Plasma corrosion resistant crystallized glass and dry etching process parts containing the same

Abstract

This relates to a new use of crystallized glass, which includes crystalline and glassy materials. Crystalline crystallized glass contains lithium disilicate as the main crystalline phase and at least one crystalline phase selected from lithium phosphate (Li3PO4), lithium metaphosphate (Li2SiO3), silica (SiO2), and zirconia (ZrO2) as a secondary crystalline phase. Since crystallized glass exhibits excellent workability and plasma corrosion resistance, it is a useful material for manufacturing parts for dry etching processes.

Description

[Technical Field]

[0001] The present invention relates to a crystallized glass having plasma corrosion resistance and a part for a dry etching process containing the same, and more particularly to a crystallized glass having plasma corrosion resistance and containing lithium disilicate as a main crystalline phase, and various parts containing the same that are useful for a dry etching process. [Background technology]

[0002] Recently, the global semiconductor market has been experiencing fierce competition to secure market share due to falling prices. As a result, in order to secure price competitiveness in the global semiconductor market, there has been active development of high-integration semiconductors and larger-diameter silicon wafer technology, and new process equipment and component materials are being actively developed to successfully develop semiconductor processes with high wafer yields due to larger diameters.

[0003] Meanwhile, processes such as deposition and etching in semiconductor and display manufacturing are primarily performed in high-temperature, high-pressure plasma. Therefore, the components inside the equipment must be resistant to heat and plasma corrosion and have excellent chemical properties. Among these processes, dry etching, which removes underlying layers according to the pattern formed on the wafer to form fine patterns, is one of the most important processes in semiconductor manufacturing. Among semiconductor processing equipment, dry etching equipment uses more expensive consumable parts than other equipment. However, the etching process, which uses gases (CF4, NF3, BCl3, CCl4, etc.) injected during plasma activation, etches (wears) not only the silicon wafer but also the ceramic components inside the equipment. Prolonged or repeated plasma etching can cause surface damage to the ceramic components, shortening the service life of consumable parts. Furthermore, particles from the ceramic etching can adhere to the silicon wafer, causing defects.

[0004] Meanwhile, among the components used in dry etching equipment, the focus ring is an essential consumable that protects the electrostatic chuck during the etching process and guides the plasma to distribute evenly, helping to ensure uniform dry etching. The electrostatic chuck holds the silicon wafer flat inside the chamber, while the edge ring guides the current so that it does not concentrate at the edge of the silicon wafer. The materials used for these three components are mainly alumina (Al2O3), quartz, or zirconia (ZrO2), which have physical properties similar to those of the wafer.

[0005] Alumina (Al2O3) has excellent high-temperature properties (1600-1700°C), is dense and hard (15-20 times harder than general metal materials), has high abrasion resistance against fluoride gas, and is inert, so it has excellent chemical corrosion resistance, making it the material most commonly used in semiconductor etching equipment. However, its low thermal shock resistance and the high generation of particles etched from the alumina material itself during the etching process result in low yields of Si wafers. In addition, the yield of powder from the material is low, and molding and processing into large vessels is very difficult, resulting in high production costs.

[0006] Quartz is cheaper than other materials, and its bonding structure, siloxane (silicon-oxygen) chain, has much higher energy than carbon-oxygen bonding, so it has the advantage of having little change in physical and mechanical properties due to temperature changes. However, due to the chemical durability of SiO2, it is limited to use with etching equipment that uses fluoride gas, and its low high-temperature strength has also been pointed out as a drawback.

[0007] Zirconia (ZrO2) is usually made of 3Y-TZP and has excellent durability and excellent wear and corrosion resistance, so it generates fewer particles than alumina (Al2O3). However, its high processing cost and low thermal shock resistance are considered to be its drawbacks.

[0008] These parts are typically replaced every 10 days in dry etching processes, making them one of the consumables with a short replacement cycle. Replacing these consumables requires a significant amount of time to reset the chamber conditions after the equipment is no longer in use, resulting in significant opportunity costs and material costs.

