store) a volume of carrier gas. The carrier gas may, for example, include at least one inert gas (e.g., at least one noble gas), such as one or more of helium (He) gas, neon (Ne) gas, and argon (Ar) gas. The carrier gas of carrier gas source 108 may be used as a suspension medium for one or more precursor materials (e.g., liquid metal-containing precursor material, solid metal-containing precursor material) contained within precursor source 102, as described in further detail below.

If present, the carrier gas source 108 may be operatively associated with the precursor source 102 in a manner that facilitates interaction (e.g., mixing) of the carrier gas from the carrier gas source 108 with the precursor material from the precursor source 102 upstream of, at, and/or within the PECVD apparatus 104. As a non-limiting example, a carrier gas source 108 may be provided upstream of the precursor source 102 and in selective fluid communication therewith such that the carrier gas from the carrier gas source 108 may mix with the precursor materials of the precursor source 102 within and/or downstream of the precursor source 102. In some embodiments, carrier gas source 108 is configured and positioned such that the carrier gas exiting carrier gas source 108 mixes with the precursor materials of precursor source 102 within precursor source 102. For example, a carrier gas may be delivered into at least one interior chamber of the precursor source 102 and mixed with the precursor materials therein. In additional embodiments, the carrier gas source 108 and the precursor source 102 are each fluidly coupled to an optional mixing apparatus 110 downstream of the precursor source 102 and upstream of the PECVD apparatus 104. The carrier gas from carrier gas source 108 and the precursor material from precursor source 102 can each be fed (e.g., flowed, pumped) into mixing apparatus 110, where the carrier gas and precursor material can be combined prior to PECVD apparatus 104. In some embodiments, the mixing apparatus 110 is configured and operated to form a gaseous mixture that includes discrete portions (e.g., discrete droplets, discrete solid particles) of the precursor material dispersed and entrained within the inert gas. For example, the mixing apparatus 110 may comprise an injector apparatus including an atomizing nozzle.

With continued reference to fig. 1, the material deposition system 100 may further include at least one ionization device 112 downstream of the precursor source 102 and upstream of the PECVD apparatus 104. If present, the ionization device 112 may be configured and operated to expose the precursor material from the precursor source 102 to an ionizing field to modify (e.g., ionize, react) the precursor in a manner that facilitates or promotes a desired material forming reaction (e.g., carbide forming reaction, boride forming reaction) within the PECVD apparatus 104. The configuration and parameters of the ionization device 112 may be tailored according to the desired effect on one or more precursor materials. As a non-limiting example, the ionization device 112 may use a laser energy source that outputs a predetermined wavelength of electromagnetic energy selected to break specific chemical bonds of one or more metal-containing precursors of the precursor material. As another non-limiting example, the ionization device 112 may use a microwave energy source that promotes ionization of one or more metal-containing precursors of the precursor materials in a predetermined manner. In additional embodiments, the ionization device 112 is omitted from the material deposition system 100 (e.g., is not present).

With continued reference to fig. 1, a PECVD apparatus 104 is located downstream of the precursor source 102. The PECVD apparatus 104 includes a housing structure 114, and each of at least one distribution assembly 116 (e.g., distribution manifold, showerhead assembly) and at least one substrate holder 118 within the housing structure 114. The dispensing assembly 116 and the substrate holder 118 may be spaced apart (e.g., separated, remote) from each other within the housing structure 114. The PECVD apparatus 104 may further include additional features (e.g., additional structures, additional devices), as described in further detail below.

The housing structure 114 of the PECVD apparatus 104 presents at least one inlet configured and positioned to receive at least one feed (e.g., inflow) fluid stream comprising precursor material from the precursor source 102 (and optionally, carrier gas from the carrier gas source 108) and at least one outlet positioned to direct at least one exhaust (e.g., outflow) fluid stream comprising reaction byproducts and unreacted material from the PECVD apparatus 104. The housing structure 114 may at least partially define at least one interior chamber 120 of the PECVD apparatus 104. The inner chamber 120 may surround and hold the distribution assembly 116 and the substrate holder 118 of the PECVD apparatus 104. The housing structure 114 may further include one or more sealable structures that facilitate access to the interior chamber 120 to permit insertion and removal of structures (e.g., substrates) in the interior chamber 120. By way of non-limiting example, as shown in fig. 1, the housing structure 114 may exhibit a removable and sealable lid 122. The housing structure 114 may be formed of and include any material (e.g., metal, alloy, glass, polymer, ceramic, composite, combinations thereof) that is compatible with the operating conditions (e.g., temperature, pressure, material exposure, generated electric field, generated magnetic field) of the PECVD apparatus 104. In some embodiments, the housing structure 114 is formed of and includes stainless steel.

The distribution assembly 116 is configured and positioned to direct one or more feed fluid streams comprising precursor materials from the precursor source 102 and/or derivatives (e.g., ions) formed from the precursor materials (and optionally, carrier gas from the carrier gas source 108) into the inner chamber 120 of the PECVD apparatus 104. In addition, the distribution component 116 can be configured to generate a glow discharge upon application of a voltage thereto, which can be used to generate a plasma from the components of the feed fluid stream. The dispensing assembly 116 may, for example, serve as an electrode (e.g., cathode) of the PECVD apparatus 104. As shown in fig. 1, the dispensing assembly 116 may be electrically connected to at least one signal generator 124 of the material deposition system 100. The signal generator 124 may include at least one power source (e.g., a variable Direct Current (DC) power source, a variable Radio Frequency (RF) power source). The signal generator 124 may also include additional components, such as at least one waveform modulator having circuitry configured for modulating the waveform, frequency, and amplitude of the output signal.

