TWI723031B - Plasma processing device and nozzle - Google Patents

Abstract

Provides an excellent durability against corrosion caused by plasma Sprinkler.

Nozzle equipped with plasma processing device (11) (22) It is configured as follows. The aforementioned shower head has: a base material (60) with: a gas discharge hole (40) for discharging processing gas into the chamber (20); a recess formed in the gas discharge The gas outlet side of the hole (40); and a cylindrical sleeve made of ceramic or stainless steel, fixed in the recess of the base material (60), on the surface of the sleeve and the base material (60), to withstand electricity The serous membrane (63) covers the surface where the sleeve is arranged. When the ceramic sleeve (61) is used, a base film (62) is provided between the surface of the substrate (60) on the side of the plasma generation space (S) and the plasma resistant film (63).

Description

Plasma processing device and nozzle

The present invention relates to a plasma processing apparatus for applying plasma processing to a substrate placed on a mounting table, and a plasma processing device that is disposed opposite to the substrate through a plasma generation space, and supplies plasma generation gas to the plasma generation space Sprinkler.

In the panel manufacturing process for flat panel displays (FPD), plasma processing equipment is used to apply plasma-based film formation processing, etching processing, and ashing processing to substrates such as glass substrates. , Forming pixel elements or electrodes, wiring, etc. on the substrate. In the plasma processing apparatus, for example, a substrate is placed on a mounting table arranged inside a processing chamber that can be decompressed, and a space above the substrate in the processing chamber is arranged opposite to the substrate through the plasma generation space. The plasma generating space is supplied with a shower head for processing gas. In this way, while supplying the processing gas from the shower head to the plasma generating space, a high-frequency electric field is generated in the plasma generating space, thereby generating plasma in the plasma generating space.

Since the nozzles are exposed to plasma, various techniques have been proposed to inhibit nozzle corrosion caused by plasma. For example, propose the following structure Fabrication: Insert an alumina sheet into the gas discharge hole of a shower head using aluminum as a base material, and cover the surface of the shower head on the side of the plasma generation space with an alumina coating film (see Patent Document 1).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 8-227874

However, as shown in the technique described in Patent Document 1, when the alumina sheet is arranged in the gas discharge hole of the shower head, there is a problem that the service life of the shower head is shortened. Specifically, even if the alumina sheet is arranged in the gas ejection hole, the diversification of the processing gas used causes the following problems: In a short period of time, the plasma generation space side of the gas ejection hole The opening part of the aluminum oxide sheet corrodes the aluminum oxide sheet and the aluminum oxide coating film, which causes the base material of the nozzle to be exposed.

In response to this problem, a method of thickening the wall thickness in the radial direction of the alumina sheet can be considered. However, when the wall thickness in the radial direction of the alumina sheet is increased, it is difficult to form a high-adhesive alumina coating film on the upper end surface of the alumina sheet. This is because the surface smoothness of the alumina sheet is high, the surface is not easily roughened even by sandblasting, etc., and the wettability of the alumina coating film is not high. because Therefore, in a short period of time, the aluminum oxide coating film will be peeled off, resulting in the problem of exposure of the base material of the nozzle.

The object of the present invention is to provide a spray head with excellent durability against corrosion caused by plasma. In addition, another object of the present invention is to provide a plasma processing apparatus equipped with a shower head with excellent durability.

In order to achieve the above-mentioned object, the shower head of the present invention is a shower head equipped in a plasma processing apparatus. The shower head is characterized in that the shower head has: a substrate, has: a gas discharge hole, discharges processing gas; and a recess formed in the foregoing The gas discharge port side of the gas discharge hole; a cylindrical sleeve made of ceramic or stainless steel and fixed to the recess; and a plasma resistant film, covering the surface of the sleeve and the base material with the sleeve The surface of the tube.

In order to achieve the above-mentioned object, the plasma processing apparatus of the present invention is provided with a mounting table having a substrate mounting surface on which the substrate is mounted, a chamber in which the mounting table is housed, and a chamber facing the mounting table placed on the mounting table. A shower head for supplying processing gas to the chamber and a plasma generating means for generating plasma caused by the processing gas in the chamber, and applying the plasma to the substrate placed on the mounting table The plasma processing apparatus for the treatment is characterized in that the shower head has: a base material having: a gas ejection hole for ejecting the processing gas into the chamber; and a recess formed in the gas ejection port of the gas ejection hole Side; a cylindrical sleeve, made of ceramic or stainless steel, fixed in the aforementioned recess; and The serous film covers the surface of the sleeve and the substrate on which the sleeve is arranged.

