KR101920002B1 - Coatable glass frit composition and the manufacturing method of coating layer for plasma sustaining ceramics - Google Patents

Abstract

The present invention relates to a method of manufacturing a glass frit composition and the coating layer for the molten coating for ceramics for the plasma, and more particularly, a) as the starting material _{Y 2 O 3, Al 2 O} 3, SiO 2 or melting their precursors To produce a glass frit; b) uniformly applying a glass frit or a glass frit paste obtained by pulverizing the glass frit to powder on a part or all of the ceramic base material; and c) heating the glass frit according to the step b) to melt the glass frit so that the glass frit is melted to coat the base metal with the glass frit, thereby providing a method of manufacturing ceramics for plasma .
As described above, according to the present invention, after the glass frit is coated on the base material by the melt coating method in the molten state, the annealing process and the recrystallization process are performed if necessary, It is expected that the crystallization rate of the excellent crystal phase is improved and thus the durability of the coating layer which can be used for the inner plasma is secured.

Description

Technical Field [0001] The present invention relates to a glass frit composition for melt coating for plasma-resistant ceramics and a method for producing the coating layer,

The present invention relates to a method of manufacturing a glass frit composition and the coating layer for the molten coating for ceramics for the plasma, and more particularly, a) as the starting material _{Y 2 O 3, Al 2 O} 3, SiO 2 or melting their precursors To produce a glass frit; b) uniformly applying a glass frit or a glass frit paste obtained by pulverizing the glass frit to powder on a part or all of the ceramic base material; c) heating and fusing the glass frit according to the step b) so that the glass frit is coated with the molten glass frit, thereby forming a coating layer on the inner surface of the ceramic frit. to provide.

As ultrafine line widths in the semiconductor manufacturing process have progressed, it has become very important to reduce the generation of contaminating particles in the chamber where the plasma process proceeds. Generally, the plasma process not only accelerates the chemical reaction with the material by generating a chemically active radical, but also the cation dissociated by the plasma enters the surface of the material to promote the reaction and accompanies the physical etching of the material .

In order to reduce the generation of contaminating particles in the plasma etching process, the adoption of a material having a low reactivity to plasma, that is, an excellent plasma resistance has been widely used. Al ₂ O ₃ is a typical plasma-resistant material, and Y ₂ O ₃ , which is superior in plasma resistance, has recently been adopted.

However, since Y ₂ O ₃ is a material showing excellent plasma resistance, it is very expensive, and recently, Y ₃ Al ₅ O ₁₂ , a representative compound between Y ₂ O ₃ and Al ₂ O ₃ , has been studied .

Korean Patent No. 0972567 discloses a method for producing a glass composition having a Y-Si-Al-ON composition. Such a method relates to an amorphous material, and such amorphous glass Is not advantageous in terms of the etching rate as compared with the crystalline glass.

In order to reduce the cost of the material, a method of using an inner plasma material instead of a bulk phase has been developed. In addition to the spraying method, aerosol deposition, sputtering, electron beam evaporation, thermal evaporation, laser deposition . However, it is well known that all of these coating techniques have a problem that peeling easily occurs like a spray coating.

In addition, Korean Patent Laid-Open Publication No. 2013-0139665, International Patent Publication No. WO 2007/013184, Korean Laid-Open Patent Application No. 2013-0090303 and the like all disclose a deposition method through spray coating, which has been pointed out as such a problem.

Particularly, in the case of spray coating, pores are generated in the base material, the amount of surface processing after coating is large, and coating on the ceramic base material has a weak impact. In addition, since the splat generated by the quenching of the molten particles is generated with a very weak bonding force, there arises a problem that coating peeling occurs in the plasma etching process and consequently contamination of the process due to dropping of the particles occurs.

In addition, the deposition method has a problem in that an expensive apparatus must be separately installed, which can act as a factor for raising the manufacturing cost.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems described above, and it is an object of the present invention to provide a method of coating a glass frit on a base material by a melt coating method, Thereby enhancing the crystallization rate of the crystal phase which is excellent in the plasma plasma characteristic in the coating layer and thus ensuring the durability of the coating layer which can be used for the inner plasma.