The substrate holder 118 is configured and positioned to support and temporarily hold at least one substrate 126 thereon or thereabove. As shown in fig. 1, the substrate holder 118 may be mounted on at least one lever structure 128 operatively associated with a motor component 130. The lever structure 128 and the motor assembly 130 may be configured and operated to adjust the position of the substrate holder 118 (and thus the substrate 126 thereon) between a relatively lower position (e.g., for loading and unloading the substrate 126) and a relatively higher position (e.g., for processing the substrate 126). In addition, the substrate holder 118 may be electrically connected to at least one additional signal generator 132 of the material deposition system 100. The additional signal generator 132 may include at least one additional power source (e.g., a DC power source, an RF power source, an Alternating Current (AC) power source). The additional signal generator 132 may also include additional components, such as at least one waveform modulator having circuitry configured for modulating the waveform, frequency, and amplitude of the output signal. The substrate holder 118 may be configured to generate a glow discharge upon application of a voltage thereto, which may be used to generate a plasma from a feed fluid stream received into the inner chamber 120 of the PECVD apparatus 104. The substrate holder 118 may, for example, serve as an additional electrode (e.g., an anode) of the PECVD apparatus 104.

Optionally, the PECVD apparatus 104 may further include at least one coil structure 134 positioned between the distribution assembly 116 and the substrate holder 118 within the inner chamber 120 of the PECVD apparatus 104. The coil structure 134 may be configured and operated to assist in generating and/or maintaining a plasma between the distribution assembly 116 and the substrate 126. As described in further detail below, the coil structure 134 may be configured and operated to inductively couple energy into a plasma generated within the inner chamber 120, inducing an electromagnetic flow in the plasma. The electromagnetic flow may heat the plasma by Ohmic heating (Ohmic heating) to maintain the plasma in a steady state. The electromagnetic flow may also contribute to a relatively denser plasma, which may promote or enhance ionization of the material of the feed fluid flow delivered into the PECVD apparatus 104. As shown in fig. 1, if present, the coil structure 134 may be electrically connected to at least one further signal generator 136 of the material deposition system 100. The further signal generator 136 may comprise at least one additional power source (e.g., RF power source, DC power source). The further signal generator 136 may also include additional components, such as an impedance matching network. The coil structure 134 may serve as a first winding of a transformer. In additional embodiments, the coil structure 134 is omitted from the PECVD apparatus 104 (e.g., is not present).

With continued reference to fig. 1, the material deposition system 100 may optionally further include at least one additional heating apparatus 137 operatively associated with the PECVD apparatus 104. If present, the additional heating apparatus 137 may comprise at least one apparatus (e.g., one or more of a heat exchanger, such as a tube-in-tube heat exchanger and/or a shell-and-tube heat exchanger, a combustion heater, a nuclear heater, a sonication heater, a resistive heater, an inductive heater, an electromagnetic heater, such as an infrared heater and/or a microwave heater) configured and operated to heat at least a portion of the PECVD apparatus 104 (e.g., at least a portion of the substrate holder 118, at least a portion of the shell structure 114). The additional heating apparatus 137 may be used to heat or maintain one or more portions of the PECVD apparatus 104 at a desired temperature, such as a temperature that facilitates the formation of at least one metal-containing material (e.g., at least one metal-containing carbon material, at least one metal-boron-containing carbon material) by PECVD using precursor materials and/or derivatives (e.g., ions) of precursor materials from the precursor source 102. In some embodiments, the additional heating apparatus 137 is configured and positioned to facilitate a temperature of greater than or equal to about 200 ℃, such as greater than or equal to about 300 ℃, greater than or equal to about 400 ℃, or greater than or equal to about 450 ℃ within the inner chamber 120 of the PECVD apparatus 104. In additional embodiments, such as some embodiments in which the precursor material of the precursor source 102 does not require supplemental heating to form the desired metal-containing material by PECVD, the additional heating apparatus 137 is omitted from the material deposition system 100.

Still referring to fig. 1, optionally, the material deposition system 100 may further comprise at least one chamber cleaning material source 138 in selective fluid communication with the PECVD apparatus 104. If present, the chamber cleaning material source 138 may be configured and operated to contain at least one chamber cleaning material (e.g., at least one gaseous chamber cleaning material)Material) that may be used to clean the inner chamber 120 of the PECVD apparatus 104 (e.g., to remove undesirable materials therefrom). The chamber cleaning material from the chamber cleaning material source 138 may be, for example, delivered into the PECVD apparatus 104 and then removed from the PECVD apparatus to clean the inner chamber 120 of the PECVD apparatus 104 before and/or after delivering one or more feed fluid streams comprising the precursor material from the precursor source 102 and/or derivatives (e.g., ions) formed from the precursor material (and optionally, an inert gas from the carrier gas source 108) into the inner chamber 120 of the PECVD apparatus 104. In some embodiments, the chamber cleaning material source 138 is configured and operated to contain one or more gaseous chamber cleaning materials. As a non-limiting example, the chamber cleaning material source 138 may comprise a storage vessel configured and operated to remain comprising molecular fluorine (F)₂) Nitrogen trifluoride (NF)₃) And Sulfur Fluoride (SF).

