TW201334035A - Plasma etch resistant films, articles bearing plasma etch resistant films and related methods - Google Patents

Abstract

The invention includes a plasma etch-resistant film for a substrate comprising a yttria material wherein at least a portion of the yttria material is in a crystal phase having a crystal lattice structure, wherein at least 50% of the yttria material is in a form of a monoclinic crystal system. The film may be treated by exposure to a fluorine gas plasma. Also included are plasma etch-resistant articles that include a substrate and a film, wherein the film comprises an yttria material and at least a portion of the yttria material is present in the film in a crystal phase having a crystal lattice structure and at least 50% of the yttria material is in a form of a monoclinic crystal system. Several methods are contemplated within the scope of the invention.

Description

Plasma-resistant etching film, article carrying plasma-resistant etching film and related method

Plasma resistance is a property required for components used in processing chambers where corrosive environments exist. Process chambers and component devices that exist in or with the processing chamber (which are used to fabricate electronic devices and MEMS) are typically constructed from a variety of substrates, such as sapphire, vermiculite, fused vermiculite, quartz, fused silica, alumina. , tantalum, aluminum, anodized aluminum, zirconia, aluminum alloys and sapphire, as these materials are known to have a certain degree of plasma resistance and/or are commonly used in semiconductor devices for other reasons.

However, such materials may be susceptible to erosion during conventional processing conditions, whether chemical, physical, and/or thermal. Typically, the substrate is presented to the harshest environment during the plasma etching process as part of an etching process or chamber cleaning. In order to improve the erosion or degradation of the substrate, attempts have been made to protect and preserve the substrate by applying a coating. The purpose of the coating is to reduce exposure to various plasmas (NF ₃ , Cl ₂ , CHF ₃ , CH ₂ F ₂ , SF ₆ and HBr) to prevent or reduce weight loss and/or to reduce during dry etching processes. Micronization (particles can be removed from the chamber wall and multiple components in the processing chamber during micronization).

Attempts have been made to develop suitable coatings using conventional membranes and methods. For example, films containing a variety of ceramic materials such as alumina, aluminum nitride, and zirconia have been prepared that are chemically stable in plasma etching conditions. Do The membranes generally exhibit improved resistance to plasma in the form of lower weight loss, but they still typically produce undesirable particulates. The particles released in the processing chamber cause the wafer to be damaged or defective, and then the wafers must be discarded, thereby increasing production costs and reducing the efficiency of the production line.

For example, alumina coated alumina or alumina coated quartz is known to exhibit a lower etch rate than bare vermiculite or quartz. However, in a fluoride containing etching environment, the alumina in the film was found to be fluorinated to form aluminum fluoride, a highly stable and non-volatile compound that accumulates on the walls of the chamber. Subsequently, the aluminum fluoride particles are detached from the chamber walls and contaminate the wafer.

Several attempts have previously been made to reduce micronization by coating a quartz substrate with yttria. Most of these attempts use very thick (typically > 50 microns) thermal spray ruthenium oxide. However, the thermal spray ruthenium oxide film is porous and still produces an undesirable degree of micronization.

Accordingly, there remains a need in the art for a film that can be applied to a substrate and that resists degradation upon exposure to the plasma and exhibits less micronization.

The present invention includes a plasma-resistant etching film for a substrate comprising a cerium oxide material, wherein at least a portion of the cerium oxide material is in a crystalline phase having a lattice structure, wherein at least 50% of the cerium oxide material is monoclinic Crystalline form.

Also included are plasma-resistant articles comprising a substrate and a film, wherein the film comprises a cerium oxide material, and at least a portion of the cerium oxide material is present in the film as a crystalline phase having a lattice structure, and at least 50 % of the cerium oxide material is in the form of a monoclinic system.

