Strong orientation yttrium oxide coating as well as preparation method and application thereof

Abstract

The invention relates to the technical field of semiconductors, and discloses a strongly-oriented yttrium oxide coating and a preparation method thereof.The strongly-oriented yttrium oxide coating is arranged on the surface of a base body, and the strongly-oriented yttrium oxide coating is of a (222)-oriented face-centered cubic phase structure which is not smaller than 70 vol%. According to the strongly oriented yttrium oxide coating provided by the invention, the plasma etching resistance of the yttrium oxide coating can be improved.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular to a strongly oriented yttrium oxide coating, a preparation method thereof, and a strongly oriented yttrium oxide coating chip. Background Art

[0002] With the rapid development of integrated circuit technology, plasma etching technology has gradually become an etching technology widely used in the manufacture of integrated circuits and micro-nano manufacturing processes at the nanometer level. With the increase in the energy of fluorine-containing plasma in the etching gas, high-energy fluorine-containing plasma will erode the cavity and internal components of the cavity, shortening the service life of the components; at the same time, during the corrosion process, non-volatile fluorides will be generated and deposited on the surface of the wafer, increasing the contamination of the wafer. Therefore, the plasma etching resistance of the materials of the etching machine cavity and internal components becomes crucial.

[0003] Y 2 O 3 is a material with very stable chemical and thermal properties, can remain stable in a strongly corrosive environment, is resistant to plasma bombardment, can greatly extend the service life of components and reduce the particles in the etching chamber. Research shows that the plasma etching resistance of the Y 2 O 3 coating is better than that of the Al 2 O 3 coating; the Al in the Al 2 O 3 will react with fluoride ions to form Al-F compounds to form particulate impurities that contaminate the wafer, while the surface particle and defect contamination caused by Y 2 O 3 is reduced; in addition, Y 2 O 3 has more excellent dielectric properties. Therefore, in the semiconductor industry, Y 2 O 3 ceramic materials have become key materials for plasma etching resistance of wafer processing equipment. Although Y 2 O 3 ceramics have excellent plasma etching resistance, they are difficult to sinter and process, and are relatively expensive, and their practicality is limited. At present, considering price factors, the materials of the etching process chamber and internal components are deposited on an aluminum alloy and alumina ceramic substrate to prepare a Y 2 O 3 coating to achieve the purpose. At present, yttrium oxide coatings are mainly prepared by spraying technology and physical vapor deposition (PVD) technology. In the Y 2 O 3 coating prepared by the spraying technology, non-dense structures, pores and cracks are likely to appear, resulting in a decrease in the corrosion resistance of the coating. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a strongly oriented yttrium oxide coating and a preparation method thereof, which can improve the plasma etching resistance of the yttrium oxide coating.

[0005] The technical problem to be solved by the present invention is to provide the application of the strongly oriented yttrium oxide coating in the preparation of an etching machine cavity and internal components of the cavity.

[0006] To solve the above technical problems, the present invention provides a strongly oriented yttrium oxide coating, which is provided on the surface of a substrate, and the strongly oriented yttrium oxide coating has a face-centered cubic phase structure with a (222) orientation of not less than 70 vol%.

[0007] In some embodiments, the thickness of the yttrium oxide coating is 1 μm to 6 μm;

[0008] The yttrium content of the yttrium oxide coating is 40 at.% to 45 at.%, and the oxygen content is 55 at.% to 60 at.%;

[0009] The content of the face-centered cubic phase structure with a (222) orientation of the yttrium oxide coating is not less than 75%.

[0010] To solve the above problems, the present invention provides a preparation method of a strongly oriented yttrium oxide coating, including the following steps:

[0011] Provide a substrate and load the substrate into the reaction chamber of a physical vapor deposition device;

[0012] Perform ion bombardment treatment on the substrate;

[0013] Turn on the closed-loop controller. The closed-loop control system sets the target voltage to 300 V to 400 V, the gas lower limit value to 0 to 2 sccm, the gas upper limit value to 2 sccm to 10 sccm in the control mode, introduce argon, introduce oxygen, use a yttrium metal sputtering cathode, turn on the substrate bias voltage, set the substrate bias voltage to -200 V to -100 V, turn on the medium-frequency power supply and the closed-loop controller, perform reactive sputtering and deposit a yttrium oxide coating on the surface of the substrate, and the obtained yttrium oxide coating has a face-centered cubic phase structure with a (222) orientation of not less than 70 vol%.

[0014] In some embodiments, during the deposition of the yttrium oxide coating, the sputtering power of the yttrium metal sputtering cathode is 300 W to 500 W; the reaction chamber pressure is 0.6 Pa to 1 Pa; the reaction chamber vacuum degree is 3×10 -5 Pa to 7×10 -5 Pa.

[0015] In some embodiments, a sample tray for loading the substrate is provided in the reaction chamber, a yttrium metal sputtering cathode is provided above the sample tray, the yttrium metal sputtering cathode is a circular twin cathode, and the circular twin cathodes are symmetrically distributed with respect to the vertical center line of the sample tray.

[0016] In some embodiments, the included angle between the circular twin cathode and the vertical center line of the sample tray is 70° to 75°;

[0017] The distance between the sputtering cathode in the circular twin cathode and the surface of the substrate to be plated is 7 cm to 10 cm;

[0018] The temperature of the sample tray is 200 °C to 400 °C.

