TW202113911A - Component for use in plasma chamber and manufacturing method thereof - Google Patents

Abstract

The invention provides a component used in a plasma chamber and a manufacturing method thereof, wherein the component in the plasma chamber is provided with a coating, the coating comprises oxyfluoride of rare earth elements, the chemical formula of the coating is RexOyFz (x is not equal to 0, y is not equal to 0, z is not equal to 0), Re is the rare earth elements, and RexOyFz is a crystalline phase. Due to the fact that the structure is a crystalline phase and has a specific structure, the coating has certain structural stability, and the structural stability can be kept in the service process, so that the cracking risk of the coating is reduced, and the stability of the cavity etching environment can be kept. Besides, oxyfluoride of rare earth elements is used as a protective material of the plasma etching cavity, so that the requirements of different etching processes such as simultaneous CF4 and O2 plasma corrosion resistance can be met, the application range is wider, the continuous production efficiency can be improved, and the production cost can be reduced due to the fact that parts do not need to be replaced frequently.

Description

Components used in plasma chamber and manufacturing method thereof

The present invention relates to the technical field of plasma processing, in particular to a component used in the interior of a plasma chamber and a manufacturing method thereof.

Plasma etching technology has played a large role in the field of semiconductor device manufacturing technology. For components inside the plasma chamber that are often exposed to corrosive environments, relatively high corrosion resistance is required. In order to better protect the components inside the plasma chamber and prevent the components inside the plasma chamber from being corroded by the plasma during long-term use, some researchers have proposed to use yttrium fluoride or yttrium oxide coatings on the inside of the plasma chamber. The protection scheme of the components can produce good plasma corrosion resistance.

However, with the continuous development of high-end semiconductor manufacturing processes (below 10x), plasma etching technology puts forward strict requirements on the stability of the etching cavity environment. Therefore, all parts in contact with plasma need: 1. The surface is highly compact, can be resistant to CF ₄ and/or O ₂ plasma corrosion at the same time, and the material structure is not changed as much as possible to maintain the stability of the cavity etching environment. 2. Shorten the initialization time of the etching machine, extend the service life of components, reduce the frequency of component replacement, and shorten the recovery time after cavity maintenance.

In response to the above requirements, the protective effects of yttrium oxide and yttrium fluoride are limited and cannot meet the actual needs. So how to provide a device that can extend the service life of components, and has high surface density, while being resistant to CF ₄ and/or O ₂ plasma corrosion, and maintaining The coating material for the stability of the cavity etching environment has become the target of further research.

In view of this, the present invention provides a component used in the interior of a plasma chamber and a manufacturing method thereof, so as to solve the problem that the coating in the prior art cannot meet the resistance to CF ₄ and/or O ₂ plasma corrosion at the same time and keep the cavity from being etched. The problem of environmental stability requirements.

To achieve the above objective, the present invention provides the following technical solutions: A component inside a plasma chamber, comprising: a component body in the plasma chamber; a coating on the component body; wherein the coating includes rare earth elements The chemical formula of the oxyfluoride is Re _x O _y F _z (x≠0, y≠0, z≠0), where Re is a rare earth element, and the Re _x O _y F _z is a crystalline phase.

Preferably, the coating further includes the oxide of the rare earth element and/or the fluoride of the rare earth element.

Preferably, the rare earth element is yttrium element, the oxide of the rare earth element is Y ₂ O ₃ , and the fluoride of the rare earth element is YF ₃ .

Preferably, the crystalline phase is a tetragonal phase, a cubic phase or a rhombus structure.

Preferably, the thickness of the coating is in the range of 0.001 μm-100um, including the endpoint value.

Preferably, the rare earth element is at least one of Y, Sc, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

Preferably, the component body includes at least one of a cover plate, a gasket, a nozzle, a gas distribution plate, a shower head, an electrostatic chuck assembly, a substrate holding frame, a processing kit, and a ceramic gasket.

The present invention also provides a manufacturing method of the inner part of the plasma chamber, which is used to form the above-mentioned part, and the manufacturing method includes:

The coating is formed on the component body inside the plasma chamber by using plasma enhanced physical vapor deposition technology.

