Yttrium fluoride spray material, yttrium oxyfluoride-deposited article, and making methods

Abstract

An yttrium fluoride spray material contains Y.sub.5O.sub.4F.sub.7 and YF.sub.3, and has an average particle size of 10-60 μm and a bulk density of 1.2-2.5 g/cm.sup.3. The Y.sub.5O.sub.4F.sub.7 and YF.sub.3 in the yttrium fluoride spray material consist of 30 to 90% by weight of Y.sub.5O.sub.4F.sub.7 and the balance of YF.sub.3. A sprayed coating of yttrium oxyfluoride is obtained by atmospheric plasma spraying of the spray material.

Claims

1. A yttrium-deposited article comprising a substrate and a coating sprayed thereon, the sprayed coating containing at least one yttrium oxyfluoride selected from the group consisting of YOF, Y.sub.5O.sub.4F.sub.7, and Y.sub.7O.sub.6F.sub.9, the sprayed coating formed by spraying a spray material consisting of 30 to 71% by weight of Y.sub.5O.sub.4F.sub.7 and the balance 29 to 70% by weight of YF.sub.3.

2. The yttrium-deposited article of claim 1 wherein the sprayed coating contains YOF and Y.sub.5O.sub.4F.sub.7.

3. The yttrium-deposited article of claim 1 wherein the substrate is selected from the group consisting of stainless steel, aluminum, aluminum alloys, nickel, nickel alloys, chromium, chromium alloys, zinc, zinc alloys, alumina, aluminum nitride, silicon nitride, silicon carbide, and quartz glass.

4. The yttrium-deposited article of claim 1 wherein the sprayed coating is free of Y.sub.2O.sub.3.

5. The yttrium-deposited article of claim 1 wherein the sprayed coating has a thickness of 50 to 500 μm.

Description

DESCRIPTION OF PREFERRED EMBODIMENTS

(1) The yttrium fluoride spray material of the invention contains yttrium oxyfluoride (Y.sub.5O.sub.4F.sub.7) along with yttrium fluoride (YF.sub.3). The yttrium fluoride spray material is preferably free of yttrium oxide (Y.sub.2O.sub.3). For example, an yttrium fluoride spray material in which yttrium oxyfluoride (Y.sub.5O.sub.4F.sub.7) and yttrium fluoride (YF.sub.3), especially, only both of Y.sub.5O.sub.4F.sub.7 and YF.sub.3 are detected as crystalline phases by X-ray diffraction is preferable. The yttrium fluoride spray material contains 30 to 90%, preferably 60 to 80% by weight of Y.sub.5O.sub.4F.sub.7 and the balance of YF.sub.3, with respect to the total of Y.sub.5O.sub.4F.sub.7 and YF.sub.3. The spray material may contains a small amount of other crystalline phases such as YOF, however, the total of Y.sub.5O.sub.4F.sub.7 and YF.sub.3 is preferably at least 90 wt %. Particularly, the spray material consisting essentially of Y.sub.5O.sub.4F.sub.7 and YF.sub.3 is more preferable. The yttrium fluoride spray material of the invention has an average particle size of 10 to 60 μm, preferably 25 to 45 μm and a bulk density of 1.2 to 2.5 g/cm.sup.3, preferably 1.3 to 2.0 g/cm.sup.3.

(2) When a sprayed coating is formed by atmospheric plasma spraying of an yttrium fluoride spray material, the sprayed coating has an oxygen concentration which is increased and a fluorine concentration which is decreased, indicating partial oxidation of the spray material. This yttrium fluoride spray material is suited to form a stable yttrium oxyfluoride coating by atmospheric plasma spraying. From the standpoint of compensating for any compositional shift during atmospheric plasma spraying, an yttrium fluoride spray material consisting essentially of 30 to 90% by weight of Y.sub.5O.sub.4F.sub.7 and the balance of YF.sub.3 is effective, with respect to the total of Y.sub.5O.sub.4F.sub.7 and YF.sub.3.

(3) Preferably the thermal spray powder material is free-flowing and composed of particles of spherical shape for thermal spraying. When a spray material is fed into a flame for thermal spraying, a poor flow may cause cumbersome operation such as clogging of a feed tube. To ensure a smooth flow, the spray material should preferably take the form of spherical particles, specifically having an aspect ratio of up to 2, more specifically up to 1.5. As used herein, the term “aspect ratio” is an index of particle configuration and refers to the ratio of length to breadth of a particle.

