KR20240012677A - Plasma-resistant member having stacked structure - Google Patents

Abstract

The disclosed plasma-resistant member may include a lower layer disposed on a substrate and including yttrium oxide, a buffer layer disposed on the lower layer, and an upper layer disposed on the buffer layer and including yttrium oxide or fluorine-enriched yttrium oxide. The buffer layer contains yttrium, oxygen, and fluorine, and may have a different composition from the upper layer.

Description

Plasma-resistant member with laminated structure {PLASMA-RESISTANT MEMBER HAVING STACKED STRUCTURE}

The present invention relates to a plasma resistant member. More specifically, the present invention relates to a plasma-resistant member having a laminated structure.

In manufacturing electronic devices such as semiconductor devices, processes using plasma, such as etching using plasma and deposition using plasma, are widely used.

In processes using plasma, highly chemically active radicals and dissociated ions are generated, which can cause physical/chemical damage to parts exposed to plasma. Accordingly, a method of forming a ceramic coating layer on the surface of a part using a method such as plasma spraying is being used.

The object of the present invention is to provide a plasma-resistant member having a laminated structure that can suppress the generation of contaminant particles and surface cracks.

The plasma-resistant member according to exemplary embodiments for achieving the object of the present invention is disposed on a substrate and includes a lower layer containing yttrium oxide, a buffer layer disposed on the lower layer, and disposed on the buffer layer and yttrium acid oxide or fluorine. and an upper layer comprising enriched yttrium oxide. The buffer layer contains yttrium, oxygen, and fluorine, and may have a different composition from the upper layer.

According to exemplary embodiments, a layered structure having anti-plasma performance may be formed through deposition. Therefore, it can have a more dense structure than the plasma-resistant coating layer formed by conventional thermal spray coating without a heat treatment process for sintering.

Additionally, the upper layer of the layered structure includes yttrium oxide or fluorine-enriched yttrium oxide, thereby suppressing the generation of contaminant particles and reducing variation in plasma composition within the chamber.

Additionally, the laminated structure can improve the quality of the upper layer by including a buffer layer disposed between the upper layer and the lower layer. Accordingly, the surface roughness of the upper layer may be reduced and the occurrence of cracks may be suppressed.

However, the effects of the present invention are not limited to the effects mentioned above, and may be expanded in various ways without departing from the spirit and scope of the present invention.

Figure 1 is a cross-sectional view showing a plasma-resistant member according to an embodiment of the present invention.
Figures 2, 3, 4 and 5 are cross-sectional views showing a buffer layer of a plasma-resistant member according to embodiments of the present invention.
Figure 6 is a schematic diagram showing a deposition apparatus for manufacturing a plasma-resistant member according to embodiments of the present invention.
Figure 7 is a flowchart of a method for manufacturing a plasma-resistant member according to an embodiment of the present invention.
Figure 8 is a scanning electron microscope (SEM) photograph showing a cross section of the layered structure obtained in Example 1 and an energy dispersive spectroscopy (EDS) graph according to depth.
Figure 9a is an SEM photograph showing the top surface of the layered structure obtained in Example 1.
Figure 9b is an SEM photograph showing the top surface of the layered structure obtained in Comparative Example 1.

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the attached drawings.

Plasma-resistant member with laminated structure

Figure 1 is a cross-sectional view showing a plasma-resistant member according to an embodiment of the present invention. Figures 2, 3, 4 and 5 are cross-sectional views showing a buffer layer of a plasma-resistant member according to embodiments of the present invention.

Referring to Figure 1, the plasma resistant member according to an embodiment of the present invention includes a substrate 10, a lower layer 20 disposed on the substrate 10, a buffer layer 30 disposed on the lower layer 20, and It includes an upper layer 40 disposed on the buffer layer 30. The laminated structure including the lower layer 20, the buffer layer 30, and the upper layer 40 may function as a corrosion resistant layer as a whole.

At least one of the lower layer 20, the buffer layer 30, and the upper layer 40 may be a vapor deposition film formed by vapor deposition. According to one embodiment, the lower layer 20, the buffer layer 30, and the upper layer 40 may be formed by deposition.

