Plasma etching resistant film and method for manufacturing the same

Abstract

A method for manufacturing a plasma etching resistant film on the surface of a substrate is disclosed. The method involves exposing the deposition surface to an alternately repeated, essentially self-limiting precursor surface reaction, where, with each exposure, the deposition surface is exposed to one precursor, thereby forming an intermediate layer of dielectric material on the substrate surface and a protective layer on the intermediate layer within the reaction space, and forming a plasma etching resistant film that prevents current from flowing through the plasma etching resistant film to the substrate. Furthermore, a plasma etching resistant film and its use are disclosed.

Description

Technical Field

[0001] The present disclosure relates to a method of forming a plasma etching resistant film (film) on the surface of a substrate. The present disclosure further relates to a plasma etching resistant film on the surface of a substrate. The present disclosure further relates to the use of a plasma etching resistant film.

Background Art

[0002] The surfaces and components of a plasma reaction chamber are exposed to harsh conditions during the processes used. Thus, plasma resistance is a desirable property for components used in process chambers where a corrosive environment exists. Thus, it is desirable to protect the components from such corrosive environments in order to extend the life of the components or chambers used. In order to reduce erosion or degradation of surfaces exposed to a corrosive environment, for example, thick coatings or films of aluminum oxide have been formed on the surfaces to be protected. The purpose of such coatings or films is to act, for example, to reduce the exposure of the protected surface to various plasmas based on NF3, CF4, CHF3, CH2F2, C2F6, SF6, C l2 and HBr. However, these coatings or films exhibit improved plasma resistance but often have a porous structure as a result of, for example, the manufacturing methods used. Thus, over time, the porous structure causes the adverse effects of the corrosive environment to penetrate through the coating to the surface being protected and / or form solid particles that contaminate the surroundings. Also, thick films are prone to cracking, thereby easily losing their protective effect. Forming a coating using, for example, plasma spraying also does not provide a conformal coating.

[0003] Thus, there is still a need for a method that enables the production of a long-lasting plasma etching resistant film having properties suitable for protecting the surfaces and components of a plasma chamber from harmful process conditions.

Summary of the Invention

[0004] A method for manufacturing a plasma etching resistant film on the surface of a substrate is disclosed. This method involves exposing the deposition surface to an alternately repeated, essentially self-limiting precursor surface reaction, wherein with each exposure, the deposition surface is exposed to one precursor, thereby introducing into the reaction space, - An intermediate layer of dielectric material on the surface of a substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides, and the thickness of the intermediate layer is 100 to 500 nm, forming an intermediate layer. - A protective layer on an intermediate layer, wherein the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, and any combination or mixture thereof, and the thickness of the protective layer is 100 to 3000 nm, comprising the step of forming a protective layer. This step forms a plasma etching resistant film that prevents current from flowing (passing) through the plasma etching resistant film to the substrate.

[0005] Furthermore, a plasma etching resistant film on the surface of a substrate is disclosed. The plasma etching resistant film comprises an intermediate layer of a dielectric material on the surface of a substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides, and the thickness of the intermediate layer is 100 to 500 nm; and a protective layer on the intermediate layer, wherein the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, and any combination or mixture thereof. The thickness of the protective layer is 100 to 3000 nm. The plasma etching resistant film prevents current from flowing through the plasma etching resistant film to the substrate.

[0006] Furthermore, the use of a plasma etching-resistant film, such as those disclosed in the current specifications, is disclosed to protect the surface of the plasma chamber from the harmful effects of the process conditions used within the plasma chamber.

[0007] Furthermore, the use of a plasma etching-resistant film, as disclosed in the current specifications, is disclosed to suppress or prevent the current used in the plasma chamber from flowing through the plasma etching-resistant film to the substrate under the voltage received in the plasma process. [Brief explanation of the drawing]

[0008] The attached drawings, which are included to provide a further understanding of the method and substrate and constitute this particular part, illustrate embodiments and, together with the description, help to illustrate the principles described above. The drawings are as follows: [Figure 1] Figure 1 is a schematic diagram of a plasma etching resistant film on a substrate according to one embodiment. [Modes for carrying out the invention]

[0009] A method for manufacturing a plasma etching resistant film on the surface of a substrate is disclosed. This method involves exposing the deposition surface to an alternately repeated, essentially self-limiting precursor surface reaction, wherein, with each exposure, the deposition surface is exposed to one precursor, thereby bringing the reaction space into which - An intermediate layer of dielectric material on the surface of a substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides, and the thickness of the intermediate layer is 100 to 500 nm, forming an intermediate layer. - A protective layer on an intermediate layer, wherein the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, and any combination or mixture thereof, and the thickness of the protective layer is 100 to 3000 nm, comprising the step of forming a protective layer. This step forms a plasma etching resistant film that prevents the current flowing to the substrate through the plasma etching resistant film.