(4) An angle of repose is an index of flow. A smaller angle of repose indicates better flow. The spray material preferably has an angle of repose of up to 45°, more preferably up to 40°. The angle of repose is determined by particle shape, particle size, particle size distribution, and bulk density. In order that the spray material have a small angle of repose, it should preferably have spherical shape, an average particle size of at least 10 μm, and a sharp particle size distribution.

(5) The spray material in particulate form preferably has an average particle size D50 of from 10 μm to 60 μm. The average particle size D50 is determined by laser light diffractometry. If the particle size of spray material is too small, such particles may evaporate off the flame, resulting in a low yield of spraying. If the particle size of spray material is too large, such particles may not be completely melted in the flame, resulting in a sprayed coating of poor quality. It is important that spray material particles obtained by granulation be solid, i.e., filled to the interior (or free of voids), for the reason that solid particles are unbreakable and stable during handling, and the tendency that voided particles trap undesirable gas component in their voids is avoided.

(6) Now the method for preparing the yttrium fluoride spray material is described. For example, 10 to 50% by weight of yttrium oxide having an average particle size of 0.01 to 3 m is mixed with the balance of the ammonium fluoride complex salt of formula: (YF.sub.3).sub.3NH.sub.4F.H.sub.2O having an average particle size of 0.01 to 3 μm, and optionally with adding a binder. Organic compounds are preferable as the binder. Examples of the binder include organic compound consisting of carbon, hydrogen and oxygen or carbon, hydrogen, oxygen and nitrogen, such as carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP). The mixture is granulated and fired, yielding the desired yttrium fluoride spray material. The method for synthesizing the ammonium fluoride complex salt is described. For example, an yttrium nitrate solution is mixed with an acidic ammonium fluoride solution at a temperature of 0° C. to 80° C., preferably 40° C. to 70° C., from which a white precipitate crystallizes out. The precipitate is filtered, washed with water, and dried. It is identified to be an ammonium fluoride complex salt of formula: (YF.sub.3).sub.3NH.sub.4F.H.sub.2O by X-ray diffractometry analysis.

(7) The firing step may be performed in vacuum or an inert gas atmosphere at a temperature of 600° C. to 1,000° C., preferably 700° C. to 900° C. for 1 to 12 hours, preferably 2 to 5 hours.

(8) Thermal spraying of the yttrium fluoride spray material to a substrate is desirably performed under atmospheric pressure (normal pressure) or reduced pressure. Although the plasma gas is not particularly limited, examples of the plasma gas include nitrogen/hydrogen, argon/hydrogen, argon/helium, argon/nitrogen, argon alone, and nitrogen gas alone, with argon/nitrogen being preferred.

(9) Examples of the substrate subject to thermal spraying include, but are not limited to, substrates of stainless steel, aluminum, nickel, chromium, zinc, and alloys thereof, alumina, aluminum nitride, silicon nitride, silicon carbide, and quartz glass, which serve as components of the semiconductor fabrication equipment. The sprayed coating typically has a thickness of 50 to 500 μm. The conditions under which the spray material is thermally sprayed are not particularly limited and may be determined as appropriate depending on the identity of substrate, a particular composition of the spray material and sprayed coating, and a particular application of the sprayed article.

(10) According to the atmospheric plasma spraying of the yttrium fluoride spray material of the invention, a sprayed coating is formed and an yttrium oxyfluoride-deposited article including a substrate and a sprayed coating formed thereon is obtained. The sprayed coating contains at least one yttrium oxyfluoride selected from the group consisting of YOF, Y.sub.5O.sub.4F.sub.7, and Y.sub.7O.sub.6F.sub.9, particularly, YOF, or YOF and Y.sub.5O.sub.4F.sub.7. The sprayed coating is preferably free of yttrium oxide (Y.sub.2O.sub.3) and desirably contains only yttrium oxyfluoride.

(11) A typical example of argon/hydrogen plasma spraying is atmospheric plasma spraying using a gas mixture of 40 L/min of argon and 5 L/min of hydrogen with air as an ambient gas. The thermal spraying conditions including a spray distance, current value, voltage value, and the feed rates of argon and hydrogen gases may be determined as appropriate depending on a particular application of the sprayed component or the like. A powder hopper is charged with a predetermined amount of spray material, which is fed with the aid of a carrier gas (typically argon) through a powder hose to the front end of the plasma spraying gun. While the spray material is continuously fed into the plasma flame, it is completely melted and liquefied, forming a liquid flame under the impetus of plasma jet. The liquid flame impinges against a substrate, whereupon molten particles are fused, solidified, and deposited thereon. On this principle, an yttrium oxyfluoride-deposited article (sprayed member) can be manufactured by forming yttrium oxyfluoride sprayed coating within a predetermined coating region on the substrate by moving the flame from right to left and/or up and down with a robot or human arm.