According to one embodiment, the deposition may be physical vapor deposition. For example, the physical vapor deposition may include thermal evaporation, electron beam evaporation, sputtering, etc. According to one embodiment, the lower layer 20, the buffer layer 30, and the upper layer 40 may be deposited by electron beam evaporation.

For example, the substrate 10 may include ceramic or metal. The ceramic may include alumina, aluminum nitride, silicon nitride, silicon carbide, zirconia, YAG (yttrium-aluminum-garnet), sapphire, quartz, or a combination thereof. The metal may include stainless steel (SUS), alloy tool steel, carbon tool steel, chrome steel, aluminum, chrome molybdenum steel, nickel chrome molybdenum steel, or a combination thereof.

According to one embodiment, the substrate 10 may include ceramics such as alumina (aluminum oxide), aluminum nitride, silicon nitride, silicon carbide, quartz, etc.

According to one embodiment, the lower layer 20 includes yttrium oxide (Y ₂ O ₃ ). Yttrium oxide has high corrosion resistance against plasma. Accordingly, the substrate 10 can be prevented from being damaged by plasma. For example, the thickness of the lower layer 20 may be 0.1 ㎛ to 100 ㎛. If the thickness of the lower layer 20 is excessively thin, the lifespan of corrosion resistance may be shortened, and if it is excessively large, manufacturing time and cost may excessively increase.

As the lower layer 20 is formed by deposition, it may have crystallinity. For example, the average crystal grain size of yttrium oxide in the lower layer 20 may be 10 nm to 1,000 nm.

According to one embodiment, the upper layer 40 includes yttrium oxide (YO _x F _y ) or fluorine-rich yttrium oxide. According to one embodiment, the upper layer 40 containing yttrium oxide or fluorine-enriched yttrium oxide forms the outermost layer of the plasma-resistant laminated structure, so that it can be exposed to plasma in a plasma treatment process.

Plasma generated in a plasma processing device may include halogen-based plasma such as fluorine plasma, chlorine plasma, etc. For example, when yttrium oxide of the lower layer 20 is exposed to fluorine plasma, contaminant particles containing fluorine may be formed on the surface. The contaminant particles may be separated during the plasma treatment process and may contaminate the wafer, thereby reducing process yield. In addition, the composition of the plasma may change depending on the region as fluorine radicals in the plasma react and diffuse with yttrium oxide, and thus the uniformity of the plasma treatment process may deteriorate.

The upper layer 40 contains yttrium oxide or fluorine-enriched yttrium oxide, and can suppress the generation of contaminant particles on the surface and improve plasma uniformity. For example, the thickness of the upper layer 40 may be 0.1 ㎛ to 100 ㎛. In one embodiment, the thickness of the upper layer 40 may be 1 ㎛ to 50 ㎛.

The composition of the upper layer 40 may vary depending on process conditions, etc. According to one embodiment, the upper layer 40 may have a YOF composition in which the atomic ratio of oxygen and fluorine is close to 1:1. However, embodiments of the present invention are not limited thereto. For example, the upper layer 40 has a composition of Y ₅ O ₄ Y ₇ , a mixture of YOF and Y ₅ O ₄ F ₇ , or yttrium fluoride (YF ₃ ) or yttrium oxide (Y ₂ O ₃ ) may further be included.

According to one embodiment, the buffer layer 30 may include yttrium, oxygen, and fluorine, and has a different composition from the upper layer 40. In the present application, “having a different composition” may mean including, in whole or in part, different substances, different contents of substances, or different ratios of combination. For example, the ratio (atomic ratio) of oxygen to fluorine in the buffer layer 30 is greater than the ratio of oxygen to fluorine in the upper layer 40. For example, the buffer layer 30 includes yttrium oxide or fluorine-enriched yttrium oxide, represented by YO _x F _y , where x and y are greater than 0, and x is greater than y. For example, x/y can be greater than 1 and less than 10. According to one embodiment, the buffer layer 30 may include yttrium oxide and at least one of YOF, Y ₅ O ₄ F ₇ and YF ₃ .