[0010] A method for manufacturing a plasma etching resistant film on the surface of a substrate is disclosed. This method involves exposing the deposition surface to an alternately repeated, essentially self-limiting precursor surface reaction, wherein, with each exposure, the deposition surface is exposed to one precursor, thereby bringing the reaction space into which - An intermediate layer of dielectric material on the surface of a substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides, and the thickness of the intermediate layer is 100 to 500 nm, forming an intermediate layer. - A protective layer on an intermediate layer, wherein the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, aluminum oxide, and any combination or mixture thereof, and the thickness of the protective layer is 100 to 3000 nm, comprising the step of forming a protective layer. This step forms a plasma etching resistant film that prevents the current flowing to the substrate through the plasma etching resistant film.

[0011] The term "electric current" is understood to refer to "the flow of electricity."

[0012] In this specification, unless otherwise specified, the terms “surface,” “substrate surface,” or “deposited surface” are used to refer to the surface of a substrate or the surface of a layer or deposit already formed on the substrate. Accordingly, the terms “surface,” “substrate surface,” and “deposited surface” include the surface of a substrate that has not yet been exposed to any precursor, and the surface that has been exposed to one or more precursors. Accordingly, the “deposited surface” changes during the deposition process when chemical substances are chemiadsorbed onto the surface.

[0013] Furthermore, a plasma etching resistant film on the surface of a substrate is disclosed. The plasma etching resistant film comprises an intermediate layer of a dielectric material on the surface of a substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides and the thickness of the intermediate layer is 100 to 500 nm, and a protective layer on the intermediate layer, wherein the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, and any combination or mixture thereof, and the thickness of the protective layer is 100 to 3000 nm. The plasma etching resistant film prevents current from flowing through the plasma etching resistant film to the substrate.

[0014] Furthermore, a plasma etching resistant film on the surface of a substrate is disclosed. The plasma etching resistant film comprises an intermediate layer of a dielectric material on the surface of a substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides and the thickness of the intermediate layer is 100 to 500 nm, and a protective layer on the intermediate layer, wherein the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, aluminum oxide, and any combination or mixture thereof, and the thickness of the protective layer is 100 to 3000 nm. The plasma etching resistant film prevents current from flowing through the plasma etching resistant film to the substrate.

[0015] Furthermore, the use of a plasma etching-resistant film, such as those disclosed in the current specifications, is disclosed to protect the surface of the plasma chamber from the harmful effects of the process conditions used within the plasma chamber.

[0016] Furthermore, the use of a plasma etching-resistant film, as disclosed in the current specifications, is disclosed to prevent or suppress the flow of current used in the plasma chamber through the plasma etching-resistant film to the substrate.

[0017] Electrical breakdown, or dielectric breakdown, is the process that occurs when an electrically insulating material, exposed to a sufficiently high voltage, suddenly becomes an electrical conductor, allowing current to flow through it. All insulating materials break down when the electric field caused by the applied voltage exceeds the dielectric strength of the material. The voltage at which a given insulating object becomes conductive is called its breakdown voltage (dielectric breakdown voltage, yield voltage), and it depends on its dielectric strength, as well as its size and shape, and the location on the object to which the voltage is applied.

[0018] The inventors have surprisingly found that it is possible to fabricate a plasma etching resistant film without the need to prepare separate films in different reaction chambers or without the need to fabricate thick films. The plasma etching resistant film includes a protective layer that has high performance with respect to plasma resistance, with an intermediate layer of dielectric material between the substrate and the protective layer assisting in providing a high-pressure-resistant structure to the plasma etching resistant film.