According to the present invention, in the state where the shower head is equipped with the plasma processing device, a sleeve made of ceramic or stainless steel with a fixed height and wall thickness is arranged on the plasma generation space side of the gas discharge hole provided in the shower head And on the side of the plasma generation space of the nozzle, a plasma-resistant film with high adhesion to the sleeve and the substrate of the nozzle is formed. In this way, a shower head with high durability against plasma treatment can be realized.

11‧‧‧Plasma processing device

20‧‧‧ Chamber

21‧‧‧Mounting table

23‧‧‧Pedestal

28‧‧‧DC power supply

40‧‧‧Gas vent hole

50‧‧‧Inductively coupled antenna

60‧‧‧Substrate

61, 61A, 61B‧‧‧Ceramic sleeve

62‧‧‧Basal membrane

63‧‧‧Plasma resistant film

63A‧‧‧Plasma resistant yttrium oxide film

71, 71A, 71B‧‧‧SUS sleeve

[Fig. 1] A perspective view showing a schematic configuration of a substrate processing system equipped with a plasma processing apparatus according to an embodiment of the present invention.

[FIG. 2] A cross-sectional view showing the schematic configuration of a plasma processing apparatus included in the substrate processing system.

[Fig. 3] A cross-sectional view and a partially enlarged cross-sectional view showing a first structural example of the gas discharge hole provided in the shower head constituting the plasma processing device.

[Fig. 4] A graph showing the result of evaluating the adhesion of the plasma-resistant film constituting the nozzle by the combination of a ceramic sleeve and a base film.

[Fig. 5] A cross-sectional view showing the partial structure of a shower head with a plasma-resistant yttrium oxide film formed.

[Figure 6] shows the gas discharge installed in the nozzle of the plasma processing device Cross-sectional views of the second and third structural examples of the exit hole.

Fig. 7 is a cross-sectional view showing a fourth structural example and a fifth structural example of the gas discharge hole provided in the shower head constituting the plasma processing device.

[Fig. 8] A cross-sectional view showing a sixth structural example of the gas discharge hole provided in the shower head constituting the plasma processing device.

[Fig. 9] A graph showing the result of evaluating the plasma resistance of the plasma resistant coating of the spray head when the constituent materials are changed.

[Fig. 10] A graph showing the result of evaluating the adhesion of the plasma-resistant film of the spray head formed of the mixed material by the combination of the ceramic sleeve, the SUS sleeve and the base film.

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

FIG. 1 is a perspective view showing a schematic configuration of a substrate processing system 10 equipped with a plasma processing apparatus 11 of this embodiment.

The substrate processing system 10 is provided with three plasma processing apparatuses 11 for applying plasma processing, such as plasma etching, to a substrate G for FPD such as a glass substrate. The three plasma processing apparatuses 11 are connected via gate valves 13, respectively, It is connected to the side surface of the transfer chamber 12 whose horizontal cross-section is a polygonal shape (for example, the horizontal cross-section is a rectangular shape). In addition, referring to FIG. 2, the configuration of the plasma processing apparatus 11 will be described later.

The transfer chamber 12 is further connected to a load lock chamber 14 via a gate valve 15. In the load lock chamber 14, the gate valve 17 is adjacent to the A substrate carry-in and carry-out mechanism 16 is provided in the connection. Two indexers 18 are provided adjacent to the board carrying-in/out mechanism 16. In the indexer 18, a cassette 19 for storing the substrate G is placed. In the cassette 19, a plurality of (for example, 25) substrates G can be stored.

The overall operation of the substrate processing system 10 is controlled by a control device not shown. In the substrate processing system 10, when plasma etching is performed on the substrate G, the substrate G stored in the cassette 19 is first carried into the load lock chamber 14 by the substrate carry-in and carry-out mechanism 16. At this time, as long as there is a plasma etched substrate G inside the load lock chamber 14, the plasma etched substrate G is carried out from the load lock chamber 14 and replaced with an unetched substrate G. When the substrate G is carried into the load lock chamber 14, the gate valve 17 is closed.

