KR102091744B1 - Yttrium oxyfluoride or yttrium fluoride powder for thin film coatings having uniform particle diameters and methods for their preparation - Google Patents

Abstract

Yttrium oxyfluoride or yttrium fluoride particles of the present invention is characterized in that the average particle diameter is 0.2㎛ ~ 5㎛, the particle size is uniform, preferably, the average particle diameter is characterized in that 0.5 ~ 1.5㎛ . The present invention provides yttrium oxyfluoride and yttrium fluoride particles having uniform particle diameters, using a material having high resistance to plasma resistance and corrosion resistance, and enabling a homogeneous thin film coating. In addition, the present invention can manufacture a semiconductor device or a display device having excellent plasma resistance and corrosion resistance by obtaining a high-density thin film through AD coating or the like.

Description

Yttrium oxyfluoride or yttrium fluoride powder for thin film coatings having uniform particle diameters and methods for their preparation}

The present invention relates to a fluorine-based yttrium oxyfluoride or yttrium fluoride powder having a uniform particle diameter.

In the manufacturing process of semiconductor devices or display devices, chlorine-based or fluorine-based highly corrosive gases are used for high etch rate and precise line width.

In semiconductor devices or display devices, Yttria or yttrium fluoride with high plasma properties is spray-coated, but the visibility and plasma-resistant particles coated by the conventional spraying method are dozens of µm and are highly used. There was a disadvantage in that the density was not high and the life span was short. That is, by using coarse particles having a high coating thickness of about several tens of µm and using non-uniform coarse particles, a film having a low density is formed, resulting in a disadvantage of poor plasma resistance and corrosion resistance.

[Prior art literature]

(Patent Document 0001) Republic of Korea Patent Information 10-2014-0126824 (2014.11.03.)

(Patent Document 0002) Republic of Korea Registered Patent Publication 10-1322783 (2013.10.29.)

(Patent Document 0003) Republic of Korea Registered Patent Publication 10-1748177 (2017.05.08.)

(Patent Document 0004) Republic of Korea Registered Patent Publication 10-1777830 (2017.07.06.)

(Patent Document 0005) Republic of Korea Registered Patent Publication 10-1817208 (2018.02.20.)

It is an object of the present invention to provide yttrium oxyfluoride or yttrium fluoride particles having a uniform particle diameter for a homogeneous thin film coating using a material having high resistance to plasma and corrosion resistance for extending life.

In addition, an object of the present invention is to provide yttrium oxyfluoride or yttrium fluoride particles having a uniform particle diameter to enable a high-density thin film coating through AD coating or the like on a semiconductor display device requiring transparency.

Yttrium oxyfluoride or yttrium fluoride particles of the present invention is characterized in that the average particle diameter is 0.2㎛ ~ 5㎛, the particle size is uniform. The average particle diameter is more preferably 0.5 ~ 1.5㎛.

In addition, the yttrium oxyfluoride or yttrium fluoride particles having a uniform particle size have a bulk density of 0.7 to 1.0 g / ml.

And it is characterized in that the tap density (Tap Density) is 0.9 ~ 1.2g / ml.

Method for producing yttrium oxyfluoride or yttrium fluoride having a uniform particle size of the present invention,

Preparing yttrium oxyfluoride slurry by mixing yttrium nitrate solution and ammonium carbonate solution to make yttrium carbonate, and aging it by adding an aqueous hydrofluoric acid solution thereto; Removing the mother liquor from the yttrium oxyfluoride slurry, followed by washing with ultrapure water and drying; After the drying, the first calcination to obtain yttrium oxyfluoride powder; The yttrium oxyfluoride powder is prepared by using ultrapure water to make a slurry having a solid content of 20 wt%, followed by wet milling and drying; And a second firing after drying to obtain yttrium oxyfluoride powder having a uniform particle size.