Several methods are encompassed within the scope of the invention. a party that manufactures goods The method comprises depositing a cerium oxide material on a substrate to form a film, wherein the film comprises a cerium oxide material and at least a portion of the cerium oxide material present in the film is in a crystalline phase having a lattice structure, wherein the film is present in the film At least 50% of the cerium oxide material is in the form of a monoclinic system. Also included is a method of increasing the plasma etch resistance of a substrate comprising depositing a cerium oxide material on a substrate to form a film on a surface of the substrate, wherein the film comprises a cerium oxide material and is present in the film at least a portion of the cerium oxide material is in a crystalline phase having a lattice structure in which at least 50% of the cerium oxide material present in the film is in the form of a monoclinic system; and an anti-plasma film having a high fracture toughness on the substrate The method comprises depositing a cerium oxide material on a substrate to form a film on a surface of the substrate, wherein the film comprises a cerium oxide material, and at least a portion of the cerium oxide material present in the film is a crystal having a lattice structure The phase wherein at least 50% of the cerium oxide material present in the film is in the form of a monoclinic system.

The invention described herein includes a plasma etch resistant film for a substrate, articles including the films applied to the substrate, methods of making the articles and/or methods of making the films, and improving the electrical resistance of the substrates Slurry etch method. Also included are films produced by the present invention that exhibit higher fracture toughness.

It is well known that coating a substrate with a film improves the plasma etch resistance of the substrate. In the prior art, this effect can be achieved in the following cases: (i) if the film is made of a sacrificial material, that is, it is gradually removed from the substrate with each successive plasma exposure, preventing the substrate from being finite time. The material itself is degraded, or (i) if the film is made of a material that is not necessarily used as a structural element in, for example, a semiconductor processing apparatus but which is more resistant to plasma than a substrate, which is suitable as a structural element. In each situation In the event that the harsh exposure to the harsh environment of the plasma ultimately and inevitably degrades the film and/or substrate, it is necessary to replace the component parts of the device. In some cases, micronization occurs as a side effect of film or substrate degradation, potentially resulting in waste of extremely expensive semiconductor wafers or equipment.

In order to reduce the costs associated with component replacement, micronization, and associated equipment downtime, those skilled in the art have continually sought materials that are less susceptible to degradation or slower degradation rates to be used as substrates or films. The present inventors have found that the degradation resistance of a substrate upon exposure to a gas plasma can be improved by forming a film having a structure containing a mixed crystal system, but at least 50% of the crystals are in the form of a monoclinic system. In some embodiments, if the film is prepared as described herein, it exhibits one or more desired properties, including (under exposure to corrosive chemicals or plasma) plasma etch rate reduction, during use in a semiconductor process The reduction in micronization and other degradation under exposure to gas plasma such as fluorine.

The invention includes a plasma resistant etch film for use on a variety of substrates. "plasma etch resistant" means that the film of the present invention degrades less when compared to conventional cerium oxide films when exposed to corrosive chemicals such as gas plasmas (and especially fluoroplasma). Degradation or non-degradation of the membrane may be carried out using any method generally accepted in the art (including visual methods such as optical or scanning electron microscopy in which cracks, cracks and undercutting areas are assessed) or by evaluation of the membrane and Adhesion of the substrate (where higher adhesion corresponds to less degradation) is evaluated.

The film is prepared by depositing a cerium oxide material on a substrate. The film is formed by depositing or coating a cerium oxide material on a substrate. The cerium oxide material can be exposed to a plasma-containing environment (especially, for example, an environment containing fluorine-based plasma) Any material containing cerium oxide or cerium oxide which is resistant to plasma resistance and/or reduced micronization. Exemplary cerium oxide materials include, but are not limited to, cerium oxide, yttrium aluminum garnet, cerium oxide containing one or more dopants or other additives, or a combination of such materials.

A cerium oxide material is deposited on the substrate such that the formed film contains a cerium oxide material having a crystalline phase having a lattice structure, and at least 50% of the crystalline phase cerium oxide material is in the form described by a monoclinic system. Thus, the film is deposited on the substrate such that at least a portion of the cerium oxide material is present in the film in a monoclinic phase. Cerium oxide can exist in a polycrystalline form and such crystals are generally understood to have a structure represented by a cubic system (cubic crystal). As is known in the art, cerium oxide is generally found to be in an amorphous form or in a cubic crystal structure, but in some cases it may be in other crystalline forms (such as in cubic, hexagonal, tetragonal). The system, the orthorhombic system, and/or the triclinic system exist.

However, in practicing the invention, in some embodiments, it may be preferred to have at least 60% cerium oxide material, at least 65% cerium oxide material, at least 70% cerium oxide material, at least 75% cerium oxide. Material, at least 80% cerium oxide material, at least 85% cerium oxide material, at least 90% cerium oxide material, at least 95% cerium oxide material, at least 98% cerium oxide material or at least 99% cerium oxide material Monoclinic form.