Preferably, the use of plasma enhanced physical vapor deposition technology to form the coating on the component body inside the plasma chamber specifically includes:

Place the solid source material in the vacuum reaction chamber;

Placing a component body inside a plasma chamber above the solid source material;

An electron gun is provided to evaporate or sputter the solid source material. When the solid source material is evaporated into gas source material atoms, molecules, and free radicals, the gas source material atoms, molecules, and free radicals drift toward the component and condense On the surface of the component body;

A first gas is injected into the vacuum reaction chamber, and the plasma or ion beam dissociated by the first gas ionizes atoms, molecules, and radicals of the gas source material to form a matrix with a dense structure and random crystal orientation. yuan;

The primitives are deposited on the surface of the component body to form the coating.

Preferably, the first gas is an active gas, and the plasma or ion beam dissociated by the active gas reacts with the atoms, molecules, and free radicals to form a compact structure with random crystal orientation primitives.

Preferably, the solid source material includes oxyfluoride of rare earth elements.

Preferably, the solid source material further includes the oxide of the rare earth element and the fluoride of the rare earth element.

Preferably, the manufacturing method further includes:

A second gas is injected into the vacuum reaction chamber, and the second gas is used to react with the atoms, molecules and free radicals to form compounds containing rare earth elements, oxygen elements and fluorine elements.

Preferably, the solid source material includes a fluoride of a rare earth element, and the second gas is oxygen.

Preferably, the solid source material further includes oxyfluoride of the rare earth element.

Preferably, the solid source material includes oxides of rare earth elements, and the second gas is fluorine gas.

Preferably, the solid source material further includes oxyfluoride of the rare earth element.

It can be seen from the above technical solutions that the internal components of the plasma chamber provided by the present invention include a component body and a dense coating disposed on the component body. The coating includes rare-earth oxyfluoride, and the chemical formula is Re _x O _y F _z (x≠0, y≠0, z≠0), where Re is a rare earth element, and the Re _x O _y F _z is a crystalline phase. That is, the oxyfluoride of the rare earth element provided in the present invention has a crystalline phase and a specific crystal structure, so that the coating has a certain structural stability, and can maintain the stability of the coating structure during service. Thereby, the risk of coating cracking is reduced, and the stability of the cavity etching environment can be maintained. In addition, the use of rare-earth oxyfluoride as the protective material of the plasma etching chamber can meet the needs of different etching processes, such as simultaneous resistance to CF ₄ and O ₂ plasma corrosion, which is better than a single yttrium oxide coating or yttrium fluoride The coating has a wider application range, and because the rare earth element oxyfluoride has high stability, it can prolong the service life of the inner parts of the plasma chamber and improve the continuous production efficiency. Because there is no need to replace parts frequently, it can also reduce production. cost.

The present invention also provides a method for manufacturing parts inside the plasma chamber, which adopts plasma enhanced physical vapor deposition technology to form a coating, so that the coating has a stable crystalline phase structure, and the coating has high compactness. Avoid the impact of particulate pollutants introduced in the coating formation process, and the coating is rare earth element oxyfluoride, containing fluorine and oxygen at the same time, the corrosion resistance to halogen plasma is more stable than that of yttrium oxide, and it is more stable to O ₂ The corrosion resistance of plasma is also more stable than that of yttrium fluoride, so the oxyfluoride of rare earth elements is more suitable for etching the protective material of the inner wall of the cavity.

As mentioned in the previous technical section, the protection of yttrium oxide and yttrium fluoride in the prior art is limited, and cannot meet actual needs, especially not able to resist CF ₄ and O ₂ plasma corrosion at the same time.

The inventor found that how to maintain the stability of the plasma etching technology chamber environment is one of the main challenges in advanced integrated circuit manufacturing. This is because, on the one hand, when the plasma completes the etching of polysilicon and metal, the inner wall of the cavity will also be corroded by the plasma. Insufficient protection will cause a certain amount of metal pollution to the wafer etching; on the other hand, the plasma The by-product of etching the wafer ( _{the polymer of CF x} ) adheres to the inner wall of the cavity, and the gradual accumulation will affect the thickness of the plasma sheath, causing the etching rate to drop and drift.