[0019] In some embodiments, the thickness of the yttrium oxide coating is 1 μm to 6 μm;

[0020] The Y content of the yttrium oxide coating is 40 at.% to 45 at.%, and the O content is 55 at.% to 60 at.%;

[0021] The content of the face-centered cubic phase structure with (222) orientation in the yttrium oxide coating is not less than 75%.

[0022] In some embodiments, the ion bombardment treatment includes:

[0023] Introduce argon gas, turn on the ion source, set the gas pressure to 0.6 Pa to 1 Pa, turn on the substrate bias voltage, set the substrate bias voltage to -800 V to -400 V, and the ion source power to 2 kW to 5 kW.

[0024] In some embodiments, before depositing the yttrium oxide layer on the substrate, it further includes:

[0025] Deposit a yttrium metal transition layer on the substrate.

[0026] In some embodiments, depositing the yttrium metal transition layer on the substrate includes:

[0027] Control the temperature of the reaction chamber at 250 °C to 350 °C, the vacuum degree at 3×10 -5 Pa to 7×10 -5 Pa, introduce argon gas, set the argon gas pressure to 0.1 Pa to 0.6 Pa, use a yttrium metal sputtering cathode, set the sputtering power of the sputtering cathode to 300 W to 500 W, turn on the substrate bias voltage, set the substrate bias voltage to -200 V to 0, and perform sputtering to deposit a yttrium metal transition layer on the substrate surface.

[0028] In some embodiments, the thickness of the yttrium metal transition layer is 0 to 0.2 μm.

[0029] In some embodiments, the substrate includes an aluminum substrate, a glass substrate, an alumina substrate, and a single crystal silicon wafer.

[0030] In some embodiments, before the ion bombardment treatment of the substrate, the following steps are further included:

[0031] Set the vacuum degree of the reaction chamber at 8×10 -4 ~9×10 -4 Pa, introduce argon gas, set the gas pressure at 1 Pa to 2 Pa, turn on the substrate bias voltage, set the substrate bias voltage at -900 V to -800 V, and perform glow cleaning on the substrate.

[0032] To solve the above problems, the present invention provides the application of a strongly oriented yttrium oxide coating in the preparation of an etching machine chamber and internal components thereof, and the strongly oriented yttrium oxide coating is used as a plasma etching resistant material in the preparation of the etching machine chamber and internal components thereof.

[0033] Implementing the present invention has the following beneficial effects:

[0034] The strongly oriented yttrium oxide coating provided by the present invention is disposed on the surface of the substrate. The strongly oriented yttrium oxide coating has a face-centered cubic phase structure with a (222) orientation of not less than 70 vol%, and a single-phase face-centered cubic structure, and is not prone to particle shedding, thus having better plasma etching resistance. Y 2 O 3 When the coating is (222) preferentially oriented, it is a close-packed plane and has better mechanical and corrosion resistance properties.

[0035] The preparation method of the strongly oriented yttrium oxide coating provided by the present invention prepares the coating by physical vapor deposition. By strictly controlling the oxygen partial pressure and the bias voltage, a dense coating structure and a single Y 2 O 3 face-centered cubic phase with a strong (222) preferential orientation are obtained, so that the film has excellent mechanical properties, such as high hardness, modulus, and strong corrosion resistance due to the dense tissue structure. Description of the Drawings

[0036] Figure 1 It is a schematic structural diagram of a circular twin cathode used in the preparation method of the strongly oriented yttrium oxide coating provided by the present invention;

[0037] Figure 2 It is an X-ray diffraction pattern of the yttrium oxide coatings prepared in Examples 1 to 3 and Comparative Example 1;

[0038] Figure 3 It is a morphological diagram after plasma etching of the alumina substrate without coating in Example 1;

[0039] Figure 4It is a depth comparison diagram after plasma etching of Example 1 and the uncoated alumina substrate;

[0040] Figure 5 It is a comparison diagram of plasma etching rates. Detailed implementation manners

[0041] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Examples of the embodiments are shown in the accompanying drawings, where the same or similar reference numerals represent the same or similar elements or elements with the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are only used to explain the present invention and should not be construed as a limitation of the present invention. In addition, it should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0042] In the description of the present invention, it should be understood that the orientation or positional relationships indicated by the terms "length", "width", "upper", "lower", "left", "right", "horizontal", "top", "bottom", etc. are based on the orientation or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation of the present invention.

[0043] In addition, the terms "first" and "second" are only used for descriptive purposes and should not be construed as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of the described features. In the description of the present invention, "a plurality" means two or more unless otherwise specifically defined.

[0044] In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, the terms "mounted", "connected" and "connected" should be understood in a broad sense. For example, it may be a fixed connection, a detachable connection or an integral connection; it may be a mechanical connection, an electrical connection or a communication with each other; it may be directly connected or indirectly connected through an intermediate medium, and it may be the internal communication of two elements or the interaction relationship between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0045] In the present invention, unless otherwise clearly specified and defined, the first feature being "on" or "under" the second feature may include direct contact between the first and second features, or may include the first and second features not being in direct contact but in contact through additional features therebetween. Moreover, the first feature being "above", "over" and "on top of" the second feature includes the first feature being directly above and obliquely above the second feature, or merely indicating that the horizontal height of the first feature is higher than that of the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly below and obliquely below the second feature, or merely indicating that the horizontal height of the first feature is less than that of the second feature.