Next, after the inside of the load lock chamber 14 is depressurized to a predetermined degree of vacuum, the gate valve 15 between the transfer chamber 12 and the load lock chamber 14 is opened. Then, after the substrate G inside the load lock chamber 14 is carried into the transfer chamber 12 by the transfer mechanism (not shown) inside the transfer chamber 12, the gate valve 15 is closed.

Next, the gate valve 13 between the transfer chamber 12 and the plasma processing device 11 is opened, and the unetched substrate G is carried into the plasma processing device 11 by the transfer mechanism. At this time, as long as there is a plasma-etched substrate G inside the substrate processing apparatus 11, the plasma-etched substrate G is carried out and replaced with an unetched substrate G. After that, plasma etching is performed on the substrate G carried in by the plasma processing apparatus 11.

FIG. 2 shows the schematic structure of the plasma processing device 11 Sectional view. As the plasma processing device 11, here is an inductive coupling type plasma processing device. The plasma processing apparatus 11 is provided with: a chamber 20 (processing chamber), which is approximately rectangular; a trapezoidal-shaped mounting table 21, is arranged below the chamber 20, and the substrate G is placed on the top, that is, the substrate is mounted Surface; inductively coupled antenna 50, which is composed of a helical conductor, is arranged in the chamber 20 through a window member (not shown) made of dielectric or metal so as to face the mounting table 21 Above; and the shower head 22, which is the gas supply part, is below the window member and supplies processing gas to the chamber 20. Inside the chamber 20, between the mounting table 21 and the shower head 22, a plasma generation space S for generating plasma is formed.

The mounting table 21 has a built-in base 23 made of a conductor, and the base 23 is connected to a high-frequency power supply 24 for bias via a matching device 25. In addition, on the upper part of the mounting table 21, an electrostatic adsorption part 26 formed of a layered dielectric is arranged. The electrostatic adsorption part 26 has: an electrostatic adsorption electrode 27 to connect the upper dielectric layer with The lower dielectric layer is sandwiched and enclosed.

The electrostatic adsorption electrode 27 is connected to a DC power supply 28. When a DC voltage is applied to the electrostatic adsorption electrode 27 from the DC power supply 28, the electrostatic adsorption unit 26 uses electrostatic force to adsorb and hold the substrate placed on the mounting table 21. G. The bias high-frequency power supply 24 supplies a relatively low-frequency high-frequency power to the susceptor 23, and generates a DC bias potential on the substrate G electrostatically attracted to the electrostatic adsorption portion 26. In addition, the electrostatic adsorption part 26 may be formed as a plate member, or may be formed as a spray film on the mounting table 21.

On the mounting table 21, there is a built-in cooling system for the mounted substrate G The cooled refrigerant flow path 29 and the refrigerant flow path 29 are connected to a heat transfer gas supply mechanism 30 that supplies heat transfer gas. As the heat transfer gas, for example, He gas is used. The heat transfer gas supply mechanism 30 has a heat transfer gas supply source 31 and a gas flow controller 32 to supply the heat transfer gas to the mounting table 21. The mounting table 21 has: a plurality of heat transfer gas holes 33 open at the upper part; and a heat transfer gas supply path 34 that connects the respective heat transfer gas holes 33 and the heat transfer gas supply mechanism 30. The mounting table 21 creates a small gap between the back surface of the substrate G electrostatically attracted to the electrostatic adsorption portion 26 and the upper part of the mounting table 21, but the heat transfer gas supplied from the heat transfer gas hole 33 is filled in the gap Thereby, the heat conduction efficiency between the substrate G and the mounting table 21 can be improved, and the cooling efficiency of the substrate G by the mounting table 21 can be improved.

The shower head 22 is arranged to face the entire surface of the substrate G placed on the mounting table 21 and is connected to the processing gas supply mechanism 35. The processing gas supply mechanism 35 includes a processing gas supply source 36, a gas flow controller 37 and a pressure control valve 38. The shower head 22 has a built-in buffer part 39 communicating with the processing gas supply mechanism 35, and the buffer part 39 communicates with the plasma generation space S through a plurality of gas discharge holes 40.