If the material deposition system 100 includes a chamber cleaning material source 138, the material deposition system 100 may optionally further include at least one additional ionization device 140 downstream of the chamber cleaning material source 138 and upstream of the PECVD apparatus 104. If present, the additional ionization device 140 is configured and operated to expose the chamber cleaning material from the chamber cleaning material source 138 to an ionizing field to modify (e.g., ionize, react) its components prior to delivery to the PECVD apparatus 104. The configuration and parameters of the additional ionization device 140 (if present) may be customized according to the desired effect on the chamber cleaning material from the chamber cleaning material source 138. As a non-limiting example, the additional ionization device 140 may use a laser energy source that outputs a predetermined wavelength of electromagnetic energy selected to break specific chemical bonds of one or more components (e.g., molecules, compounds) of the chamber cleaning material. As another non-limiting example, the additional ionization device 140 may use a microwave energy source that facilitates modification of one or more of the components of the chamber cleaning material. As another non-limiting example, the additional ionization device 140 may use electromagnetic energy within the Ultraviolet (UV) spectrum or another spectrum to modify one or more of the components of the chamber cleaning material. Electromagnetic energy may be radiated toward the chamber cleaning material, for example, using one or more slotted planar antennas (slot planar antennas). The configuration and operation of the additional ionization device 140 (if present) may be tailored to the material composition of the material to be removed within the inner chamber 120. For example, the configuration and operation of the additional ionization device 140 (if present) can be tailored to facilitate the formation of chemicals (e.g., reactive fragments, ions, ligands) from chamber cleaning materials that are capable of etching and/or volatilizing materials from surfaces within the inner chamber 120.

If present, the additional ionization devices 140 may be separate and discrete from the ionization devices 112. For example, the additional ionization device 140 may not be configured and positioned to receive and act on precursor material from the precursor source 102, and the ionization device 112 may not be configured and positioned to receive and act on chamber cleaning material from the chamber cleaning material source 138. As shown in fig. 1, in some embodiments, ionization device 112 and additional ionization device 140 are each positioned on or above lid 122 of PECVD apparatus 104. The additional ionization device 140 may be spaced apart from the ionization device 112, for example, on the lid 122 of the PECVD apparatus 104. In additional embodiments, one or more of the ionization device 112 (if present) and the additional ionization device 140 (if present) are provided at different locations relative to the PECVD apparatus 104 and/or to each other, such as locations that are not on or above the lid 122 of the PECVD apparatus 104. In further embodiments, the additional ionization device 140 is omitted from the material deposition system 100 (e.g., is not present).

With continued reference to fig. 1, optionally, the material deposition system 100 may further include at least one vacuum apparatus 142 operatively associated with at least one outlet of the housing structure 114 of the PECVD apparatus 104. If present, the vacuum apparatus 142 may be configured and operated to help control the pressure within the inner chamber 120 of the PECVD apparatus 104 and to remove reaction byproducts and/or unreacted materials (e.g., unreacted precursor materials, unreacted chamber cleaning materials, unreacted derivatives thereof) from the inner chamber 120 of the PECVD apparatus 104. The vacuum apparatus 142 may be configured and operated to apply a negative pressure to the inner chamber 120 of the PECVD apparatus 104. In additional embodiments, the vacuum apparatus 142 is omitted (e.g., not present) from the material deposition system 100.

Still referring to fig. 1, the material deposition system 100 may further include at least one flow path switching device 144 (e.g., at least one flow path switching valve, at least one bypass valve) downstream of the PECVD apparatus 104 (e.g., downstream of the vacuum apparatus 142). The flow path switching device 144 may be configured and positioned to divert one or more of the effluent fluid streams exiting the PECVD apparatus 104 to one or more additional apparatuses along different flow paths downstream of the flow path switching device 144. By way of non-limiting example, as shown in fig. 1, the flow path switching device 144 may be configured and positioned to switchably direct at least one effluent fluid stream exiting the PECVD apparatus 104 to the chamber cleaning material source 138 along a first flow path downstream of the flow path switching device 144 or to the effluent fluid processing apparatus 146 along a second flow path downstream of the flow path switching device 144. For example, the flow path switching device 144 may be configured and operated to direct chamber cleaning byproducts and unreacted chamber cleaning materials generated during cleaning operations of the PECVD apparatus 104 to the chamber cleaning material source 138 (and/or to another apparatus associated with retrieval and/or processing of chamber cleaning materials and/or chamber cleaning process byproducts), and to direct reaction byproducts and unreacted precursors generated during material deposition (e.g., PECVD) operations of the PECVD apparatus 104 to the effluent fluid processing apparatus 146.

Still referring to fig. 1, the effluent fluid treatment apparatus 146 may be located downstream of the PECVD apparatus 104 (e.g., downstream of the flow path switching device 144). The effluent fluid treatment apparatus 146 can be configured and operated to treat (e.g., scrub) effluent fluid (e.g., exhaust gas) exiting the PECVD apparatus 104 to at least partially remove one or more materials (e.g., reaction byproducts, unreacted precursors, toxic materials, hazardous materials, contaminants) therefrom. In some embodiments, the effluent fluid treatment apparatus 146 is configured and positioned to remove (e.g., trap, wash) unreacted metal-containing precursor and/or other desired materials from at least one effluent fluid stream exiting the PECVD apparatus 104. For example, the effluent fluid treatment apparatus 146 may include one or more of a precursor sequestration apparatus and a scrubber apparatus (e.g., a wet scrubber apparatus, a dry scrubber apparatus). In additional embodiments, the outflow fluid handling apparatus 146 is omitted from the material deposition system 100 (e.g., is not present).