In the above manufacturing method, the primary firing temperature is 400 to 600 ° C, and the secondary firing temperature is 600 to 1100 ° C.

Meanwhile, the yttrium oxyfluoride and yttrium fluoride of the present invention can be coated with a density of 2 to 10 μm or less by aerosol deposition to form a thin film for a transparent display device.

The present invention uses yttrium oxyfluoride or yttrium fluoride particles having a uniform particle diameter to use a material having high resistance to plasma and corrosion resistance and enables a homogeneous thin film coating.

In addition, the present invention can manufacture a semiconductor device or a display device having excellent plasma resistance and corrosion resistance by obtaining a high-density thin film through AD coating or the like.

In addition, the present invention can be used to coat a semiconductor display device, etc., which requires transparency because a high-density thin film coating is possible through AD coating or the like.

1 is a SEM image of yttrium oxyfluoride powder after primary firing of YOF in Example 1 of the present invention,
Figure 2 is a SEM image of yttrium oxyfluoride powder after wet grinding of YOF of Example 1 of the present invention,
3 is a SEM image of yttrium oxyfluoride powder after secondary firing of YOF in Example 1 of the present invention,
4 is a graph of XRD data of the final powder of YOF in Example 1 of the present invention.
5 is a SEM image of yttrium oxyfluoride powder after primary firing of Y4O5F7 of Example 2 of the present invention,
6 is a SEM image of yttrium oxyfluoride powder after wet grinding of Y4O5F7 of Example 2 of the present invention,
7 is a SEM image of yttrium oxyfluoride powder after secondary firing of Y4O5F7 of Example 2 of the present invention,
8 is a graph of XRD data of the final powder of Y4O5F7 in Example 2 of the present invention,
9 is a SEM image of yttrium oxyfluoride powder after primary firing of YF3 of Example 3 of the present invention,
10 is a SEM image of yttrium oxyfluoride powder after wet grinding of YF3 of Example 3 of the present invention,
11 is a SEM image of yttrium oxyfluoride powder after secondary firing of YF3 of Example 3 of the present invention,
12 is a graph showing particle distribution as a result of XRD and SEM confirmation of the final powder of Example 3 of the present invention.
13 is a SEM image of yttrium oxyfluoride powder after firing by direct heat treatment of YOF of Comparative Example 1 of the present invention,
14 is a SEM image of yttrium oxyfluoride powder after firing by direct heat treatment of Y4O5F7 of Comparative Example 2 of the present invention,
15 is a SEM image of yttrium oxyfluoride powder after firing by direct heat treatment of YF3 of Comparative Example 2 of the present invention.

Yttrium oxyfluoride or yttrium fluoride powder particles of the present invention, represented by YOF, Y5O4F7, YF3. The powder particles have an average particle diameter of 0.2 µm to 5 µm, and the particle size is uniform. The average particle diameter is more preferably 0.5 ~ 1.5㎛. Yttrium oxyfluoride or yttrium fluoride particles having a uniform particle size of the present invention is a material having high resistance to plasma resistance and corrosion resistance, and enables a homogeneous thin film coating.

The particles of the present invention can obtain a high-density thin film through AD coating or the like, thus manufacturing a semiconductor device or a display device having excellent plasma resistance and corrosion resistance. In addition, since the AD coating enables a high-density thin film coating, it can be used in a semiconductor display device requiring transparency.

In addition, yttrium oxyfluoride and yttrium fluoride particles having a uniform particle size are characterized by having a bulk density of 0.7 to 1.0 g / ml. And it is characterized in that the tap density (Tap Density) is 0.9 ~ 1.2g / ml.