[0046] The following disclosure provides many different embodiments or examples for implementing different structures of the present invention. To simplify the disclosure of the present invention, the components and settings of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. In addition, the present invention may repeat reference numerals and / or reference letters in different examples, and this repetition is for the purpose of simplification and clarity, and does not itself indicate the relationship between the various embodiments and / or settings discussed. In addition, the present invention provides examples of various specific processes and materials, but those of ordinary skill in the art can be aware of the application of other processes and / or the use of other materials.

[0047] In the present invention, "preferred" and "more preferred" are only used to describe embodiments or examples with better effects, and it should be understood that they do not constitute a limitation on the protection scope of the present invention. In the present invention, among the technical features described in an open-ended manner, there are included closed technical solutions composed of the listed features, as well as open technical solutions including the listed features. In the present invention, regarding numerical ranges, unless otherwise specified, both endpoints of the numerical range are included.

[0048] On the one hand, the present invention provides a strongly oriented yttrium oxide coating, and the strongly oriented yttrium oxide coating is provided on the surface of a substrate, and the strongly oriented yttrium oxide coating has a face-centered cubic phase structure with a (222) orientation of not less than 70 vol%.

[0049] The strongly oriented yttrium oxide coating provided by the present invention has a face-centered cubic phase structure with a (222) orientation of not less than 70 vol%, and a single-phase face-centered cubic structure, and is not prone to particle shedding, so as to have better plasma etching resistance. Y 2 O 3 When the coating is (222) preferentially oriented, it is a close-packed plane and has better mechanical and corrosion resistance properties.

[0050] In some embodiments, the thickness of the yttrium oxide coating is 1 μm to 6 μm, and its exemplary thicknesses are 2 μm, 3 μm, 4 μm or 5 μm, and are not limited to the above listing.

[0051] In some embodiments, the Y content of the yttrium oxide coating is 40 at.% to 45 at.%, and the O content is 55 at.% to 60 at.%.

[0052] In some embodiments, the substrate includes an aluminum substrate, a glass substrate, an alumina substrate, and a single crystal silicon wafer.

[0053] Preferably, the content of the face-centered cubic phase structure with (222) orientation in the yttrium oxide coating is not less than 75%.

[0054] It should be noted that the face-centered cubic phase structure, also known as the FCC crystal structure, has a very dense atomic arrangement, with atoms located at each corner and each face center of the cube. The (222) orientation refers to a specific crystal plane or direction of the crystal. For the face-centered cubic structure, (222) refers to a high-symmetry direction in the crystal. (222) represents the lattice arrangement along a certain crystal plane direction of the face-centered cubic structure. In this orientation, the (222) plane in the unit cell is the main characteristic plane of the crystal structure.

[0055] On the other hand, the present invention provides a method for preparing a strongly oriented yttrium oxide coating, including the following steps:

[0056] 1) Provide a substrate and load the substrate into the reaction chamber of a physical vapor deposition device;

[0057] In some embodiments, before loading the substrate into the reaction chamber of the physical vapor deposition device, it further includes: polishing the substrate, and after polishing, the sample reaches a mirror effect. Then, the substrate for deposition is successively ultrasonically cleaned in a metal cleaning agent solution and absolute ethanol to remove adsorbed impurities and pollutants on the surface. After completion, the sample is taken out and dried.

[0058] 2) Perform ion bombardment treatment on the substrate;

[0059] In some embodiments, the ion bombardment treatment includes: introducing argon, turning on the ion source, setting the gas pressure to 0.6 Pa to 1 Pa, turning on the substrate bias voltage, setting the substrate bias voltage to -800 V to -400 V, and the ion source power to 2 kW to 5 kW.

[0060] Preferably, set the gas pressure to 0.7 Pa to 0.9 Pa, turn on the substrate bias voltage, set the substrate bias voltage to -700 V to -300 V, and the ion source power to 3 kW to 4 kW.

[0061] Performing ion bombardment under the above conditions can not only clean the surface of the substrate, remove the surface oxide layer and pollutants, but also increase the surface roughness.

[0062] In some embodiments, before the ion bombardment treatment of the substrate, the following steps are further included: setting the vacuum degree of the reaction chamber at 8×10 -4 ~9×10 -4 Pa, introducing argon gas, setting the gas pressure at 1 Pa to 2 Pa, turning on the substrate bias voltage, setting the substrate bias voltage at -900 V to -800 V, and performing glow cleaning on the substrate.

[0063] Preferably, the vacuum degree is set at 8.5×10 -4 ~8.9×10 -4 Pa, the gas pressure is set at 1.1 Pa to 1.8 Pa, and the substrate bias voltage is set at -880 V to -830 V.

[0064] Performing glow cleaning under the above-mentioned implementation conditions can not only effectively remove the organic substances, oxide layers and other pollutants on the surface of the substrate, providing a clean surface for the subsequent deposition of the thin film, but also provide a rough surface to provide more bonding points for the thin film, which helps to improve the adhesion of the thin film.

[0065] 3) Turn on the closed-loop controller. The closed-loop control system sets the target voltage at 300 V to 400 V, the gas lower limit value at 0 to 2 sccm, the gas upper limit value at 2 sccm to 10 sccm in the control mode, introduce argon gas, introduce oxygen gas, use a yttrium metal sputtering cathode, turn on the substrate bias voltage, set the substrate bias voltage at -200 V to -100 V, turn on the medium-frequency power supply and the closed-loop controller, perform reactive sputtering and deposit a yttrium oxide coating on the surface of the substrate. The obtained yttrium oxide coating has a face-centered cubic phase structure with a (222) orientation of not less than 70 vol%.