According to one embodiment, the buffer layer 30 may have a coefficient of thermal expansion corresponding to a value between the coefficient of thermal expansion of the lower layer 20 and the coefficient of thermal expansion of the upper layer 40. For example, the thermal expansion coefficient (unit ppm/°C) of the buffer layer 30 may be 8 to 20. Preferably, the thermal expansion coefficient of the buffer layer 30 may be 10 to 15. More preferably, the thermal expansion coefficient of the buffer layer 30 may be 11 to 14.

Yttrium oxide of the lower layer 20 and yttrium oxide or fluorine-enriched yttrium oxide of the upper layer 40 have different coefficients of thermal expansion. Accordingly, when the upper layer 40 is deposited directly on the lower layer 20, the surface roughness and cracks of the upper layer 40 may increase due to the difference in thermal expansion coefficient. This may increase the generation of contaminant particles on the surface of the upper layer 40 and reduce the lifespan of the laminated structure.

According to embodiments of the present invention, the difference in thermal expansion coefficient between the buffer layer 30 and the upper layer 40 is smaller than the difference in thermal expansion coefficient between the lower layer 20 and the upper layer 40. Accordingly, when the upper layer 40 is deposited on the buffer layer 30, the surface roughness of the upper layer 40 may be reduced and crack generation may be suppressed.

For example, the upper layer 40 deposited on the buffer layer 30 may have an rms (root mean square) surface roughness of 10 nm or less, and preferably 5 nm or less.

For example, the thickness of the buffer layer 30 may be 0.1 ㎛ to 100 ㎛. In one embodiment, the thickness of the buffer layer 30 may be 1 ㎛ to 50 ㎛.

According to one embodiment, the thickness of the lower layer 20 may be greater than the thickness of the buffer layer 30 and the upper layer 40.

According to embodiments, the buffer layer 30 may have a multi-layer structure. For example, referring to Figures 1 and 2, the buffer layer 30 may include a first sub-buffer layer 32, a second sub-buffer layer 34, and a third sub-buffer layer 36 stacked in that order. .

The first sub-buffer layer 32 is adjacent to the lower layer 20, and the uppermost third sub-buffer layer 36 is adjacent to the upper layer 40. For example, the first sub-buffer layer 32 may contact the lower layer 20, and the third sub-buffer layer 36 may contact the upper layer 40.

The first to third sub-buffer layers 32, 34, and 36 contain yttrium, oxygen, and fluorine and have different compositions. The atomic ratio of fluorine to oxygen in the first to third sub-buffer layers 32, 34, and 36 may increase closer to the upper layer 40.

For example, the first sub-buffer layer 32, the second sub-buffer layer 34, and the third sub-buffer layer 36 are represented by YO _x1 F _y1 , YO _x2 F _y2 , and YO _x3 F _y3, respectively. It contains whitetrium or fluorine-enriched yttrium oxide, and x1, x2, x3, y1, y2, and y3 are greater than 0, and y1/x1 < y2/x2 < y3/x3 may be satisfied. Alternatively, the first sub-buffer layer 32, the second sub-buffer layer 34, and the third sub-buffer layer 36 each include yttrium oxide and at least one of YOF, Y ₅ O ₄ F ₇ , and YF ₃ The atomic ratio of fluorine to oxygen in the second sub-buffer layer 34 is greater than the atomic ratio of fluorine to oxygen in the first sub-buffer layer 32, and the atomic ratio of fluorine to oxygen in the second sub-buffer layer 34 is greater than that of the third sub-buffer layer 36. The atomic ratio of fluorine to oxygen may be greater than the atomic ratio of fluorine to oxygen of the second sub-buffer layer 34.

2 to 4, the buffer layer 30 is described as having a three-layer structure, but embodiments of the present invention are not limited thereto, and may have two bus buffer layers or four or more layers, for example. For example, it may have 10 or more sub-buffer layers.

