A Y-site doped Y5O4F7 ceramic thermal spray powder and its preparation method

Abstract

This invention discloses a Y-site-doped Y5O4F7 ceramic thermal spray powder and its preparation method, relating to the field of medium-entropy ceramic materials technology. The chemical formula of the Y-site-doped Y5O4F7 ceramic thermal spray powder is (Y... 0.25 Eu 0.25 Yb 0.25 Sm 0.25 Y5O4F7. This invention employs entropy design at the Y-site of Y5O4F7 ceramic, incorporating four elements with similar chemical properties and ionic radii in an equimolar ratio into the Y-site lattice of the Y5O4F7 ceramic. This induces a lattice distortion effect in Y5O4F7, increasing its disorder and improving its corrosion resistance. Applying the Y-site-doped Y5O4F7 ceramic thermal spray powder of this invention to the surface of an electrostatic chuck significantly reduces the etching rate of the electrostatic chuck and improves its corrosion resistance. Compared to an electrostatic chuck coated with Y5O4F7 ceramic thermal spray powder, the etching rate can be reduced by 4.2 nm / min.

Description

Technical Field

[0001] This invention relates to the field of medium-entropy ceramic materials technology, and in particular to a Y-site doped Y5O4F7 ceramic thermal spraying powder and its preparation method. Background Technology

[0002] As semiconductor chips rapidly develop towards higher density, higher integration, and smaller linewidths, the requirements for patterning accuracy in the etching process continue to increase. As the core carrier for fixing chips in the etching process, the performance stability of the electrostatic chuck directly determines the process consistency, chip yield, and product reliability of the etching process. The etching process often employs highly corrosive etchants (such as fluorine- or chlorine-based corrosive gases or solutions). While etching the chip pattern, these highly corrosive etchants inevitably react with the surface and critical internal structure of the electrostatic chuck. On one hand, fluorine- or chlorine-based corrosive gases or solutions chemically erode the substrate material of the electrostatic chuck, causing damage such as corrosion pits, cracks, and peeling on the surface. This compromises the flatness and structural integrity of the chuck surface, affecting the bonding accuracy between the chip and the chuck and leading to process defects such as etched pattern misalignment and uneven linewidth. On the other hand, corrosion products may adhere to the chuck surface or seep into the internal electrode gaps. This not only reduces the stability of the electrostatic adsorption force of the electrostatic chuck, causing micro-displacement or even chip detachment during etching, but may also cause electrode short circuits, decreased insulation performance, and other malfunctions, shortening the lifespan of the electrostatic chuck. Furthermore, impurity particles generated by corrosion may detach and contaminate the etching environment and chip surface, further exacerbating the reduction in chip yield. Currently, the semiconductor manufacturing industry has increasingly stringent requirements for chip production capacity and quality. The corrosion problem of electrostatic chucks has become a key bottleneck restricting the improvement of etching process precision, production cost control, and equipment operational stability. Frequent replacement of electrostatic chucks due to corrosion not only increases equipment maintenance costs and production downtime but also affects process consistency due to performance differences between different chucks. Furthermore, etching defects caused by corrosion directly reduce chip yield, resulting in significant economic losses. Therefore, improving the corrosion resistance of electrostatic chucks in highly corrosive etching environments, and ensuring their structural integrity, adsorption stability, and process adaptability during long-term use, has become an urgent technical requirement in the semiconductor manufacturing field, and is of great significance for promoting the continuous advancement of semiconductor chip manufacturing technology.

[0003] Y5O4F7 ceramic material, due to its unique crystal structure, possesses certain corrosion resistance properties, demonstrating potential application value in the field of corrosion-resistant materials and gradually becoming one of the candidate materials for electrostatic chuck protective coatings. However, in the harsh corrosive environment of actual semiconductor etching, the corrosion resistance of traditional Y5O4F7 ceramic material still has room for improvement. When applied to the surface protection of electrostatic chucks used in the etching process, it cannot fully meet the stringent requirements of high corrosion resistance and long service life for electrostatic chucks. Therefore, how to further optimize the corrosion resistance of Y5O4F7 ceramic material to better suit the protection needs of electrostatic chucks used in semiconductor etching processes has become an urgent technical problem to be solved in this field. Summary of the Invention

[0004] The purpose of this invention is to provide a Y-site doped Y5O4F7 ceramic thermal spray powder and its preparation method, so as to solve the problems existing in the prior art.