[0066] The preparation method of the strongly oriented yttrium oxide coating provided by the present invention prepares the coating by physical vapor deposition method. By strictly controlling the oxygen partial pressure and the bias voltage, a dense coating structure and a single Y 2 O 3 face-centered cubic phase are obtained, and it has a strong (222) preferred orientation. Furthermore, the thin film has excellent mechanical properties, such as high hardness, modulus and strong corrosion resistance due to the dense tissue structure.

[0067] It should be noted that the closed-loop controller in a Physical Vapor Deposition (PVD) device is an automated control system used to monitor and adjust various parameters during the deposition process in real time to ensure the coating quality. The closed-loop controller is usually based on a regulation mechanism with sensor feedback, enabling the deposition process to be dynamically adjusted according to the target set value, thereby achieving high-precision thin film preparation. During the PVD process, the type and flow rate of the gas have an important impact on the composition and quality of the thin film. The closed-loop control system monitors the gas flow rate and pressure and adjusts the gas flow control valve or flowmeter to maintain the required atmosphere conditions. In the present invention, in the control mode, the target voltage is set to 300V - 400V, the lower limit value of the gas is 0 - 2 sccm, and the upper limit value of the gas is 2 sccm - 10 sccm. Preferably, in the control mode, the target voltage is set to 300V - 350V, the lower limit value of the gas is 0 - 1 sccm, and the upper limit value of the gas is 2 sccm - 5 sccm. Sufficient oxygen partial pressure is beneficial to the growth of the close-packed plane structure of the face-centered cubic crystal. Too high oxygen partial pressure is likely to cause poisoning on the surface of the target. It is necessary to ensure the growth of the FCC(111) structure thin film under a certain oxygen partial pressure. The present invention controls the input amount of oxygen through the closed-loop control system. Under sufficient oxygen partial pressure, it can promote the formation of the face-centered cubic phase YO with (222) orientation and help improve the densification and uniformity of the film layer.

[0068] In addition, the substrate bias is a key parameter in physical vapor deposition, especially when it is necessary to control the energy on the substrate surface and the quality of the deposited thin film during the deposition process. The substrate bias usually refers to the voltage applied to the substrate, which is used to control the charge accumulation on the substrate surface, the kinetic behavior of the deposited particles, and the properties of the thin film. Usually, the bias voltage applied to the substrate is negative (negative substrate bias), making the substrate become the cathode. In this case, the ions in the source are accelerated and bombarded onto the substrate surface, increasing the energy of the particles and improving the quality, adhesion, and density of the deposited film. Preferably, the substrate bias is set to -150V - -100V. Appropriate bias promotes the migration of deposited atoms and helps the preferential growth of the close-packed plane of the thin film with (222) orientation, forming a strong face-centered cubic phase structure with (222).

[0069] In some embodiments, during the process of depositing the yttrium oxide coating, the sputtering power of the yttrium metal sputtering cathode is 300W - 500W; the reaction chamber gas pressure is 0.6Pa - 1Pa; the reaction chamber vacuum degree is 3×10 -5 Pa - 7×10 -5 Pa. Preferably, the sputtering power of the yttrium metal sputtering cathode is 350W - 450W; the reaction chamber gas pressure is 0.7Pa - 0.9Pa; the reaction chamber vacuum degree is 4×10 -5 Pa - 6×10 -5Pa. Among them, an appropriate sputtering power is required to ensure that the deposited particles have sufficient energy for uniform deposition and crystallization. A lower gas pressure helps to improve the crystallinity and density of the thin film, thereby promoting the formation of (222) orientation. A higher reaction chamber vacuum can reduce impurity interference, ensure a higher particle energy during the deposition process, promote crystal growth, and facilitate the formation of a single (222) face-centered cubic phase.

[0070] Furthermore, as Figure 1 shown, in some embodiments, a sample disk 2 for loading the substrate is provided in the reaction chamber. Above the sample disk 2, a yttrium metal sputtering cathode is provided. The yttrium metal sputtering cathode is a circular twin cathode 1, and the circular twin cathode 1 is symmetrically distributed with respect to the vertical center line of the sample disk 2.

[0071] It should be noted that a twin cathode generally refers to using two cathode targets of the same or different materials in the sputtering deposition process and sputtering alternately in a parallel manner. In the twin cathode system of the present invention, an intermediate frequency power pulse mode is adopted. The Y target materials of the same composition are respectively used as cathodes alternately within one voltage cycle. By alternately using the twin cathodes as cathodes, the static charges accumulated on the target surface due to the deposition of non-conductive materials during the deposition of oxides are neutralized, and the target poisoning phenomenon that affects the deposition stability of the insulating thin film is eliminated, forming a stable deposition environment for the Y 2 O 3 thin film material.

[0072] In some embodiments, the included angle between the circular twin cathode and the vertical center line of the sample disk is 70° - 75°; the distance between the sputtering cathode in the circular twin cathode and the surface of the substrate to be plated is 7 cm - 10 cm. Preferably, the included angle between the circular twin cathode and the vertical center line of the sample disk is 15°; the distance between the sputtering cathode in the circular twin cathode and the surface of the substrate to be plated is 8 cm - 9 cm. The circular twin cathode can eliminate the target poisoning phenomenon that affects the deposition stability of the insulating thin film. The currently preferred angle and height settings between the two cathodes can enhance the ionization and energy of the deposited ions, thereby improving the density of the deposited thin film.