The remainder of the cerium oxide material present in the film may be present in any crystal structure. For example, if 55% of the cerium oxide material present in the film is present in a monoclinic form, the remaining 45% may be present in 100% of any other form or other form of mixing. For example, the remainder of the cerium oxide material may be in the form of an alternative or phase or form or a mixture of phases, including For example, an amorphous system, a cubic system, a hexagonal system, a tetragonal system, an orthorhombic system, and/or a triclinic system. This remainder is hereinafter referred to as "non-monoclinic".

In the film, the cerium oxide material in a monoclinic (and other phases or forms present) may contain a random crystallite orientation or a preferred crystallite orientation. For example, a monoclinic phase can contain completely random crystallite orientation or at ( Orientation of orientation (which may be preferred in some cases). Similarly, the non-monoclinic portion of the film may also have a random or preferred orientation. For example, a non-monoclinic phase can contain a completely random crystallite orientation or (222) orientation.

The film can have any average crystallite size or grain size, and the grain size can vary with the thickness of the film. However, in some embodiments of the invention or in the practice of the invention, as measured by X-ray diffraction, it may be preferred that the average crystal size of the crystallites present in the film is from about 100 Å to about 1000 Å or about 200 Å to about 500 Å. The monoclinic portion and the non-monoclinic portion may have the same or may have different average crystal sizes.

The film can be of any thickness and the thickness will vary depending on the particular end use or end use application of the substrate/film article. In most cases, it may be desirable for the thickness of the film to be from about 0.1 to about 30 microns, from about 0.5 to about 25 microns, from about 1 micron to about 5 microns, from about 10 microns to about 20 microns, and/or about 15 microns. Up to about 25 microns.

A cross-sectional view of the polycrystalline anti-corrosion film on the substrate is shown in FIG.

The film can be coated/deposited continuously or discontinuously along the surface of the substrate. Discontinuous means that the film may be present only on one or more portions of the substrate (eg, in a block form), with the remainder being a bare substrate or coated with another material. The The continuity/discontinuity of the film will necessarily vary depending on the intended end use of the film coated substrate.

The film of the invention is deposited on one or more substrates. The substrate can be any substrate known in the art, but it may be preferred that the substrate selected is commonly used in semiconductor processing and may have some degree of plasma etching, high temperature, corrosive chemicals and/or high pressure. Intrinsic resistance. For example, in some cases, it may be preferred that the substrate be one or more high performance properties independent of the film (such as corrosion resistant chemical resistance, high temperature and/or high pressure resistance, gas plasma resistance, Material of mechanical strength, hardness, etc.). Exemplary substrates can include polymers, metals, vermiculite, fused vermiculite, fused silica, quartz, alumina, sapphire, tantalum, tantalum nitride, tantalum carbide, aluminum, aluminum oxide, anodized aluminum, and/or zirconia. . In some cases, tantalum, alumina and/or quartz materials may be preferred.

In some embodiments, the substrate can be in the form of a portion of a semiconductor processing device assembly or a semiconductor processing device assembly. These components include any component known or developed in the art. Exemplary components may include, without limitation, chamber walls, chamber floors, screws, wafer boats, or other tools or devices for positioning wafers, fasteners, windows, dispersion trays, showerheads, electrostatic chucks, fasteners, cooling Plate, CEL plate, focus ring, inner ring, outer ring, capture ring, insert ring, gas transfer tube and heating element.

The film of the present invention may be deposited or coated onto a substrate by any means known in the art including, but not limited to, physical vapor deposition (PVD) processes including, but not limited to, evaporation deposition. (electron beam vapor deposition), sputter deposition, arc vapor deposition, and ion plating electron beam vapor deposition; And chemical vapor deposition processes, including but not limited to: atmospheric pressure CVD (APCVD), low pressure CVD (LPCVD), aerosol assisted CVD (AACVD), plasma enhanced CVD (PECVD), atomic layer CVD (ALCVD or ALD) ), organometallic CVD (MOCVD) and initiated CVD (iCVD). The particular process parameters of the coated/deposited film may vary depending on the method of coating or deposition used, but such minor variations are within the skill of the art in the art. In one embodiment, it may be preferred to form the film by depositing a yttria material on a substrate having a temperature of from about 21 ° C to about 500 ° C.