Another object of the present invention is to coat the glass frit for plasma with the base material by the melt coating method so that the facility can be minimized by using a simple coating method while at the same time the inner plasma glass is easily penetrated into the base material, .

In order to achieve the above-mentioned object, the present invention relates to a method for producing a glass frit, comprising the steps of: a) melting a Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ or a precursor thereof as a starting material to prepare a glass frit; b) uniformly applying a glass frit or a glass frit paste obtained by pulverizing the glass frit to powder on a part or all of the ceramic base material; and c) heating the glass frit according to the step b) to melt the glass frit so that the glass frit is melted to coat the base metal with the glass frit, thereby providing a method of manufacturing ceramics for plasma .

The method may further include, after the step c), d-1) processing the coating layer of the ceramic base material on which the glass frit is melt-coated.

The content of Y ₂ O ₃ , Al ₂ O ₃ and SiO ₂ is 15 mol% to 40 mol%, 10 mol% to 50 mol% and 30 mol% to 60 mol%, respectively, based on the sum of the above three components desirable.

And recrystallizing the coating layer at a recrystallization temperature lower than the melting temperature after step c), d-2).

In the step d-2), the glass frit is coated on the base material, and after cooling to room temperature, the temperature is raised again to reach the recrystallization temperature and recrystallization is performed, or the glass frit is coated on the ceramic base material to reach the recrystallization temperature It is preferable to perform recrystallization.

In the step b), it is preferable to further perform a process of flattening the glass frit powder so that the glass frit powder is applied at a uniform thickness.

In the step a), the glass frit is preferably manufactured at a temperature of 1400 to 1700 ° C.

In the step c), the temperature for coating the glass frit is preferably in the range of the softening point of the glass frit to the glass frit production temperature.

The recrystallization temperature is preferably a two-step heat treatment method in which a heat treatment is performed at a temperature higher by 15 to 25 ° C than a transition temperature of glass and then a heat treatment is performed again at a recrystallization temperature.

The thickness of the coating layer is preferably 50 to 150 mu m.

In addition, the present invention is manufactured by the manufacturing method of the plasma ceramics described above, Y ₂ O ₃ is 15 mol% to about 40mol%, Al ₂ O ₃ is 10 mol% to 50 mol%, SiO ₂ is 30 mol% to 60 mol% of the glass frit composition constitutes a coating layer of the ceramic base material, and the glass frit composition is distributed at the interface of the base material.

The invention also Y ₂ O _3, Al ₂ O _3, is composed of SiO _2, based on the sum of the three components above, Y ₂ O ₃ is 15 mol% to about 40mol%, Al ₂ O ₃ is 10 mol% to 50 mol%, SiO ₂ provides a glass frit composition for the manufacture of ceramics for the plasma, characterized in that 30 mol% to 60 mol%.

The present invention also provides a method for producing a glass frit for the production of a plasma-enhanced ceramics, which is produced by using the glass frit composition of claim 11 and is produced by melting at a temperature of 1400 to 1700 ° C.

As described above, according to the present invention, after the coated glass frit is coated in the molten state by the melt coating method, the annealing process and the recrystallization process are performed if necessary, It is expected that the crystallization rate of the excellent crystal phase is improved and thus the durability of the glass frit which can be used for plasma is secured.

In addition, by coating the glass frit for plasma with the base material by the melt coating method, it is possible to minimize the facility by using a simple coating method, and at the same time, the plasma glass can be easily penetrated into the base material, Is expected.

1 is an X-ray graph for examining the phase distribution for Example 1 of the present invention.
2 is an X-ray graph for examining the phase distribution for Example 2 of the present invention.
3 is a SEM photograph taken in order to confirm the phase distribution when the content of SiO _{2 in} the present invention is 47.4 mol% based on YAS.
4 is a SEM photograph taken in order to confirm the phase distribution when the content of SiO _{2 in} the present invention is 33 mol% based on YAS.
FIG. 5 is a SEM photograph taken in order to confirm the result of performing plasma etching on YAS prepared using 47.4 mol% SiO ₂ in the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in more detail below on the basis of preferred embodiments and the accompanying drawings.