(12) The sprayed article is evaluated for particle release, for example, by a simple particle test. The deposited article is immersed in a predetermined volume of pure water for a predetermined time under ultrasonic agitation. Nitric acid is added to the collected immersion solution to dissolve particles. The yttrium content of the solution is measured by inductively coupled plasma (ICP) spectroscopy. A lower yttrium content indicates fewer particles.

EXAMPLE

(13) Examples are given below by way of illustration and not by way of limitation. In Table, wt % is percent by weight.

Reference Example 1

Preparation of Ammonium Fluoride Complex Salt

(14) A 1 mol/L yttrium nitrate solution, 1 L, was heated at 50° C. and mixed with 1 L of a 1 mol/L acidic ammonium fluoride solution at 50° C. for about 30 minutes with stirring. A white precipitate crystallized out. The precipitate was filtered, washed with water and dried. On X-ray diffractometry analysis, it was identified to be an ammonium fluoride complex salt of formula: (YF.sub.3).sub.3NH.sub.4F.H.sub.2O. It had an average particle size of 0.7 μm as measured by laser light diffractometry.

Examples 1 to 5 and Comparative Examples 1 and 2

Preparation of Spray Powder (Spray Material)

(15) A spray powder material was obtained by mixing predetermined amounts of ingredients to form a mix as shown in Table 1, dispersing the mix in water, with adding a binder in Examples 1 to 4 and Comparative Examples 1 and 2 or without adding a binder in Example 5, shown in Table 1 to form a slurry, granulating by means of a spray dryer, and firing under the conditions shown in Table 1. The resulting spray powder was identified and measured for crystal structure, particle size distribution, bulk density, angle of repose, and yttrium, fluorine, oxygen, carbon and nitrogen concentrations. The results are shown in Table 1. Notably, the identification was performed by X-ray diffractometry, the particle size distribution was measured by laser light diffractometry, the bulk density and angle of repose were measured by a powder tester, yttrium concentration was analyzed by ethylenediamine tetraacetic acid (EDTA) titration method of dissolved samples, the fluorine concentration was analyzed by dissolution ion chromatography, and the oxygen, carbon and nitrogen concentrations were analyzed by the infrared (IR) method after combustion. In each of Examples 1-5 and Comparative Examples 1 and 2, carbon and nitrogen were not detected, i.e., carbon and nitrogen concentrations were 0 wt %, respectively. Each of contents of the yttrium compound components was determined as follows. In Examples 1 to 5 and Comparative Example 1, Y.sub.5O.sub.4F.sub.7 content was calculated based on the oxygen concentration, and YF.sub.3 content was calculated as the balance. In Comparative Example 2, content of each of three substances (crystalline phases), which was identified by X-ray diffractometry, was calculated from scale factors of the crystalline phases.

Preparation of Sprayed Article

(16) Each of the spray powder materials in Examples 1 to 5 and Comparative Examples 1 and 2 was deposited onto an aluminum substrate by atmospheric plasma spraying using a gas mixture of 40 L/min of argon and 5 L/min of hydrogen with air as an ambient gas. The deposited article (sprayed member) had a sprayed coating of about 200 μm thick. The sprayed coating was scraped off the coated article. The sprayed coating was identified by X-ray diffractometry, and analyzed for yttrium concentration by ethylenediamine tetraacetic acid (EDTA) titration method of dissolved samples, fluorine concentration by dissolution ion chromatography, and oxygen concentrations by the combustion IR method. The results are shown in Table 2.

(17) In Examples 1 to 5, the yttrium fluoride spray material which had been prepared by mixing 10 to 50% by weight of yttrium oxide with the balance of ammonium fluoride complex salt of (YF.sub.3).sub.3NH.sub.4F.H.sub.2O, granulating and firing was a mixture of 30 to 90% by weight of Y.sub.5O.sub.4F.sub.7 and the balance of YF.sub.3. When the spray material was deposited onto an aluminum substrate by atmospheric plasma spraying using a gas mixture of 40 L/min of argon and 5 L/min of hydrogen with air as an ambient gas, the sprayed coating consisted of at least one yttrium oxyfluoride selected from among YOF, Y.sub.5O.sub.4F.sub.7, and Y.sub.7O.sub.6F.sub.9.