As a non-limiting general embodiment of practicing the present invention, a deposition process using a quartz substrate and an electron beam process may include pre-cleaning the bare substrate and preheating the electron beam using a solvent such as an organic solvent such as isopropyl alcohol. The chamber is at a temperature ranging from about 25 ° C to about 600 ° C.

Depending on the quality of the substrate, the time necessary to achieve preheating of the substrate is typically from about 0.5 to about 4 hours; the substrate is optionally pre-cleaned using an ion beam as appropriate. If this pre-cleaning step is carried out, the gas used may be argon (most typical), oxygen, oxygen/argon blend or other inert gas such as helium. An exemplary process can use a high purity tantalum metal ingot having a purity such as 90% or more, preferably 98% or more. The ruthenium metal ingot is pre-melted in a single step or multiple steps prior to deposition and may be deposited on the substrate at a rate of from about 0.1 to about 10 microns per hour. During deposition, oxygen is introduced into the chamber as an ambient background gas, within a partial pressure range of about 1 x 10 ^-5 to 1 x 10 ^-3 Torr.

In some embodiments, ion beam assisted deposition (IBAD) can be used for deposition using a separate vaporization source and bombardment source. For example, In this process, base metal is thermally evaporated via electron beam evaporation and oxygen is introduced as a source of bombardment. In some embodiments, oxygen can be mixed with other gases such as argon, helium or neon to enhance densification. In another embodiment, the film can be grown by evaporating the crucible and still introducing oxygen as the ambient background gas while using an ion gun to bombard the membrane with a second gas such as argon or helium to increase the membrane density.

After deposition, the film coated substrate is allowed to cool back to room temperature in a controlled manner (e.g., at a rate of from about 1 ° C to about 200 ° C / hour).

Regardless of the process selected, it may be desirable to have the yttrium oxide material at a substrate temperature of from about room temperature (21 ° C) to about 500 ° C, from about 100 ° C to about 500 ° C, and/or from about 400 ° C to about 500 ° C. The substrate is grown to form a film.

In any of the processes described herein, the cerium oxide material can be deposited or applied directly onto the surface of the substrate (i.e., the film is formed to directly oppose the surface of the substrate). Alternatively, the substrate may be coated with other materials (forming one or more intervening layers of the film) prior to depositing the yttria material. Alternatively or additionally, the film of the present invention, once formed, can be coated with other layers (e.g., an additional sacrificial layer of alumina) to further enhance overall plasma resistance. The invention also includes a method of making a plasma resistant film having fracture toughness on a substrate and the resulting film.

In some embodiments of the invention, it may be desirable to subject the film to a post deposition process or treatment to enhance, improve or further produce one or more desired properties of the film, substrate and/or film-substrate combination. The process can include any method known or to be developed in the art. In one embodiment, it may be desirable to subject the substrate carrying the film to a fluorine plasma treatment. This process can use this Any means in the art is performed, for example, without limitation, by using a remote plasma source treatment or a reactive ion etching treatment. In some embodiments, the substrate carrying the film can be exposed to a fluorochemical treatment for about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, or about 10 hours or more. Many hours.

The film exposed to the fluorine gas plasma exhibits higher fracture resistance under thermal cycling conditions than the conventional film not exposed to the plasma treatment and/or the film of the present invention.

Example 1

Two sets of yttrium oxide films were grown by reactive deposition using electron beam evaporation on a fused silica test piece (size: 1 吋 x 吋; 1/8 吋 thick). Each test piece was placed in an electron beam membrane chamber and the chamber was placed under vacuum overnight. The membrane chamber vacuum is maintained at 5 x 10 ^-6 Torr (or below 5 x 10 ^-6 Torr) and preheated for at least 1 hour to ensure temperature equilibrium is achieved.

A high purity (>99.9%) base metal target is vaporized by electron beam and oxygen is incorporated into the chamber to maintain a chamber process pressure between 5.5 x 10 ^-5 Torr and 1 x 10 ^-4 Torr. Each test piece was coated for 4 hours to reach a target thickness of about 4 microns. The temperature of the substrate is maintained between about 250 ° C and about 350 ° C during the film processing.