Thus, in accordance with an embodiment of the present disclosure, a material deposition system includes a precursor source and a chemical vapor deposition apparatus in selective fluid communication with the precursor source. The precursor source is configured to contain at least one metal-containing precursor material in one or more of a liquid state and a solid state. The chemical vapor deposition apparatus includes a housing structure, a distribution manifold, and a substrate holder. The housing structure is configured and positioned to receive at least one feed fluid stream comprising the at least one metal-containing precursor material. The distribution manifold is within the housing structure and is in electrical communication with a signal generator. The substrate holder is within the housing structure, spaced apart from the dispensing assembly, and in electrical communication with an additional signal generator.

During use and operation of the material deposition system 100, the substrate 126 may be delivered into the PECVD apparatus 104. The substrate 126 may be provided into the inner chamber 120 of the PECVD apparatus 104 in any desired manner. In some embodiments, one or more conventional robotic technical equipment (e.g., robotic arms, robots) are used to deliver the substrate 126 into the PECVD apparatus 104.

After delivering the substrate 126 into the PECVD apparatus 104, one or more feed fluid streams 148 may be introduced into the interior chamber 120 of the PECVD apparatus 104 through one or more inlets in the housing structure 114 (e.g., in the sealable lid 122 of the housing structure 114). The feed fluid stream 148 may include one or more precursor materials and/or derivatives thereof from the precursor source 102 (e.g., ions generated from precursor materials using the ionization device 112). Optionally, the feed fluid stream 148 may also include one or more additional materials (e.g., a carrier gas for the metal-containing precursor material). The material of the received feed fluid stream 148 can stabilize the inner chamber 120 at a desired operating pressure of the PECVD apparatus, such as an operating pressure in a range from about 1 millitorr (mTorr) to about 50mTorr (e.g., in a range from about 1mTorr to about 25, from about 5mTorr to about 20mTorr, or from about 10mTorr to about 20 mTorr). The vacuum apparatus 142 of the material deposition system 100, if present, may be used to help maintain a desired operating pressure within the inner chamber 120 of the PECVD apparatus 104 by controlling the flow of one or more effluent fluid streams 150 from the inner chamber 120 through one or more outlets in the housing structure 114.

Next, one or more of the signal generators (e.g., one or more of the signal generator 124, the additional signal generator 132, and the further signal generator 136) may apply a voltage to one or more components of the PECVD apparatus 104 (e.g., one or more of the distribution assembly 116, the substrate holder 118, and the coil structure 134) to generate a plasma from the material (e.g., metal-containing precursor material, derivatives thereof, inert gas) feeding the fluid flow 148 within the interior chamber 120 of the PECVD apparatus 104. In some embodiments, energy is directed from the signal generator 124 to the distribution assembly 116 and additional energy is directed from the additional signal generator 132 to the substrate holder 118 to generate a plasma within the inner chamber 120 of the PECVD apparatus 104. In some embodiments in which the PECVD apparatus 104 includes a coil structure 134, additional energy may be directed from an additional signal generator 136 to the coil structure 134 to help generate, maintain, and/or energize a plasma.

As the material from the feed fluid stream 148 passes through the plasma and toward the substrate 126, at least some neutral elements (e.g., atoms, molecules) of the material and/or ions formed from the material (e.g., metal-containing ions, carbon-containing ions, boron-containing ions) may react with each other, the material (e.g., ions) of the plasma, and/or additional material (e.g., additional metal-containing precursor material) delivered into the PECVD apparatus 104 before reaching the substrate 126. In further embodiments, neutral elements of the material (e.g., atoms, molecules) and/or ions formed from the material (e.g., metal-containing ions, carbon-containing ions, boron-containing ions) travel through the plasma and toward the substrate 126 without substantially reacting with each other, the material of the plasma, or additional material delivered into the PECVD apparatus 104.

After traveling through the plasma, a material (e.g., a reaction product material, an unreacted material) may be deposited on, over, or within the substrate 126 to form a metal-containing material (e.g., a metal-containing carbon material, a metal-containing boron-carbon material) on, over, or within the substrate 126. The metal-containing material may include carbonAnd atoms of one or more of boron and atoms of one or more metals (e.g., one or more of Ta, Hf, Zn, V, Ir, Zr, W, Nb, and Sc) from the precursor material of precursor source 102. By way of non-limiting example, the metalliferous material may be formed from M₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_y、M₁M₂B_xC_yAnd include the one or more, wherein M₁And M₂Are metals selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc, respectively. Formulae herein (e.g., M) including one or more of "x" and "y₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_y、M₁M₂B_xC_y) Representing for another element (e.g., M)₁、M₂) Contains an average ratio of "x" atoms of one element to "y" atoms of an additional element, if present. Because the chemical formulas represent relative atomic ratios and relaxed chemical structures, the metal-containing material formed can include one or more stoichiometric compounds and/or one or more non-stoichiometric compounds, and the values of "x" and "y" (if present) can be integers or can be non-integers. As used herein, the term "non-stoichiometric compound" means and includes a compound having a certain elemental composition that cannot be represented by a ratio of well-defined natural numbers and that violates the law of definite ratios (law of definitite properties). In some embodiments, the metal-containing material comprises TaC_x、VC_x、NbC_xAnd TaHfC_xOne or more of (a). As described in further detail below, depending on the operating conditions (e.g., material flow rate, applied bias, bias continuity, operating pressure) used during formation of the metal-containing material, the metal-containing material may exhibit a substantially uniform distribution of its elements (e.g., such that the elements are substantially uniformly distributed throughout the metal-containing material) or elements thereofNon-uniform distribution of one or more of (e.g., such that one or more elements are non-uniformly distributed throughout one or more dimensions of the metal-containing material). The metal-containing material can be formed to have a desired thickness. In some embodiments, the metal-containing material is formed to have a thickness that facilitates its use as a hard mask material for a subsequent etch process (e.g., a High Aspect Ratio (HAR) etch process, such as a low temperature etch process) to be performed on the substrate 126. By way of non-limiting example, the metal-containing material can be formed to have a thickness in a range from about 2 micrometers (μm) to about 3 μm.

