Nano-powders, nano-ceramic materials and methods of making and use thereof

Abstract

To provide nano-powders.SOLUTION: Provided are nano-powders containing nanoparticles having core particles with thin film coatings. The core particles and thin film coatings are, independently, formed from at least one of a rare earth metal-containing oxide, a rare earth metal-containing fluoride, a rare earth metal-containing oxyfluoride, or combinations thereof. The thin film coatings may be formed using a non-line-of-sight technique such as atomic layer deposition (ALD).SELECTED DRAWING: Figure 3A

Description

Technical Field

[0001] Embodiments of the present specification relate to nano powders, nano ceramic materials, and methods for manufacturing and using them. The nano powder includes nanoparticles having thin-film coated core particles. The core particles and the thin-film coating are each independently formed from at least one of a rare earth metal-containing oxide, a rare earth metal-containing fluoride, a rare earth metal-containing fluoroacid, or a combination thereof. The thin-film coating can be formed using a non-transparent technique such as atomic layer deposition (ALD). Background

[0002] Various semiconductor manufacturing processes use high temperatures, high-energy plasmas, mixtures of corrosive gases, high stress, and combinations thereof. These extreme conditions expose components in the processing chamber to plasma irradiation, leading to process drift and particle generation. For example, fluorine-based plasmas used in dry etching and cleaning processes can cause fluorination of the surfaces of components. Components in the chamber typically contain alumina. This has caused serious erosion and particle generation problems in the manufacture of nanometer-scale devices.

[0003] Protective coatings are typically deposited on chamber components by various methods (such as thermal spraying, sputtering, plasma spraying, or evaporation techniques, etc.). However, such coatings may have mechanical properties (such as bending strength and fracture toughness) that are insufficient for semiconductor processing. Such coatings typically have a microcrystalline structure. Summary

[0004] The embodiments described herein are nano-powders containing a plurality of nanoparticles, wherein at least a part of the plurality of nanoparticles includes core particles containing a first material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof, and a thin film coating on the core particles, the thin film coating including a second material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof.

[0005] Furthermore, the embodiments described herein include a step of performing atomic layer deposition to form a plurality of nanoparticles, the step including forming a thin film coating on the core particles, the core particles including a first material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof, and the thin film coating including a second material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof.

[0006] Furthermore, the embodiments described herein are methods of forming nano-ceramic components, including: (a) filling a mold with a plurality of nanoparticles, at least a part of the plurality of nanoparticles including core particles containing a first material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof, and a thin film coating on the core, the thin film coating including a second material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof; and (b) sintering the plurality of nanoparticles to form a nano-ceramic component.

Brief Description of the Drawings

[0007] This disclosure is shown by way of example and not limitation in the figures of the accompanying drawings in which like references indicate like elements. It should be noted that different references to "one" or "a" embodiment in this disclosure are not necessarily references to the same embodiment, and such references mean at least one.

Figure 1

Figure 2

Figure 3A

Figure 3B

Figure 4

[0008] Embodiments described herein relate to nano-powders, nano-ceramic materials, and methods for their preparation and use. The nano-powders include nanoparticles having core particles at least partially coated with a thin film. The core particles and the thin film coating are composed of different materials independently selected from at least one of rare earth metal-containing oxides, rare earth metal-containing fluorides, or rare earth metal-containing oxyfluorides.

[0009] Figure 1 represents a nano-powder 100 containing a plurality of nanoparticles 105 according to the embodiments described herein. As shown in Figure 1, at least a portion of each nanoparticle includes a core particle 110 and a thin film coating 115 on the core particle. In certain embodiments, the core particle 110 of the nanoparticle 105 is formed from a powder containing a first material selected from rare earth metal-containing oxides, rare earth metal-containing fluorides, rare earth metal-containing oxyfluorides, or combinations thereof. In certain embodiments, the size of the core particle 110 is from about 5 nm to about 100 nm, from about 10 nm to about 90 nm, from about 20 nm to about 80 nm, or from about 30 nm to about 70 nm. In some embodiments, the size of the core particle is about 5 nm, about 10 nm, about 20 nm, about 30 nm, or less than about 100 nm.

[0010] It should be noted that the embodiments are described herein with reference to nanoparticles. However, it should be understood that the embodiments also function with microparticles having sizes on the order of about 1 to 100 microns.