[0005] To achieve the above objectives, the present invention provides the following solution:

[0006] One of the technical solutions of the present invention: a Y-site doped Y5O4F7 ceramic thermal spray powder, wherein the chemical formula of the Y-site doped Y5O4F7 ceramic thermal spray powder is (Y 0.25 Eu 0.25 Yb 0.25 Sm 0.25 )5O4F7. The molar ratio of the four metal atoms occupying the Y site is equal.

[0007] This invention employs entropy design at the Y-site of Y5O4F7 ceramics, incorporating four elements with similar chemical properties and ionic radii in an equimolar ratio into the Y-site lattice of Y5O4F7 ceramics. This induces a lattice distortion effect in Y5O4F7, increasing its disorder and thus enhancing the corrosion resistance of Y5O4F7 ceramics.

[0008] The second technical solution of the present invention: a method for preparing the above-mentioned Y-site doped Y5O4F7 ceramic thermal spray powder, comprising the following steps:

[0009] Weigh Y2O3, Eu2O3, Yb2O3, YF3, EuF3, YbF3, Sm2O3, and SmF3 powders according to their chemical formulas and stoichiometric ratios, mix and ball-mill to obtain a mixed powder; add a binder to the mixed powder and stir evenly to obtain a ceramic slurry; granulate, sinter, and sieve the ceramic slurry to obtain the Y-site doped Y5O4F7 ceramic thermal spray powder.

[0010] The preparation method of the present invention uses target element oxides and fluorides as raw materials, mixes them by ball milling, and then prepares Y-site doped Y5O4F7 ceramic thermal spray powder by high-temperature sintering. The sintering process does not require specific atmosphere control and does not require the addition of sintering aids. The process is short, the preparation cost is low, and the preparation efficiency is high.

[0011] Furthermore, during the mixed ball milling process, anhydrous ethanol and zirconium oxide balls are used as the ball milling media, and the mass ratio of anhydrous ethanol, zirconium oxide balls and ball milling raw materials is 5:1:5.

[0012] Furthermore, the mixing ball mill is operated at a speed of 300 rpm for 12 to 24 hours.

[0013] Furthermore, the adhesive includes gum arabic.

[0014] Furthermore, the mass ratio of the binder to the mixed powder is 2:100.

[0015] Optionally, the stirring time is 30 minutes.

[0016] Furthermore, the granulation adopts spray drying granulation method, with parameters including: inlet air temperature of 280~300℃, outlet air temperature of 100~150℃, and atomization speed of 16800rpm.

[0017] Furthermore, the granulation is carried out in a high-speed centrifugal spray drying tower.

[0018] Furthermore, the sintering conditions include: heating to 980~1020℃ at a heating rate of 6℃ / min and holding at that temperature for 3~4 hours.

[0019] Furthermore, after the sintering is completed, the process also includes a step of cooling the furnace to room temperature.

[0020] Furthermore, the mesh size of the sieve used for sieving is 180-270 mesh.

[0021] Preferably, the sieving process specifically involves passing the material through a 180-mesh sieve and a 270-mesh sieve in sequence.

[0022] The Y-doped Y5O4F7 ceramic thermal spray powder of the present invention has excellent corrosion resistance. When sprayed onto the surface of an electrostatic chuck, it can significantly reduce the etching rate of the electrostatic chuck and improve its corrosion resistance.

[0023] The present invention discloses the following technical effects:

[0024] (1) The present invention effectively improves the corrosion resistance of Y5O4F7 ceramic by performing entropy design on the Y site.

[0025] (2) The preparation process of the present invention is simple, does not require atmosphere sintering, and only requires ordinary muffle furnace for sintering. It has the characteristics of short sintering time, simple process, low production cost and high efficiency.

[0026] (3) Preparation of (Y) in this invention 0.25 Eu 0.25 Yb 0.25 Sm 0.25 No sintering aids are required during the thermal spraying of 5O4F7 ceramic powder.

[0027] (4) The (Y) prepared by the present invention 0.25 Eu 0.25 Yb 0.25 Sm 0.25 After Y5O4F7 ceramic thermal spray powder is sprayed onto the surface of the electrostatic chuck, the etching rate of the electrostatic chuck can be significantly reduced and its corrosion resistance can be improved. Compared with the electrostatic chuck sprayed with Y5O4F7 thermal spray powder, the etching rate is reduced by 4.2 nm / min. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 (Y) prepared in Example 1 0.25 Eu 0.25 Yb 0.25 Sm 0.25 XRD pattern of 5O4F7 ceramic thermal spray powder.