Due to the chemical and physical stability, yttrium oxide (Y ₂ O ₃ ) coatings have been proven to be used to protect the surfaces of etched components or processing chamber parts exposed to halogen-containing plasma, resulting in good plasma resistance. However, actual production found that with the increase in the number of processed wafers, due to the penetration of fluorine or chlorine gas, _{the oxygen contained in Y 2} O ₃ is gradually replaced by fluorine or chlorine in the processing gas, and Y ₂ O ₃ is corroded into YOF , YCl or YOCl micro-particles, these micro-particles continue to accumulate and eventually fall on the etched wafer to cause particulate pollution, which affects the technical stability of the process. For this reason, these parts must be replaced every interval of time in actual production to restore the stability of the etching. The operation of shutdown/replacement/recovery actually greatly increases the cost of production and reduces the efficiency of continuous production.

In order to solve the problem of poor halogen plasma corrosion resistance of the yttrium oxide coating, it is proposed in the prior art to fluoride yttrium oxide or use yttrium fluoride to replace the yttrium oxide coating to protect the inner wall of the etching cavity. Wherein the fluorinated surface coating is exposed to the plasma of the fluorine-containing substance (e.g., a density of about ^{1 × 10 9 e - / cm} 3 between the CF ₄ plasma or CF ₃ / CF ₄ plasma) Long enough time to fluorinate the coating surface to form a YOF film to improve the corrosion resistance of the element against halogen plasma. For YF ₃ , on the one hand, the improvement effect of halogen corrosion resistance _{is not obvious compared with Y 2} O ₃ , and on the other hand, YF _{3 will be oxidized in the process of treating O 2} containing plasma, so the practical application is not Not extensive.

Moreover, the inventor found that in the prior art, yttrium oxide is fluorinated into YOF by fluorination for a long time, or yttrium fluoride is oxidized into YOF by oxidation, and the composition of YOF formed by either method is actually Y _{The mixture of 2} O ₃ and YF ₃ , and the conventional oxidation or fluorination technology can easily cause the original coating to crack. This is because _{the unit cell volume of Y 2} O ₃ and YF ₃ is inconsistent. The fluorination or oxidation process causes compressive or tensile stress in the coating, which causes the coating to crack easily, which in turn causes damage to the protective function of the coating, and causes Issues such as particle contamination and even metal contamination in the etching chamber.

Specifically, the conventional fluorination or oxidation technology, the composition and structure of the coating are not stable, and it is easy to cause the performance of the etching cavity to drift: the fluorination or oxidation process of _{Y 2} O ₃ and YF _{3 is a long-term diffusion} During the process, the concentration of O or F on the surface of the coating is always higher than the concentration inside the coating, so that there is always a concentration gradient of O or F on the surface of the coating. The environment is unstable, causing the performance of the etching cavity to drift.

Based on this, the present invention provides a component inside the plasma chamber, including:

The component body in the plasma chamber;

A coating on the body of the component;

Wherein, the coating includes rare earth element oxyfluoride, the chemical formula is Re _x O _y F _z (x≠0, y≠0, z≠0), wherein Re is a rare earth element, and the Re _x O _y F _z is the crystalline phase.

The coating on the parts inside the plasma chamber provided by the present invention is a rare earth element oxyfluoride, and its structure is a crystalline phase and has a specific structure, so that the coating has a certain stability and maintains a stable structure during service. It reduces the risk of coating cracking. In addition, the rare earth oxyfluoride contains both oxygen and fluorine, and has the characteristics of high density (close to 100% of the theoretical density), which can reduce the diffusion process of F or O in the coating and effectively protect the plasma Parts in the chamber.

The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by a person with ordinary knowledge in the technical field without making progressive work shall fall within the protection scope of the present invention.

An embodiment of the present invention provides components inside a plasma chamber, including: a component body in the plasma chamber; a coating on the component body; wherein the coating includes rare earth element oxyfluoride, chemical formula Is Re _x O _y F _z (x≠0, y≠0, z≠0), where Re is a rare earth element, and the Re _x O _y F _z is a crystalline phase.

It should be noted that in order to increase the concentration of F or O in the coating, eliminate the concentration gradient of the boundary layer, and maintain the stability of the boundary environment of the etching cavity. In other embodiments of the present invention, the coating may further include the oxide of the rare earth element or the fluoride of the rare earth element.

The specific elements of the rare earth elements are not limited in the embodiments of the present invention, and the rare earth elements may be Y, Sc, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu One or more of. It should be noted that in the conventional technology stage, considering cost issues and industrial application effects, the rare earth element that is often used is yttrium element, that is, the material of the coating in the embodiment of the present invention is YOF of crystalline phase, but with the development of the industry, Oxyfluoride of other rare earth elements can also be used, and since the atomic molar mass of other rare earth elements is larger, the plasma etching resistance is expected to be better and more stable.