[0011] In certain embodiments, the thin film coating 115 on the core particle 110 is formed from a second material selected from rare earth metal-containing oxides, rare earth metal-containing fluorides, rare earth metal-containing oxyfluorides, or combinations thereof. The second material of the thin film coating 115 is different from the first material of the core particle 110. In certain embodiments, the thickness of the thin film coating 115 can be from about 1 nm to about 500 nm, from about 1 nm to about 250 nm, from about 1 nm to about 100 nm, from about 1 nm to about 50 nm, from about 1 nm to about 25 nm, from about 1 nm to about 10 nm, from about 1 nm to about 5 nm, from about 30 nm to about 40 nm, or from about 3 nm to about 5 nm. In some embodiments, the thickness of the thin film coating can be about 1 nm, about 3 nm, about 4 nm, about 5 nm, about 10 nm, about 25 nm, about 50 nm, or about 100. In an embodiment, the thin film coating 115 is about 1 g / cm 3 ~ about 20 g / cm 3 、 about 2 g / cm 3 ~ about 15 g / cm 3 、 about 3 g / cm 3 ~ about 10 g / cm 3or 4 g / cm 3 ~ about 7 g / cm 3 and has a density. In some embodiments, the density of the thin film coating 115 is about 1 g / cm 3 about 2 g / cm 3 about 3 g / cm 3 about 4 g / cm 3 about 5 g / cm 3 about 6 g / cm 3 or about 7 g / cm 3 and has a density. The nanoparticles 105 in the nanopowder 100 according to the embodiments described herein are about 5 nm to about 600 nm, about 10 nm to about 300 nm, about 25 nm to about 250 nm, or about 50 nm to about 100 nm.

[0012] As shown in FIG. 1, at least a portion of the nanoparticles 105 in the nanopowder 100 have a thin film coating 115. In some embodiments, at least a portion of the nanoparticles are completely coated with a thin film coating 120. In some embodiments, at least a portion of the nanoparticles are partially coated with a thin film coating 125. In certain embodiments, at least about 5%, about 10%, about 25%, about 50%, about 75%, about 90%, or about 95% of the nanoparticles 105 in the nanopowder 100 are at least partially coated. In certain embodiments, at least about 5%, about 10%, about 25%, about 50%, about 75%, about 90%, or about 95% of the nanoparticles 105 in the nanopowder 100 are completely coated with a thin film coating.

[0013] The first material of the core particles 110 and the second material of the thin film coating 115 are independently selected from rare earth metal-containing oxides, rare earth metal-containing fluorides, rare earth metal-containing oxyfluorides, and combinations thereof. The first material and the second material can contain common elements, but the first material is different from the second material. The rare earth metals in the first material and / or the second material can be selected from yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, and / or dysprosium. Examples of rare earth metal-containing oxides include, but are not limited to, yttria (Y2O3), erbium oxide (Er2O3), dysprosium oxide (Dy2O3), gadolinium oxide (Gd2O3), scandium oxide (Sc2O3), combinations thereof, and the like. Examples of rare earth metal-containing fluorides include, but are not limited to, yttrium fluoride (YF3), erbium fluoride (ErF3), dysprosium fluoride (DyF3), gadolinium fluoride (GdF3), scandium fluoride (ScF3), combinations thereof, and the like. Examples of rare earth metal-containing oxyfluorides include, but are not limited to, yttrium oxyfluoride (Y x O y F z or YOF), erbium oxyfluoride (Er x O y F z ), dysprosium fluoride (DyF3), dysprosium oxyfluoride (Dy x O y F z ), gadolinium oxyfluoride (Gd x O y F z ), scandium oxyfluoride (Sc x O y F z ), combinations thereof, and the like.

[0014] In certain embodiments, the core particles 110 and / or the thin film coating 115 are Y2O3, Y3Al5O 12 (YAG), Y4Al2O9 (YAM), YF3, YOF, Er2O3, Er3Al5O 12(EAG), ErF3, EOF, La2O3, Lu2O3, Sc2O3, ScF3, ScOF, Gd2O3, Sm2O3, or Dy2O3 can be included. Further, the core particles 110 and / or the thin film coating 115 can be YAlO3 (YAP), Er4Al2O9 (EAM), ErAlO3 (EAP), or other ternary variants of lanthanum, lutetium, scandium, gadolinium, samarium, or dysprosium. The aforementioned rare earth metal-containing materials may contain trace amounts of other materials (e.g., ZrO2, Al2O3, SiO2, B2O3, Er2O3, Nd2O3, Nb2O5, CeO2, Sm2O3, Yb2O3, and / or other oxides, etc.).