[0019] This method may include forming a plasma etching resistant film having a breakdown voltage value of at least 200V, or at least 230V, or at least 250V, or at least 270V, or at least 300V, when measured for a plasma etching resistant film described herein with a total thickness of 700 nm. A plasma etching resistant film may have a breakdown voltage value of at least 200V, or at least 230V, or at least 250V, or at least 270V, or at least 300V, when measured for a plasma etching resistant film described herein with a thickness of 700 nm. The breakdown voltage value may be influenced by the thickness of the plasma etching resistant film. The thicker the plasma etching resistant film, the higher the breakdown voltage. However, plasma etching resistant films such as those disclosed herein offer a high breakdown voltage value while also having the added benefit of being considerably thin in total thickness.

[0020] The breakdown voltage value can be measured by increasing the voltage applied until dielectric breakdown occurs, using a plasma etching resistant film manufactured on the substrate surface. Since the breakdown voltage value of the substrate material is known, the corresponding value of the plasma etching resistant film can be calculated. Therefore, the breakdown voltage value can be measured by performing IV (current-voltage) measurements on a sample of a film with a size of 4 cm × 4 cm and a total thickness of 700 nm using an IV plotter equipped with a mercury probe having a front-back configuration. The voltage is swept from 0 V to 1000 V in 10 V steps. The breakdown voltage is determined at a current of 1 μA.

[0021] The dielectric material is a nanolaminate of two or more different metal oxides. In one embodiment, the dielectric material is an aluminum titanate (ATO) nanolaminate.

[0022] In one embodiment, the nanolaminate of two or more different metal oxides is a nanolaminate of aluminum oxide and a rare earth metal oxide. In one embodiment, the nanolaminate of two or more different metal oxides is a nanolaminate of aluminum oxide and yttrium oxide.

[0023] The inventors have surprisingly found that using a nanolaminate of two or more different metal oxides as an intermediate layer provides good adhesion to the substrate and has the additional usefulness of effectively preventing current from flowing from the surroundings to the substrate through the plasma etching resistant film.

[0024] As used herein, unless otherwise specified, the term "nanolaminate" is used to address distinct layers of different metal oxide materials stacked on top of each other. The distinct layers of different materials may not diffuse or mix with each other. The thickness of the distinct layers in the nanolaminate may be on the nanoscale, such as 0.5 to 20 nm. Thus, the distinct layers of the material may have a monolayer thickness. The nanolaminate may include at least 6, or at least 8, or at least 10, or at least 15 layers of each of the different metal oxides. The nanolaminate may include 6 to 500, or 8 to 400, or 10 to 300, or 15 to 200, or 20 to 100, or 25 to 50, or 30 to 40 layers of each of the different metal oxides.

[0025] In one embodiment, the material of the protective layer is aluminum oxide.

[0026] In one embodiment, the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, and any combination or mixture thereof. Thus, the material of the protective layer may be a rare earth metal oxide, a rare earth metal fluoride, a rare earth metal oxyfluoride, or any combination or mixture thereof. Thus, the material of the protective layer may be a combination of a rare earth metal oxide, a rare earth metal fluoride, and / or a rare earth metal oxyfluoride. In one embodiment, the material of the protective layer is a rare earth metal oxide. The rare earth metal-based protective layer has the additional utility of providing high protection of the substrate against the harsh conditions used in the plasma chamber.

[0027] The rare earth metal may be selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In one embodiment, the rare earth metal is yttrium.

[0028] According to the International Union of Pure and Applied Chemistry (IUPAC), lanthanides, as well as yttrium and scandium, are considered rare earth metals.

[0029] The rare earth metal oxide may be yttrium oxide, cerium oxide, dysprosium oxide, erbium oxide, or gadolinium oxide. In one embodiment, the rare earth metal oxide is yttrium oxide.

[0030] The rare earth metal fluoride may be yttrium fluoride, cerium fluoride, dysprosium fluoride, erbium fluoride, or gadolinium fluoride. In one embodiment, the rare earth metal fluoride is yttrium fluoride. The rare earth metal oxyfluoride may be yttrium oxyfluoride, cerium oxyfluoride, dysprosium oxyfluoride, erbium oxyfluoride, or gadolinium oxyfluoride. In one embodiment, the rare earth metal oxyfluoride is yttrium oxyfluoride.

[0031] The various precursors used in the methods described herein for producing the materials for the intermediate and protective layers are generally available and will be apparent to those skilled in the art.

[0032] The substrate may be formed from ceramic, metal, and / or glass. In one embodiment, the substrate is formed from metal. The metal may be a porous metal. The glass may be a porous glass.