The yttrium oxyfluoride of the present invention is prepared by mixing yttrium nitrate solution and ammonium carbonate solution to make yttrium carbonate, and then aging it by adding an aqueous hydrofluoric acid solution to prepare yttrium oxyfluoride slurry. After removing the mother liquor from the yttrium oxyfluoride slurry, it is washed with ultrapure water and dried. After drying, primary sintering is performed to obtain yttrium oxyfluoride powder. The primary firing is heat-treated in an inert atmosphere (using Ar gas) at 600 ° C. for 2 hr. Thereafter, the yttrium oxyfluoride powder is made of ultra-pure water to make a slurry having a solid content of 20 wt%, and is dried after wet milling. After drying, secondary baking is performed, followed by secondary baking, followed by heat treatment at 900 ° C. for 2 hr in an inert atmosphere (using Ar gas) to obtain a powder having a uniform particle size.

In this way, in the present invention, in order to prepare a powder having a uniform particle diameter, the first calcination is followed by the wet calcination to perform the second calcination. Since the particle size is not uniform after the first firing, particles having a uniform size can be obtained by subjecting to secondary firing after wet grinding.

The particles may be coated with a density of 2 to 10 µm or less by aerosol deposition to form a high-density and transparent thin film, and have excellent corrosion resistance and plasma resistance, and thus can be used in semiconductor display devices and the like.

Hereinafter, the present invention will be described in more detail with reference to examples and drawings. However, the scope of the present invention is not limited to these examples.

Example 1: [Preparation of yttrium oxy: Y: O: F = 1: 1: 1]

While stirring 2 L of a 1 mol / L yttrium nitrate solution in a 10 L beaker, 3 L of a 1 mol / L ammonium carbonate solution was slowly added to make yttrium carbonate, and then 1 L of 2 mol / L hydrofluoric acid solution (50%) was slowly added thereto, followed by completion for 1 hr. Aging yielded a yttrium oxyfluoride (Y: 0: F = 1: 1: 1) slurry. Next, the mother liquor was removed using a centrifugal dehydrator, followed by washing with ultrapure water four times and drying. The drying temperature and time were 24 hrs at 120 ° C in a hot air dryer.

After drying, the yttrium oxyfluoride (Y: 0: F = 1: 1: 1) powder was recovered by heat treatment at 600 ° C for 2 hr in an atmospheric atmosphere by primary firing. (FIG. 1)

The obtained yttrium oxyfluoride (Y: 0: F = 1: 1: 1) powder was made using ultrapure water to make a slurry having a solid content of 20wt%, and then wetted using a 0.1mm zirconia beads after a 2hr ball mill through a ball mill. After 3pass with the milling equipment, drying was performed. The drying temperature and time was 24 hr at 120 ° C in a hot air dryer. (FIG. 2)

After the drying, yttrium oxyfluoride (Y: 0: F = 1: 1: 1) powder having a uniform particle size was recovered by heat treatment at 1000 ° C. for 2 hr in an atmospheric atmosphere by secondary firing. (FIG. 3)

When confirmed by XRD and SEM of the powder thus obtained, it was confirmed that yttrium oxyfluoride (Y: 0: F = 1: 1: 1) crystal structure was obtained, and uniform particles having a round shape of 1 μm at 500 nm were obtained. (Figure 4)

Example 2: [Preparation of yttrium oxy: Y: O: F = 5: 4: 7]

After stirring 5 L of a 1 mol / L yttrium nitrate solution in a 20 L beaker, 7.5 L of a 1 mol / L ammonium carbonate solution was slowly added to make yttrium carbonate, and then, after slowly adding 3.5 L of 2 mol / L hydrofluoric acid solution (50%), Aging for 1 hr yielded a yttrium oxyfluoride (Y: 0: F = 5: 4: 7) slurry.

Next, the mother liquor was removed using a centrifugal dehydrator, followed by washing with ultrapure water four times and drying. The drying temperature and time were 24 hrs at 120 ° C in a hot air dryer.