[0015] In some embodiments, the nano-powder 100 containing a plurality of nanoparticles 105 comprises from about 40 mol% to about 90 mol%, from about 50 mol% to about 80 mol%, or from about 60 mol% to about 70 mol% of yttrium oxide and from about 10 mol% to about 60 mol%, from about 20 mol% to about 50 mol%, or from about 30 mol% to about 40 mol% of zirconium oxide. In certain embodiments, the nano-powder 100 containing a plurality of nanoparticles 105 comprises from about 60 mol% to about 70 mol% of yttrium oxide and from about 30 mol% to about 40 mol% of zirconium oxide. In some embodiments, the core particles 110 are zirconium oxide and the thin film coating 115 is yttrium oxide. In some embodiments, the core particles 110 are yttrium oxide and the thin film coating 115 is zirconium oxide. In some embodiments, the ratio of the rare earth metal-containing oxide, rare earth metal-containing fluoride, rare earth metal-containing oxyfluoride, or combinations thereof in the core to the rare earth metal-containing oxide, rare earth metal-containing fluoride, rare earth metal-containing oxyfluoride, or combinations thereof in the thin film coating can be from about 1:100 to about 100:1, from about 1:75 to about 75:1, from about 1:50 to about 50:1, from about 1:35 to about 35:1, from about 1:20 to about 20:1, from about 1:15 to about 15:1, from about 1:10 to about 10:1, from about 1:5 to about 5:1, or from about 1:100 to about 35:1.

[0016] In certain embodiments where the core particles are formed of ZrO2, have a size of about 100 nm, and the thin film coating is formed of Y2O3 with various thicknesses, the concentration (mol %) of each component can be shown in Table 1. Similarly, Table 1 shows the concentration of each component where the core particles are formed of Y2O3, have a size of about 100 nm, and the thin film coating is formed of ZrO2 with various thicknesses.

[0017] [Table 1] JPEG2025106378000003.jpg161169

[0018] Referring to Table 1, in certain embodiments, for a composition where the ratio of Y2O3 (thin film coating) to ZrO2 (core particles) achieves about 60 mol % to about 70 mol %, the thickness of the Y2O3 thin film coating (i.e., the "shell") should be in the range of about 30 nm to about 40 nm. Similarly, for Y2O3 core particles of about 100 nm, in certain embodiments, for a composition where the ratio of Y2O3 (core particles) to ZrO2 (thin film coating) achieves about 60 mol % to about 70 mol %, the thickness of the ZrO2 thin film coating should be in the range of about 3 nm to about 5 nm.

[0019] Figure 2 shows the nanoparticles 205 in the nanopowder 200 according to at least one embodiment described herein. At least a portion of the nanoparticles 205 can have a spherical shape with a deep indentation 210 on the opposite side of the sphere. That is, some of the nanoparticles 205 can have a donut shape 215. Without being bound by a particular theory, in some embodiments, a nanocoating formed from a nanopowder 200 having nanoparticles 205 with a donut shape 215 can be thought to have improved morphology and porosity compared to nanocoatings formed with nanoparticles of other shapes. For example, a nanocoating formed from nanoparticles 205 having a donut shape 215 can have fewer nodules and splats due to improved melting of the nanopowder, reduced roughness, and reduced porosity, all of which contribute to improved on-wafer particle performance.

[0020] A nanopowder having a plurality of nanoparticles according to the embodiments described herein can be formed using atomic layer deposition (ALD). ALD enables the controlled self-limiting deposition of materials through chemical reactions with the surface of a substrate (e.g., the starting material of the core particles). ALD is not only a conformal process but also a uniform process and can form very thin films, for example, of about 1 nm or more. The same or approximately the same amount of material is deposited on all exposed surfaces of the core particles. A typical reaction cycle of the ALD process begins with a precursor (i.e., a single chemical A) being injected into the ALD chamber and adsorbed onto the exposed surfaces of the core particles. Next, a reactant (i.e., a single chemical R) is introduced into the ALD chamber, followed by rinsing away the excess precursor from the ALD chamber before it is rinsed away. In the case of ALD, each reaction cycle grows a layer of a specific thickness that is one atomic layer or a fraction of an atomic layer, so the final thickness of the material depends on the number of reaction cycles executed. The ALD technique can deposit thin layers of materials at relatively low temperatures (e.g., about 25°C to about 350°C) without damaging the starting material.

[0021] ALD is particularly useful for forming rare earth metal-containing nanopowders as described herein. In conventional in-situ deposition methods, thicker coatings are produced on the core particles than those deposited by ALD. In fact, such conventional methods can cause aggregation leading to micron-sized particles. Such particles are too large to be used in nanoscale device manufacturing. Thus, the result of several embodiments herein is to apply a thin film coating to the core particles to produce a nanopowder containing a plurality of nanoparticles that are resistant to the harsh plasma and reactant conditions within the processing chamber. Such nanopowders can be used, for example, as a base material for a plasma spraying process, to form a target for an ion assist evaporation sputtering device, or to form a nanoceramic component (e.g., filling a mold of a component with the nanopowder and sintering the nanopowder to form a nanoceramic component).