The type and amount of precursor material and/or derivatives (e.g., metal-containing ions, carbon-containing ions, boron-containing ions) formed from the precursor material introduced into the PECVD apparatus 104 may be controlled (e.g., maintained, adjusted) during use and operation of the material deposition system 100 to control the amount and distribution of metal, carbon, and boron within the metal-containing material formed. By way of non-limiting example, the type and/or amount of precursor material and/or derivative formed from the precursor material introduced into the PECVD apparatus 104 may be controlled to control the type, amount, and distribution of atoms (e.g., metal atoms, carbon atoms, and boron atoms) within different regions (e.g., different vertical regions) of the metal-containing material formed. Accordingly, adjusting one or more of the type and amount of the precursor material and/or derivatives formed therefrom may facilitate the formation of metal-containing materials that exhibit a non-uniform distribution of one or more of metal, carbon, and boron throughout their height (e.g., vertical dimension).

The operating pressure of the PECVD apparatus 104 may also be controlled (e.g., maintained, adjusted) during use and operation of the material deposition system 100 to control characteristics of metal-containing materials formed on, over, or within the substrate 126. Increasing the operating pressure of the PECVD apparatus 104 may increase the frequency of collisions between plasma (e.g., noble gas ions, metal-containing ions, carbon-containing ions, boron-containing ions) and neutral cells (e.g., carbon atoms, boron atoms, carbon-containing molecules, boron-containing molecules, metal atoms, metal-containing molecules) within the inner chamber 120 of the PECVD apparatus 104 to increase the amount of time that material remains in (e.g., remains in and reacts with) the plasma. Thus, a near isotropic directional distribution of materials (e.g., reaction product materials, unreacted materials) can be formed on, over, or within the substrate 126. Conversely, reducing the operating pressure of the PECVD apparatus 104 may reduce the frequency of collisions between plasma ions and neutral cells within the inner chamber 120 of the PECVD apparatus 104 to reduce the amount of time that material remains in the plasma (e.g., remains therein and reacts). Accordingly, a relatively large (as compared to the effects of a relatively large operating pressure) angular distribution of materials (e.g., reaction product materials, unreacted materials) may be formed on, over, or within the substrate 126.

Applying (or not applying) a bias to one or more components of the PECVD apparatus 104, such as one or more of the distribution assembly 116, the substrate holder 118, and the coil structure 134, if present, may also be used to control characteristics of metal-containing materials formed on, over, or within the substrate 126. For example, biasing the distribution assembly 116 may attract plasma ions toward a reactant (e.g., precursor, ions formed from the precursor) directed into the inner chamber 120 of the PECVD apparatus 104 to enhance collisions with and reactions between the reactants. As another example, biasing the substrate holder 118 may attract ionized deposition material (e.g., ionized material, such as ionized, reacted material and/or ionized, unreacted material) toward the substrate 126. Biasing the substrate holder 118 may attract the ionized deposition material toward the substrate 126 relatively more uniformly than unbiased substrate holder 118. Thus, the bias may be applied to different components of the PECVD apparatus 104 at different times. For example, during the first stage of the process, power may be supplied from the signal generator 124 to the distribution assembly 116 while the substrate holder 118 remains electrically neutral (e.g., no power is supplied from the additional signal generator 132 to the substrate holder 118); and during a second stage of the process, power may be supplied to the substrate holder 118 from the additional signal generator 132 while the dispensing assembly 116 remains electrically neutral (e.g., no power is supplied to the dispensing assembly 116 from the signal generator 124). As another example, during the first stage of the process, power may be supplied to the dispensing assembly 116 from the signal generator 124 while the substrate holder 118 remains electrically neutral; and during a second stage of the process, both the dispensing assembly 116 and the substrate holder 118 may remain electrically neutral. As another example, during the first stage of the process, power may be supplied to the dispensing assembly 116 from the signal generator 124 while the substrate holder 118 remains electrically neutral; during the second stage of the process, both the dispensing assembly 116 and the substrate holder 118 may remain electrically neutral; and during a third phase of the process, power may be supplied to the substrate holder 118 from the additional signal generator 132 while the dispensing assembly 116 remains electrically neutral.