[0073] In some embodiments, the temperature of the sample disk is 200°C - 400°C. Preferably, the temperature of the sample disk is 250°C - 350°C, and the sample disk is rotated to heat the sample evenly.

[0074] In some embodiments, before depositing the yttrium oxide layer on the substrate, it further includes:

[0075] Depositing a yttrium metal transition layer on the substrate.

[0076] In some embodiments, depositing the yttrium metal transition layer on the substrate includes:

[0077] Control the temperature of the reaction chamber at 250 °C to 350 °C, and control the vacuum degree at 3×10 -5 Pa to 7×10 -5 Pa. Introduce argon gas, set the argon gas pressure at 0.1 Pa to 0.6 Pa, use a yttrium metal sputtering cathode, set the sputtering power of the sputtering cathode at 300 W to 500 W, turn on the substrate bias voltage, set the substrate bias voltage at -200 V to 0, and perform sputtering to deposit a yttrium metal transition layer on the surface of the substrate.

[0078] Preferably, control the temperature of the reaction chamber at 270 °C to 300 °C, and control the vacuum degree at 4×10 -5 Pa to 6×10 - 5 Pa, set the argon gas pressure at 0.2 Pa to 0.5 Pa, set the sputtering power of the sputtering cathode at 350 W to 450 W, and set the substrate bias voltage at -100 V to 0.

[0079] In some embodiments, the thickness of the yttrium metal transition layer is 0 to 0.2 μm; its exemplary thicknesses are 0.05 μm, 0.1 μm, 0.14 μm or 0.18 μm, and are not limited to the above listing.

[0080] It should be noted that depositing a yttrium metal transition layer on the substrate and then precipitating yttrium oxide can improve the interfacial bonding between the yttrium oxide thin film and the substrate.

[0081] In some embodiments, the thickness of the yttrium oxide coating is 1 μm to 6 μm; its exemplary thicknesses are 2 μm, 3 μm, 4 μm or 5 μm, and are not limited to the above listing; the Y content of the yttrium oxide coating is 40 at.% to 45 at.%, and the O content is 55 at.% to 60 at.%; the content of the face-centered cubic phase structure with (222) orientation in the yttrium oxide coating is not less than 75%.

[0082] In some embodiments, the substrate includes an aluminum substrate, a glass substrate, an alumina substrate, and a single crystal silicon wafer. Preferably, the aluminum substrate includes a high-purity aluminum substrate and an anodized aluminum substrate.

[0083] In a third aspect, the present invention provides an application of a strongly oriented yttrium oxide coating in the preparation of an etching machine chamber and internal components of the chamber. The strongly oriented yttrium oxide coating is used as a plasma etching-resistant material in the preparation of the etching machine chamber and internal components of the chamber. The internal components of the etching machine include a window mirror, a gas dispersion disk, a nozzle, an insulating ring, a cover plate, a focusing ring, and an electrostatic chuck. The strongly oriented yttrium oxide coating provided by the present invention has a face-centered cubic phase structure with (222) orientation of not less than 70 vol%, a face-centered cubic phase single-phase structure, and is not prone to particle shedding, thus having better plasma etching resistance. Y 2 O3 When the coating is in (222) preferred orientation, it is a close-packed plane and has better mechanical and corrosion resistance properties.

[0084] The present invention will be further described below with specific embodiments:

[0085] Example 1

[0086] This example provides a method for preparing a strongly oriented yttrium oxide coating, which includes the following steps:

[0087] (1) Provide a substrate and load the substrate into the reaction chamber of a physical vapor deposition device;

[0088] Specifically, an aluminum sheet is selected as the substrate, and the substrate is polished using a polishing cloth and a polishing liquid. After polishing, the sample reaches a mirror finish with a roughness of about 40 nm. The polished substrate is placed in a metal cleaning agent solution for ultrasonic cleaning for 20 min, and then placed in anhydrous ethanol for ultrasonic cleaning for 20 min to remove adsorbed impurities and contaminants on the surface. After completion, the sample is taken out and dried.

[0089] (2) Perform ion bombardment treatment on the substrate;

[0090] Specifically, the substrate is placed at the center position of the sample disk. When the vacuum degree of the process chamber reaches 9×10 -4 Pa, 100 sccm of argon gas is introduced, the set pressure is 1.0 Pa, the substrate bias voltage is turned on with a value of -800 V, and glow cleaning of the substrate is performed for 30 min. Then, ion bombardment treatment is performed on the substrate. 70 sccm of argon gas is introduced, the ion source is turned on, the set pressure is 0.7 Pa, the substrate bias voltage is -500 V, the ion source power is 2.5 kW, and the time is 15 min.

[0091] (3) Deposit a yttrium metal transition layer on the substrate;

[0092] Specifically, the heating temperature is set to 300 °C and the rotation speed of the turntable is 20 r / min. When the temperature of the sample disk reaches 300 °C and the vacuum degree of the cavity reaches 5×10 -5 Pa, start depositing the yttrium metal transition layer. 33 sccm of argon gas is introduced, the cavity pressure is stabilized at 0.5 Pa, the cathode sputtering power of the medium-frequency power supply is set to 300 W, the bias voltage is -100 V, and sputtering is performed for 3 min to deposit a yttrium metal transition layer with a thickness of about 0.1 μm on the surface of the substrate.