After drying, the yttrium oxyfluoride (Y: 0: F = 5: 4: 7) powder was recovered by heat treatment at 600 ° C for 2hr in an atmospheric atmosphere by primary firing. (FIG. 5)

The obtained yttrium oxyfluoride (Y: 0: F = 5: 4: 7) powder was used to make a slurry with 20% by weight of solids using ultrapure water, followed by a 2hr ball mill through a ball mill and then using 0.1mm zirconia beads. After 3pass with wet milling equipment, drying was performed. The drying temperature and time was 24 hr at 120 ° C. in a hot air dryer (FIG. 6).

After drying, the yttrium oxyfluoride (Y: 0: F = 5: 4: 7) powder having a uniform particle size was recovered by heat treatment at 950 ° C. for 2 hr in an atmosphere by secondary firing. (FIG. 7)

When confirmed by XRD and SEM of the powder thus obtained, it was confirmed that yttrium oxyfluoride (Y: 0: F = 5: 4: 7) crystal structure was obtained, and uniform particles having a round shape of 1 μm at 500 nm were obtained. (Fig. 8)

Example 3: [Preparation of Yttrium Fluoride: YF3]

While stirring 2 L of a 1 mol / L yttrium nitrate solution in a 20 L beaker, 3 L of a 1 mol / L ammonium carbonate solution was gradually added to make yttrium carbonate, and 2 L / L of 3% hydrofluoric acid solution (50%) was slowly added thereto, followed by completion for 1 hr. Aging yielded a yttrium fluoride (YF3) slurry.

Next, the mother liquor was removed using a centrifugal dehydrator, followed by washing with ultrapure water four times and drying. The drying temperature and time were 24 hrs at 120 ° C in a hot air dryer.

After drying, yttrium fluoride (YF3) powder was recovered by heat treatment at 600 ° C for 2 hr in an inert atmosphere (using Ar gas) by primary firing. (FIG. 9)

The obtained yttrium fluoride (YF3) powder was made using ultrapure water to make a slurry having a solid content of 20 wt%, followed by a 2 hr ball mill through a ball mill, followed by 3 passes with a wet milling equipment using 0.1 mm zirconia beads to dry. Did. The drying temperature and time was 24 hr at 120 ° C. in a hot air dryer. (FIG. 10)

After drying, the yttrium fluoride (YF3) powder having a uniform particle size was recovered by heat treatment at 900 ° C for 2 hr in an inert atmosphere (using Ar gas) by secondary firing. (FIG. 11)

When confirmed by XRD and SEM of the powder thus obtained, it was confirmed that yttrium fluoride (YF3) crystal structure was obtained, and uniform particles having a round shape of 1 μm at 500 nm were obtained (FIG. 12).

Comparative Example 1: [Preparation of yttrium oxy: Y: O: F = 1: 1: 1]

While stirring 2 L of a 1 mol / L yttrium nitrate solution in a 10 L beaker, 3 L of a 1 mol / L ammonium carbonate solution was slowly added to make yttrium carbonate, and then 1 L of 2 mol / L hydrofluoric acid solution (50%) was slowly added thereto, followed by completion for 1 hr. Aging yielded a yttrium fluoride (Y: 0: F = 1: 1: 1) slurry.

Next, the mother liquor was removed using a centrifugal dehydrator, followed by washing with ultrapure water four times and drying. The drying temperature and time were 24 hrs at 120 ° C in a hot air dryer.

after drying The yttrium fluoride (Y: 0: F = 1: 1: 1) powder having a non-uniform particle size was recovered by heat treatment at 1000 ° C for 2 hr in an atmospheric atmosphere by firing.

When confirmed by XRD and SEM of the powder thus obtained, it was confirmed that yttrium fluoride (Y: 0: F = 1: 1: 1) crystal structure was obtained, and non-uniform particles were obtained with 5 μm at 100 nm.