The continuity (or discontinuity) of the bias applied to a given component of the PECVD apparatus 104 (e.g., the dispensing assembly 116, the substrate holder 118, and the coil structure 134) over a given period of time may also be used to control the characteristics of the metal-containing material formed on, over, or within the substrate 126. Pulsed signals (e.g., pulsed RF (prf) signals, pulsed DC (pdc) signals) may be used to bias different components of the PECVD apparatus 104, and/or non-pulsed signals (e.g., continuous signals, such as continuous RF signals, continuous DC signals) may be used to bias different components of the PECVD apparatus 104. In some embodiments, a pulsed signal including a burst of current (e.g., RF current, DC) is used to bias one or more components of the PECVD apparatus 104. For example, pulsing the applied current may facilitate heat dissipation during the quiet period. Duty cycle (t) of the applied bias waveform if a pulsed signal is used₁/T₁Wherein t is₁Is the pulse width and T₁The frequency of the pulsed or modulated signal) may be controlled to facilitate desired characteristics of metal-containing materials formed on, over, or within the substrate 126. For example, increasing the duty cycle of the bias waveform applied to one or more of the substrate holder 118 and the dispensing assembly 116 may reduce (or even eliminate) undesirable impurities and/or void spaces within the metal-containing material.

During and/or after the formation of the metal-containing material on, over, or within the substrate 126, an exhaust gas comprising unreacted material (e.g., precursor material, inert gas, noble gas ions, metal atoms, metal-containing molecules, metal-containing ions, carbon atoms, carbon-containing molecules, carbon-containing ions, boron atoms, boron-containing molecules, boron-containing ions, carrier gas) and/or reaction byproducts may exit the PECVD apparatus 104. The at least one effluent fluid stream 150 comprising unreacted materials and/or reaction byproducts may then be directed (e.g., by the flow path switching device 144) to one or more additional apparatuses (e.g., effluent fluid treatment apparatus 146) and further processed, utilized, and/or disposed of as desired.

Before and/or after forming the metal-containing material on, over, or within the substrate 126, the PECVD apparatus 104 may perform at least one chamber cleaning process to remove one or more materials (e.g., contaminant materials; residual materials, such as one or more of residual unreacted materials, residual reaction product materials, and residual reaction byproduct materials) from the surfaces of the PECVD apparatus 104 within the inner chamber 120. The chamber cleaning process may include directing one or more chamber cleaning fluid flows 152 (e.g., one or more gaseous chamber cleaning fluid flows) into the inner chamber 120 of the PECVD apparatus 104 through one or more inlets in the housing structure 114 (e.g., in the lid 122 of the housing structure 114). The chamber cleaning fluid stream 152 may include one or more chamber cleaning materials and/or derivatives thereof from the chamber cleaning material source 138 (e.g., ions generated from the chamber cleaning materials by the additional ionization device 140).

Within the inner chamber 120, chamber cleaning materials and/or derivatives thereof may interact with and remove undesirable materials of the surface of the PECVD apparatus 104. The chamber cleaning process may be accomplished with or without generating a plasma (e.g., using voltages applied to one or more of the distribution assembly 116, the substrate holder 118, and the coil structure 134) within the inner chamber 120 of the PECVD apparatus 104 (e.g., from chamber cleaning materials and/or derivatives thereof).

During and/or after removing undesirable materials from the surfaces of the PECVD apparatus 104 within the inner chamber 120, exhaust gases including unreacted materials (e.g., chamber cleaning materials, unreacted ions formed from the chamber cleaning materials) and/or reaction products may exit the PECVD apparatus 104. The at least one effluent cleaning fluid stream 154 comprising unreacted materials and/or reaction products may then be directed (e.g., by the flow path switching device 144) to one or more additional apparatuses (e.g., the chamber cleaning material source 138, another apparatus) and further processed, utilized, and/or disposed of as desired.

Thus, in accordance with an embodiment of the present disclosure, a method of forming a microelectronic device includes directing a feed fluid stream into a chemical vapor deposition apparatus containing a substrate structure. The feed fluid stream includes at least one metal-containing precursor material in one or more of a liquid state and a solid state. Forming a plasma within the chemical vapor deposition apparatus using the at least one feed fluid stream. Forming a metal-containing material on the base structure using the plasma.

Fig. 2 illustrates a simplified partial cross-sectional view of a microelectronic device structure 200 that may be formed using the material deposition system 100 and the method previously described with reference to fig. 1, in accordance with an embodiment of the present disclosure. The microelectronic device structure 200 may be used within and/or may be used to form the microelectronic device of the present disclosure. As shown in fig. 2, the microelectronic device structure 200 may include a base structure 202 and a metal-containing material 204 on or over the base structure 202. The base structure 202 may correspond to the substrate 126 previously described with reference to FIG. 1, and the metal-containing material 204 may correspond to a metal-containing material formed on the substrate 126 using the PECVD process previously described with reference to FIG. 1. In some embodiments, the metal-containing material 204 includes M₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_y、M₁M₂B_xC_yWherein M is₁And M₂Are metals selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc, respectively.

As shown in fig. 2, the metal-containing material 204 may be formed to include a region 204A on the base structure 202, and at least one additional region 204B on the region 204A. The additional region 204B may be formed to be substantially similar to the region 204A (e.g., having substantially the same material composition, material distribution, and thickness), or may be formed to be different from the region 204A (e.g., having a different material composition, different material distribution, and/or different thickness). In some embodiments, region 204A and additional region 204B each include atoms of one or more of B and C and atoms of one or more of Ta, Hf, Zn, V, Ir, Zr, W, Nb, and Sc, respectively. The region 204A and the additional region 204B may each be substantially free of void space and/or elements other than B, C, Ta, Hf, Zn, V, Ir, Zr, W, Nb, and Sc, respectively.