[0093] (4) Deposit a yttrium oxide coating on the yttrium metal transition layer;

[0094] Specifically, in the closed-loop control system control mode, the target voltage is set to 380V, the lower limit of the control gas is set to 0 sccm, and the upper limit of the control oxygen gas is set to 5 sccm. 33 sccm of argon gas is introduced, the chamber pressure is stabilized at 0.5 Pa, the cathode sputtering power of the medium-frequency power supply is set to 300W, and the bias voltage is -100V. The medium-frequency power supply and the closed-loop controller are turned on, and reactive sputtering is carried out for 120 min to deposit a yttrium oxide coating with a thickness of about 2 μm on the substrate surface.

[0095] As Figure 2 shown, the prepared sample is analyzed by X-ray diffraction. The X-ray source is a Cu source, and the measured 2θ ranges from 15° to 70°. The results show that the prepared yttrium oxide coating has a cubic phase with strong (222) orientation. According to the estimation of the integral intensity of the XRD diffraction peak, the volume content of the (222) orientation is approximately 95%.

[0096] Example 2

[0097] This example provides a method for preparing a strongly oriented yttrium oxide coating, including the following steps:

[0098] 1) Provide a substrate and load the substrate into the reaction chamber of a physical vapor deposition device;

[0099] Specifically, a glass substrate is selected, put into a metal cleaning agent solution for ultrasonic cleaning for 20 min, and then put into absolute ethanol for ultrasonic cleaning for 20 min to remove adsorbed impurities and pollutants on the surface. After completion, the sample is taken out and dried.

[0100] 2) Perform ion bombardment treatment on the substrate;

[0101] Specifically, the vacuum degree of the process chamber reaches 9×10 -4 Pa, 100 sccm of argon gas is introduced, the pressure is set to 1.0 Pa, the substrate bias voltage is turned on, the value is -800V, and the substrate is subjected to glow cleaning for 30 min. Then the substrate is etched, 70 sccm of argon gas is introduced, the ion source is turned on, the pressure is set to 0.7 Pa, the substrate bias voltage is -500V, and the ion source power is 2.5 kW, and the time is 15 min.

[0102] 3) Deposit a yttrium oxide coating on the substrate;

[0103] Specifically, the heating temperature is set to 300°C, the rotation speed of the turntable is 20 r / min. Wait until the temperature of the sample disk reaches 300°C and the chamber vacuum degree reaches 5×10 -5When the pressure reaches 0.5 Pa, the deposition of the yttrium oxide coating begins. In the closed-loop control system control mode, the target voltage is set to 350 V, the lower limit value of the control gas is set to 0 sccm, and the upper limit value of the control gas is set to 7 sccm. 33 sccm of argon gas is introduced, and the chamber pressure is stabilized at 0.5 Pa. The intermediate frequency power supply sets the cathode sputtering power to 500 W and the bias voltage to -100 V. The intermediate frequency power supply and the closed-loop controller are turned on, and reactive sputtering is carried out for 120 min to deposit a yttrium oxide coating with a thickness of about 4 μm on the substrate surface.

[0104] The prepared sample was detected for light transmittance using an LS155 color difference haze meter. The light transmittance of the glass covered with the yttrium oxide coating within the visible light wavelength range of 400 nm to 700 nm was 76.3% to 88.4%. As Figure 2 shown, the prepared sample was analyzed by X-ray diffraction. The X-ray source was a Cu source, and the 2θ tested ranged from 15° to 70°. The results showed that the prepared yttrium oxide coating had a cubic phase with a strong (222) orientation, and at the same time, there were weak monoclinic phase diffraction peaks, and weak cubic phase (221) and monoclinic phase (40 - 2) diffraction peaks. According to the estimation of the integral intensity of the XRD diffraction peaks, the volume content of the (222) orientation was approximately 83%.

[0105] Example 3

[0106] This example provides a method for preparing a strongly oriented yttrium oxide coating, including the following steps:

[0107] (1) Provide a substrate and load the substrate into the reaction chamber of a physical vapor deposition device;

[0108] Specifically, the substrate is selected as alumina, placed in a metal cleaning agent solution for ultrasonic cleaning for 20 min, and then placed in absolute ethanol for ultrasonic cleaning for 20 min to remove adsorbed impurities and pollutants on the surface. After completion, the sample is taken out and dried.

[0109] (2) Perform ion bombardment treatment on the substrate;

[0110] Specifically, the substrate is placed at the center position of the sample disk. The vacuum degree of the process chamber reaches 9×10 -4 Pa, 100 sccm of argon gas is introduced, the pressure is set to 1.0 Pa, the substrate bias voltage is turned on, and the value is -800 V. The substrate is subjected to glow cleaning for 30 min. Then, the substrate is etched. 70 sccm of argon gas is introduced, the ion source is turned on, the pressure is set to 0.7 Pa, the substrate bias voltage is -500 V, and the ion source power is 2.5 kW. The time is 15 min.