Comparative Example 2: [Preparation of yttrium oxy: Y: O: F = 5: 4: 7]

While stirring 2 L of a 1 mol / L yttrium nitrate solution in a 10 L beaker, 3 L of a 1 mol / L ammonium carbonate solution was slowly added to make yttrium carbonate, and then 1 L of 2 mol / L hydrofluoric acid solution (50%) was slowly added thereto, and then 1 hr. Aging for a while yielded a yttrium fluoride (Y: 0: F = 5: 4: 7) slurry.

Next, the mother liquor was removed using a centrifugal dehydrator, followed by washing with ultrapure water four times and drying. The drying temperature and time were 24 hrs at 120 ° C in a hot air dryer.

After drying, heat treatment was performed at 1000 ° C. for 2 hr in an atmospheric atmosphere by firing to recover yttrium fluoride (Y: 0: F = 5: 4: 7) powder having a non-uniform particle size.

When confirmed by XRD and SEM of the powder thus obtained, it was confirmed that yttrium fluoride (Y: 0: F = 5: 4: 7) crystal structure was obtained, and particles having non-uniformity from 100 nm to 5 µm were obtained (FIG. 14).

Comparative Example 3: [Production of yttrium oxyfluoride: YF3]

While stirring 2 L of a 1 mol / L yttrium nitrate solution in a 10 L beaker, 3 L of a 1 mol / L ammonium carbonate solution was slowly added to make yttrium carbonate, and then 1 L of 2 mol / L hydrofluoric acid solution (50%) was slowly added thereto, followed by completion for 1 hr. Aging yielded a yttrium fluoride (YF3) slurry.

Next, the mother liquor was removed using a centrifugal dehydrator, followed by washing with ultrapure water four times and drying. The drying temperature and time were 24 hrs at 120 ° C in a hot air dryer.

after drying The yttrium fluoride (YF3) powder having a non-uniform particle size was recovered by heat treatment at 1000 ° C for 2 hr in an atmosphere by firing.

When confirmed by XRD and SEM of the powder thus obtained, it was confirmed that yttrium fluoride (YF3) crystal structure was obtained, and particles irregularly formed at 5 μm at 100 nm were obtained (FIG. 15).

On the other hand, the yttrium oxyfluoride or yttrium fluoride of Examples 1 to 3 was coated on a thin film such as a semiconductor display device using aerosol deposition. Therefore, the yttrium oxyfluoride or yttrium fluoride of the present invention is coated with a thin film having a density of 2 to 10 µm or less to produce a semiconductor display device having excellent corrosion resistance and plasma resistance and transparency.

Claims (7)

Yttrium oxyfluoride powder with an average particle diameter of 0.5 to 1.5 μm, a tap density of 0.9 to 1.2 g / ml, a bulk density of 0.7 to 1.0 g / ml, and a uniform particle size in a round shape. Yttrium fluoride powder having an average particle diameter of 0.5 to 1.5 µm, a tap density of 0.9 to 1.2 g / ml, a bulk density of 0.7 to 1.0 g / ml, and a uniform particle size in a round shape. delete delete Preparing yttrium oxyfluoride slurry by mixing yttrium nitrate solution and ammonium carbonate solution to make yttrium carbonate, and then aging with a hydrofluoric acid solution;
Removing the mother liquor from the yttrium oxyfluoride slurry, followed by washing with ultrapure water and drying;
After the drying, the first calcination at 400 ~ 600 ℃ to obtain a yttrium oxyfluoride powder;
The yttrium oxyfluoride powder is prepared by using ultrapure water to make a slurry having a solid content of 20 wt%, followed by wet milling and drying; And
After the drying, a second firing at 600 ~ 1100 ℃ to obtain a yttrium oxyfluoride powder;
It contains an average particle diameter of 0.5 ~ 1.5㎛. Method for producing yttrium oxyfluoride powder having a uniform particle size in a round shape. delete A thin film for a transparent display device formed by coating the yttrium oxyfluoride powder of claim 1 or the yttrium fluoride powder of claim 2 to a thickness of 2 to 10 μm by aerosol deposition.

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