A set of films is grown to produce a yttria film containing about 50% cubic phase and 50% monoclinic phase. The second set is grown to produce a film that mainly contains monoclinic phase cerium oxide (50% or more).

Figure 2, comprising Figures 2a and 2b, shows X-ray diffraction (XRD) measurements of the two films. Figure 2a shows a typical XRD pattern containing about 50% monoclinic phase and 50% cubic phase. A line marker overlay is provided to identify peaks belonging to the monoclinic and cubic phases. The peak labeled (1) belongs to the cubic phase and the peak labeled (2) belongs to the monoclinic phase. Note that for the same amount of yttrium oxide, the reflection intensity of the cubic phase is approximately four times the reflection intensity of the monoclinic phase. Therefore, for an equal amount of cubic phase and monoclinic phase yttrium oxide, the ratio of the integrated XRD intensity of the cubic phase to the monoclinic phase will be 4 to 1. Figure 2b shows the X-ray diffraction spectrum of the electron beam deposited Y ₂ O ₃ film on fused silica, showing a ratio of cubic phase Y ₂ O ₃ to monoclinic phase Y ₂ O ₃ of about 18%: about 82% .

Figure 3 shows a typical XRD pattern containing about 50% monoclinic phase and 50% cubic phase. A line mark overlay is provided to identify peaks belonging to the monoclinic phase and the cubic phase. The peak labeled (1) belongs to the cubic phase and the peak labeled (2) belongs to the monoclinic phase.

Figure 4 shows a cross-sectional SEM image of the mixed cubic phase and monoclinic phase yttria film on fused silica prior to direct NF ₃ plasma etching (5A) and after (5B). Rietveld XRD analysis of the coated film indicated that it consisted of 72% monoclinic phase yttrium oxide and 28% cubic phase yttrium oxide. Figure 4B basically shows that there is no change in the thickness of the ruthenium oxide film after 4 hours of NF ₃ plasma etching. On the other hand, uncoated fused silica will exhibit a loss of surface material of about 100 microns in 4 hours under the same plasma conditions.

Figure 5 shows an optical image of a partially coated fused silica substrate exposed to a remote NF ₃ plasma for 80 hours. The central area of the fused silica sheet is masked and thus uncoated. The left and right sides of the sample were coated with mixed phase cerium oxide. The Ritterwell analysis indicated that the film consisted of about 65% monoclinic phase yttrium oxide and 35% cubic phase yttrium oxide. Examination of the etched area shows that fused silica is etched away to a depth of about 1 mm, corresponding to an etch rate of about 0.2 microns/minute. On the other hand, the ruthenium oxide coated region protects the underlying fused silica from etching.

Example 2

Three sets of yttrium oxide films on quartz test pieces were prepared using standard deposition conditions. A set of films is further processed by exposing the film to a direct NF ₃ plasma in a capacitively coupled parallel plate reactive ion etching (RIE) reactor. Another group was processed by exposing the film to a remote NF ₃ plasma source. The third set of films was not further processed after coating. The film was then thermally cycled on a microscope equipped with a hot stage and the point of break formation was recorded. The ruthenium oxide film used for the thermal cycle experiment was grown on a fused silica test piece (size: 1 吋 × 1 吋; 1/8 吋 thick) by electron beam evaporation. Each test piece was placed in an electron beam membrane chamber and the chamber was placed under vacuum overnight. The membrane chamber vacuum is maintained at 5 x 10 ^-6 Torr (or below 5 x 10 ^-6 Torr) and preheated for at least 1 hour to ensure temperature equilibrium is achieved. A high purity (>99.9%) base metal target is vaporized by electron beam and oxygen is incorporated into the chamber to maintain a chamber process pressure between 5.5 x 10 ^-5 Torr and 1 x 10 ^-4 Torr. The temperature of the substrate is maintained between about 250 ° C and about 350 ° C during the film processing. Two coating operations were carried out at deposition times of 220 minutes and 160 minutes to produce two test pieces having a thickness of 2.8 and 3.9 μm.