[0030] Figure 2 (Y) prepared in Example 1 0.25 Eu 0.25 Yb 0.25 Sm 0.25 SEM image of 5O4F7 ceramic thermal spray powder.

[0031] Figure 3 The (Y) prepared according to Examples 1-3 respectively 0.25 Eu 0.25 Yb 0.25 Sm 0.25 The etching rate of the electrostatic chuck after the Y5O4F7 ceramic thermal spray powder and the Y5O4F7 ceramic thermal spray powder prepared in Comparative Example 1 are sprayed onto the surface of the electrostatic chuck. Detailed Implementation

[0032] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0033] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0034] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0035] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0036] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0037] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0038] In the following embodiments and comparative examples of the present invention, room temperature refers specifically to 20-30°C.

[0039] Unless otherwise specified, all raw materials used in the following embodiments and comparative examples of this invention are commercially available products.

[0040] Example 1

[0041] A Y-site doped Y5O4F7 ceramic thermal spray powder, with the chemical formula (Y 0.25 Eu 0.25 Yb 0.25 Sm 0.25 The preparation steps of 5O4F7 are as follows:

[0042] (1) According to (Y) 0.25 Eu 0.25 Yb 0.25 Sm 0.25 Weigh out the stoichiometric proportions of Y2O3, Eu2O3, Yb2O3, YF3, EuF3, YbF3, Sm2O3, and SmF3 powders. Place the powders into a ball mill and ball mill them for 12 hours at a mass ratio of 5:1:5 for anhydrous ethanol, zirconia balls, and the raw materials (the powders). The ball mill rotates at 300 rpm to obtain a mixed powder. Then, add gum arabic to the mixed powder and stir for 30 minutes at a mass ratio of 2:100 for a ceramic slurry.

[0043] (2) The ceramic slurry obtained in step (1) is placed in a high-speed centrifugal spray drying tower for granulation. The inlet temperature of the drying tower is 280°C and the outlet temperature of the drying tower is 130°C. The atomization speed of the high-speed centrifugal spray drying tower during granulation is 16800 rpm, and ceramic particles are obtained.

[0044] (3) Place the ceramic particles obtained in step (2) into a crucible, place the crucible into a muffle furnace, heat it to 1000°C at a heating rate of 6°C / min, keep it in the muffle furnace for 3 hours, and then cool it to room temperature with the furnace. Then pass the sintered ceramic particles through 180 mesh and 270 mesh sieves in sequence to obtain Y5O4F7 ceramic thermal spray powder doped at Y site.

[0045] Example 2

[0046] A Y-site doped Y5O4F7 ceramic thermal spray powder, with the chemical formula (Y 0.25 Eu 0.25 Yb 0.25 Sm 0.25 The preparation steps of 5O4F7 are as follows:

[0047] (1) According to (Y) 0.25 Eu 0.25 Yb 0.25 Sm 0.25Weigh out the stoichiometric proportions of Y2O3, Eu2O3, Yb2O3, YF3, EuF3, YbF3, Sm2O3, and SmF3 powders. Place the powders into a ball mill and ball mill them for 12 hours at a mass ratio of 5:1:5 for anhydrous ethanol, zirconia balls, and the raw materials (the powders). The ball mill rotates at 300 rpm to obtain a mixed powder. Then, add gum arabic to the mixed powder and stir for 30 minutes at a mass ratio of 2:100 for a ceramic slurry.

[0048] (2) The ceramic slurry obtained in step (1) is placed in a high-speed centrifugal spray drying tower for granulation. The inlet temperature of the drying tower is 290°C and the outlet temperature is 125°C. The atomization speed of the high-speed centrifugal spray drying tower during granulation is 16800 rpm, and ceramic particles are obtained.

[0049] (3) Place the ceramic particles obtained in step (2) into a crucible, place the crucible into a muffle furnace, heat it to 980°C at a heating rate of 6°C / min, keep it in the muffle furnace for 3 hours, and then cool it to room temperature with the furnace. Then pass the sintered ceramic particles through 180 mesh and 270 mesh sieves in sequence to obtain Y5O4F7 ceramic thermal spray powder doped at Y site.