For example, the atomic ratio of fluorine to oxygen in the buffer layer 30 may gradually increase from the bottom layer to the top layer in the range of 0.1 to 10. In another embodiment, the atomic ratio of fluorine to oxygen in the buffer layer 30 may gradually increase from the bottom layer to the top layer in the range of 0.1 to 0.9.

Referring to FIG. 3, the buffer layer 30 may include a first sub-buffer layer 31, a second sub-buffer layer 33, and a third sub-buffer layer 35 stacked in order. The first to third sub-buffer layers 31, 33, and 35 may each include a plurality of sub-layers.

For example, the first sub-buffer layer 31 may include a first sub-layer 31a and a second sub-layer 31b disposed on the first sub-layer 31a, and the second sub-buffer layer (33) may include a first sub-layer 33a and a second sub-layer 33b disposed on the first sub-layer 33a, and the third sub-buffer layer 35 may include a first sub-layer (33b). 35a) and a second sub-layer 35b disposed on the first sub-layer 35a. The first sub-layer may be referred to as a lower layer or lower sub-layer, and the second sub-layer may be referred to as an upper layer or upper sub-layer.

According to one embodiment, the sub-layers within each sub-buffer layer have different compositions.

For example, the first sub-layers 31a, 33a, and 35a include at least one of yttrium oxide, yttria-stabilized zirconia (YSZ), and yttrium aluminum garnet (YAG), and the second sub-layers 31b , 33b, 35b) may include yttrium fluoride. Yttria-stabilized zirconia and yttrium aluminum garnet have similar evaporation temperatures and crystal structures to yttrium oxide, so they may be suitable as a buffer layer.

For example, the first sub-layers 31a, 33a, and 35a include at least one of yttrium oxide, yttria-stabilized zirconia (YSZ), and yttrium aluminum garnet (YAG), and the second sub-layers 31b , 33b, 35b) may include yttrium bicarbonate or fluorine-enriched yttrium oxide.

For example, the first sub-layers (31a, 33a, 35a) and the second sub-layers (31b, 33b, 35b) include yttrium oxide or fluorine-enriched yttrium oxide, and the first sub-layers The atomic ratio of oxygen to fluorine in (31a, 33a, 35a) may be greater than the atomic ratio of oxygen to fluorine in the second sub-layers (31b, 33b, 35b).

According to one embodiment, the first sub-layers 31a, 33a, and 35a may have the same composition, and the second sub-layers 31b, 33b, and 35b may have the same composition. Additionally, the thickness ratio of the first sub-layer and the second sub-layer within each sub-buffer layer may be the same. Accordingly, the thermal expansion coefficient of each sub-buffer layer may be the same.

According to another embodiment, the thermal expansion coefficient of each sub-buffer layer may be different. For example, each sub-buffer layer may have a larger thermal expansion coefficient as it approaches the upper layer 40.

For example, the first sub-layers 31a, 33a, and 35a may have different compositions. For example, as the first sub-layers 31a, 33a, and 35a are closer to the lower layer 20, the atomic ratio of oxygen to fluorine may increase.

For example, the second sub-layers 31b, 33b, and 35b may have different compositions. For example, as the second sub-layers 31b, 33b, and 35b are closer to the upper layer 40, the atomic ratio of fluorine to oxygen may increase.

Referring to FIG. 4, the buffer layer 30 may include a plurality of sub-buffer layers 31, 33, and 35, each having a plurality of sub-layers.

For example, the first sub-buffer layer 31 may include a first sub-layer 31a and a second sub-layer 31b disposed on the first sub-layer 31a, and the second sub-buffer layer (33) may include a first sub-layer 33a and a second sub-layer 33b disposed on the first sub-layer 33a, and the third sub-buffer layer 35 may include a first sub-layer (33b). 35a) and a second sub-layer 35b disposed on the first sub-layer 35a.

According to one embodiment, the sub-layers within each sub-buffer layer have different compositions. The composition of the sub-layers may be the same as that described with reference to FIG. 3.