Two types of plasma treatments for fluorinating the yttrium oxide film are used. All plasma treatments were performed on a Trion Phantom II RIE system equipped with a remote plasma source (MKS ASTRONEX AX7685 RPS). The direct etch experiment uses an RIE process. The reactive ion etching treatment conditions are as follows:

The remote plasma conditions are as follows:

The thermal cycle experiment was carried out on an Olympus microscope (model: BX60F5) equipped with a Linkam hot stage (model: LTS420). The test piece was placed on the hot stage with the film side down and the rupture of the film was monitored via a quartz substrate, and the 50x objective lens was focused on the film surface. The hot stage was programmed to ramp from 40 ° C to 200 ° C at a rate of 10 ° C / min for 10 or more complete cycles.

Table I summarizes the results of the effect of fluorination on rupture. All films that did not receive any fluorination treatment exhibited cracking during the first few thermal cycles. Films that received the fluorination treatment (whether remote or direct etch) did not exhibit cracking after 10 or more cycles.

*The samples were cycled up to 30 times without cracking.

As evidenced by the data in the table, by using the present invention to fluorinate the cerium oxide film using a fluorine-based plasma, the film fracture toughness is improved during thermal cycling. The test piece coated according to the present invention showed no cracks, while the control test piece showed cracks almost immediately (for example, in the first, second or third cycles).

It will be appreciated by those skilled in the art that changes may be made to the specific embodiments described above without departing from the broad inventive concept of the invention. Therefore, the invention is to be understood as not limited to the specific embodiments disclosed, and the scope of the invention is intended to be included within the spirit and scope of the invention as defined by the appended claims.

The previous abstract, together with the detailed description of the specific embodiments of the invention, may be better understood when read in conjunction with the drawings. However, it should be understood that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings.

1 is a cross-sectional view of a polycrystalline anti-corrosion ruthenium oxide film on a substrate; and FIG. 2, including FIGS. 2a and 2b, showing X-ray diffraction (XRD) measurement results of two films prepared according to the present invention; It is an XRD pattern of a polycrystalline Y ₂ O ₃ film containing both a monoclinic phase and a cubic phase on fused silica.

Figure 4 includes Figures 4a and 4b. 4a shows a cross-sectional SEM image of fused silica coated with cubic/monoclinic mixed phase Y ₂ O ₃ prior to direct NF ₃ plasma exposure; 4b is the same Y in Figure 4a after 4 hours of direct NF ₃ etching Cross-sectional SEM image of a ₂ O ₃ coated fused silica sample.

Figure 5 shows an optical image of fused silica with coated and uncoated areas exposed to a remote NF ₃ plasma for 80 hours. The uncoated region was etched by NF ₃ remote plasma, resulting in a quartz removal of about 1 mm, which was related to an etch rate of about 210 nm/min. In contrast, the areas coated with the mixed crystalline phase Y ₂ O ₃ did not show signs of etching, thereby exhibiting protective coating capabilities.

Claims (65)