[0050] Example 3

[0051] A Y-site doped Y5O4F7 ceramic thermal spray powder, with the chemical formula (Y 0.25 Eu 0.25 Yb 0.25 Sm 0.25 The preparation steps of 5O4F7 are as follows:

[0052] (1) According to (Y) 0.25 Eu 0.25 Yb 0.25 Sm 0.25 Weigh out the stoichiometric proportions of Y2O3, Eu2O3, Yb2O3, YF3, EuF3, YbF3, Sm2O3, and SmF3 powders. Place the powders into a ball mill and ball mill them for 12 hours at a mass ratio of 5:1:5 for anhydrous ethanol, zirconia balls, and the raw materials (the powders). The ball mill rotates at 300 rpm to obtain a mixed powder. Then, add gum arabic to the mixed powder and stir for 30 minutes at a mass ratio of 2:100 for a ceramic slurry.

[0053] (2) The stirred ceramic slurry obtained in step (1) is placed in a high-speed centrifugal spray drying tower for granulation. The inlet temperature of the drying tower is 300℃ and the outlet temperature of the drying tower is 145℃. The atomization speed of the high-speed centrifugal spray drying tower during granulation is 16800rpm, and ceramic particles are obtained.

[0054] (3) Place the ceramic particles obtained in step (2) into a crucible, place the crucible into a muffle furnace, heat it to 1020°C at a heating rate of 6°C / min, keep it in the muffle furnace for 3.8 hours, and then cool it to room temperature with the furnace. Then pass the sintered ceramic particles through 180 mesh and 270 mesh sieves in sequence to obtain Y5O4F7 ceramic thermal spray powder doped at Y site.

[0055] Comparative Example 1

[0056] A Y5O4F7 ceramic thermal spray powder, with the chemical formula Y5O4F7, is prepared as follows:

[0057] (1) Weigh Y2O3 and YF3 powders according to the stoichiometric ratio of Y5O4F7; put the above powders into a ball mill and ball mill them for 12 hours at a mass ratio of 5:1:5 for anhydrous ethanol, zirconium oxide balls and ball milling raw materials (i.e. the above powders) and the ball mill speed is 300 rpm to obtain mixed powder; then add gum arabic to the obtained mixed powder and stir for 30 minutes. The mass ratio of gum arabic to mixed powder is 2:100 to obtain the stirred ceramic slurry.

[0058] (2) The ceramic slurry obtained in step (1) is placed in a high-speed centrifugal spray drying tower for granulation. The inlet temperature of the drying tower is 280°C and the outlet temperature of the drying tower is 130°C. The atomization speed of the high-speed centrifugal spray drying tower during granulation is 16800 rpm, and ceramic particles are obtained.

[0059] (3) Place the ceramic particles obtained in step (2) into a crucible, place the crucible into a muffle furnace, heat it to 1000°C at a heating rate of 6°C / min, keep it in the muffle furnace for 3 hours, and then cool it to room temperature with the furnace. Then pass the sintered ceramic particles through 180 mesh and 270 mesh sieves in sequence to obtain Y5O4F7 ceramic thermal spray powder.

[0060] Test Example 1

[0061] Characterization data:

[0062] Figure 1 (Y) prepared in Example 1 0.25 Eu 0.25 Yb 0.25 Sm 0.25The XRD pattern of 5O4F7 ceramic thermal spray powder shows that the (Y) prepared in Example 1... 0.25 Eu 0.25 Yb 0.25 Sm 0.25 The 5O4F7 ceramic thermal spray powder has a single-phase perovskite structure with only extremely small impurity peaks.

[0063] Figure 2 (Y) prepared in Example 1 0.25 Eu 0.25 Yb 0.25 Sm 0.25 SEM image of 5O4F7 ceramic thermal spray powder. The image shows that the (Y) prepared in Example 1... 0.25 Eu 0.25 Yb 0.25 Sm 0.25 The sphericity of the 5O4F7 ceramic thermal spray powder is very good.