[0022] The thin film coating on the core particles described herein can be formed using ALD with a rare earth metal-containing precursor and one or more reactants consisting of or containing oxygen and / or fluorine. Oxygen reactants suitable for forming a metal oxide layer may be oxygen, water vapor, ozone, pure oxygen, oxygen radicals, or other oxygen sources. Suitable fluoride reactants for forming a metal fluoride layer may be, for example, fluorides (e.g., TiF4, HF) or other fluorine sources.

[0023] The rare earth metal-containing precursor can include, but is not limited to, yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, or dysprosium. Examples of suitable yttrium precursors include, but are not limited to, tris(N,N-bis(trimethylsilyl)amide)yttrium(III) or yttrium(III) butoxide, and the corresponding reactant may be O2, H2O, or O3. Examples of suitable erbium precursors include, but are not limited to, tris-methylcyclopentadienylerbium(III) (Er(MECp)3), erbium boranamide (Er(BA)3), Er(TMHD)3, erbium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), or tris(butylcyclopentadienyl)erbium(III), and the corresponding reactant may be O2, H2O, or O3.

[0024] There are various types of ALD processes, and a specific type can be selected based on several factors such as the substrate to be coated, the coating material, and the chemical interaction between the surface and the coating material. The principle of various ALD processes involves growing a thin film layer by repeatedly exposing the surface to be coated to pulses of gaseous chemical precursors that react chemically with the surface one at a time in a self-limiting manner.

[0025] In an exemplary embodiment, a first process for forming a rare earth metal-containing oxyfluoride thin film coating can include performing x atomic layer deposition (ALD) cycles to form a first rare earth oxide layer on core particles. The process can further include performing y ALD cycles to form a first rare earth fluoride thin film layer on the first rare earth oxide thin film layer. The first rare earth oxide layer and the first rare earth fluoride layer can include the same rare earth metal. The process can further include performing in situ at least one of diffusion of fluorine from the first rare earth fluoride layer into the first rare earth metal-containing oxide layer or diffusion of oxygen from the first rare earth metal-containing oxide layer into the first rare earth metal-containing fluoride layer to form a first rare earth metal-containing oxyfluoride thin film coating. The first rare earth metal-containing oxyfluoride thin film coating can have a molar ratio of oxygen to fluorine based on x and y.

[0026] In an exemplary embodiment, a second process for forming a rare earth oxyfluoride thin film coating on core particles can include performing ALD cycles to form a first rare earth oxyfluoride layer on the surface of the core particles. The first rare earth oxyfluoride layer can have a target molar oxygen to fluorine ratio. The ALD cycles can include forming a first absorption layer of a rare earth metal on the surface of the core particles by injecting a rare earth metal-containing precursor into a deposition chamber containing the core particles. Further, the ALD cycles can include co-injecting at least one oxygen-containing reactant at a first dosage rate and at least one fluorine-containing reactant at a second dosage rate into the deposition chamber to react the at least one oxygen-containing reactant and the at least one fluorine-containing reactant with the first absorption layer.

[0027] In an exemplary embodiment, a third process for forming a rare earth fluoride thin film coating on the core particles can include performing z ALD cycles to form a first rare earth metal-containing oxide layer on the surface of the core particles. Further, the process can include exposing the core particles to a fluorine-containing species. Further, the process can include converting the first rare earth metal-containing oxide layer to a first rare earth metal-containing fluorinated oxide thin film coating. Further, the process can include performing at least one additional ALD cycle to form an additional rare earth oxide layer. Further, the process can include exposing the core particles to a fluorine-containing species. Further, the process can include converting the additional rare earth metal-containing oxide layer to an additional rare earth metal-containing fluorinated oxide thin film coating.

[0028] These processes can be repeated to form additional rare earth fluoride layers until the target thickness is reached.

[0029] Figure 3A shows a method 300 for preparing a nanopowder comprising a plurality of nanoparticles according to an embodiment. At block 304, method 300 can optionally begin by selecting a starting material of core particles or by forming the starting material using an inverse strike co-precipitation process for controlling the particle size distribution known to those skilled in the art. The selection or formation of the starting material may be performed by the same entity or a different entity that forms the nanopowder by ALD. In some embodiments, the core particles in the starting material may be pure yttrium oxide, pure zirconium oxide, or a composite of yttrium oxide and zirconium oxide of about 60 mol% to about 70 mol% yttrium oxide and about 30 mol% to about 40 mol% zirconium oxide.