A plasma-resistant etching film for a substrate comprising a cerium oxide material, wherein at least a portion of the cerium oxide material has a crystal phase having a lattice structure, wherein at least 50% of the cerium oxide material is in a monoclinic form . The film of claim 1, wherein at least 60% of the cerium oxide material is in the form of a monoclinic system. The film of claim 1, wherein at least 65% of the cerium oxide material is in the form of a monoclinic system. The film of claim 1, wherein at least 70% of the cerium oxide material is in the form of a monoclinic system. The film of claim 1, wherein at least 75% of the cerium oxide material is in the form of a monoclinic system. The film of claim 1, wherein at least 80% of the cerium oxide material is in the form of a monoclinic system. The film of claim 1, wherein at least 85% of the cerium oxide material is in the form of a monoclinic system. The film of claim 1, wherein at least 90% of the cerium oxide material is in the form of a monoclinic system. The film of claim 1, wherein the cerium oxide material is selected from the group consisting of a heterogeneous crystal system, a hexagonal system, a tetragonal system, an orthorhombic system, and a triclinic system. The form of one or more. The film of claim 1, wherein the substrate is selected from the group consisting of vermiculite, fused vermiculite, quartz, fused silica, alumina, and sapphire. The film of claim 1, wherein the substrate is selected from the group consisting of Tantalum carbide, tantalum nitride, aluminum, anodized aluminum, zirconia and aluminum alloy. The film of claim 1, wherein the film has a thickness of from about 0.1 micron to about 30 microns. The film of claim 1, wherein the film has a thickness of from about 0.5 microns to about 25 microns. The film of claim 1, wherein the film has a thickness of from about 1 micron to about 5 microns. The film of claim 1, wherein the cerium oxide material is cerium oxide. The film of claim 1, wherein the cerium oxide material is a cerium oxide-derived composite. The film of claim 1, wherein the film is selected from the group consisting of a physical vapor deposition (PVD) process, an evaporation deposition process, an electron beam vapor deposition process, a sputtering deposition process, an arc vapor deposition process, and an ion plating process. The process is formed. For example, in the film of claim 1, wherein the film is subjected to a chemical vapor deposition (CVD) process, an atmospheric pressure CVD (APCVD) process, a low pressure CVD (LPCVD) process, an aerosol assisted CVD (AACVD) process, and a plasma enhanced process. A CVD (PECVD) process, an atomic layer CVD (ALCVD or ALD) process, an organometallic CVD (MOCVD) process, and an initiating CVD (iCVD) process are formed. The film of claim 1, wherein the substrate is a semiconductor processing device component. Such as the film of claim 19, wherein the semiconductor processing package The component is selected from the group consisting of a chamber wall, a chamber bottom plate, a screw, a wafer boat, a fastener, a window, a dispersion plate, a shower head, an electrostatic chuck, a cooling plate, a CEL plate, a focus ring, an inner ring, an outer ring, a capture ring, and an insertion ring. , gas transfer tube and heater block. The film of claim 1, wherein the film is formed by a process comprising heating the substrate to a temperature of from about 21 ° C to about 500 ° C when the film is deposited. The film of claim 1, wherein the film has been exposed to a fluorine gas plasma. An anti-plasma etching article comprising a substrate and a film, wherein the film comprises a cerium oxide material, and at least a portion of the cerium oxide material is present in the film as a crystalline phase having a lattice structure, and at least 50% of the The cerium oxide material is in the form of a monoclinic system. An article of claim 23, wherein the film has been exposed to a fluorine gas plasma. A method of making an article comprising depositing a cerium oxide material on a substrate to form a film, wherein the film comprises the yttria material and at least a portion of the yttria material present in the film is a crystal having a lattice structure The phase wherein at least 50% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 25, wherein at least 70% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 25, wherein at least 80% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 25, wherein at least 90% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 25, wherein the cerium oxide material present in the film in a portion not in a monoclinic form is selected from the group consisting of a heterogeneous crystal system, a hexagonal system, a tetragonal system, and an orthorhombic crystal. And one or more forms of the triclinic system. The method of claim 25, wherein the substrate is selected from the group consisting of vermiculite, molten vermiculite, quartz, fused silica, alumina, and sapphire. The method of claim 25, wherein the substrate is selected from the group consisting of ruthenium, tantalum carbide, tantalum nitride, aluminum, anodized aluminum, zirconia, and an aluminum alloy. The method of claim 25, wherein the film has a thickness of from about 1 micron to about 5 microns. The method of claim 25, wherein the cerium oxide material is cerium oxide. The method of claim 25, wherein the cerium oxide material is a cerium oxide-derived composite. The method of claim 25, wherein the film is formed by at least one selected from the group consisting of a physical vapor deposition (PVD) process, an evaporation deposition process, an electron beam vapor deposition process, a sputtering deposition process, an arc vapor deposition process, and The process of the ion plating process is deposited. The method of claim 25, wherein the film is subjected to a chemical