The processing gas supplied from the processing gas supply mechanism 35 to the buffer unit 39 is introduced into the plasma generation space S from the gas discharge hole 40. The plurality of gas discharge holes 40 are dispersedly arranged to face the entire surface of the substrate G placed on the mounting table 21, whereby the processing gas can be uniformly introduced into the plasma generation space S on the substrate G. In addition, the detailed structure of the gas discharge hole 40 is mentioned later.

The inductively coupled antenna 50 is connected to a high-frequency power supply 41 for plasma generation via a matching device 42. The high-frequency power supply 41 for plasma generation supplies a relatively high-frequency plasma generation high-frequency power to the inductive coupling. Antenna 50. The inductively coupled antenna 50 supplied with high-frequency power for plasma generation generates an electric field in the plasma generation space S. In addition, the plasma processing device 11 is provided with an exhaust pipe 43 communicating with the inside of the chamber 20, and the gas inside the chamber 20 can be exhausted through the exhaust pipe 43, so that the inside of the chamber 20 becomes a predetermined Decompression state.

The actions of the constituent elements of the plasma processing device 11 are controlled by the device controller 44 executing a predetermined program under the overall control of the control device of the substrate processing system 10. When plasma etching is performed on the substrate G by the plasma processing device 11, the plasma generation space S is reduced in pressure, the processing gas is introduced into the plasma generation space S, and the inductively coupled antenna 50 is supplied for plasma generation The high frequency power. As a result, an electric field is generated in the plasma generation space S. The processing gas introduced into the plasma generation space S is excited by an electric field to generate plasma. The cations in the plasma are introduced to the substrate G by the DC bias potential generated on the substrate G via the mounting table 21 The substrate G is subjected to plasma etching. In addition, the radicals in the plasma reach the substrate G, and the substrate G is subjected to plasma etching.

In the plasma processing device 11, the inductively coupled antenna 50 is configured to cover the entire surface of the substrate G, thereby, since the plasma can be generated to cover the entire surface of the substrate G, the entire surface of the substrate G can be evenly distributed. Plasma etching is applied to the ground.

Next, explain about the gas discharge hole 40 in the nozzle 22 的结构。 The structure.

Fig. 3(a) is a cross-sectional view showing a first structural example of the gas discharge hole 40 provided in the shower head 22; Fig. 3(b) is an enlarged cross-sectional view of the area A shown in Fig. 3(a).

The base 60 of the shower head 22 is made of, for example, aluminum. On the plasma generation space S side of the gas ejection hole 40, that is, on the gas ejection port side of the gas ejection hole 40, a recessed portion in which a ceramic sleeve 61 having a cylindrical shape is arranged is formed. An anodized aluminum film 65 is formed on the wall surface where the recess and the gas ejection hole 40 are formed.

A ceramic sleeve 61 is fitted in the recess provided in the base 60, whereby the center hole of the ceramic sleeve 61 forms a part of the gas discharge hole 40. The ceramic sleeve 61 is bonded and fixed to the recessed portion using a silica-based adhesive 64 or the like. As the ceramic sleeve 61, for example, an alumina (Al ₂ O ₃ ) sleeve is used.

1~2mm、外徑為

4~8mm、高度(厚度)為3mm~5mm的形狀。陶瓷套筒61之徑方向的壁厚度(=(外徑-內徑)/2)，係1mm以上為較佳，藉此，可獲得對電漿之所期望的耐久性。另外，陶瓷套筒61的高度，係因應電漿侵入至氣體吐出孔40的何種深度來設定，在內徑較大時，係使高度變高為較佳。 The ceramic sleeve 61, for example, has an inner diameter of

1~2mm, outer diameter is

4~8mm, height (thickness) is 3mm~5mm shape. The wall thickness (=(outer diameter-inner diameter)/2) of the ceramic sleeve 61 in the radial direction is preferably 1 mm or more, so that the desired durability against plasma can be obtained. In addition, the height of the ceramic sleeve 61 is set according to the depth to which the plasma penetrates into the gas discharge hole 40. When the inner diameter is large, it is better to increase the height.