(18) In Comparative Examples 1 and 2, the yttrium fluoride spray material was prepared by mixing predetermined amounts of yttrium oxide (Y.sub.2O.sub.3) and yttrium fluoride (YF.sub.3), granulating and firing. When the spray material was deposited onto an aluminum substrate by atmospheric plasma spraying using a gas mixture of 40 L/min of argon and 5 L/min of hydrogen with air as an ambient gas and deposited article was obtained, the sprayed coating contained Y.sub.2O.sub.3.

(19) The deposited articles of Examples 1 to 5 and Comparative Examples 1 and 2 were washed with running pure water at a flow rate of 100 L/hr before they were immersed in 10 L of pure water for 10 minutes under ultrasonic agitation. To the collected immersion solution, 100 mL of 2 mol/L nitric acid was added. The yttrium content of the solution was measured by ICP. The results are shown in Table 3.

(20) TABLE-US-00001 TABLE 1 Comparative Example Example 1 2 3 4 5 1 2 Ingredients, Y.sub.2O.sub.3 (D50 = 0.3 μm) particle size, 20 wt % 30 wt % 40 wt % 50 wt % 20 wt % 10 wt % 50 wt % and mixing ratio (YF.sub.3).sub.3NH.sub.4FH.sub.2O (D50 = 0.7 μm) YF.sub.3 (D50 = 1.4 μm) 80 wt % 70 wt % 60 wt % 50 wt % 80 wt % 90 wt % 50 wt % Granulation Mix 25 wt % 25 wt % 25 wt % 25 wt % 25 wt % 25 wt % 25 wt % conditions Binder* CMC CMC PVA PVP none CMC CMC  8 wt %  8 wt %  8 wt %  8 wt %  8 wt %  8 wt % Firing Atmo- N.sub.2 vacuum N.sub.2 N.sub.2 N.sub.2 N.sub.2 N.sub.2 conditions sphere Temper- 800° C. 900° C. 900° C. 800° C. 800° C. 800° C. 800° C. ature Analysis of spray powder Particle D10, μm 23 18 25 21 23 22 23 size D50, μm 37 28 38 33 37 37 34 distribution D90, μm 54 48 65 47 54 59 64 Bulk density, g/cm.sup.3 1.3 1.6 1.7 1.3 1.3 1.3 1.4 Angle of repose, ° 39 38 36 39 39 42 41 Y concentration, wt % 66.9 68.4 67.4 67.9 66.9 65.6 72.7 F concentration, wt % 28.8 24.5 24.6 22.9 28.8 32.1 16.4 O concentration, wt % 4.3 7.1 8.0 9.2 4.3 2.3 10.9 X-ray diffraction Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 analysis 43 wt % 71 wt % 80 wt % 92 wt % 43 wt % 23 wt % 87 wt % YF.sub.3 YF.sub.3 YF.sub.3 YF.sub.3 YF.sub.3 YF.sub.3 YF.sub.3 57 wt % 29 wt % 20 wt %  8 wt % 57 wt % 77 wt %  9 wt % Y.sub.2O.sub.3  4 wt % *CMC: carboxymethyl cellulose, PVA: polyvinyl alcohol, PVP: polyvinyl pyrrolidone

(21) TABLE-US-00002 TABLE 2 Analysis Comparative of sprayed Example Example coating 1 2 3 4 5 1 2 Y concen- 66 69.6 72.4 71.5 66 66 73 tration, wt % F concen- 26.7 21.4 16.6 15 26.7 30.4 14.3 tration, wt % O concen- 7.3 9 11 13.5 7.3 3.6 12.7 tration, wt % X-ray Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 YOF Y.sub.5O.sub.4F.sub.7 Y.sub.5O.sub.4F.sub.7 YOF diffraction YOF YOF YOF YOF YF.sub.3 Y.sub.2O.sub.3 analysis Y.sub.2O.sub.3

(22) TABLE-US-00003 TABLE 3 Comparative Simple particle Example Example test 1 2 3 4 5 1 2 Y concentration, 3 5 7 10 3 20 30 mg/L

(23) Japanese Patent Application No. 2015-208616 is incorporated herein by reference.

(24) Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.