The present invention discloses a method for surface modification of ceramics through a molten coating as a new coating technique for developing plasma-resistant materials in view of the problems of the prior art. When the prepared glass is coated on the surface of ceramics by the melt coating method, not only a thick coating layer is formed on the surface but also a coating layer is formed by melting and the remaining YAS melt penetrates into the ceramic base material, It increases the strength. At the same time, the interfacial energy between the crystal grains of the base material becomes a driving force, and the glass penetrates to about 950 탆 or more along the grain boundary, filling the bore of the base material, thereby enhancing the mechanical strength of the base material.

In the case of the conventional spray coating, as a method of laminating and coating the molten particles while quenching, the coating thickness range of 50 to 500 mu m is obtained depending on how much the coating is laminated. However, it is difficult to form a dense coating layer because the solidified molten particles are laminated and coated immediately in the spraying process.

Also, as the thickness of the coating layer becomes thicker, the splat generated by the quenching of the molten particles is weakly bonded, so that the coating peeling is likely to occur during plasma etching compared to the coating layer formed by the present invention.

In addition, in the case of spray coating, the interfacial strength at the interface between the coating layer and the base material is small because the cooling time from the surface to the solid is very short and the penetration time into the base material is physically very limited.

In the present invention, YAS (Y ₂ O ₃ -Al ₂ O ₃ -SiO ₂ ) based glass containing Y ₂ O _{3, which} is known to have excellent plasma resistance as a starting material, was selected as a glass to be melt-coated on a base material, YAS-based glass has high chemical durability due to Y ₂ O ₃ , has good mechanical properties and optical properties, and is widely used in structural ceramics and functional ceramics.

In the present invention, since the YAS-based glass frit is prepared and the surface of the alumina is modified by melt coating on alumina having a relatively low cost to produce a plasma-resistant material, the cost of the material itself is lowered, And equipment can lower the overall process cost. In addition, since a part of the coating layer through the melt coating penetrates into the matrix and the reaction with the matrix material, it is possible to solve the problem of particle dropping due to peeling of the coating, which is a problem of the prior art.

The present invention proposes a method of coating a YAS-based glass on a base material by a melt coating method. However, if the present invention is expanded, all the sintered ceramics are melt-coated by using a glass frit having excellent plasma resistance It is natural to be able to.

<Production Example>

The process of coating the surface of the base material by the manufacturing process of the glass frit and the melt coating process according to the present invention will be described as follows.

1. Manufacture of glass frit

First, raw material powders of Y ₂ O ₃ , Al ₂ O ₃ and SiO ₂ were prepared. Of course, the above-mentioned raw material powder may be in the form of an oxide which is a final producing material, but it is also possible to use the raw material powder in the form of a precursor such as anhydrous salt, salt or the like.

SiO ₂ is a network-forming oxide, Al ₂ O ₃ is a material for adjusting viscosity, intermediate oxide is both a network forming function and a mesh forming function, and Y ₂ O ₃ is a mesh-forming oxide.

Preferably, the crystallinity is better than that of plasma, which is experimentally understood. Therefore, it is preferable that the direction of decreasing SiO ₂ be small. However, since there is a problem that the melting itself becomes very difficult, the optimum content range of each component is determined as follows .

The range of the desirable content and the critical significance thereof are as follows.

The content of SiO ₂ is preferably 30 mol% to 60 mol% based on the raw material powder. When the content of SiO ₂ falls below 30 mol%, each powder is not sufficiently melted and is plasticized or obtained as a powder. When 60 mol% or more of SiO ₂ is contained, a coating layer having various kinds of crystalline for thermal plasma resistance is manufactured , There is a problem that the Y ₂ O ₃ mole fraction, which is important for expressing plasma characteristics, is relatively reduced.

The content of Y ₂ O ₃ is preferably 15 mol% to 40 mol% based on the raw material powder. When the content of Y ₂ O ₃ is more than 40 mol%, the powder is not sufficiently melted and is obtained as plasticizate or powder, and when the content is lower than 15 mol%, the plasma resistance is decreased.