A base film 62 (primer film) is formed on the surface of the substrate 60 and the surface of the ceramic sleeve 61 on the plasma generation space S side. The base film 62 is, for example, yttrium oxide (hereinafter referred to as "yttrium oxide base film") Or aluminum (hereinafter referred to as "aluminum base film"), the thickness of which is 10 μm to 50 μm, preferably 20 μm to 30 μm.

A plasma resistant film 63 is formed on the base film 62. The plasma resistant film 63 is, for example, alumina (hereinafter referred to as "plasma resistant alumina film") and yttrium oxide (hereinafter referred to as "plasma resistant yttrium oxide film"). The thickness of the plasma resistant film 63 is 50 μm to 400 μm, preferably 100 μm to 200 μm.

The shower head 22 having the gas discharge hole 40 of the structure shown in FIG. 3 can be manufactured by the following procedure, for example. Initially, an anodized aluminum film 65 is formed on the surface of the substrate 60 by a method such as general anodization treatment on the substrate 60 on which the gas ejection holes 40 and recesses are formed. In addition, the gas discharge hole 40 or the recess can be easily formed by machining (cutting) using a drill, an end mill, or the like.

In addition, the ceramic sleeve 61 is bonded to the recessed portion using a silica-based adhesive 64 or the like. At this time, since the ceramic sleeve 61 is positioned in the recessed portion of the base 60 formed by machining or the like in accordance with the dimensional accuracy, no special jig or the like is required for the adhesion of the ceramic sleeve 61. Easy access to the writing industry.

Next, the surface of the substrate 60 on which the ceramic sleeve 61 is arranged (when assembled in the plasma processing apparatus 11, it becomes the surface on the plasma generation space S side, and includes the surface of the ceramic sleeve 61 (hereinafter referred to as " The film-forming surface of the substrate 60")) is subjected to sandblasting or the like. Thereby, the film-forming surface of the base material 60 is thickened, and the surface roughness is increased. This is to improve the adhesion of the base film 62 by the anchoring effect.

In addition, as shown in FIG. 3( b ), in this embodiment, the anodized aluminum film 65 is not formed on the film forming surface of the substrate 60. This is because the sandblasting process causes the anodized aluminum film 65 formed on the film forming surface of the substrate 60 to be removed. However, it is also possible to perform sandblasting in such a way that the anodized aluminum film 65 remains on the film-forming surface of the base 60.

The aluminum constituting the base 60 and the anodized aluminum film formed on the surface thereof and the ceramic sleeve 61 are different in material, so the processing speed due to sandblasting is different. Therefore, even if a part of the base 60 is formed with a predetermined surface roughness, the surface of the ceramic sleeve 61 is generally not formed with the same surface roughness. In this case, if the plasma-resistant film 63 is directly formed on the film-forming surface of the substrate 60 after the sandblasting process, the plasma-resistant film 63 can achieve high adhesion even on a part of the substrate 60 due to the anchoring effect. An anchoring effect cannot be obtained in a part of the ceramic sleeve 61, resulting in a decrease in adhesion. Therefore, on the film forming surface of the substrate 60, a base film 62 having high wettability to both the ceramic sleeve 61 and the plasma resistant film 63 is formed. Thereby, a dense plasma resistant film 63 can be formed on the surface of the ceramic sleeve 61.

The base film 62 can be formed by, for example, APS (Atmospheric Plasma Spraying). Here, when the yttrium oxide base film is formed as the base film 62, even if the plasma resistant film 63 is directly formed on the surface thereafter, the plasma resistant film 63 showing high adhesion can be formed. On the other hand, when the aluminum base film is formed as the base film 62, although the plasma-resistant film 63 can be directly formed on the surface, it is preferable to apply sandblasting to the extent that the surface becomes rough. The treatment is better, and the adhesion of the plasma resistant film 63 can be improved by the anchoring effect. In addition, even when the yttrium oxide base film is formed, it is possible to perform sandblasting to the extent that the surface becomes rough.

On the base film 62 formed in this way, the plasma resistant film 63 is formed by, for example, the APS spray method or the like. With this, the production of the shower head 22 provided with the gas discharge hole 40 of the first structural example shown in FIG. 3 is completed.

FIG. 4 is a graph showing the result of evaluating the adhesion of the plasma resistant film 63 by the combination of the ceramic sleeve 61 and the base film 62. In addition, the ceramic sleeve 61 is made of alumina. Although the base film 62 is an yttrium oxide base film and an aluminum base film, in the case of an aluminum base film, sandblasting is performed before the formation of the plasma resistant film 63.