[0009] Due to the high material costs involved in dry etching processes, parts are often reused after cleaning with acid or alkali instead of being replaced at regular intervals. However, this method results in a problem in that the surface of the part material becomes rough due to surface damage, and pores are formed during the etching process, leading to moisture adsorption, which results in a long time required to control the atmosphere inside the chamber.

[0010] In recent years, the increasing integration of semiconductors has led to the use of high-power plasma, but there is also a demand for strengthened plasma resistance for related parts. As component materials become larger, there is a demand for materials that are easy to process, have dimensional accuracy, are durable, and have a competitive unit price.

[0011] For this reason, the surface of the alumina material is spray-coated with Y2O3, which has excellent plasma resistance, before use. However, due to the difference in thermal expansion coefficient between the surface of the material and Y2O3, the coating film often peels off or breaks, resulting in a short service life and the need to recoat.

[0012] Silicon carbide (SiC) materials have excellent high-temperature properties, wear resistance, and corrosion resistance, and are more resistant to thermal shock than existing alumina, zirconia, and quartz. They also have the advantage of generating fewer particles, and have been actively developed recently. However, the manufacturing process is complicated, as the physical properties of the product vary even within the furnace during the sintering process, and SiC is difficult to cut due to its high hardness.

[0013] As an example of the conventional technology for improving plasma corrosion resistance as described above, Patent Document 1 (Korean Patent Registration No. 10-1491568) discloses a sintered solid solution-containing ceramic coating for use on the surface of semiconductor processing equipment exposed to halogen plasma, the sintered solid solution-containing ceramic coating providing advantageous coating mechanical properties, the coating being formed from zirconium oxide in a molar concentration range of 96 mol% to 94 mol% and yttrium oxide in a molar concentration range of 4 mol% to 6 mol%, and the average particle size of the sintered solid solution-containing ceramic coating being in the range of 0.5 μm to 8.0 μm.

[0014] Korean Patent Publication No. 10-2011-0086851 also discloses compositions of metal oxyfluoride-containing glazes, glass ceramics, and combinations thereof used as plasma corrosion-resistant protective coatings on other substrates, such as solid substrates made of aluminum oxide, aluminum nitride, quartz, silicon carbide, and silicon nitride, and components of semiconductor processing equipment including the same. Specifically, the disclosure discloses a semiconductor processing equipment component including a ceramic or glass substrate having a melting point greater than about 1600°C, whose surface is exposed to a halogen-containing reactive plasma during semiconductor processing, and a protective coating applied to one or more surfaces of the substrate, the coating comprising one or more yttrium-based fluoride crystalline phases, one or more yttrium-based oxyfluoride crystalline phases, one or more amorphous phases containing yttrium and fluorine, or a combination thereof.

[0015] Additionally, Patent Document 3 (Korean Patent Registration No. 10-1514197) discloses a corrosion-resistant ceramic component bonded to reactive plasma in relation to a component structure useful as a device in a plasma processing chamber, the bonded ceramic component including a glass-ceramic bonding layer, and the glass-ceramic bonding layer including 0.1% to 50% by volume of a non-solid phase of the glass-ceramic bonding layer.

[0016] Furthermore, Patent Document 4 (International Patent Publication WO2010 / 011113A2) discloses a plasma-resistant ceramic coated body. Specifically, the document discloses a plasma-resistant ceramic coated body comprising a coated body to be used in a plasma processing apparatus, and a ceramic coating film formed on the surface of the coated body, the ceramic coating film having a corrosion rate of 13 to 25 nm / min in plasma generated at 800 W power and a porosity content of 0.1 to 1%, wherein the coated body includes aluminum, stainless steel, quartz, or a ceramic material and is any one selected from the group consisting of a gas distribution plate, an electrostatic chuck, a showerhead, an inner wall of a chamber, a cylinder, and a focus ring.

[0017] Patent Document 5 (Korean Patent Registration No. 10-0972567) discloses a plasma-resistant member and a method for manufacturing the same, which describes a glass composition having a Y-Si-Al-ON composition, the glass composition being an amorphous plasma-resistant member containing 5-30 mol% Y2O3, 15-40 mol% Al2O3, 10-80 mol% SiO2, and 40-20 mol% Si3N, and essentially states that such a plasma-resistant member can be manufactured by coating the glass composition on a substrate selected from alumina, quartz, and metal to form a coating layer. The document also states that the coating can be performed using any one of thermal spraying, aerosol deposition, sputtering, electron beam evaporation, thermal evaporation, and laser deposition.