When the rare earth element is yttrium in this embodiment, the crystalline phase may include rhomboid, cubic, and tetragonal YOF phases. The chemical composition of the oxyfluoride of the rare earth element may include YOF, Y ₅ O ₄ F ₇ , Y ₇ O ₆ F ₉ and other YOF with a single phase, or may include YOF with Y ₂ O ₃ , YF ₃ mixture. That is, the composition of the coating may also include rare earth element oxides and/or rare earth element fluorides. It should be noted that the mixture described in this embodiment refers to a mixture of rare earth element oxyfluoride and rare earth element oxide and/or rare earth element fluoride in the single layer structure of the coating, rather than rare earth element The layered structure of oxyfluoride and rare earth element oxide and/or rare earth element fluoride.

In addition, it should be noted that when the rare earth element is a rare earth element other than yttrium, the corresponding crystal phase is the crystal phase formed by the combination of the corresponding rare earth element, oxygen element and fluorine element. This is not done in this embodiment. Detailed description. No matter what kind of rare earth element, oxygen element and fluorine element, the rare earth element oxyfluoride has the characteristics of high density (close to 100% theoretical density), which can reduce the diffusion process of F or O in the coating. Effectively protect the structure of the internal components of the plasma chamber.

It should be noted that the conventional YOF, such as sprayed YOF, contains 3%-5% pores, so it needs to be 100μm~200μm thick to prevent the plasma from corroding the substrate (usually aluminum or ceramic) through these pores. Pieces). However, because the material coated by the method of the present invention has high compactness, the thickness of the coating can be reduced. In the actual use process, there is no major requirement for its thickness. According to actual needs, the thickness range can be It is 0.001μm-100μm, including the endpoint value. Typically, it can be greater than 10μm and less than 60μm. A thinner coating thickness can also prevent the parts exposed to plasma from being corroded.

High-frequency RF power (greater than 13MHz) and low-frequency RF power (less than or equal to 2MHz) are usually applied simultaneously in the plasma reaction chamber. For high-frequency RF power, the surface coating YOF of the components in the reaction chamber is an insulating material. The thickness of -200μm will not affect the distribution of high-frequency RF power, and the high-frequency RF power can still effectively penetrate the insulating coating. However, for low-frequency RF power, the thickness of the surface coating will significantly affect the penetration of the RF power, that is, the thicker the coating, the more difficult it is for the low-frequency RF power to penetrate. When coating the plasma corrosion-resistant material layer on the lining, gas shower head, conductive base, inner wall of the reaction chamber and other parts in the plasma processing chamber, if the coating material is too thick, it will cause the low-frequency RF power to be unable to effectively couple To the components that need to be coupled. The coating method of the present invention can not only obtain a sufficiently stable corrosion-resistant material layer YOF, but because the material layer is dense and thin, low-frequency radio frequency power can be efficiently coupled between different parts coated with the coating of the present invention. In addition, according to the level of F and O content in the manufacturing process, the level of F and O in the coating and the thickness of the coating can be designed accordingly to achieve long-life service of the etching cavity components.

The embodiment of the present invention does not limit the specific structures of the components inside the plasma chamber. Optionally, it is the various components that release the plasma in the plasma chamber, including: cover plates, gaskets, nozzles, gas distribution plates, At least one of spray head, electrostatic chuck assembly, substrate holding frame, processing kit, ceramic gasket, etc.

In this embodiment, in order to obtain the above-mentioned high-density rare earth element oxyfluoride with a crystalline phase, it can be achieved by an enhanced PVD method, a plasma enhancement method or an ion beam enhancement method.

Specifically, in an exemplary manufacturing process, a plasma enhanced physical vapor deposition (PEPVD) technology is used to produce an enhanced yttrium oxyfluoride coating with good/compact grain structure and random crystal orientation. , For example _{, coatings based on Y 5} O ₄ F ₇ and Y ₇ O ₆ F ₉ , where (1) deposition is performed in a low-pressure or vacuum chamber environment; (2) at least one deposition element or component is obtained from a material source Evaporated or sputtered, the evaporated or sputtered material is concentrated on the surface of the substrate substrate (this part of the process is a physical process, here called physical vapor deposition or PVD part); (3) At the same time, a Or multiple plasma sources are used to emit ions or generate plasma to surround the surface of the substrate. At least one deposited element or component is ionized and combined with the evaporated or sputtered element or component in the plasma or on the surface of the substrate Reaction; (4) The substrate is coupled to a negative voltage, so that it is bombarded by ionized atoms or ions during the deposition process. The reactions in (3) and (4) refer to the "plasma enhanced" (PE) function in PEPVD.