[0033] This method may include forming a plasma etching resistant film having a total thickness of 200-3500 nm, 150-6000 nm, 300-5500 nm, 450-2300 nm, or 650-1100 nm. The plasma etching resistant film may have a thickness of 200-3500 nm, 150-6000 nm, 300-5500 nm, 450-2300 nm, or 650-1100 nm. The ability to form a fairly thin plasma etching resistant film while simultaneously having a high breakdown voltage has the additional benefit of requiring fewer starting materials, i.e., precursor chemicals, in the manufacturing process, as well as reducing manufacturing costs and time. The ability to form a fairly thin plasma etching resistant film has the further additional benefit of providing good adhesion to the substrate surface.

[0034] This method may include forming an intermediate layer having a thickness of 100-500 nm, 130-450 nm, 150-400 nm, or 200-300 nm. The intermediate layer may have a thickness of 100-500 nm, 130-450 nm, 150-400 nm, or 200-300 nm.

[0035] This method may include forming a protective layer having a thickness of 100-2000 nm, 200-1500 nm, 300-1000 nm, 400-900 nm, or 500-800 nm. The protective layer may have a thickness of 100-2000 nm, 200-1500 nm, 300-1000 nm, 400-900 nm, or 500-800 nm.

[0036] Plasma etching-resistant films can be fabricated on the surface of a substrate in a reaction space by an atomic layer deposition (ALD) process. When the intermediate and protective layers are fabricated on the substrate surface by an ALD process, excellent conformability and uniformity are achieved for the formed layers.

[0037] The ALD process is a method for depositing uniform, conformal deposits or layers on substrates of various shapes, even on complex three-dimensional structures. In the ALD process, the substrate is alternately exposed to at least two different precursors (chemical substances), usually one precursor per exposure, and deposits or layers are formed by alternating, essentially self-limiting surface reactions between the substrate surface (and, in later stages, naturally, the surface of layers or deposits already formed on the substrate) and the precursors. As a result, the deposited material "grows" on the substrate, layer by layer.

[0038] A characteristic feature of the ALD process is that the surface to be deposited is exposed to two or more different precursors in an alternating manner, usually accompanied by a purge period between precursor pulses. During the purge period, the deposited surface is exposed to a flow of gas that does not react with the precursors used in the process. This gas, often called a carrier gas or purge gas, is therefore inert to the precursors used in the process and removes, for example, excess precursors and by-products resulting from the chemiadsorption reaction of the previous precursor pulse. This purge can be constructed by different means. A fundamental requirement of the ALD process is that the deposited surface is purged between the introduction of a metallic precursor and the introduction of a non-metallic precursor. The purge period ensures that vapor phase growth is restricted and that only surfaces exposed to the precursor gas participate in growth. However, according to one embodiment, the step of purging with an inert gas can be omitted in the ALD process when two process gases, i.e., different precursors, that do not react with each other are applied. It can be mentioned, simply as an example, that the purge period can be omitted between two precursors that do not react with each other. In other words, the purging period can be omitted in some embodiments, for example, when two different oxygen precursors do not react with each other.

[0039] Alternating or sequential exposure of the deposition surface to different precursors can be carried out in different ways. In a batch process, at least one substrate is placed in the reaction space, into which the precursor and purge gas are introduced in predetermined cycles. Spatial atomic layer deposition is an ALD-type process based on the spatial separation of precursor gases or vapors. Different precursor gases or vapors can be confined to specific process areas or zones while the substrate passes through. In a continuous ALD-type process, spatially separated constant gas flow zones and a moving substrate are used to obtain time sequential exposure. By moving the substrate through stationary zones and providing precursor exposure and purge areas, a continuous coating process is achieved in the reaction space, enabling roll-to-roll coating of the substrate. In a continuous ALD-type process, the cycle time depends on the speed at which the substrate moves between gas flow zones.

[0040] Other names besides atomic layer deposition (ALD) are also used for these types of processes, in which the alternating introduction or exposure of two or more different precursors often results in layer growth via essentially self-limiting surface reactions. These other names or process variations include atomic layer epitaxy (ALE), atomic layer chemical vapor deposition (ALCVD), and corresponding plasma-enhanced, photo-assisted, and electron-enhanced variations. Unless otherwise specified, these processes are also treated collectively as ALD-type processes in this specification.

[0041] The method disclosed herein has the additional utility of providing a plasma etching resistant film having a high breakdown voltage value that prevents current from flowing to the substrate through the plasma etching resistant film.