[0018] According to the above-mentioned series of prior art, generally, parts are manufactured from materials such as aluminum oxide, aluminum nitride, quartz, silicon carbide, silicon nitride, etc., and ceramic coating compositions such as yttrium-based glass compositions or glass ceramics containing fluorinated groups, zirconia-based ceramics, etc. are proposed as protective coating compositions to impart or improve plasma corrosion resistance to such parts, and it can be seen that parts to which such coating layers are bonded are disclosed. [Prior art documents] [Patent documents]

[0019] [Patent Document 1] Korean Patent No. 10-1491568 [Patent Document 2] Korean Patent Publication No. 10-2011-0086851 [Patent Document 3] Korean Patent No. 10-1514197 [Patent Document 4] International Patent Publication No. WO2010 / 011113A2 [Patent Document 5] Korean Patent Registration No. 10-0972567 Summary of the Invention [Problem to be solved by the invention]

[0020] The present invention aims to provide a new use for crystallized glass, and in particular to provide crystallized glass that contains lithium disilicate as the main crystalline phase and has excellent processability, thereby making it easy to process and effective in reducing product processing costs and time, and that has a low etching rate, little weight loss after etching, and plasma corrosion resistance.

[0021] In addition, the present invention aims to provide a dry etching process part that can improve the processing difficulty and thermal shock stability of existing semiconductor and electronic material ceramics during large-area manufacturing by using a crystallized glass containing lithium disilicate as the main crystalline phase and having excellent processability, and that can increase durability during semiconductor plasma etching, thereby extending the replacement life of the process part. [Means for solving the problem]

[0022] The present invention provides plasma corrosion-resistant crystallized glass, which includes a crystalline and a glassy material, and the crystalline material contains lithium disilicate as a main crystalline phase and at least one crystalline phase selected from lithium phosphate (Li3PO4), lithium metaphosphate (Li2SiO3), silica (SiO2), and zirconia (ZrO2) as a secondary crystalline phase.

[0023] In the plasma corrosion-resistant crystallized glass of the present invention, the silica crystal phase may be at least one selected from the group consisting of cristobalite, low-temperature quartz (α-quartz), and tridymite.

[0024] In the plasma corrosion-resistant crystallized glass of the present invention, the crystalline phase may have an average particle size of 0.05 to 5 μm.

[0025] In the plasma corrosion-resistant crystallized glass according to one embodiment of the present invention, the crystalline phase may have an average particle size of 0.05 to 0.5 μm.

[0026] In the plasma corrosion-resistant crystallized glass according to one embodiment of the present invention, the crystalline phase may have an average particle size of 0.5 to 5 μm.

[0027] The plasma corrosion-resistant crystallized glass according to one embodiment of the present invention preferably has a surface roughness (Ra) of 0.1 μm at most.

[0028] Another embodiment of the present invention is a composition comprising 60-85 wt% SiO2, 10-15 wt% Li2O, 1-6 wt% P2O5, and Me II O(where Me II is Ca, Mg, Zn, Ba or Be), or a mixture thereof, 0.1 to 5% by weight of Me I 2O (where Me I 0.1 to 5% by weight of monovalent element oxides represented by the formula (K, Na, Rb or Cs) alone or in combination with these oxides and Me III 2O3 (where Me III The present invention provides a method for producing crystallized glass having plasma corrosion resistance, which comprises subjecting a melt of a glass composition containing 1 to 10 wt % of a trivalent element oxide represented by the formula (Al, B, Y, La, Ga, or In), either alone or in a mixture, to a primary crystallization heat treatment at 400 to 850°C.

[0029] In a method for producing plasma corrosion-resistant crystallized glass according to a preferred embodiment of the present invention for increasing strength, a secondary crystallization heat treatment can be performed at 800 to 950°C after a primary crystallization heat treatment.