It should be noted that the plasma source can (1) be used to ionize, decompose and excite the reaction gas so that the deposition process can be performed at a low substrate temperature and a high coating growth rate (because the plasma generates more ions and free Base), or (2) are used to generate energetic ions for the substrate, so that the ions bombard the substrate surface and help to form a thick and concentrated coating thereon. More specifically, the plasma source is used to alternatively or jointly perform functions (1) and/or (2) to form a coating on the substrate. This kind of coating has a structure with sufficient thickness and compactness, and is referred to herein as an "enhanced coating" (Advanced coating, hereinafter referred to as A coating).

In the traditional plasma spraying process, the coating is deposited in an atmospheric environment. Unlike the traditional plasma spraying process, the enhanced coating provided by the present invention is in a low pressure or vacuum environment. In the deposition. In addition, the traditional plasma spraying process uses small powder particles to deposit the coating, and the enhanced coating of the present invention uses atoms radicals or particles to condense on the surface of the material to achieve deposition. Therefore, the properties of the coating obtained therefrom are different from those of the prior art coating, even if it uses materials of the same composition. For example, the yttrium oxyfluoride coating obtained according to a specific embodiment of the present invention is basically free of porosity, and its surface roughness is better than 1 μm, and it is better than the YOF coating obtained by the conventional plasma spraying method (PS). Has higher etching resistance.

Specific embodiments of the present invention will be described below in conjunction with the drawings. First, the device and method for depositing the enhanced coating are introduced. Fig. 1 shows an apparatus for depositing an enhanced coating according to a specific embodiment of the present invention. The device uses a process called PEPVD to deposit the enhanced coating, wherein the PE and PVD components are shown by dashed lines in FIG. 1. Traditionally, chemical vapor deposition (CVD) or plasma-enhanced chemical vapor deposition (PECVD) refers to a chemical process in which a substrate is exposed to one or more volatile precursors. It reacts or decomposes on the surface of the substrate to produce the expected deposited film on the surface of the substrate. In addition, PVD refers to a coating production method, which includes a purely physical process, which causes a vaporized or sputtered expected thin film material to condense, thereby depositing a thin film on the surface of the substrate, the expected thin film material is usually solid Source material. Therefore, it can be understood that the aforementioned PEPVD is a mixture of these two processes. That is, the PEPVD includes the condensation (PVD part) and plasma chemical reaction (PE part) of atoms, free radicals or molecules that are physical technologies that are carried out in the chamber and on the surface of the substrate.

In FIG. 1, the chamber 100 is evacuated by a vacuum pump 115. The component to be coated, that is, the component body 110 is coated with a coating. In this embodiment, the gas shower head, focus ring, cover ring, confinement ring, etc. are connected to the support ring 105. In addition, a negative bias voltage is applied to the part to be coated 110 through the support ring 105.

A source material 120 includes the components to be deposited, which are generally in solid form. For example, if the film to be deposited is YOF, the solid source material 120 should include yttrium (or fluorine, or oxygen)-there may be other materials, such as oxygen, fluorine (or yttrium), etc. To form physical deposition, the solid source material is evaporated or sputtered. In the specific embodiment shown in FIG. 1, an electron gun 125 is used to perform evaporation, which directs an electron beam 130 onto the solid source material 120. When the solid source material is evaporated to form atoms, molecules or free radicals of the gas source material, the atoms, molecules or free radicals of the gas source material drift towards the component body 110 and condense on the component body 110, as shown by dotted arrows in the figure.