[0030] At block 305, the starting material comprising the core particles is loaded into an ALD deposition chamber. For example, the core particles may be in the form of a powder introduced into the reaction chamber using various methods known to those skilled in the art.

[0031] In block 310, method 300 includes depositing a thin film coating on at least a portion of the core particles using ALD. Surface reactions (e.g., half-reactions) are performed continuously, and the precursor and reactant do not contact in the embodiment. Before introducing the precursor or reactant material, the chamber in which the ALD process is performed can be purged with an inert carrier gas (such as nitrogen or air) to remove unreacted precursors and / or surface precursor by-products. The ALD process can be executed at various temperatures depending on the type of the process. The optimal temperature range of a specific ALD process is called the "ALD temperature window". At temperatures below the ALD temperature window, the growth rate decreases and non-ALD type deposition may occur. At temperatures above the ALD temperature window, reactions via chemical vapor deposition (CVD) mechanisms may occur. The ALD temperature window may be in the range of about 100°C to about 650°C. In some embodiments, the ALD temperature window is about 20°C to about 200°C, about 25°C to about 150°C, about 100°C to about 120°C, or about 20°C to 125°C.

[0032] The ALD process can provide a conformal thin film coating having a uniform thickness on the core particles. Sufficient exposure time of the precursor to the surface of the core particles enables the precursor to disperse and react completely with the core particles. Further, the ALD technology is superior to other commonly used coating technologies because it enables on-demand material synthesis on-site of a specific composition or formulation without the long and difficult manufacturing of source materials (such as powder raw materials and sintered targets).

[0033] The thin film coating can have a thickness of from about 1 nm to about 500 nm, from about 1 nm to about 250 nm, from about 1 nm to about 100 nm, from about 1 nm to about 50 nm, from about 1 nm to about 25 nm, from about 1 nm to about 10 nm, or from about 1 nm to about 5 nm. In some embodiments, the thickness of the thin film coating may be about 1 nm, about 5 nm, about 25 nm, about 50 nm, or about 100 nm. In some embodiments, the ratio of the rare earth metal-containing oxide, rare earth metal-containing fluoride, rare earth metal-containing oxyfluoride or combinations thereof in the core to the rare earth metal-containing oxide, rare earth metal-containing fluoride, rare earth metal-containing oxyfluoride or combinations thereof in the thin film coating may be from about 1:100 to about 100:1, from about 1:75 to about 75:1, from about 1:50 to about 50:1, from about 1:35 to about 35:1, from about 1:20 to about 20:1, from about 1:15 to about 15:1, from about 1:10 to about 10:1, from about 1:5 to about 5:1, or from about 1:100 to about 35:1. In some embodiments, at least about 90%, at least about 80%, at least about 70%, at least about 60%, at least about 50%, at least about 40%, at least about 30%, at least about 20%, at least about 10%, at least about 5%, at least about 1% of the core particles in the nanopowder are coated with the thin film. In the case of individual nanoparticles, the thin film coating can cover the entire core particle or only a portion of the core particle (e.g., about 90%, about 80%, about 70%, about 60%, about 50%, about 40%, about 30%, about 20%, about 10%, about 5%, or about 1%).

[0034] In block 315, the generated nano-powder containing a plurality of nano-particles is collected. The nano-particles in the nano-powder may be from about 5 nm to about 600 nm, from about 10 nm to about 300 nm, from about 25 nm to about 250 nm, or from about 50 nm to about 100 nm. The nano-particles are spherical, and all sides may be rounded, or in some embodiments, they may have a donut shape as described above. In some embodiments, the weight ratio of the rare-earth metal-containing oxide, rare-earth metal-containing fluoride, rare-earth metal-containing oxyfluoride, or combinations thereof in the core particles to the rare-earth metal-containing oxide, rare-earth metal-containing oxyfluoride, rare-earth metal-containing oxyfluoride, or combinations thereof in the thin-film coating is from about 1:100 to about 100:1, from about 1:75 to about 75:1, from about 1:50 to about 50:1, from about 1:35 to about 35:1, from about 1:20 to about 20:1, from about 1:15 to about 15:1, from about 1:10 to about 10:1, from about 1:5 to about 5:1, or from about 1:100 to about 35:1.