In addition, the content of Al ₂ O ₃ is preferably 10 mol% to 50 mol% based on the raw material powder. When the content of Al ₂ O ₃ falls below 10 mol%, the powder is not sufficiently melted, and if it is more than 50 mol%, the plasma resistance is also decreased due to the relative decrease of the Y ₂ O ₃ mole fraction.

Therefore, SiO ₂ , Y ₂ O ₃ , and Al ₂ O ₃ are critical in the above range. In particular, the stomach content range of the ingredients is a key concept that implements the features of the invention that can not be achieved by spray coating.

In order to mix the above raw material powders, a process such as ball milling or a tubular mixer or equipment is used. In this case, it is possible to apply both dry and wet processes. The method of mixing may be carried out by any other method possible, and therefore, it is obvious that the mixing method is not limited.

The final YAS frit was prepared by melting at 1400 to 1700 캜 according to the frit composition. When the temperature is lower than the above temperature, the raw material powder is not sufficiently melted and the YAS-based glass frit is not formed, and further temperature is not required. Therefore, the melting temperature has its critical significance in the above range. In addition, the holding time is sufficient for the glass to melt and sufficiently homogenize.

The crystallinity of the glass frit is irrelevant. That is, it may be made of only glass, or some crystallization may have proceeded.

The glass frit may be used in powder form or a glass frit paste may be used.

2. Molten coating

An appropriate amount of frit is applied on the surface of the ceramics sintered body, which is the base material, in consideration of the surface area of the base material, and then the resultant is melted at a temperature of 50 to 150 ° C lower than the frit production temperature for 1 hour. Here, when the melt coating is performed at a temperature higher than the glass frit production temperature, the penetration of the glass is deep, but the coating layer does not remain on the surface of the ceramics. When the frit is coated on the base material, There is a problem that excessive penetration causes breakage of the base material.

Here, the coating thickness of the glass frit is preferably as uniform as possible, and the uniformity of the thickness can be achieved through the planarization work, and any kind of mechanical planarization work can be used.

The operating condition of the coating process is to melt for 30 minutes to 2 hours at a temperature between the softening point of the glass frit and the frit production temperature according to the composition.

When the melt is coated at a temperature below the softening point, the frit is not sufficiently melted and the viscosity is so high that the melt glass interface can not be absorbed. When the melt is applied at a temperature higher than the frit production temperature, all the frit melt is absorbed into the mother material to form a coating layer . Since the depth to be absorbed is proportional to the initial application amount, the temperature and the holding time, if absorbed for 30 minutes or longer, absorption into the base material is excessively generated and bending of the base material may occur. The lower limit of the coating thickness is a thickness that uniformly applies the base material, but 50 to 150 mu m is appropriate considering the durability of the plasma material. If it is too thin outside of the above range, durability will be lowered. If the coating thickness is too thick, adjust it to the proper thickness through processing.

After fusing with the frit, surface processing is performed through surface polishing to finally produce an inner plasma material coated with YAS-based glass. At this time, the amount and degree of surface processing is smaller than that in the case of melt coating, which is advantageous for spray coating of molten coating. In addition, the penetration depth can be controlled according to the coating thickness of the glass frit, and all the methods such as applying the paste and the powder as the coating method are possible.

Meanwhile, in order to clarify the merits of the melt coating in the present invention, a recrystallization process is performed in the process of cooling the coating layer after the melt coating. The reason for performing the recrystallization process is to increase the degree of crystallization of the molten coating layer. Through such crystallization, it is possible to improve the durability of the coating layer such as plasma resistance and durability.

The recrystallization may be carried out at a slightly lower temperature by cooling after the melt coating, or by cooling to room temperature after the melt coating and then heating again. In this case, the glass transition temperature T _g Followed by heat treatment at a temperature higher than 15 to 25 ° C, preferably 20 ° C for 1 to 3 hours and then heat treatment at a crystallization temperature T _c for 6 to 10 hours. When the crystal phase of the coating layer is recrystallized, the plasma fraction of the high plasma resistance is increased and a further enhanced plasma effect can be obtained. The T _g and T _c temperatures are different for each frit composition and the embodiments of this patent were subjected to a heat treatment at 1200 ° C for 8 hours to recrystallize. The plasma characteristics increase when the crystalline phase, especially YAG phase fraction, increases in the coating layer.