[0042] The method disclosed herein has the additional benefit of being able to produce plasma etching resistant films having a high breakdown voltage while maintaining a thin film thickness.

[0043] The methods disclosed herein have the additional benefit of providing a method for producing plasma etching-resistant films in an economical manner. [Examples]

[0044] The embodiments described herein will be referenced in detail, and examples thereof are shown in the accompanying drawings.

[0045] The following description discloses several embodiments in detail so that those skilled in the art may utilize the methods based on this disclosure. Not all steps of the embodiments are discussed in detail, and many of the steps will be apparent to those skilled in the art based on this specific information.

[0046] For the sake of brevity, in the following exemplary embodiments, the sign of the component (item) is maintained when the component is repeated.

[0047] Figure 1 shows a plasma etching resistant film on the surface of a substrate according to one embodiment.

[0048] As described above, ALD processes are methods for depositing uniform, conformal films or layers on substrates of various shapes. Furthermore, as described above, in ALD processes, the layers or films are grown by alternating and repeating essentially self-limiting surface reactions between a precursor and the surface to be coated. The prior art discloses many different apparatuses suitable for performing ALD processes. The configuration of process tools suitable for carrying out the methods in the following embodiments will be obvious to those skilled in the art in light of this disclosure. The tools can be, for example, conventional ALD tools suitable for handling process chemicals. Steps associated with handling such tools, such as delivering the substrate to the reaction space, pumping down the reaction space to a low pressure, or, if the process is carried out at atmospheric pressure, regulating the gas flow in the tool, heating the substrate and the reaction space, will be obvious to those skilled in the art. Also, in order to highlight relevant aspects of the various embodiments of the present invention, many other known operations or features are not described in detail or mentioned herein.

[0049] Figure 1 shows a plasma etching resistant film 1 on the surface of a substrate 2 according to one embodiment. This exemplary embodiment can be manufactured by placing the substrate 2 into the reaction space of a typical reactor tool, for example, a tool suitable for carrying out an ALD process as a batch process. The reaction space is then pumped down to a pressure suitable for forming the plasma etching resistant film 1, for example, using a mechanical vacuum pump, or, in the case of an atmospheric pressure ALD system and / or process, the flow is typically set to protect the deposition zone from the atmosphere. Furthermore, the substrate 2 is heated to a temperature suitable for forming the film 1, depending on the method used. The substrate 2 can be introduced into the reaction space, for example, via an airtight load lock system, or simply via a loading hatch. The substrate 2 can be heated in situ or ex situ, for example, by a resistance heating element that heats the entire reaction space.

[0050] After the substrate 2 and the reaction space have reached the target temperature and other conditions suitable for deposition, the surface of the substrate may be conditioned, conditioned, or polished so that different layers 1a and 1b can be deposited intrinsically and directly on the surface. This surface conditioning typically involves chemical purification of the surface of the substrate 2 from impurities and / or oxidation. In particular, the removal of oxides is beneficial when the surface is transferred to the reaction space through an oxidizing environment, for example, when transporting an exposed substrate from one deposition tool to another. Details of the process for removing impurities and / or oxides from the surface of the substrate will be apparent to those skilled in the art upon consideration of this specification. In some embodiments of the present invention, conditioning can be performed off-situ, i.e., outside of the tools suitable for the ALD type process. An example of an off-situ conditioning process is etching in a 1% HF solution for 1 minute followed by rinsing in DI water. Another example of an off-situ conditioning process is exposing the substrate to ozone gas or oxygen plasma to remove oxygen impurities from the substrate surface in the form of volatile gases.

[0051] After the surface of substrate 2 is prepared, alternating exposure of the deposited surface to different chemicals is initiated, and a plasma etching-resistant film 1 is directly formed on the surface of substrate 2.

[0052] Precursors are preferably introduced into the reaction space in their gaseous form. This can be achieved by first evaporating the precursors in their respective supply containers, which may or may not be heated depending on the properties of the precursor chemicals themselves. The evaporated precursors can then be delivered into the reaction space, for example, by administration through piping of a reactor tool that includes a channel for delivering the vaporized precursors into the reaction space. Controlled administration of vapors into the reaction space can be achieved by valves or other flow controllers installed in the channel. These valves are typically called pulse valves in systems suitable for ALD-type deposition.