[0030] In a method for producing crystallized glass having plasma corrosion resistance according to one embodiment of the present invention, a grinding step is performed after a primary crystallization heat treatment, and a polishing step is performed after a secondary crystallization heat treatment at 800 to 950°C. In the method for manufacturing crystallized glass having plasma corrosion resistance according to another embodiment of the present invention, grinding and polishing processes may be performed after the secondary crystallization heat treatment.

[0031] In the method for manufacturing crystallized glass having plasma corrosion resistance according to one embodiment of the present invention, the polishing step may be carried out so that the average roughness (Ra) becomes 0.1 μm at most.

[0032] Another embodiment of the present invention provides a dry etching process part including the plasma corrosion-resistant crystallized glass according to the embodiment, and further provides a dry etching process part made of the plasma corrosion-resistant crystallized glass according to the embodiment.

[0033] According to an embodiment, the dry etching process part may be at least one selected from a focus ring, an electrostatic chuck, and an edge ring. [Effects of the Invention]

[0034] The present invention provides a plasma corrosion-resistant material that is easier to process than alumina or zirconia materials, which are expensive and time-consuming to process due to their high hardness, and is therefore effective in reducing product processing costs and time, while also having superior strength compared to general glass materials. Furthermore, the present invention provides a plasma corrosion-resistant material that has a lower etching rate than existing materials and therefore less weight loss after etching.

[0035] As a result, the present invention provides dry etching process parts with excellent processability and plasma corrosion resistance, thereby flexibly coping with the trend toward higher integration of semiconductors and larger diameter Si wafers. [Brief explanation of the drawings]

[0036] [Figure 1a] Images (×3K) of the microstructures after dry etching observed with a scanning electron microscope, (a) a glass-ceramics test piece according to the present invention, (b) an alumina test piece, and (c) a zirconia test piece. [Figure 1b] Images (×3K) of the microstructures after dry etching observed with a scanning electron microscope, (a) a glass-ceramics test piece according to the present invention, (b) an alumina test piece, and (c) a zirconia test piece. [Figure 1c] Images (×3K) of the microstructures after dry etching observed with a scanning electron microscope, (a) a glass-ceramics test piece according to the present invention, (b) an alumina test piece, and (c) a zirconia test piece. [Figure 2] FIG. 1 shows a method for masking a test specimen with Kapton tape (polyimide) to measure the etching rate. DETAILED DESCRIPTION OF THE INVENTION

[0037] The above and further aspects of the present invention will become more apparent from the following detailed description of preferred embodiments thereof, which are given with reference to the accompanying drawings. The present invention will now be described in detail so that those skilled in the art can easily understand and reproduce these embodiments.

[0038] The present invention relates to a crystallized glass having excellent workability (machinability) and plasma corrosion resistance, and a part for use in a dry etching process that includes the same.

[0039] Materials used in dry etching processes can be used if they can withstand harsh environments such as fluoride gas. In the present invention, a glass composition that can be used with fluoride gas and is easier to process than existing ceramic materials has been developed, thereby providing crystallized glass that has the plasma corrosion resistance and easy processability required in dry etching processes, and a method for manufacturing the same.

[0040] Specifically, such plasma corrosion-resistant crystallized glass includes crystalline and glassy phases, and the crystalline phase contains lithium disilicate as the main crystalline phase and at least one crystalline phase selected from lithium phosphate (Li3PO4), lithium metaphosphate (Li2SiO3), silica (SiO2), and zirconia (ZrO2) as a secondary crystalline phase. When considering workability and plasma corrosion resistance, the crystallized glass preferably contains at least 30% by weight, and more preferably 40 to 80% by weight, of crystalline material.

[0041] In the above and following descriptions, the term "main crystalline phase" is understood to mean a crystalline phase that accounts for at least 50% by weight based on the total weight of the crystalline material. However, when considering processability and plasma corrosion resistance, it is preferable that the glass-ceramics contain at least 55% by weight, and preferably 60 to 95% by weight, of the total crystalline phase as the lithium disilicate main crystalline phase.

[0042] In the plasma corrosion-resistant crystallized glass of the present invention, the silica crystalline phase as a secondary crystalline phase can have various crystalline forms, but is not limited thereto. In terms of plasma corrosion resistance, strength, and processability, it is preferable that the silica crystalline phase contains at least one selected from the group consisting of cristobalite, low-temperature quartz (α-quartz), and tridymite.