The first sub-layers 31a, 33a, and 35a may have different thicknesses, or the second sub-layers 31b, 33b, and 35b may have different thicknesses. Accordingly, the thickness ratio of the first sub-layer and the second sub-layer within each sub-buffer layer may vary. Accordingly, even if the first sub-layers 31a, 33a, and 35a have the same composition or the second sub-layers 31b, 33b, and 35b have the same composition, the overall thermal expansion coefficient of the sub-buffer layers is gradually increased. It can change.

For example, the first sub-layer 31a of the first sub-buffer layer 31 may have a greater thickness than the first sub-layer 33a of the second sub-buffer layer 33. The first sub-layer 33a of the second sub-buffer layer 33 may have a greater thickness than the first sub-layer 35a of the third sub-buffer layer 35.

For example, the second sub-layer 31b of the first sub-buffer layer 31 may have a greater thickness than the first sub-layer 33a of the second sub-buffer layer 33. The first sub-layer 33a of the second sub-buffer layer 33 may have a greater thickness than the first sub-layer 35a of the third sub-buffer layer 35.

For example, in the first sub-buffer layer 31 corresponding to the lowest layer, the thickness of the first sub-layer 31a may be greater than the thickness of the second sub-layer 31b, and the thickness of the first sub-layer 31a may be greater than the thickness of the second sub-layer 31b. In the third sub-layer 35, the thickness of the first sub-layer 35a may be smaller than the thickness of the second sub-layer 35b.

In one embodiment, the sub-buffer layers 31, 33, and 35 may have substantially the same thickness. However, embodiments of the present invention are not limited to this, and the sub-buffer layers 31, 33, and 35 may have different thicknesses.

In one embodiment, the thickness of the buffer layer 30 may be 0.1 ㎛ to 100 ㎛.

In embodiments including sub-layers of different compositions, the thickness of each sub-buffer layer may be 1 nm to 100 nm, preferably 1 nm to 10 nm. If the thickness of the sub-buffer layer is excessively large, the difference in thermal expansion coefficients of adjacent sub-layers or the difference in thermal expansion coefficients of adjacent sub-buffer layers may substantially increase, thereby deteriorating the film quality of the buffer layer 30 or the upper layer 40. You can.

In one embodiment, in order to form a buffer layer of an appropriate thickness while maintaining an appropriate thickness (thin thickness) of the sub-buffer layer, sub-buffer layers of the same configuration may be repeatedly stacked. For example, referring to FIG. 5, the buffer layer 30 includes a first sub-buffer layer 31 including a first sub-layer 31a and a second sub-layer 31b, a first sub-layer 33a, and A configuration in which a plurality of second sub-buffer layers 33 including a second sub-layer 33b and a plurality of third sub-buffer layers 35 including a first sub-layer 35a and a second sub-layer 35b are each stacked. You can have it.

Additionally, in the embodiments shown in FIGS. 2 to 5, each sub-buffer layer may include three or more sub-layers. For example, each sub-buffer layer may include a lower sub-layer, a middle sub-layer, and an upper sub-layer. The middle sub-layer may have a composition (fluorine/oxygen ratio) between the lower sub-layer and the upper sub-layer. When the lower sub-layer and the upper sub-layer have different thicknesses, the middle sub-layer may have a thickness between the lower western layer and the upper sub-layer.

The plasma-resistant member according to embodiments may be a component of a plasma processing device, such as a plasma deposition device or a plasma etching device. For example, the plasma resistant member may be applied to a dielectric window, showerhead, electrostatic chuck, heater, chamber liner, focus ring, wall liner, etc. However, embodiments of the present invention are not limited thereto and can be applied to various parts that can be exposed to plasma.

According to embodiments of the present invention, a layered structure having anti-plasma performance is formed through deposition. Therefore, it can have a more dense structure than the plasma-resistant coating layer formed by conventional thermal spray coating without a heat treatment process for sintering.

Additionally, the upper layer of the layered structure includes yttrium oxide or fluorine-enriched yttrium oxide, thereby suppressing the generation of contaminant particles and reducing variation in plasma composition within the chamber.

Additionally, the laminated structure can improve the quality of the upper layer by including a buffer layer disposed between the upper layer and the lower layer. Accordingly, the surface roughness of the upper layer may be reduced and the occurrence of cracks may be suppressed.