[0053] Other mechanisms for bringing substrate 2 into contact with the chemicals in the reaction space are also conceivable. One alternative is to move the surface of the substrate (instead of vaporized chemicals) through the region occupied by the gaseous chemicals.

[0054] A reactor suitable for ALD-type deposition is equipped with a system for introducing a carrier gas, such as nitrogen or argon, into the reaction space, thereby allowing the reaction space to be purged of excess chemicals and reaction byproducts before introducing the next chemical. This feature, along with the controlled administration of vaporized precursors, allows for the alternating exposure of the substrate surface to the precursors without significant mixing of different precursors in the reaction space or other parts of the reactor. In practice, the carrier gas flow is usually continuous through the reaction space throughout the entire deposition process, with only different precursors being introduced alternately into the reaction space along with the carrier gas. Obviously, purging the reaction space does not necessarily result in the complete removal of excess precursors or reaction byproducts from the reaction space, as residues of these or other materials may always be present.

[0055] Following various preparation steps, an intermediate layer 1a of a dielectric material, wherein the dielectric material is a nanolaminate of two or more different metal oxides, is deposited on the deposition surface by exposing the deposition surface to alternately repeated surface reactions of selected precursors, wherein with each exposure the deposition surface is exposed to one precursor, until a predetermined thickness of the intermediate layer is achieved. Then, a protective layer 1b of a rare earth metal oxide, a rare earth metal fluoride, a rare earth metal oxyfluoride, aluminum oxide, or any combination or mixture thereof is formed on the intermediate layer 1a until a predetermined thickness of the protective layer 1b is reached.

[0056] Each time the deposition surface is exposed to a precursor, additional deposits are formed on the deposition surface as a result of an adsorption re-reaction between the corresponding precursor and the deposition surface. The thickness of the plasma etching resistant film 1 on the surface of the substrate 2 can be increased by repeating exposure to different precursors one or more times. The film thickness is increased until a target thickness is reached, after which the alternating exposures are stopped and the process ends. As a result of the deposition process, the plasma etching resistant film 1 is formed on the surface of the substrate 2 having an intermediate layer 1a and a protective layer 1b. The plasma etching resistant film 1 also has excellent thickness uniformity and compositional uniformity along the deposition surface.

[0057] The following examples illustrate how plasma etching-resistant films can be fabricated on the surface of a substrate.

[0058] Example 1 - Formation of a plasma etching resistant film on a substrate In this example, a plasma etching-resistant film was prepared on the substrate surface in the manner described above. A comparative example was also formed. The breakdown voltage of the prepared samples was measured as described above.

[0059] The following table shows the formed film and the test results.

[0060] [Table 1] TMA = Trimethylaluminum (MeCp)3Y=Tris(methylcyclopentadienyl)yttrium *Nanolaminate = 20 × (5nm Y2O3 + 5nm Al2O3)

[0061] The results in Table 1 show that the plasma etching resistant film of Example 1 exhibits a higher measured breakdown voltage value than the film of Comparative Example 1.

[0062] Those skilled in the art will see that, with technological advancements, the basic idea can be implemented in a variety of ways. Therefore, the embodiments are not limited to the examples given above, but rather may vary within the scope of the claims.

[0063] The embodiments described above may be used in any combination of each other. Some of the embodiments may also be combined to form further embodiments. Methods, plasma etching resistant films, or uses disclosed herein may include at least one of the embodiments described earlier herein. It will be understood that the above benefits and advantages may relate to one embodiment or to several embodiments. Embodiments are not limited to those that solve any or all of the described problems, or to having any or all of the described benefits and advantages. It will be further understood that a reference to “one” component refers to one or more of these components. The term “comprising” is used herein to mean including subsequent features or actions without prejudice to the presence of one or more additional features or actions.

Claims

1. A method for producing a plasma etching resistant film (1) on the surface of a substrate (2), comprising exposing the deposited surface to an alternately repeated, essentially self-limiting precursor surface reaction, wherein each exposure exposes the deposited surface to one precursor, thereby bringing into the reaction space, An intermediate layer (1a) of dielectric material on the surface of the substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides, and the thickness of the intermediate layer is 100 to 500 nm, is formed. The process includes the step of forming a protective layer (1b) on the intermediate layer (1a), wherein the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, and any combination or mixture thereof, and the thickness of the protective layer is 100 to 3000 nm. A method for forming a plasma etching resistant film (1) that prevents current from flowing to the substrate through the plasma etching resistant film, by the step described above.