[0043] Such crystallized glass is preferable in terms of workability and has a hardness (Vickers hardness, Hv) of 720 to 750 kg / mm 2 It can be.

[0044] Furthermore, in the plasma corrosion-resistant crystallized glass of the present invention, the average grain size of the crystalline phase is preferably 0.05 to 5 μm in consideration of strength, plasma corrosion resistance, and processability. For example, in terms of processability, the average grain size of the crystalline phase is preferably 0.05 to 0.5 μm, but when considering strength and plasma corrosion resistance, the preferred average grain size of the crystalline phase may be 0.5 to 5 μm.

[0045] The plasma corrosion-resistant crystallized glass of the present invention exhibits high strength different from that of general glass materials from the viewpoint of strength. Specifically, the breaking strength is 350 to 500 MPa based on the three-point flexural strength (based on the method specified in ISO 4049, ANSI / ADA Specification No. 27), making it a high-strength material.

[0046] Such plasma corrosion-resistant crystallized glass with a maximum surface roughness (Ra) of 0.1 μm can be useful as fine ceramics for dry etching processes.

[0047] There is no limitation on the manufacturing method as long as the crystallized glass satisfies these conditions. As an example, the crystallized glass having plasma corrosion resistance is composed of 60-85% by weight of SiO2, 10-15% by weight of Li2O, 1-6% by weight of P2O5, and Me II O(where Me II is Ca, Mg, Zn, Ba or Be), or a mixture thereof, 0.1 to 5% by weight of Me I 2O (where Me I is K, Na, Rb or Cs), either alone or in admixture of 0.1 to 5% by weight of monovalent element oxides, and Me III 2O3 (where Me III can be produced from a glass composition containing 1 to 10 wt % of a trivalent element oxide represented by the formula (Al, B, Y, La, Ga or In) alone or in a mixture thereof.

[0048] In the glass composition, P2O5 acts as a nucleating agent, and Me II Oxides of divalent elements represented by O can play a role in increasing the softening point and plasma corrosion resistance of glass, and Me I Oxides of monovalent elements represented by MeO can play a role in lowering the melting temperature of glass. III The oxides of trivalent elements represented by 2O3 act as intermediates in the glass and can affect the corrosion resistance.

[0049] In the method for producing crystallized glass from such a glass composition, first, a glass melt is produced according to a conventional method.

[0050] The glass melt is produced by weighing and mixing the above-mentioned glass composition. At this time, Li2CO3 can be added instead of Li2O, but this is because the carbon dioxide (CO2) in Li2CO3 is released as a gas during the glass melting process.I For example, in the case of oxides of monovalent elements represented by 2O, K2CO3 or Na2CO3 can be added instead of K2O or Na2O, respectively, because carbon dioxide (CO2) is released as a gas during the glass melting process.

[0051] The glass composition is mixed using a dry mixing process, which may include a ball milling process. Specifically, the starting materials are loaded into a ball milling machine, which rotates at a constant speed to mechanically pulverize and uniformly mix the starting materials. The balls used in the ball milling machine may be made of a ceramic material such as zirconia or alumina, and the balls may be all the same size or may have at least two different sizes. The ball size, milling time, and rotation speed of the ball milling machine are adjusted based on the target particle size. For example, the ball size may be set to a range of approximately 1 mm to 30 mm, and the rotation speed of the ball milling machine may be set to a range of approximately 50 to 500 rpm. Ball milling is preferably performed for 1 to 48 hours, taking into account the target particle size. Through ball milling, the starting materials are pulverized into fine particles, resulting in a uniform particle size and uniform mixing.

[0052] The mixed starting materials are placed in a crucible and heated to melt the glass composition. Here, "melting" refers to the transformation of the glass composition into a viscous liquid state, rather than a solid state. The melting furnace is preferably made of a material that has a high melting point, high strength, and a small contact angle to prevent the molten material from sticking together. For this reason, the melting furnace is preferably made of a material such as platinum (Pt), diamond-like carbon (DLC), or chamotte, or is coated with a material such as platinum (Pt) or diamond-like carbon (DLC).