In some embodiments, the region 204A and the additional region 204B of the metal-containing material 204 are each respectively formed to exhibit a substantially uniform distribution of its elements (e.g., metals, such as one or more of Ta, Hf, Zn, V, Ir, Zr, W, Nb, and Sc; other elements, such as one or more of C and B) such that the elements of the region 204A and the additional region 204B are substantially uniformly distributed throughout the region 204A and the additional region 204B. In additional embodiments, at least one of the region 204A and the additional region 204B of the metal-containing material 204 is formed to exhibit a non-uniform distribution of one or more elements thereof, such that the elements of the region 204A and/or the additional region 204B are non-uniformly distributed throughout the region 204A and/or the additional region 204B. For example, the region 204A and the additional region 204B may each exhibit a non-uniform distribution of their metals. In such embodiments, the amount of metal may vary throughout the thickness (e.g., the vertical dimension in the Z-direction) of the region 204A and/or the additional region 204B. If the region 204A and/or the additional region 204B exhibit a non-uniform distribution of its elements, the amount of the elements may change stepwise (e.g., abruptly) or may change continuously (e.g., progressively, such as in a linear or parabolic manner) throughout the thickness of the region 204A and/or the additional region 204B.

The metal-containing material 204, including its different vertical regions, such as the region 204A and the additional region 204B, may exhibit a desired height H (e.g., an overall vertical dimension in the Z-direction). The height H of the metal-containing material 204 may be selected based at least in part on the desired function of the metal-containing material 204. By way of non-limiting example, in some embodiments in which the metal-containing material 204 serves as a hard mask material for a subsequent HAR etch process (e.g., a low temperature etch process) to form HAR structures (e.g., structures having an aspect ratio of greater than or equal to about 5:1 (e.g., greater than or equal to 10:1, greater than or equal to 25:1, greater than or equal to 50:1, greater than or equal to 100:1, or in a range from about 5:1 to about 100: 1) from portions of the base structure 202, the metal-containing material 204 may be formed to have a height H in a range from about 2 micrometers (μm) to about 3 μm.

Thus, in accordance with an embodiment of the present disclosure, a microelectronic device includes a microelectronic device structure including a metal-containing material formed by plasma-enhanced chemical vapor deposition overlying a base structure. The metal-containing material comprises M on the base structure₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_yAnd M₁M₂B_xC_yWherein M is₁And M₂Are metals selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc, respectively.

After forming the metal-containing material 204, the microelectronic device structure 200 may be subjected to further processing, if desired. In some embodiments, the microelectronic device structure 200 is subjected to at least one etching process to form HAR structures from portions of the base structure 202 using one or more portions of the metal-containing material 204 as a hard mask. For example, the microelectronic device structure 200 may be subjected to at least one low temperature etching process to form HAR structures using the metal-containing material 204 as a hard mask. The metal-containing material 204 may alleviate many of the problems associated with forming HAR structures using conventional hard mask materials. For example, the metal-containing material 204 may be thinner than conventional hard mask materials, may have improved stress characteristics compared to conventional hard mask materials, and/or may require less processing for its formation and/or use compared to conventional hard mask materials.

Thus, in accordance with an embodiment of the present disclosure, a method of forming a microelectronic device includes forming a metal-containing material on a base structure by plasma-enhanced chemical deposition. The metal-containing material comprises one or more of carbon and boron; and one or more of tantalum, hafnium, zinc, vanadium, iridium, zirconium, tungsten, niobium, and scandium. Etching the base structure using the metal-containing material as a hard mask.

The material deposition systems (e.g., material deposition system 100 (fig. 1)), methods, microelectronic device structures (e.g., (microelectronic device structure 200 (fig. 2)), and microelectronic devices of the present disclosure facilitate reduced costs (e.g., manufacturing costs, material costs), increased miniaturization of components, increased performance, and greater packaging density as compared to conventional material deposition systems, conventional methods, conventional microelectronic device structures, conventional microelectronic devices, and conventional electronic systems.

Non-limiting example embodiments may include:

example 1: a material deposition system, comprising: a precursor source configured to contain at least one metal-containing precursor material in one or more of a liquid state and a solid state; and a chemical vapor deposition apparatus in selective fluid communication with the precursor source and comprising: a housing structure configured and positioned to receive at least one feed fluid stream comprising the at least one metal-containing precursor material; a distribution manifold within the housing structure and in electrical communication with a signal generator; and a substrate holder within the housing structure and spaced apart from the distribution manifold, the substrate holder in electrical communication with an additional signal generator.

Example 2: the material deposition system of embodiment 1, further comprising an ionization device downstream of the precursor source and upstream of the chemical vapor deposition apparatus, the ionization device configured to at least partially ionize the at least one metal-containing precursor material.

Example 3: the material deposition system of embodiment 2, further comprising: a chamber cleaning material source configured to contain at least one chamber cleaning material; and an additional ionization device downstream of the source of chamber cleaning material and upstream of the chemical vapor deposition apparatus, the additional ionization device configured to at least partially ionize the at least one chamber cleaning material.

Example 4: the material deposition system of embodiment 3, wherein the ionization device and the additional ionization device are spaced apart from each other on a sealable cover of the containment structure.

Example 5: the material deposition system of any of embodiments 1-4, wherein the precursor source is configured to contain a flowable solid form of the at least one metal-containing precursor material and is positioned on or over a sealable lid of the containment structure.