The plasma-enhanced component is composed of a gas injector 135, which injects an active or inactive source gas into the chamber 100, such as a gas containing argon, oxygen, and fluorine, which is shown by a dotted line in the figure. The gas injector 135 is provided with at least a pair of electrodes, and a high voltage is applied to the electrodes, so that the flowing gas is ionized by the high voltage to form plasma, and the plasma is injected into the chamber 100 by the gas injector 135. The plasma is maintained in the space below the component body 110. In this embodiment, the electromagnetic field generated by the coil 145 coupled to the radio frequency source 150 exemplarily causes the ions in the plasma 140 to be driven by the electric field to move in a circular motion, so that the component body 110 is below the electromagnetic field. The ions are accelerated and maintained at a sufficient concentration. Without being bound by theory, several processes occur in the PE part. First, an inactive ionized gas component, such as argon, bombards the component body 110, and when it is collected, the film becomes dense. The effect of ion bombardment originates from the application of a negative bias voltage to the component body 110 and the support ring 105, or from ions emitted from a plasma source and aligned with the component body 110. In addition, reactive gas components or radicals such as oxygen or fluorine react with vaporized or sputtered gas source materials, and the reaction is located either on the surface of the component body 110 or in the chamber. Therefore, the above process has physical processes (bombardment and condensation) and chemical processes (for example, oxidation and ionization).

That is, in the embodiment of the present invention, the use of plasma enhanced physical vapor deposition technology to form the coating on the component body inside the plasma chamber specifically includes: placing a solid source material in a vacuum reaction chamber; The component body inside the slurry chamber is placed above the solid source material; an electron gun is set to evaporate or sputter the solid source material. When the solid source material is evaporated into gas source material atoms, molecules and free radicals, The gas source material atoms, molecules and free radicals drift toward the component and condense on the surface of the component body; inject a first gas into the vacuum reaction chamber, and the plasma or ion beam dissociated from the first gas will The gas source material atoms, molecules and free radicals are ionized to form primitives with a dense structure and random crystal orientation; the primitives are deposited on the surface of the component body to form the coating. Among them, ionization can make the primitives with a dense structure and random crystal orientation to be deposited to form a coating at a low substrate temperature and a high growth rate. Therefore, a highly dense coating can be formed by plasma enhancement or ion beam enhancement.

It should be noted that the first gas may be any gas capable of generating plasma, such as Ar, O ₂ , N _2, etc., which is not specifically limited in the embodiment of the present invention. That is, the first gas may be an active gas, such as an inactive gas. When the first gas is an active gas, the plasma or ion beam dissociated from the active gas reacts with the atoms, molecules and free radicals to form Dense structure and random crystal orientation primitives.

In this embodiment, there are many methods for forming rare earth oxyfluoride. In an embodiment of the present invention, the solid source material is rare earth oxyfluoride, which may be a rare earth oxyfluoride with a porous structure. The plasma enhancement or ion beam enhancement process is used to form a denser oxyfluoride coating with a crystalline phase of rare earth elements. It can also be a solid source material including the oxide of the rare earth element and the fluoride of the rare earth element, or it can directly form a denser rare earth element with a crystalline phase through the plasma enhancement or ion beam enhancement process. Oxyfluoride coating. In other embodiments of the present invention, it may further include injecting a second gas into the vacuum reaction chamber, where the second gas is used to react with the atoms, molecules, and free radicals to form rare earth elements, oxygen elements, and fluorine. Compounds of the elements. For example, the solid source material includes rare earth element fluoride, the second gas is oxygen, or the raw material may also include rare earth element oxyfluoride; or, the solid source material includes rare earth element oxide, and The second gas is fluorine gas, or may also include oxyfluoride of rare earth elements.

In order to clearly illustrate the formation process of the rare earth oxyfluoride in this embodiment, the formation of yttrium oxyfluoride is taken as an example for description in this embodiment.