[0035] Figure 3B shows method 301 using the nano powder formed by method 300. The nano powder collected from the ALD chamber at block 315 can be used in a variety of different ways. In one example, at block 320, the nano powder can be used to form a sputtering target for an ion assisted deposition (IAD) process. The nano powder can be used to form a protective coating on an article using the IAD process. The material source is a target formed from the nano powder that provides a flux of the deposition material, while the energy particle source provides a flux of energy particles (i.e., nano particles from the target). Both of these impinge on the article throughout the IAD process. The target used to provide the deposition material may be a bulk sintered ceramic formed from a nano powder as described herein. In embodiments, one or more plasmas or beams can be utilized to provide the deposition material and the high energy ion source. Reactant species can also be provided during the deposition of the protective coating. In the IAD process, the energy particles can be controlled by an energy ion (or other particle) source independent of the other deposition parameters. The composition, structure, crystal orientation, and particle size of the protective coating on the article can be manipulated by the energy (e.g., velocity) and the density and angle of incidence of the energy ion flux. Additional parameters that can be adjusted are the temperature of the article during deposition and the deposition time. Ion energy is broadly divided into low energy ion assist and high energy ion assist. The ions are irradiated at a higher speed with high energy ion assist than with low energy ion assist.

[0036] In other examples, at block 325, the nano powder can be plasma sprayed (sprayed) onto an article. For example, the nano powder can be plasma sprayed onto an article, and the article can include, but is not limited to, a chamber wall, a shower head, a nozzle, a plasma generation unit (e.g., a high-frequency electrode having a housing), a diffuser, and a gas line. Before plasma spraying the nano powder to form a coating, the article can be roughened. Roughening can be performed, for example, by bead blasting the article. Roughening the article provides anchor points for creating a mechanical bond between the plasma-sprayed nano powder and the surface of the article, achieving better adhesion. The coating obtained from the plasma-sprayed nano powder can have a thickness of up to about 200 microns or more as sprayed, and in some embodiments, can be polished down to a final thickness of about 50 microns. The plasma-sprayed nano powder coating can have a porosity of about 2% to about 4%.

[0037] In other examples, at block 330, the mold for the component can be filled with nano powder and then formed into a nanoceramic component (e.g., by sintering).

[0038] At block 335, a nano powder containing a plurality of nanoparticles can be sintered to form a nanoceramic material. Sintering is a method of forming a bulk material from a powder using heat, pressure, and / or energy. In some embodiments, the plurality of nanoparticles are sintered by applying a temperature of about 2730°F to about 3275°F and / or a pressure of about 25 MPa to about 1 GPa. The powder can be various materials (e.g., metals, ceramics, etc.) having particles of various sizes in the range from nanometers to micrometers. The powder can be single-phase or more complex having two or more components.

[0039] Examples of sintering techniques include, but are not limited to, atmospheric pressure sintering, spark plasma sintering, and high pressure sintering. In an embodiment, the nano powder is sintered using a spark plasma sintering process (SPS). SPS is a pressure-assisted rapid sintering method using a high temperature plasma (i.e., spark plasma), which is instantaneously generated in the gas between powder materials by discharge during on and off direct current (DC) pulses. The DC current may generate several effects including spark plasma, spark impact pressure, Joule heating, and electric field diffusion effect. Due to these effects, SPS can rapidly consolidate the power to a density close to the theory through the combined effects of rapid heating, pressure, and cleaning of the powder surface.

[0040] In other embodiments, the nano powder is sintered using an enhanced pressure-assisted sintering process (EPAS). EPAS utilizes a pressure-assisted sintering approach, but incorporates strict environmental control during all steps of nano powder processing and during sintering, so the nano particle surface is clean and free of adsorbates, additives, or sintering aids. Essentially, the surface of the clean nano particles is in a high potential state where the surface energy is maximized and the diffusion mechanisms involved in densification are enhanced. The combination of the pressure effect (such as an increase in the densification rate) and the highly active nano particle surface results in an improved densification rate with controlled coarsening. This makes it possible to produce materials with unprecedented structures, compositions, properties, submicron or nano-scale materials, and composite materials with unique / non-general compositions / performances. EPAS can be used to effectively retard the coarsening mechanism, thereby enabling the retention of the crystallite size of the nano powder.