[0064] Test Example 2

[0065] The (Y) prepared in Examples 1-3 were respectively 0.25 Eu 0.25 Yb 0.25 Sm 0.25 Y5O4F7 ceramic thermal spray powder and Y5O4F7 ceramic thermal spray powder prepared in Comparative Example 1 were sprayed onto the surface of an electrostatic chuck. Then, the etching rate of the sprayed electrostatic chuck was tested. The specific spraying and testing methods were as follows: Y5O4F7 ceramic thermal spray powder prepared in Examples 1-3 was sprayed onto the surface of an electrostatic chuck using a plasma device. 0.25 Eu 0.25 Yb 0.25 Sm 0.25 Y5O4F7 ceramic thermal spray powder or the Y5O4F7 ceramic thermal spray powder prepared in Comparative Example 1 was sprayed onto the surface of an electrostatic chuck to obtain a coating with a thickness of 150 μm. Then, the sprayed electrostatic chuck was etched using a mixed gas of CF4 and Ar (25 vol% CF4 + 75 vol% Ar). The etching conditions included: a chamber pressure of 12 Pa, a temperature of 25 °C, and a lower electrode bias power of 100 W.

[0066] Figure 3 The (Y) prepared according to Examples 1-3 respectively 0.25 Eu 0.25 Yb 0.25 Sm 0.25 The etching rate diagram of the electrostatic chuck after spraying Y5O4F7 ceramic thermal spray powder and Y5O4F7 ceramic thermal spray powder prepared in Comparative Example 1 onto the surface of the electrostatic chuck shows that the etching rate of the electrostatic chuck after spraying Y5O4F7 ceramic thermal spray powder prepared in Example 1 is as follows: 0.25 Eu 0.25 Yb0.25 Sm 0.25 The electrostatic chuck coated with Y5O4F7 ceramic thermal spray powder showed a significantly lower etching rate compared to the electrostatic chuck coated with Y5O4F7 ceramic thermal spray powder prepared in Comparative Example 1, with a reduction of 4.2 nm / min. This demonstrates that the (Y5O4F7) ceramic thermal spray powder prepared in this invention exhibits superior etching performance. 0.25 Eu 0.25 Yb 0.25 Sm 0.25 5O4F7 ceramic thermal spray powder has excellent corrosion resistance and can significantly improve the corrosion resistance of electrostatic chucks.

[0067] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A Y-site doped Y5O4F7 ceramic thermal spray powder, characterized in that, The chemical formula of the Y-doped Y5O4F7 ceramic thermal spray powder is (Y 0.25 Eu 0.25 Yb 0.25 Sm 0.25 )5O4F7.

2. A method of producing a Y-site doped Y5O4F7 ceramic thermal spray powder as claimed in claim 1, characterized in that, Includes the following steps: Weigh Y2O3, Eu2O3, Yb2O3, YF3, EuF3, YbF3, Sm2O3, and SmF3 powders according to their chemical formulas and stoichiometric ratios, mix and ball-mill to obtain a mixed powder; add a binder to the mixed powder and stir evenly to obtain a ceramic slurry; granulate, sinter, and sieve the ceramic slurry to obtain the Y-site doped Y5O4F7 ceramic thermal spray powder.

3. The method of producing a Y-site doped Y5O4F7 ceramic thermal spray powder according to claim 2, characterized in that, During the mixed ball milling process, anhydrous ethanol and zirconium oxide balls are used as the ball milling media, and the mass ratio of anhydrous ethanol, zirconium oxide balls and ball milling raw materials is 5:1:

5. And / or, the mixing ball milling speed is 300 rpm, and the time is 12 to 24 hours.

4. The method of claim 2, wherein the Y-site doped Y5O4F7 ceramic thermal spray powder is prepared by the steps of: preparing a precursor powder comprising Y203, Fe203, and F- ions; and sintering the precursor powder at a temperature of 600- 1000 °C in a reducing atmosphere. 5 The adhesive includes gum arabic.

5. The method of making a Y-site doped Y5O4F7 ceramic thermal spray powder of claim 2, wherein, The mass ratio of the binder to the mixed powder is 2:

100.

6. The method for preparing Y-site doped Y5O4F7 ceramic thermal spray powder as described in claim 2, characterized in that, The granulation is carried out by spray drying granulation method, with parameters including: inlet air temperature of 280~300℃, outlet air temperature of 100~150℃, and atomization speed of 16800rpm.

7. The method of making a Y-site doped Y5O4F7 ceramic thermal spray powder of claim 2, wherein, The sintering conditions include: heating to 980~1020℃ at a heating rate of 6℃ / min and holding at that temperature for 3~4 hours.

8. The method of making a Y-site doped Y5O4F7 ceramic thermal spray powder of claim 2, wherein, The mesh size of the sieve used for sieving is 180-270 mesh.

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