Please refer to Figure 2-7, Figure 2-7 is a schematic diagram of plasma enhanced physical vapor deposition technology to form a yttrium oxyfluoride coating. As shown in Figure 2, YOF is directly used as the evaporation source, after thermal evaporation (achieved by electron beam heating or resistance heating or other heating methods) gasification, and then after the enhancement of plasma or ion beam, the substrate ( That is, a high-density YOF coating is formed on the components in the plasma chamber described in the above embodiment. As shown in Figure 3, YOF, Y ₂ O ₃ and YF _{3 are} directly used as evaporation sources, and vaporized by thermal evaporation (realized by electron beam heating or resistance heating or other heating methods), and then passed through plasma or ion beam After the enhancement effect of, a high-density YOF coating is formed. It should be noted that while YOF is used as the evaporation source in this embodiment, Y ₂ O ₃ and YF ₃ are added to increase the content of O and F in the coating. , There is no need to continue to convert Y ₂ O ₃ and YF ₃ into YOF. As shown in Figure 4, YF _{3 is} used as the evaporation source. After gasification, it _{reacts with O 2} by chemical reaction Y+F+O→YOF, and then is enhanced by plasma or ion beam to form a high-density YOF coating. Floor. As shown in Figure 5, Y ₂ O _{3 is} used as the evaporation source. After gasification, the _{chemical reaction Y+O+F→YOF with F 2 is carried} out, and after the enhancement of plasma or ion beam, a highly dense YOF coating. As shown in Figure 6, YOF and Y ₂ O _{3 are} used as the evaporation source, and F _{2 is introduced} as the reaction gas. After the enhancement of plasma or ion beam, a high-density YOF coating is formed; as shown in Figure 7 , Using YOF and YF ₃ as the evaporation source, and passing O ₂ as the reaction gas, after the enhancement of plasma or ion beam, a high-density YOF coating is formed.

Please refer to FIG. 8 and FIG. 9. FIG. 8 and FIG. 9 are both SEM pictures of the YOF coating formed by the method shown in FIG. 2. Among them, Figure 8 is the surface topography of the coating, and Figure 9 is the longitudinal section of the coating; it can be seen from Figure 8 that under the condition of 5000 times magnification, the surface of the coating still remains smooth, and as shown in Figure 9 According to the SEM picture of the longitudinal section, under the condition of 50,000 times magnification, no pore analogs are observed in the coating, and the surface coating has high density.

It should be noted that the traditional yttrium oxyfluoride coating is made by plasma spraying technology. This technology uses plasma heating to sputter micron-sized yttrium oxyfluoride particles on the workpiece substrate in a semi-melted state in an atmospheric environment. The yttrium oxyfluoride particles are cooled, shrinked in volume, and stacked to form a porous structure coating. The porosity is generally 3%-5%.

The yttrium oxyfluoride provided by the embodiment of the present invention uses an enhanced PVD technology to deposit a thin film in a low-pressure or vacuum environment, which can effectively reduce the influence of impurities in the environment. The YOF coating has a low synthesis temperature, which effectively reduces the influence of internal stress caused by the mismatch of the thermal expansion coefficient between the substrate and the coating, and avoids the coating and the substrate from falling off. In addition, YOF coating uses nano-scale gas atoms, molecules, and free radicals to condense on the surface of the material to achieve deposition, and the structure is 100% dense. Due to the high density of the structure, the thickness of tens of micrometers can achieve effective resistance to plasma corrosion, shorten the technical time, and reduce the cost of coating technology.

Moreover, coatings with specific structures (such as cubic phase, tetragonal phase, rhombic structure, etc.) have certain structural stability, which can maintain structural stability during service and reduce the risk of coating cracking. In addition, YOF can also _{form a mixture with Y 2} O ₃ and/or YF _{3 to} reduce the diffusion and corrosion of F and/or O in the boundary layer of the coating and maintain the stability of the boundary environment of the etching cavity. The use of YOF coating as a protective material for the etching cavity can simultaneously meet the needs of different etching processes (CF ₄ /O ₂ plasma ratio), and has a wider application range _{than a single Y 2} O ₃ coating or YF _{3 coating.}

It should be noted that the various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. For the same and similar parts between the various embodiments, refer to each other. can.

It should also be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply these entities or operations. There is any such actual relationship or order between. Moreover, the terms "including", "including" or any other variations thereof are intended to cover non-exclusive inclusion, so that an article or device including a series of elements includes not only those elements, but also other elements that are not explicitly listed. Or it also includes elements inherent to such items or equipment. If there are no more restrictions, the element defined by the sentence "including a..." does not exclude the existence of other same elements in the article or equipment that includes the above elements.