[0041] Sintering converts the nano powder into a nano ceramic material. The nano ceramic material is, for example, Y3Al5O 12 (YAG), Y4Al2O9 (YAM), YAlO3 (YAP), Y2O3-ZrO2 solid solution, Er3Al5O 12It can include a compound selected from (EAG), Er4Al2O9 (EAM), and ErAlO3 (EAP). In an embodiment, the obtained nanoceramic material can be resistant to fluorine and hydrogen plasmas used during the semiconductor manufacturing process. The nanoceramic material has a density of about 1 kg / cm 3 to about 10 kg / cm 3 ; about 2 kg / cm 3 to about 8 kg / cm 3 ; about 3 kg / cm 3 to about 6 kg / cm 3 ; about 5 kg to about 6 kg / cm 3 ; about 3 kg / cm 3 ; about 4 kg / cm 3 ; about 5 kg / cm 3 ; or about 5.25 kg / cm 3 ; or it can have a density of about 6 kg / cm3. The flexural strength of the obtained nanoceramic material may be about 170 MPA to about 250 MPA, about 190 MPA to about 230 MPA, or about 200 MPA to about 225 MPA. The elastic modulus of the obtained nanoceramic material may be about 100 GPA to about 300 GPA, about 150 GPA to about 275 GPA, or about 195 GPA to about 250 GPA. The Vickers hardness of the obtained nanoceramic material may be about 1 GPA to about 50 GPA, about 5 GPA to about 25 GPA, about 9 GPA to about 20 GPA, or about 9.4 GPA to about 18 GPA. The fracture toughness of the obtained nanoceramic material is about 0.1 Mpam 1 / 2 to about 5.0 Mpam 1 / 2 ; about 0.5 Mpam 1 / 2 to about 4.0 Mpam 1 / 2 ; or about 1.1 Mpam 1 / 2 to about 3.0 Mpam 1 / 2 ; and it may be. The coefficient of thermal expansion (RT - 800C) of the obtained nanoceramic material is about 1.0×10 6 to about 15×10 6 ; about 5.0×10 6 to about 10×10 6 ; or about 8.3×10 6 to about 9.5×10 6 ; and it may be. The volume resistivity of the obtained nanoceramic material is about 1.0×10 16Ohm-cm ~ about 10×10 16 Ohm-cm, about 2.0×10 16 Ohm-cm ~ about 8.0×10 16 Ohm-cm, or about 4.0×10 16 Ohm-cm ~ about 6.0×10 16 Ohm-cm may also be acceptable. The dielectric constant at 13.56 MHz of the resulting nanoceramic material may be about 5 to about 25, about 10 to about 20, or about 15 to about 16.5. The dielectric tangent at 13.56 MHz may be less than about 10×10 4 The thermal conductivity of the resulting nanoceramic material may be about 1.0 W / mK to about 15 W / mK, about 2.5 W / mK to about 10.0 W / mK, or about 3.6 W / mK to about 5.0 W / mK.

[0042] FIG. 4 is a cross-sectional view of a semiconductor processing chamber 400 having one or more chamber components coated or formed with a nanopowder according to an embodiment. The base material of the chamber can include one or more of aluminum (Al), titanium (Ti), and stainless steel (SST). The processing chamber 400 can be used in a process where a corrosive plasma environment having plasma processing conditions is provided. For example, the processing chamber 400 can be a chamber for a plasma etcher, i.e., a plasma etching reactor, a plasma cleaner, a plasma enhanced CVD or ALD reactor, etc. Examples of chamber components that can have a nanoceramic coating or can be formed from the nanopowders described herein include, but are not limited to, showerheads, gas distribution plates, chamber lids, and / or nozzles. A nanoceramic material having a nanocrystalline structure can provide a bulk material having a particle size of less than about 100 nm and properties not seen in microcrystalline materials previously known in the art.

[0043] In one embodiment, the processing chamber 400 includes a chamber body 402 that encloses an internal volume 406 and a showerhead 430. The showerhead 430 can include a showerhead base and a showerhead gas distribution plate. Alternatively, the showerhead 430 can be replaced by a lid and nozzles in some embodiments, or by a plurality of pie-shaped showerhead compartments and a plasma generation unit in other embodiments. The chamber body 402 may be fabricated from other suitable materials such as aluminum, stainless steel, or titanium (Ti). The chamber body 402 generally includes sidewalls 408 and a bottom 410. An outer liner 416 can be disposed adjacent to the sidewalls 408 to protect the chamber body 402.

[0044] An exhaust port 426 can be defined within the chamber body 402 and the internal volume 406 can be coupled to a pump system 428. The pump system 428 can include one or more pumps and throttle valves and can be utilized for evacuating and pressure regulating the internal volume 406 of the processing chamber 400.