&Lt; Evaluation example &

Hereinafter, the characteristics of the plasma-resistant plasma-treated material as described above are evaluated. At this time, as a comparative example, an inner plasma material of an amorphous-type registered patent No. 972567 is presented.

Comparative Example) Plasma Property Evaluation (Patent No. 972567) Sample Etching depth (탆) Etching rate (占 퐉 / h) Plasma resistance in comparison with quartz (%) quartz 4 120 100 Alumina 0.8 24 20 Comparative Example 0.73-0.8 21.9-24 18.25-20

After the plasma etching, the quartz was etched to about 4 탆, and in the case of alumina, the comparative example of 0.8 탆 was also etched to a level similar to that of alumina of about 0.73 to 0.8 탆. When the etching rate was expressed as quartz, quartz was etched at 120 탆 per hour The comparison example with alumina shows an etching rate of about 24 탆 per hour. When the plasma resistance of quartz was compared with that of quartz, the degree of etching of alumina was comparable to that of the comparative example, and the comparative example shows no significant advantage in plasma resistance compared with alumina.

The composition and the etching conditions of the comparative example are described in the registered patent No. 972567. In the amorphous state, Y ₂ O ₃ (20 to 22.2 mol%), Al ₂ O ₃ (19 to 21.1 mol%) and SiO ₂ (61 to 51.1 mol %), Si ₃ N ₄ (0 to 5.6 mol%).

Example 1) The etching rate and the plasma resistance of YAS (Y ₂ O ₃ -Al ₂ O ₃ -SiO ₂ ) Sample Weight etching rate (%) Plasma resistance in comparison with quartz (%) quartz 0.739 100 Alumina 0.253 34 Y ₂ O ₃ 0.066 9 Example (YAS) 0.122 17

Table 2 shows the etching rates of the respective materials, and the etching rate of the embodiment of the present invention was found to be 0.122. This value is lower than that of alumina, which is less than twice the etching rate of Y ₂ O ₃ , and the etching rate is very low. In addition, plasma plasmas are much higher than Y ₂ O _{3 in} comparison with quartz. Therefore, it shows superiority in plasma resistance compared with Table 1.

Here, the composition of Example 1 was within the composition range of the present invention.

Example 2) The etch rate and plasma resistance of the recrystallized YAS of the present invention Sample Weight etching rate (%) Plasma resistance in comparison with quartz (%) quartz 0.739 100 Alumina 0.253 34 Y ₂ O ₃ 0.066 9 Example (YAS) 0.093 12.6

Table 3 shows the etch rate of each material after adding a recrystallization process to YAS for high plasma resistance. In this example, the etch rate is 0.093. This value is lower than that of alumina, which is less than twice the etching rate of Y ₂ O ₃ , and the etching rate is very low. In addition, plasma plasmas are much higher than Y ₂ O _{3 in} comparison with quartz. Therefore, it shows superiority in plasma resistance in comparison with Tables 1 and 2.

Here, the composition of Example 2 was within the scope of the present invention, and the composition of Example 2 was the same as that of Example 1.

In addition, the etching according to the above Examples 1 and 2 was carried out under the following conditions.

Item Condition Pressure (mtorr) 10 RF upper (W) -27 MHz 900 RF lower (W) -27 MHz 200 Ar (sccm) 10 CHF3 (sccm) 0 CF4 (sccm) 30 O2 (sccm) 10 Time (hr) 10 Temperature up / low 20/20

Although the etching conditions are somewhat lower than those of the comparative example, they are effective conditions for the criteria specified in the method of measuring the plasma resistance of KS C 6520: 2008 Semiconductor process parts. In the comparative example, Was carried out under severe conditions than the conditions of the comparative example by carrying out 10 hours, so that it can be suitably prepared with the comparative example.

On the other hand, phase analysis for the above Examples 1 and 2 was conducted to examine the distribution of the crystalline materials, which are shown in FIG. 1 and FIG. 2, respectively.