Method for manufacturing a plasma-resistant member with a laminated structure

Figure 6 is a schematic diagram showing a deposition apparatus for manufacturing a plasma-resistant member according to embodiments of the present invention.

Referring to FIG. 6 , the deposition apparatus 100 includes a process chamber 110, a source vaporization unit 120, and a fixing unit 130.

The process chamber 110 provides a processing space sealed from external space. The process chamber 110 may include a door for opening and closing the processing space, a vacuum pump for maintaining the processing space in a vacuum state and exhausting reaction by-products to the outside, as needed.

A fixing part 130 for fixing the substrate 140 (or base material) may be disposed in the process chamber 110. For example, the fixing part 130 and the substrate 140 may be placed in the upper area of the processing space, and the fixing part 130 may clamp the substrate 140 or apply electrostatic force or suction force. It can be fixed by If necessary, the fixing part 130 may be configured to apply a bias voltage to the substrate 140.

According to one embodiment, the fixing part 130 may be rotatable. By rotating the fixing part 130 while the substrate 140 is being coated, the uniformity of the coating layer can be increased. Additionally, if necessary, the fixing part 130 may have a configuration that allows tilting to change the deposition angle or deposition area.

According to one embodiment, the source vaporization unit 120 may include an evaporation source accommodating part 122 that accommodates an evaporation source and an electron gun 124 that generates an electron beam.

The electron gun 124 is connected to a power supply and generates an electron beam according to the applied power. The electron beam is incident on the evaporation source and vaporizes the evaporation source. Accordingly, vapor deposition particles 150 may be generated, and the vapor deposition particles 150 may be deposited on the substrate 140 to form a coating layer. For example, the electron gun 124 may include a filament for emitting hot electrons.

The evaporation source receiving portion 122 may be, for example, a crucible with an open top. If necessary, the evaporation source receiving portion 122 may further include a shutter capable of opening and closing the upper opening. The evaporation source receiving unit 122 may include a plurality of units. For example, if the coating layer to be deposited requires a plurality of evaporation sources, a plurality of crucibles that each accommodate a plurality of evaporation sources may be used. Additionally, a plurality of crucibles may be used to control the composition of elements within the coating layer.

Additionally, the source vaporization unit 120 may further include a magnetic member 126. The magnetic member 126 may deflect the electron beam generated by the electron gun 124 so that the electron beam can be incident on the evaporation source within the evaporation source receiving portion 122. For example, the magnetic member 126 may be a permanent magnet.

According to one embodiment, the deposition apparatus 100 may include a gas providing unit 160 for providing a process gas into the process chamber 110. For example, the process gas may be oxygen gas. For example, depending on the concentration of the oxygen gas, the ratio of oxygen in the coating layer deposited on the substrate 140 may be adjusted. However, embodiments of the present invention are not limited thereto, and the process gas may include an inert gas such as argon, helium, etc.

According to one embodiment, the deposition apparatus 100 may further include a sensor (not shown) for measuring the thickness of the coating layer deposited on the substrate 140. Through the sensor, information on the thickness of the coating layer, deposition rate, etc. can be obtained, and process conditions can be adjusted through this.

According to one embodiment, the deposition apparatus 100 may further include a heating unit for heating the substrate 140. For example, the substrate 140 may be heated before the deposition process to remove impurities such as moisture.

Figure 7 is a flowchart of a method for manufacturing a plasma-resistant member according to an embodiment of the present invention.

Referring to FIGS. 1 and 7, the lower layer 20 is deposited on the substrate 10 (S10).

For example, if the lower layer 20 includes yttrium oxide, yttrium oxide may be used as an evaporation source. The yttrium oxide in the evaporation source may be powder or sintered body. When yttrium oxide sintered body is used as an evaporation source, the crystal orientation of the lower layer 20 can be increased.

Next, the buffer layer 30 is deposited on the lower layer 20 (S20).