[0111] (3) Deposit a yttrium metal transition layer on the substrate;

[0112] Specifically, set the heating temperature to 300 °C, the turntable rotation speed to 20 r / min. When the temperature of the sample plate reaches 300 °C and the chamber vacuum reaches 5×10 -5 Pa, start depositing the yttrium metal transition layer. Introduce 33 sccm of argon gas, and the chamber pressure is stabilized at 0.5 Pa. Set the cathode sputtering power of the medium-frequency power supply to 300 W and the bias voltage to -100 V. Perform sputtering for 3 min to deposit a yttrium metal transition layer with a thickness of about 0.1 μm on the substrate surface.

[0113] (4) Deposit a yttrium oxide coating on the yttrium metal transition layer;

[0114] Specifically, set the target voltage to 350 V in the closed-loop control system control mode, the lower limit value of the control gas to 0 sccm, and the upper limit value of the control gas to 6 sccm. Introduce 33 sccm of argon gas, and the chamber pressure is stabilized at 0.5 Pa. Set the cathode sputtering power of the medium-frequency power supply to 400 W and the bias voltage to -100 V. Turn on the medium-frequency power supply and the closed-loop controller, and perform reactive sputtering for 120 min to deposit a yttrium oxide coating with a thickness of about 3 μm on the substrate surface.

[0115] As Figure 2 shown, perform X-ray diffraction analysis on the prepared sample. The X-ray source is a Cu source, and the 2θ for testing ranges from 15° to 70°. The results show that the prepared yttrium oxide coating has a cubic phase with a strong (222) orientation, and there are weak monoclinic phase diffraction peaks, as well as weak cubic phase (211) and monoclinic phase (40 - 2) diffraction peaks. According to the integral intensity estimation of the XRD diffraction peaks, the (222) orientation content is approximately 75%.

[0116] Comparative Example 1

[0117] This comparative example provides a method for preparing a yttrium oxide coating, including the following steps:

[0118] 1) Provide a substrate and load the substrate into the reaction chamber of the physical vapor deposition equipment;

[0119] Specifically, the substrate is selected as a pure aluminum sheet. Use a polishing cloth and polishing liquid to polish the substrate. After polishing, the sample reaches a mirror effect with a roughness of about 40 nm. After polishing, the substrate is placed in a metal cleaning agent solution for ultrasonic cleaning for 20 min, and then placed in anhydrous ethanol for ultrasonic cleaning for 20 min to remove adsorbed impurities and contaminants on the surface. After completion, take out the sample and dry it.

[0120] 2) Perform ion bombardment treatment on the substrate;

[0121] Specifically, place the substrate at the center position of the sample plate, put it into the loading and unloading chamber, and perform rough evacuation to reach 9×10 -4Pa, introduce 100 sccm of argon gas, set the gas pressure to 1.0 Pa, turn on the substrate bias voltage with a value of -800 V, and perform glow cleaning on the substrate for 30 minutes. Then, etch the substrate, introduce 70 sccm of argon gas, turn on the ion source, set the gas pressure to 0.7 Pa, the substrate bias voltage to -500 V, the ion source power to 2.5 kW, and the time to 15 minutes.

[0122] 3) Deposit a yttrium oxide coating on the substrate;

[0123] Specifically, set the heating temperature to 300 °C and the turntable rotation speed to 20 r / min. When the temperature of the sample disk reaches 300 °C and the chamber vacuum reaches 5×10 -4 Pa, start depositing the yttrium oxide coating. Introduce 33 sccm of argon gas and 5 sccm of oxygen gas. The gas pressure in the chamber is stabilized at 0.5 Pa. Set the cathode sputtering power of the medium-frequency power supply to 300 W, and perform reactive sputtering for 120 minutes to deposit a yttrium oxide coating with a thickness of approximately 2 μm on the surface of the substrate.

[0124] The XRD results of the deposited yttrium oxide coating are as Figure 2 shown. It can be seen that the phase structure of the yttrium oxide coating includes a face-centered cubic crystal with a (222) orientation; there is also a monoclinic phase, including diffraction peaks of (310), (402), (51-1), and (421) crystal planes. According to the integral area calculation, the volume content of the FCC (222) orientation is approximately 17%.

[0125] Perform plasma etching tests on the strongly oriented yttrium oxide coatings, uncoated aluminum alloy substrates, and uncoated alumina substrates prepared in Examples 1 to 3 and Comparative Example 1. The etching parameters are: ion source power: 1500 W, bias voltage: 200 V, CF 4 : 100 sccm, Ar: 150 sccm, gas pressure: 1.5 Pa, time: 60 minutes.

[0126] The results show that:

[0127] The etching depth of the uncoated aluminum alloy is 4.45 μm.

[0128] The etching depth of the uncoated alumina substrate is 1.92 μm.

[0129] The etching depth of the yttrium oxide coating on the aluminum substrate prepared in Comparative Example 1 is 1.32 μm.

[0130] The etching depth of the strongly oriented yttrium oxide coating on the aluminum substrate prepared in Example 1 is 0.62 μm.

[0131] The etching depth of the strongly oriented yttrium oxide coating on the glass substrate prepared in Example 2 is 0.85 μm.

[0132] The etching depth of the strongly oriented yttrium oxide coating on the alumina substrate prepared in Example 3 is 0.72 μm.