vapor deposition (CVD) process, an atmospheric pressure CVD (APCVD) process, a low pressure CVD (LPCVD) process, an aerosol assisted CVD (AACVD) process, and a plasma process. Enhanced CVD (PECVD) process, atomic layer CVD (ALCVD or ALD) deposition of at least one of a process, an organometallic CVD (MOCVD) process, and an initiating CVD (iCVD) process. The method of claim 25, wherein the film is formed by depositing the cerium oxide material on a substrate that has been heated to a temperature of from about 21 ° C to about 500 ° C. A method of improving plasma etch resistance of a substrate, comprising depositing a cerium oxide material on the substrate to form a film on a surface of the substrate, wherein the film comprises the cerium oxide material and is present in the film At least a portion of the yttria material is in a crystalline phase having a lattice structure wherein at least 50% of the yttria material present in the film is in the form of a monoclinic system. The method of claim 38, wherein at least 70% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 38, wherein at least 80% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 38, wherein at least 90% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 38, wherein the cerium oxide material present in the film in a portion not in a monoclinic form is selected from the group consisting of a heterogeneous crystal system, a hexagonal system, a tetragonal system, and an orthorhombic crystal. And one or more forms of the triclinic system. The method of claim 38, wherein the substrate is selected from the group consisting of vermiculite, molten vermiculite, quartz, fused silica, alumina, and sapphire. The method of claim 38, wherein the substrate is selected from the group consisting of ruthenium, tantalum carbide, tantalum nitride, aluminum, anodized aluminum, zirconia, and an aluminum alloy. The method of claim 38, wherein the film has a thickness of from about 1 micron to about 5 microns. The method of claim 38, wherein the cerium oxide material is cerium oxide. The method of claim 38, wherein the cerium oxide material is a cerium oxide-derived composite. The method of claim 38, wherein the film is processed by a physical vapor deposition (PVD) process, an evaporation deposition process, an electron beam vapor deposition process, a sputtering deposition process, an arc vapor deposition process, and an ion plating process. At least one of them is deposited. The method of claim 38, wherein the film is subjected to a chemical vapor deposition (CVD) process, an atmospheric pressure CVD (APCVD) process, a low pressure CVD (LPCVD) process, an aerosol assisted CVD (AACVD) process, and a plasma process. At least one of a CVD (PECVD) process, an atomic layer CVD (ALCVD or ALD) process, an organometallic CVD (MOCVD) process, and an initiating CVD (iCVD) process is deposited. The method of claim 38, wherein the film is formed by depositing the cerium oxide material on a substrate that has been heated to a temperature of from about 21 ° C to about 500 ° C. The method of claim 38, further comprising exposing the film to a fluorine gas plasma. The method of claim 51, wherein the film is exposed for at least about 4 hours. For example, the method of claim 51, wherein the exposure is selected This is achieved by a process of remote plasma exposure and reactive ion etching. A method of producing a plasma resistant film having higher fracture toughness on a substrate, comprising depositing a cerium oxide material on the substrate to form a film on a surface of the substrate, wherein the film comprises the yttrium oxide material and The yttria material present in at least a portion of the film is in a crystalline phase having a lattice structure, wherein at least 50% of the yttria material present in the film is in a monoclinic form; and exposing the film to Fluorine gas plasma. The method of claim 54, wherein the film is exposed for at least about 4 hours. The method of claim 54, wherein the exposing is performed using a process selected from the group consisting of remote plasma exposure and reactive ion etching. The method of claim 54, wherein at least 70% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 54, wherein at least 80% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 54, wherein at least 90% of the cerium oxide material present in the film is in the form of a monoclinic system. The method of claim 54, wherein the cerium oxide material present in the film in a portion not in a monoclinic form is selected from the group consisting of a heterogeneous crystal system, a hexagonal crystal system, a tetragonal system, and an orthorhombic crystal. And one or more forms of the triclinic system. The method of claim 54, wherein the substrate is selected from the group consisting of vermiculite, molten vermiculite, quartz, fused silica, alumina, and sapphire. The method of claim 54, wherein the substrate is selected from the group consisting of Niobium, tantalum carbide, tantalum nitride, aluminum, anodized aluminum, zirconia and aluminum alloy. The method of claim 54, wherein the film has a thickness of from about 1 micron to about 5 microns. The method of claim 54, wherein the film is subjected to a physical vapor deposition (PVD) process, an evaporation deposition process, an electron beam vapor deposition process, a sputtering deposition process, an arc vapor deposition process, and an ion plating process. At least one of them is deposited. The method of claim 54, wherein the film is subjected to a chemical vapor deposition (CVD) process, an atmospheric pressure CVD (APCVD) process, a low pressure CVD (LPCVD) process, an aerosol assisted CVD (AACVD) process, and a plasma process. At least one of a CVD (PECVD) process, an atomic layer CVD (ALCVD or ALD) process, an organometallic CVD (MOCVD) process, and an initiating CVD (iCVD) process is deposited.