[0053] Melting is preferably carried out at 1,400 to 2,000°C at atmospheric pressure for 1 to 12 hours. If the melting temperature is below 1,400°C, the starting materials may not be melted in advance, while if the melting temperature exceeds 2,000°C, excessive energy consumption is required, which is uneconomical. Therefore, melting within the above-mentioned temperature range is preferred. Furthermore, if the melting time is too short, the glass composition may not be sufficiently melted, while if the melting time is too long, excessive energy consumption is required, which is uneconomical. The temperature rise rate of the melting furnace is preferably approximately 5 to 50°C / min. However, if the temperature rise rate of the melting furnace is too slow, it takes a long time and productivity decreases. If the temperature rise rate of the melting furnace is too fast, the sudden temperature rise may increase the amount of volatilization of the starting materials, which may deteriorate the physical properties of the crystallized glass. Therefore, it is preferable to raise the temperature of the melting furnace at a temperature rise rate within the above-mentioned range. Melting is preferably carried out in an oxidizing atmosphere such as oxygen (O2) or air.

[0054] After obtaining the molten glass composition by the above-mentioned method, the molten glass composition is poured into a predetermined mold to obtain crystallized glass for forming a molded product of a desired shape and size. The mold is preferably made of a material that has a high melting point, high strength, and a small contact angle to prevent the molten glass from sticking to it. For this reason, it is preferably made of a material such as graphite or carbon, and is preferably preheated to 200 to 300°C to prevent thermal shock before pouring the molten glass into the mold.

[0055] To produce glass-ceramics having the plasma corrosion resistance required by the present invention from the melt of the glass composition prepared in this manner, it is preferable to perform heat treatment at 400 to 850°C (hereinafter, this is referred to as the "primary crystallization heat treatment"). Through this primary crystallization heat treatment, glass-ceramics containing lithium disilicate as the primary crystalline phase and at least one crystalline phase selected from lithium phosphate (LiPO), lithium metaphosphate (LiSiO), silica (SiO), and zirconia (ZrO) as the secondary crystalline phase can be obtained. This glass-ceramics may also be glass-ceramics containing the above crystalline phase and the remaining glass phase. The crystalline phase in this case has an average grain size of 0.05 to 0.5 μm, and exhibits appropriate cutting strength while satisfying the strength of the final product, making it easy to process.

[0056] On the other hand, as part of the process of further increasing the strength of the crystallized glass that has undergone the primary crystallization heat treatment, further heat treatment can be performed (in the above and following descriptions, such additional heat treatment is referred to as "secondary crystallization heat treatment"). The secondary crystallization heat treatment can be preferably performed at 800 to 950 ° C, and such heat treatment causes the crystalline phase to grow and the grain size of the crystalline phase to increase. Preferably, through the secondary crystallization heat treatment under the conditions described above, the average grain size of the crystalline phase is 0.5 to 5 μm, which can maintain processability while increasing the strength.

[0057] In order to use the crystallized glass of the present invention as a fine ceramic for semiconductor processing, a grinding or polishing step may be performed. The grinding or polishing step may be performed after the primary crystallization heat treatment or after the secondary heat treatment.

[0058] As an example, after the primary crystallization heat treatment, a grinding step can be performed, and after the secondary crystallization heat treatment, a polishing step can be performed. As another example, after the secondary crystallization heat treatment, a grinding and polishing step can be performed.

[0059] In this case, the polishing step is preferably carried out so that the average roughness (Ra) becomes a maximum of 0.1 μm, so that the surface ultimately has a roughness that is useful for fine ceramics. [Example]

[0060] The hardness values ​​confirm that the glass-ceramics according to the present invention (hereinafter referred to as "glass-ceramics") are advantageous in terms of processability (cutting force). Table 1 below shows the results of measuring the hardness (Vickers hardness, Hv) of the glass-ceramics compared with alumina and zirconia, which are mainly used as materials for focus rings, which are semiconductor processing parts. The test specimens used were 15 x 15 x 0.6 mm in size and had a surface roughness (Ra) of 0.5 μm.