The above description of the disclosed embodiments enables those with ordinary knowledge in the technical field to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

100: chamber 105: Support ring 110: Component body 115: support ring 120: source material 125: electron gun 130: electron beam 135: Gas Syringe 140: Plasma 145: Coil 150: RF source

In order to more clearly describe the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are merely It is an embodiment of the present invention. For those with ordinary knowledge in the technical field, other schemas can be obtained according to the provided schema without making progressive labor. FIG. 1 is a schematic diagram of a plasma enhanced physical vapor deposition apparatus provided by an embodiment of the present invention; 2-7 are schematic diagrams of forming a yttrium oxyfluoride coating using plasma enhanced physical vapor deposition technology according to embodiments of the present invention; Fig. 8 is a surface topography diagram of a yttrium oxyfluoride coating provided by an embodiment of the present invention; Fig. 9 is a longitudinal section view of a yttrium oxyfluoride coating provided by an embodiment of the present invention.

Claims (17)

A component for the inside of a plasma chamber, comprising: a component body in the plasma chamber; a coating on the component body; wherein the coating includes a rare earth element oxyfluoride, the chemical formula is Re _x O _y F _z (x≠0, y≠0, z≠0), where Re is a rare earth element, and Re _x O _y F _z is a crystalline phase. The component used for the inside of a plasma chamber according to claim 1, wherein the coating further includes an oxide of the rare earth element and/or a fluoride of the rare earth element. The component used in the interior of the plasma chamber according to claim 2, wherein the rare earth element is yttrium element, the oxide of the rare earth element is Y ₂ O ₃ , and the fluoride of the rare earth element is YF ₃ . The component for the inside of the plasma chamber according to claim 3, wherein the crystalline phase is a tetragonal phase, a cubic phase, or a rhombus structure. The component for the inside of a plasma chamber according to claim 3, wherein the thickness of the coating is in the range of 0.001 μm to 100 μm, inclusive. The component for the inside of a plasma chamber according to claim 1, wherein the rare earth element is Y, Sc, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, At least one of Lu. The component used in the interior of the plasma chamber according to claim 1, wherein the component body includes: a cover plate, a gasket, a nozzle, a gas distribution plate, a shower head, an electrostatic chuck assembly, a substrate holding frame, and a processing sleeve At least one of the group and ceramic liner. A manufacturing method for a component inside a plasma chamber, which is used to form the component according to any one of claims 1-7, the manufacturing method comprising: Plasma enhanced physical vapor deposition technology is used to form the coating on the component body inside the plasma chamber. The method for manufacturing a component inside a plasma chamber according to claim 8, wherein the adopting plasma enhanced physical vapor deposition technology to form the coating on the component body inside the plasma chamber specifically includes: Placing a solid source material in a vacuum reaction chamber; Placing a component body inside the plasma chamber above the solid source material; An electron gun is provided to evaporate or sputter the solid source material. When the solid source material is evaporated into a gas source material atom, molecule, and free radical, the gas source material atom, molecule, and free radical drift toward the component body and condense on the solid source material. A deposition material layer is formed on the surface of the component body; Injecting an ionized first gas into the vacuum reaction chamber, and the ions in the first gas bombard the deposition material layer upward under the driving of an electric field to form a primitive with a dense structure and random crystal orientation; The primitive is deposited on the surface of the component body to form the coating. The method for manufacturing a component inside a plasma chamber according to claim 9, wherein the first gas is an active gas, and the plasma or ion beam dissociated by the active gas interacts with atoms, molecules, and free radicals of the gas source material. The radicals react to form a compact structure with random crystal orientation primitives. The method for manufacturing a component used in the interior of a plasma chamber according to claim 9, wherein the solid source material includes a rare earth element oxyfluoride. The method for manufacturing a component inside a plasma chamber according to claim 11, wherein the solid source material further includes an oxide of the rare earth element and a fluoride of the rare earth element. The manufacturing method for the inner part of the plasma chamber according to claim 9, wherein the manufacturing method further includes: A second gas is injected into the vacuum reaction chamber, and the second gas is used to react with atoms, molecules and free radicals of the gas source material to form a compound containing rare earth elements, oxygen elements and fluorine elements. The method for manufacturing a component inside a plasma chamber according to claim 13, wherein the solid source material includes the fluoride of the rare earth element, and the second gas is oxygen. The method for manufacturing a component inside a plasma chamber according to claim 14, wherein the solid source material further includes oxyfluoride of the rare earth element. The method for manufacturing a component inside a plasma chamber according to claim 13, wherein the solid source material includes an oxide of the rare earth element, and the second gas is fluorine gas. The method for manufacturing a component inside a plasma chamber according to claim 16, wherein the solid source material further includes oxyfluoride of the rare earth element.

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