For example, the buffer layer 30 includes yttrium, oxygen, and fluorine. For example, the buffer layer 30 includes yttrium oxide or fluorine-enriched yttrium oxide, represented by YO _x F _y , where x and y are greater than 0 and x is greater than y.

For example, the buffer layer 30 is a mixture containing at least one of yttrium oxide, yttria-stabilized zirconia (YSZ), and yttrium aluminum garnet (YAG), and at least one of yttrium oxide, fluorine-enriched yttrium oxide, and yttrium fluoride. It can be included.

For example, the buffer layer 30 may include a plurality of sub-buffer layers so that the composition gradually changes along the vertical direction. The sub-buffer layers may have different fluorine/oxygen atomic ratios.

For example, the buffer layer 30 may include a plurality of sub-buffer layers including a lower sub-layer and an upper sub-layer having different compositions. For example, the lower sublayer includes at least one of yttrium oxide, yttria stabilized zirconia (YSZ), and yttrium aluminum garnet (YAG), and the upper sublayer includes yttrium bicarbonate, fluorine-enriched yttrium oxide, and yttrium fluoride. It may include at least one selected.

For example, the evaporation source for forming the buffer layer 30 includes at least one of yttrium oxide, aluminum oxide, zirconium oxide, yttria-stabilized zirconia, yttrium aluminum garnet, yttrium bicarbonate, fluorine-enriched yttrium oxide, and yttrium fluoride. can do.

In one embodiment, the number of crucibles accommodating each evaporation source can be adjusted to form sub-buffer layers with different compositions. For example, yttrium oxide and yttrium fluoride can be used as evaporation sources to form the buffer layer 30, and the number of crucibles containing yttrium oxide can be increased to increase the oxygen content and increase the fluorine content. To achieve this, the number of crucibles containing yttrium fluoride can be increased.

In one embodiment, to form sub-buffer layers with different compositions, the crucible accommodates a mixture of a plurality of evaporation sources, and the ratio of the evaporation sources within the mixture can be adjusted. For example, yttrium oxide and yttrium fluoride can be used as evaporation sources to form the buffer layer 30, the ratio of yttrium oxide can be increased to increase the oxygen content, and yttrium fluoride can be increased to increase the fluorine content. The ratio can be increased.

Additionally, a method of increasing the oxygen gas flow rate may be used to increase the oxygen content.

Next, the upper layer 40 is deposited on the buffer layer 30 (S30).

For example, if the upper layer 40 includes yttrium bicarbonate or fluorine-enriched yttrium oxide, yttrium bicarbonate, fluorine-enriched yttrium oxide, or a combination of yttrium oxide and yttrium fluoride may be used as the evaporation source.

According to one embodiment, the lower layer 20, the buffer layer 30, and the upper layer 40 may be formed by physical vapor deposition, for example, using the deposition apparatus shown in FIG. 6. there is.

Evaporation sources for forming the lower layer 20, the buffer layer 30, and the upper layer 40 may have a solid phase. For example, the solid phase may have the form of pellets, flakes, ingots, etc. Evaporation sources for forming the lower layer 20, the buffer layer 30, and the upper layer 40 may be referred to as a first evaporation source, a second evaporation source, and a third evaporation source, respectively.

For example, in the deposition process, the temperature of the substrate 10 may be 100°C to 700°C. The power applied to the electron gun may be 1 kW to 10 kW. While the evaporation source is evaporating, the vacuum degree of the process chamber may be 0.01 mTorr to 1 mTorr. The deposition rate of the layers may be 10 nm/min to 200 nm/min. The rotation speed of the fixing part may be 1 rpm to 100 rpm. Additionally, in the deposition process, oxygen gas may be provided, and the flow rate may be 1 sccm to 1,000 sccm. However, the above conditions are illustrative, and the embodiments of the present invention are not limited thereto, and various ranges and combinations may be used as needed.

Hereinafter, the effects of the present invention will be examined through specific examples.

Example 1

A 50 mm diameter silicon substrate mirror polished to an average surface roughness of 10 nm or less was mounted on the fixture of an electron beam evaporation apparatus having substantially the same configuration as shown in FIG. 4 (distance from the evaporation source 480 mm).