[0061] As shown in Table 1 below, the hardness of the crystallized glass proposed in the present invention is about half that of other materials, demonstrating its excellent cutting ability. This suggests that when manufacturing components such as focus rings using the crystallized glass of the present invention, much time and money will not be consumed in the grinding and polishing processes.

[0062] [Table 1]

[0063] Next, to examine the plasma corrosion resistance of the crystallized glass of the present invention, a dry etching process was evaluated under the following conditions: Specifically, the three types of test pieces (test piece dimensions: 15 x 15 x 0.6 (mm)) described above were subjected to dry etching under the following conditions at the request of the Korea Institute of Industrial Technology. (1) Equipment: 2300 Poly Lam Research (USA) (2) Test conditions 1)Power-RF Power(Source):1,000W;RF Power(Bias):500W 2) Gas: Total 10mmTorr CF4:120sccm / Ar:60sccm / O2:20sccm 3) Time - 10 minutes exposure followed by a 5 minute break, repeated 6 times

[0064] After dry etching was performed using the method described above, the microstructure of each specimen was observed using a scanning electron microscope and is shown in Figure 1.

[0065] As mentioned above, typical dry etching processes result in the formation of pores not only in the wafer but also in process components such as focus rings and edge rings. This can be easily confirmed from the SEM images of alumina (FIG. 1b) and zirconia (FIG. 1c) after etching, both of which are conventional materials. However, in contrast, the SEM image (FIG. 1a) of the crystallized glass of the present invention shows that almost no pores or etching marks are formed after etching.

[0066] Furthermore, the surface roughness of each test piece was measured before and after the etching process, and the results are shown in Table 2. At this time, the surface roughness was measured using an AFM (Atomic Force Microscope).

[0067] In Table 2 below, the change in average surface roughness is calculated by subtracting the surface roughness value (Ra) before etching from the surface roughness value (Ra) after etching for each test piece, and then calculating the average value of these changes in surface roughness.

[0068] The results in Table 2 show that the change in surface roughness before and after dry etching is about four times smaller than that of alumina and about 1.5 times smaller than that of zirconia, and the surface after etching is uniform as shown in Figure 1, demonstrating that it has superior plasma corrosion resistance compared to existing materials.

[0069] [Table 2]

[0070] In addition, the weight change before and after dry etching was measured using a precision electronic balance, and the results are shown in Table 3 below. The measurement results show that the weight loss of the crystallized glass of the present invention was reduced by about 11% compared to existing materials. This shows that the crystallized glass of the present invention is less etched under harsh plasma atmospheric conditions. In Table 3 below, the average weight change is the weight change obtained by subtracting the weight value after etching from the weight value before etching for each test piece, and then calculating the average of these weight changes.

[0071] [Table 3]

[0072] Meanwhile, for each test piece, when dry etching was performed, half of the test piece was covered with Kapton tape (polyimide tape) to prevent it from being exposed to the plasma (non-plasma-exposed surface), as shown in Figure 2, and the other half was exposed to the plasma and etched (plasma-exposed surface). Then, a confocal microscope was used to determine the height difference between the plasma-exposed surface and the non-exposed surface, and the etching rate was measured from this. The results are shown in Table 4 below. From the results in Table 4, it can be seen that the crystallized glass of the present invention was etched about twice as little as alumina, and showed an etching rate similar to that of zirconia.

[0073] [Table 4]

[0074] In the above-mentioned example of the experiment, the glass-ceramics of the present invention was evaluated as an example of a glass-ceramic containing lithium disilicate as the main crystalline phase and silica (SiO2) crystals as the secondary crystalline phase, but it goes without saying that equivalent effects can be obtained with various glass-ceramics that satisfy the composition or physical properties of the above-mentioned embodiment. For reference, the following Table 5 shows an example of the type of fine ceramic parts that can be used in the dry etching process, the main applicable materials, and the general replacement period.

[0075] [Table 5]

[0076] From Table 5, it can be seen that various fine ceramic parts are required for the dry etching process, and that most of these parts are consumable parts. It can also be seen that alumina (Al2O3) is used as the main material for these parts. However, as mentioned above, the crystallized glass proposed in the present invention exhibits superior processability and plasma corrosion resistance compared to these existing materials, and therefore can be seen to be useful as a substitute for these materials.