2. The method according to claim 1, comprising the step of forming a plasma etching resistant film (1) with a total film thickness of 700 nm having a breakdown voltage value of at least 200 V, or at least 230 V, or at least 250 V, or at least 270 V, or at least 300 V when measured for a plasma etching resistant film as described herein.

3. The method according to claim 1 or 2, wherein the dielectric material is an aluminum titanium oxide (ATO) nanolaminate.

4. The method according to any one of claims 1 to 3, wherein the nanolaminate of two or more different metal oxides is a nanolaminate of aluminum oxide and the rare earth metal oxide.

5. The method according to any one of claims 1 to 4, wherein the rare earth metal is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

6. The method according to any one of claims 1 to 5, wherein the substrate (2) is formed from ceramic, metal, and / or glass.

7. The method according to any one of claims 1 to 6, comprising forming a plasma etching resistant film (1) having a total thickness of 200 to 3500 nm, or 150 to 6000 nm, or 300 to 5500 nm, or 450 to 2300 nm, or 650 to 1100 nm.

8. The method according to any one of claims 1 to 7, comprising forming an intermediate layer (1a) having a thickness of 100 to 500 nm, or 130 to 450 nm, or 150 to 400 nm, or 200 to 300 nm.

9. The method according to any one of claims 1 to 8, comprising forming a protective layer (1b) having a thickness of 100 to 2000 nm, or 200 to 1500 nm, or 300 to 1000 nm, or 400 to 900 nm, or 500 to 800 nm.

10. The method according to any one of claims 1 to 9, wherein the plasma etching resistant film (1) is fabricated on the surface of the substrate in the reaction space by an atomic layer deposition process.

11. A plasma etching resistant film (1) on the surface of the substrate (2), wherein the plasma etching resistant film is An intermediate layer (1a) of dielectric material on the surface of the substrate, wherein the dielectric material is a nanolaminate of two or more different metal oxides, and the thickness of the intermediate layer is 100 to 500 nm, The intermediate layer (1a) comprises a protective layer (1b) on which the material of the protective layer is selected from the group consisting of rare earth metal oxides, rare earth metal fluorides, rare earth metal oxyfluorides, and any combination or mixture thereof, and the thickness of the protective layer is 100 to 3000 nm. The plasma etching resistant film is a plasma etching resistant film that prevents the current flowing through the plasma etching resistant film to the substrate.

12. The plasma etching resistant film (1) according to claim 11, wherein the plasma etching resistant film (1) has a breakdown voltage value of at least 200 V, or at least 230 V, or at least 250 V, or at least 270 V, or at least 300 V when measured for the plasma etching resistant film described herein with a total film thickness of 700 nm.

13. The plasma etching resistant film according to claim 11 or 12, wherein the dielectric material is an aluminum titanium oxide (ATO) nanolaminate.

14. The plasma etching resistant film according to any one of claims 11 to 13, wherein the nanolaminate of two or more different metal oxides is a nanolaminate of aluminum oxide and the rare earth metal oxide.

15. The plasma etching resistant film according to any one of claims 11 to 14, wherein the rare earth metal is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

16. The substrate (2) is formed from ceramic, metal, and / or glass, according to any one of claims 11 to 15, and is a plasma etching resistant film.

17. The plasma etching resistant film (1) according to any one of claims 11 to 16, wherein the plasma etching resistant film (1) has a total thickness of 200 to 3500 nm, or 150 to 6000 nm, or 300 to 5500 nm, or 450 to 2300 nm, or 650 to 1100 nm.

18. The plasma etching resistant film according to any one of claims 11 to 17, wherein the intermediate layer (1a) has a thickness of 100 to 500 nm, or 130 to 450 nm, or 150 to 400 nm, or 200 to 300 nm.

19. The protective layer (1b) has a thickness of 100 to 2000 nm, or 200 to 1500 nm, or 300 to 1000 nm, or 400 to 900 nm, or 500 to 800 nm, according to any one of claims 11 to 18.

20. Use of the plasma etching resistant film (1) according to any one of claims 11 to 19 to protect the surface of a plasma chamber from the harmful effects of process conditions used within the plasma chamber.

21. The use of the plasma etching resistant film (1) according to any one of claims 11 to 19 for suppressing or preventing the flow of current used in the plasma chamber to the substrate (2) through the plasma etching resistant film under the voltage experienced in the plasma process.

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