Under the following process conditions, an electron beam is incident on the evaporation source, once the evaporation source is melted and vaporization begins, the shutter on top of the evaporation source is opened, and a 5 ㎛ thick bottom layer, a 1 ㎛ thick buffer layer and 1 on the substrate. The upper layers of ㎛ were formed sequentially.

* Substrate temperature: 600℃

* Board rotation speed: 20 rpm

* Oxygen flow rate: 5 sccm

* Chamber vacuum: 0.1 mTorr

* Deposition rate: 2 nm/sec

* Lower layer evaporation source: Y ₂ O ₃

* Buffer layer evaporation source: Y ₂ O ₃ /YF ₃ (molar ratio 2:1)

* Upper layer evaporation source: Y ₂ O ₃ /YF ₃ (molar ratio 1:1)

Comparative Example 1

A stacked structure of an upper layer and a lower layer was formed on the substrate in the same manner as in Example 1, except that the buffer layer was not formed.

Figure 8 is a scanning electron microscope (SEM) photograph showing a cross section of the layered structure obtained in Example 1 and an energy dispersive spectroscopy (EDS) graph according to depth.

Referring to FIG. 8, it can be seen that an upper layer containing yttrium oxide (Y, F, O), a buffer layer containing yttrium, oxygen, and fluorine, and a lower layer containing yttrium oxide (Y, O) have been formed.

Figure 9a is an SEM photograph showing the top surface of the layered structure obtained in Example 1. Figure 9b is an SEM photograph showing the top surface of the layered structure obtained in Comparative Example 1.

Referring to FIGS. 9A and 9B, it can be confirmed that cracks were suppressed by forming an upper layer containing yttrium oxide or fluorine-enriched yttrium oxide on the buffer layer.

Although the present invention has been described above with reference to embodiments, those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that it is possible.

Embodiments of the present invention can be used in the manufacture and coating of devices that generate plasma or parts that can be exposed to plasma.

10: substrate 20: lower layer
30: buffer layer 40: upper layer
100: deposition device 110: process chamber
120: Source vaporization unit 130: Fixing unit
140: substrate 150: deposition particles
160: Gas provision unit

Claims (10)

a lower layer disposed over the substrate and comprising yttrium oxide;
a buffer layer disposed on the lower layer; and
An upper layer disposed on the buffer layer and comprising yttrium bicarbonate or fluorine-enriched yttrium oxide,
The buffer layer contains yttrium, oxygen, and fluorine, and has a different composition from the upper layer. The plasma-resistant member of claim 1, wherein the lower layer, the buffer layer, and the upper layer are formed by vapor deposition. The plasma-resistant member according to claim 1, wherein the atomic ratio of oxygen to fluorine in the buffer layer is greater than the atomic ratio of oxygen to fluorine in the upper layer. According to claim 1, The buffer layer is a plasma-resistant member comprising a plurality of sub-buffer layers stacked in a vertical direction. The plasma-resistant member of claim 4, wherein the sub-buffer layers have a larger oxygen/fluorine atomic ratio as they are closer to the upper layer. The plasma-resistant member of claim 4, wherein the sub-buffer layers each include a lower sub-layer and an upper sub-layer having different compositions. 7. The method of claim 6, wherein the lower sublayer comprises at least one of yttrium oxide, yttria stabilized zirconia (YSZ), and yttrium aluminum garnet (YAG), and the upper sublayer comprises at least one of yttrium fluoride, yttrium bicarbonate, and Including, plasma resistance member. The plasma-resistant member of claim 6, wherein the lower buffer layer of the sub-buffer layers has a smaller thickness as it approaches the upper layer, and the upper buffer layer of the sub-buffer layers has a greater thickness as it approaches the upper layer. According to clause 6,
A plasma-resistant member wherein the sub-buffer layer has a thickness of 1 nm to 10 nm. The plasma-resistant member of claim 1, wherein the thickness of the lower layer, the buffer layer, and the upper layer is each 0.1 ㎛ to 100 ㎛.