[0077] Thus, in one embodiment of the present invention, a dry etching process part can be provided that includes a plasma corrosion-resistant crystallized glass that includes a crystalline material and a glassy material, wherein the crystalline material includes lithium disilicate as a main crystalline phase and at least one crystalline phase selected from lithium phosphate (LiPO), lithium metaphosphate (LiSiO), silica (SiO), and zirconia (ZrO) as a secondary crystalline phase.

[0078] Here, dry etching process parts containing crystallized glass having plasma corrosion resistance can be understood to include both cases where the crystallized glass having plasma corrosion resistance of the present invention is laminated with conventional dissimilar materials, and cases where the crystallized glass having plasma corrosion resistance of the present invention is used as a coating layer.

[0079] Preferably, the dry process part according to one embodiment of the present invention includes a crystalline material and a glass material, and the crystalline material may be made of plasma corrosion-resistant crystallized glass containing lithium disilicate as a main crystalline phase and at least one crystalline phase selected from lithium phosphate (LiPO), lithium metaphosphate (LiSiO), silica (SiO), and zirconia (ZrO) as a secondary crystalline phase.

[0080] These dry etching process parts have excellent plasma corrosion resistance and processability, so they can flexibly accommodate the increasing integration of semiconductors and the increasing diameter of Si wafers.

[0081] The present invention has been described with reference to one embodiment shown in the drawings, but this is by way of example only, and various modifications and equivalent alternative embodiments are possible for those skilled in the art. [Industrial Applicability]

[0082] The present invention uses highly processable crystallized glass to improve the processability or thermal shock stability of existing semiconductor and electronic material ceramics during large-area manufacturing, and is useful for manufacturing dry etching process parts that can increase durability during semiconductor plasma etching and extend the replacement life of process parts.

Claims

1. The glass contains crystalline and vitreous materials, and the crystalline material comprises at least 30% by weight. Among the crystalline substances consisting of a main crystalline phase and a sub crystalline phase, the main crystalline phase is contained in an amount of at least 55% by weight, The average grain size of the crystalline phase is 0.5 to 5 μm, hardness (Vickers hardness, Hv) of 720 to 750 kg / mm ​​2; A method for producing crystallized glass having plasma corrosion resistance, in which the average weight change after dry etching (sample size: 15 x 15 x 0.6 mm, power: 1,000 W (Source), 500 W (Bias), pressure: 10 mmTorr, atmosphere: CF4: 120 sccm / Ar: 60 sccm / O2: 20 sccm, exposure time: 10 minutes followed by a 5-minute break, repeated 6 times) is 2.308 mg or less, SiO ２ 60-85% by weight, Li ２ O10-15% by weight, P ２ O ５ 1-6% by weight, Me ＩＩ O (where Me ＩＩ is Ca, Mg, Zn, Ba or Be), either alone or in admixture of these, 0.1 to 5% by weight, Me Ｉ ２ O (where Me Ｉ 0.1 to 5% by weight of a monovalent element oxide represented by the formula (wherein K, Na, Rb or Cs) alone or in a mixture thereof, and Me ＩＩＩ ２ O ３ (Here, Me ＩＩＩ a molded article of a glass composition containing 1 to 10 wt % of a trivalent element oxide, either singly or as a mixture thereof, represented by the formula (I) is Al, B, Y, La, Ga, or In, is subjected to a primary crystallization heat treatment at 400 to 850°C, After the primary crystallization heat treatment, a secondary crystallization heat treatment is performed at 800 to 950°C.

1. A method for producing crystallized glass having plasma corrosion resistance, comprising:

2. After the primary crystallization heat treatment, a grinding step is performed, and after a secondary crystallization heat treatment is performed at 800 to 950°C, a polishing step is performed. A method for producing the plasma corrosion-resistant crystallized glass according to claim 1.

3. After the secondary crystallization heat treatment, grinding and polishing processes are carried out. A method for producing the plasma corrosion-resistant crystallized glass according to claim 1.

4. The polishing process is carried out so that the average roughness (Ra) is 0.1 μm at most. A method for producing crystallized glass having plasma corrosion resistance according to claim 2 or 3.

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