[0045] The showerhead 430 can be supported on the sidewalls 408 of the chamber body 402. The showerhead 430 (or lid) can be opened to allow access to the internal volume 406 of the processing chamber 400 and can provide a seal for the processing chamber 400 in a closed state. A gas panel 458 can be coupled to the processing chamber 400 to provide process and / or cleaning gases to the internal volume 406 via the showerhead 430 or lid and nozzles. The showerhead 430 can be used in a processing chamber for dielectric etching (etching of dielectric materials). The showerhead 430 can include a gas distribution plate (GDP) and can have a plurality of gas delivery holes 432 across the GDP. The showerhead 430 can include a GDP coupled to an aluminum base or an anodized aluminum base. The GDP may be made from Si or SiC, or Y2O3, Al2O3, Y3Al5O 12It may also be a ceramic such as (YAG).

[0046] In a processing chamber used for conductor etching (etching of a conductive material), a lid can be used instead of a showerhead. The lid can include a central nozzle that fits into the central hole of the lid. The lid may be a ceramic such as Al2O3, Y2O3, YAG, or a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2. Further, the nozzle may be a ceramic such as Y2O3, YAG, or a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2.

[0047] Examples of the processing gas that can be used to process the substrate in the processing chamber 400 include, among others, halogen-containing gases such as C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, SiF4, and other gases such as O2 and N2O. Examples of the carrier gas include N2, He, Ar, and other gases (e.g., non-reactive gases) that are inert to the process gas.

[0048] The heater assembly 448 is disposed within the internal volume 406 of the showerhead 430 or the processing chamber 400 under the lid. The heater assembly 448 includes a support 450 that holds the substrate 444 during processing. The support 450 is attached to the end of a shaft 452 coupled to the chamber body 402 via a flange 454. The support 450, shaft 452, and flange 454 can be constructed of a heater material including AlN, e.g., an AlN ceramic. Further, the support 450 can include a mesa 456 (e.g., a depression or a protrusion). Additionally, the support can include wires, e.g., tungsten wires (not shown), embedded within the heater material of the support 450. In one embodiment, the support 450 can include a metal heater and sensor layer sandwiched between AlN ceramic layers. Such an assembly can be sintered in a high-temperature furnace to create a monolithic assembly. The layers can include a heater circuit, sensor elements, a ground plane, a high-frequency grid, a combination of metal and ceramic flow channels. The heater assembly 448 can provide a heater temperature of up to about 650° C. under vacuum conditions (e.g., from about 1 mTorr to about 5 Torr). The nanoceramic coating 460 formed from the nanopowders according to the embodiments described herein can be deposited on the support 450 within the chamber 400 or on all surfaces of the heater assembly 448 (including the support 450, shaft 452, and flange 454).

[0049] The advantages of the nanopowders, nanoceramic materials, and methods of making and using them will be apparent to those skilled in the art. Additionally, it should be noted that the nanomaterials formed and described herein can have improved mechanical properties such as flexural strength and fracture toughness compared to known micro-grain materials. Further, the bulk nanomaterials (e.g., having a particle size of less than 100 nm) formed and described herein can have advantageous properties over their microcrystalline counterparts. The nanomaterials formed and described herein can form high-density nanocomposite materials while retaining a nanocrystalline structure with limited or no explosive particle growth.

[0050] The foregoing description has set forth numerous specific details, such as examples of particular systems, components, methods, etc., to provide a thorough understanding of some of the embodiments described herein. However, it will be apparent to those skilled in the art that at least some of the embodiments described herein may be practiced without these specific details. In other instances, well-known components or methods have not been described in detail, or are presented in a simple block diagram format, to avoid unnecessarily obscuring the present invention. Accordingly, the specific details set forth are merely illustrative. Specific implementations may vary from these illustrative details and still be contemplated as within the scope of the present invention.

[0051] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular configuration, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Further, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". When the terms "about" or "approximately" are used herein, it is intended that the recited nominal value is accurate within ±10%. When the term "at least about" is used herein, it is meant that the recited nominal value is accurate within -10% and greater. Similarly, when the term "less than about" is used herein, it is intended that the recited nominal value is accurate within +10% and lower.

[0052] The operations of the methods herein are shown and described in a particular order, but each method operation may be changed and thereby the particular operations may be performed in reverse order, and the particular operations may be performed, at least in part, concurrently with other operations. In other embodiments, the instructions or sub-operations of the separate operations may be intermittent and / or alternating.

[0053] It should be understood that the above description is intended to be illustrative and not limiting. Upon reading and understanding the above description, many other embodiments will be apparent to those skilled in the art. Accordingly, the scope should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

Claim 1 A nano-powder containing a plurality of nano-particles, at least a part of the plurality of nano-particles being core particles containing a first material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof, and a nano-powder including a thin film coating on the core particles, the thin film coating containing a second material selected from the group consisting of rare-earth metal-containing oxides, rare-earth metal-containing fluorides, rare-earth metal-containing oxyfluorides, and combinations thereof.

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