[0133] Figure 3 It is the morphology diagram after plasma etching of Example 1 and the alumina substrate without coating; Figure 4 It is the depth comparison diagram after plasma etching of Example 1 and the alumina substrate without coating. Figure 5 It is the etching rate comparison diagram. Through comprehensive comparison, it can be seen that the etching depth of the strongly oriented yttrium oxide coating is significantly less than that of the polycrystalline yttrium oxide coating in Comparative Example 1. This shows that the yttrium oxide coating with a strong (222) orientation cubic phase can effectively resist plasma etching.

[0134] In the description of this specification, the descriptions with reference to terms such as "some embodiments", "schematic embodiments", "examples", "specific examples", or "some examples" etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiments or examples are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0135] The above is the preferred implementation manner of the invention. It should be noted that for those of ordinary skill in the art of this technology, without departing from the principle of the present invention, several improvements and retouches can still be made, and these improvements and retouches are also regarded as the protection scope of the present invention.

Claims

1. A strongly oriented yttrium oxide coating, characterized in that: The strongly oriented yttrium oxide coating is arranged on the surface of the substrate, and the strongly oriented yttrium oxide coating has a face-centered cubic phase structure with a (222) orientation of not less than 70 vol%.

2. The strongly oriented yttrium oxide coating according to claim 1, characterized in that: The thickness of the yttrium oxide coating is 1 μm to 6 μm; The Y content of the yttrium oxide coating is 40 at.% to 45 at.%, and the O content is 55 at.% to 60 at.%; The content of the (222) oriented face-centered cubic phase structure of the yttrium oxide coating is not less than 75%.

3. A method for preparing a strongly oriented yttrium oxide coating, characterized in that: The following steps are involved: Providing a substrate, and loading the substrate into a reaction chamber of a physical vapor deposition device; performing ion bombardment treatment on the substrate; The closed-loop controller is turned on. In the control mode, the target voltage is set to 300V-400V, the gas lower limit is set to 0-2sccm, the gas upper limit is set to 2sccm-10sccm, argon gas is introduced, oxygen gas is introduced, an yttrium metal sputtering cathode is used, the substrate bias is turned on, the substrate bias is set to -200V--100V, the medium frequency power supply and the closed-loop controller are turned on, reactive sputtering is performed and an yttrium oxide coating is deposited on the substrate surface. The obtained yttrium oxide coating has a face-centered cubic phase structure with a (222) orientation of not less than 70vol%.

4. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: During the deposition of the yttrium oxide coating, the sputtering power of the yttrium metal sputtering cathode is 300W to 500W; the pressure in the reaction chamber is 0.6Pa to 1Pa; and the vacuum degree in the reaction chamber is 3×10 -5 Pa~7×10 -5 Pa.

5. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: The reaction chamber is provided with a sample tray for loading the substrate, and a yttrium metal sputtering cathode is provided above the sample tray. The yttrium metal sputtering cathode is a circular twin cathode, and the circular twin cathode is symmetrically distributed with the mid-vertical line of the sample tray as the symmetry axis.

6. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: The angle between the circular twin cathode and the perpendicular bisector of the sample disk is 70° to 75°; The distance between the sputtering cathode in the circular twin cathode and the surface of the substrate to be plated is 7 cm to 10 cm; The temperature of the sample tray is 200°C to 400°C.

7. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: The thickness of the yttrium oxide coating is 1 μm to 6 μm; The Y content of the yttrium oxide coating is 40 at.% to 45 at.%, and the O content is 55 at.% to 60 at.%; The content of the (222) oriented face-centered cubic phase structure of the yttrium oxide coating is not less than 75%.

8. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: The ion bombardment treatment comprises: Introduce argon gas, turn on the ion source, set the gas pressure to 0.6Pa~1Pa, turn on the substrate bias, set the substrate bias to -800V~-400V, and the ion source power to 2kW~5kW.

9. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: Before depositing the yttrium oxide layer on the substrate, the method further comprises: A yttrium metal transition layer is deposited on the substrate.

10. The method for preparing a strongly oriented yttrium oxide coating according to claim 9, characterized in that: Depositing the yttrium metal transition layer on the substrate comprises: The temperature of the reaction chamber was controlled at 250℃~350℃ and the vacuum degree was controlled at 3×10 -5 Pa~7×10 -5 Pa, introduce argon gas, set the argon gas pressure to 0.1Pa~0.6Pa, use yttrium metal sputtering cathode, set the sputtering power of the sputtering cathode to 300W~500W, turn on the substrate bias, set the substrate bias to -200V~0, and perform sputtering to deposit a yttrium metal transition layer on the substrate surface.

11. The method for preparing a strongly oriented yttrium oxide coating according to claim 9, characterized in that: The thickness of the yttrium metal transition layer is 0-0.2 μm.

12. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: The substrate includes an aluminum substrate, a glass substrate, an aluminum oxide substrate, and a single crystal silicon wafer.

13. The method for preparing a strongly oriented yttrium oxide coating according to claim 3, characterized in that: Before the substrate is subjected to ion bombardment treatment, the method further comprises: The vacuum degree of the reaction chamber was set at 8 × 10 -4 ~9×10 -4 Pa, introduce argon gas, set the gas pressure to 1Pa~2Pa, turn on the substrate bias, set the substrate bias to -900V~-800V, and perform glow cleaning on the substrate.

14. Use of the strongly oriented yttrium oxide coating according to claim 1 or 2 in preparing an etching machine cavity and its internal components, characterized in that: The strongly oriented yttrium oxide coating is used as a plasma etching resistant material for preparing the chamber and components in the chamber of the etcher.

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