Example 6: the material deposition system of any of embodiments 1-4, wherein the precursor source is configured to contain a liquid form of the at least one metal-containing precursor material and is in selective fluid communication with the chemical vapor deposition apparatus through an insulated wire.

Example 7: the material deposition system of any of embodiments 1-6, further comprising a heating apparatus configured and positioned to heat the precursor source.

Example 8: the material deposition system of any of embodiments 1-7, further comprising an effluent fluid treatment apparatus downstream of the chemical vapor deposition apparatus, the effluent fluid treatment apparatus configured to remove one or more materials from at least one effluent fluid stream exiting the housing structure of the chemical vapor deposition apparatus.

Example 9: the material deposition system of embodiment 8, further comprising a bypass apparatus downstream of the chemical vapor deposition apparatus and upstream of the effluent fluid treatment apparatus.

Example 10: the material deposition system of any of embodiments 1-9, further comprising a carrier gas source in selective fluid communication with the precursor source.

Example 11: the material deposition system of any of embodiments 1-10, wherein the chemical vapor deposition apparatus further comprises a coil structure between the distribution manifold and the substrate holder and in electrical communication with another signal generator.

Example 12: a method of forming a microelectronic device, comprising: directing a feed fluid stream into a chemical vapor deposition apparatus containing a substrate structure, the feed fluid stream comprising at least one metal-containing precursor material in one or more of a liquid state and a solid state; forming a plasma within the chemical vapor deposition apparatus using the at least one feed fluid stream; and forming a metal-containing material on the base structure using the plasma.

Example 13: the method of embodiment 12, further comprising selecting the at least one metal-containing precursor material to comprise one or more of a tantalum-containing precursor material, a hafnium-containing precursor material, a zinc-containing precursor material, a vanadium-containing precursor material, an iridium-containing precursor material, a zirconium-containing precursor material, a tungsten-containing precursor material, a niobium-containing precursor material, and a scandium-containing precursor material.

Example 14: the method of one of embodiments 12 and 13, further comprising selecting the at least one metal-containing precursor material to comprise: one or more of boron and carbon; and one or more of tantalum, hafnium, zinc, vanadium, iridium, zirconium, tungsten, niobium, and scandium.

Example 15: the method of any one of embodiments 12-14, further comprising forming the feed fluid stream to include one or more of droplets and solid particles of the at least one metal-containing precursor suspended in a carrier gas.

Example 16: the method of any of embodiments 12-15, wherein forming a plasma within the chemical vapor deposition apparatus comprises applying a voltage to one or more of a distribution manifold, a substrate holder offset from the distribution manifold, and a coil structure between the distribution manifold and the substrate holder to form the plasma from a component of the at least one feed fluid stream.

Example 17: the method of any one of embodiments 12-16, further comprising ionizing at least a portion of the at least one metal-containing precursor material of the feed fluid stream prior to directing the feed fluid stream into the chemical vapor deposition apparatus.

Example 18: the method of any one of embodiments 12-17, wherein forming a metal-containing material on the base structure using the plasma comprises forming one or more of a metal boride-containing material, a metal carbide-containing material, and a metal borocarbide-containing material on the base structure using the plasma.

Example 19: the method of any of embodiments 12-18, further comprising trapping one or more of unreacted precursors and reaction byproducts of the at least one metal-containing precursor material from the formation of the metal-containing material in at least one effluent fluid treatment apparatus downstream of the chemical vapor deposition apparatus.

Example 20: a microelectronic device comprising a microelectronic device structure including a metal-containing material overlying a base structure formed by plasma-enhanced chemical vapor deposition, the metal-containing material comprising M on the base structure₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_yAnd M₁M₂B_xC_yWherein M is₁And M₂Are each a metal selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc.

Example 21: the microelectronic device of embodiment 20, wherein the metal-containing material has a thickness in a range from about 2 microns to about 3 microns.

Example 22: the microelectronic device of one of embodiments 20 and 21, wherein the metal-containing material has a non-uniform distribution of one or more elements thereof.

Example 23: a method of forming a microelectronic device, comprising: forming a metal-containing material on a base structure by plasma-enhanced chemical deposition, the metal-containing material comprising: one or more of carbon and boron; and one or more of tantalum, hafnium, zinc, vanadium, iridium, zirconium, tungsten, niobium, and scandium; and etching the base structure using the metal-containing material as a hard mask.

Example 24: the method of embodiment 23, wherein forming a metal-containing material on a base structure comprises forming a M on the base structure₁C_x、M₁M₂C_x、M₁B_x、M₁M₂B_x、M₁B_xC_yAnd M₁M₂B_xC_yWherein M is₁And M₂Are metals selected from Ta, Hf, Zn, V, Ir, Zr, W, Nb and Sc, respectively.

Example 25: the method of any one of embodiments 23 and 24, wherein etching the base structure using the metal-containing material as a hard mask comprises low temperature etching the base structure.

Example 26: the method of any of embodiments 23-25, wherein etching the base structure using the metal-containing material as a hard mask comprises forming high aspect ratio structures from portions of the base structure, the high aspect ratio structures having aspect ratios in a range from about 5:1 to about 100:1, respectively.

While the disclosure is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, the disclosure is not intended to be limited to the particular forms disclosed. Rather, the disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the following appended claims and their legal equivalents. For example, elements and features disclosed with respect to one embodiment may be combined with elements and features disclosed with respect to other embodiments of the present disclosure.