As shown in the figure, XRD analysis of the prepared frit exhibited 90% or more of crystallinity and the crystallinity of the coating layer was 90% or more.

Also, in the case of Example 2, XRD analysis of the prepared frit showed a crystalline quality of 95% or more, and the crystallinity of the coating layer was also 95% or more.

The exemplary crystal phase confirmed in Examples 1 and 2 is Y ₃ Al ₅ O _12.

Therefore, when the content of SiO ₂ is the lowest and the content of Y ₂ O ₃ is the highest, the crystal phase of YAG is mainly formed when recrystallized after the melt coating, and the plasma is most excellent.

It can be seen from the SEM photographs taken in order to confirm the phase distribution when the contents of SiO ₂ in FIGS. 3 and 4 are 47.4 mol% and 33 mol% based on YAS, respectively. That is, when the content of SiO ₂ is high, the YAS amorphous content is high and the content of crystalline such as Y ₃ Al ₅ O ₁₂ and Y ₂ Si ₂ O ₇ is low, whereas when the content of SiO ₂ is low, , Y ₃ Al ₅ O _12, is relatively higher in an amount of Y ₂ Si ₂ O ₇ can be understood from the point.

In FIG. 5, plasma etching was performed on YAS prepared using 47.4 mol% of SiO ₂ , and Y ₃ Al ₅ O ₁₂ was almost etched due to plasma characteristics, while YAS amorphous was etched. Able to know.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (13)

a) melting the Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ or their precursors as starting materials to produce a glass frit;
b) uniformly applying a glass frit or a glass frit paste obtained by pulverizing the glass frit to powder on a part or all of the ceramic base material;
c) heating the glass frit according to the step b) to melt the glass frit so that the glass frit is coated by the glass frit;
d-2) recrystallizing the coating layer at a recrystallization temperature below the melting temperature;
, &Lt; / RTI &
In step c), the temperature for the coating of the glass frit is in the range from the softening point of the glass frit to the glass frit production temperature,
Wherein a crystalline material including Y ₃ Al ₅ O ₁₂ and Y ₂ Si ₂ O ₇ is produced in the glass frit as a result of the reaction between the starting materials. The method according to claim 1,
After step c)
d-1) processing the coating layer of the ceramic base material on which the glass frit is melt-coated;
Further comprising the steps of: preparing a coating layer for plasma-resistant ceramics; The method according to claim 1,
The contents of Y ₂ O ₃ , Al ₂ O ₃ and SiO ₂ are, respectively,
Wherein the total amount of the three components is from 15 mol% to 40 mol%, from 10 mol% to 50 mol%, and from 30 mol% to 60 mol%, based on the sum of the three components. delete The method according to claim 1,
In the step d-2), the glass frit is coated on the base material, and after cooling to room temperature, the temperature is raised again to reach the recrystallization temperature and recrystallization is performed, or the glass frit is coated on the ceramic base material to reach the recrystallization temperature Wherein the recrystallization is carried out by lowering the temperature of the coating layer. The method according to claim 1,
In the step b)
Wherein the glass frit powder is further subjected to planarization so that the glass frit powder is applied at a uniform thickness. The method according to claim 1,
In the step a)
Wherein the glass frit is manufactured at a temperature of 1400 to 1700 ° C. delete The method according to claim 1,
Wherein the recrystallization is performed by a two step heat treatment method in which a heat treatment is performed at a temperature higher by 15 to 25 캜 than a transition temperature of glass and then a heat treatment is performed again at a recrystallization temperature. The method according to claim 1,
Wherein the thickness of the coating layer is 50 to 150 占 퐉. A process for producing a polyurethane foam comprising the steps of:
The glass frit composition comprising 15 mol% to 40 mol% of Y ₂ O ₃ , 10 mol% to 50 mol% of Al ₂ O ₃ , and 30 mol% to 60 mol% of SiO ₂ constitutes a coating layer of the ceramic base material , A crystalline material including Y ₃ Al ₅ O ₁₂ and Y ₂ Si ₂ O ₇ is produced in the glass frit as a result of the reaction between the starting materials, and the glass frit composition is also distributed at the interface of the base material Ceramics for plasma. delete delete

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