Further, as shown in FIG. 4 of the plasma-resistant film "SUS (Steel Use Stainless; stainless steel)" line as a plasma-resistant film 63 of the SUS film (hereinafter referred to as "SUS-resistant plasma coating"), plasma-resistant film SUS The film-forming method of APS can be used. In addition, the "SUS sleeve" shown in FIG. 4 and its results will be described later.

The evaluation of the adhesion of the plasma resistant film 63 is based on the ease of peeling off the plasma resistant film 63 when the jig is mounted on the plasma resistant film 63 by an adhesive and the jig is pulled by a fixed force. "○" means that high density has been obtained.

When the plasma-resistant alumina film as the plasma-resistant film 63 is directly formed on the ceramic sleeve 61, there are problems with low adhesion and durability. However, when the plasma resistant alumina film is formed on the base skin When the film 62 was on, it was confirmed that the plasma-resistant alumina film had high adhesion.

In addition, when the plasma-resistant yttrium oxide film is formed as the plasma-resistant film 63, even if the base film 62 is not formed, high adhesion can be obtained. We believe that this is due to the higher wettability of yttrium oxide with respect to alumina. In this case, the structure of the gas ejection hole 40 is as shown in the cross-sectional view of FIG. 5, and is formed into the following structure: the base film 62 is not formed on the film forming surface of the substrate 60, but is formed as a plasma resistant film 63's plasma resistant yttrium oxide film 63A. In addition, the plasma-resistant SUS film, which is an example of the plasma-resistant film 63, does not adhere to the ceramic sleeve 61.

As described above, the first structural example of the gas ejection hole 40 provided in the shower head 22 can be formed by arranging a ceramic sleeve 61 with a fixed height and wall thickness on the plasma generation space S side of the gas ejection hole 40 The plasma resistant film 63 has high adhesion to the ceramic sleeve 61. Thereby, a shower head 22 having high durability against plasma processing can be realized.

FIG. 6(a) is a cross-sectional view showing a second structural example of the gas discharge hole 40 provided in the shower head 22. As shown in FIG.

As already explained, it is not easy to directly form a high-adhesion plasma resistant film 63 on the surface of the ceramic sleeve 61. Therefore, in order to form a plasma resistant film 63 with high adhesion on the surface of the ceramic sleeve 61, it is preferable to provide a base film 62. On the other hand, the surface of the aluminum of the base 60 is made rough, for example, by sandblasting, etc., so that the plasma resistant film 63 can be directly formed without providing the base film 62.

Therefore, the second structural example of the gas discharge hole 40 is prepared The ceramic sleeve 61 in which the base film 62 is formed in advance on one end surface in the height (thickness) direction is the same as in the first structural example, and then to the recess provided in the base 60. After that, the plasma resistant film 63 is formed on the surface where the ceramic sleeve 61 is arranged on the base 60. Thereby, the plasma resistant film 63 having high adhesion to both the base 60 and the ceramic sleeve 61 can be formed. Since the second structural example of the gas ejection hole 40 does not require the formation of the base film 62 on the substrate 60, the cost required for the formation of the base film 62 can be reduced.

FIG. 6(b) is a cross-sectional view showing a third structural example of the gas discharge hole 40 provided in the shower head 22. As shown in FIG. The third structural example is that a through hole is formed in the base 60, a ceramic sleeve 61A is inserted into the through hole, and it has a structure fixed with a silica-based adhesive or the like. This point is similar to the first structural example (Figure 3) It is different, but the other structure is the same as the first structural example.

In the third configuration example, the center hole of the ceramic sleeve 61A is formed as the gas discharge hole 40. The ceramic sleeve 61A has a shape such that the outer diameter is fixed, and the wall thickness on the gas discharge port side of the gas discharge hole 40 is thicker than the wall thickness on the gas inflow port side, that is, on the buffer portion 39 side. The inner diameter difference is partially provided. This is based on the consideration that the gas outlet side must be exposed to the plasma, so the durability against the plasma must be improved. On the other hand, since the buffer 39 side is less likely to be exposed to the plasma, the wall thickness can also be reduced. By. The wall thickness on the gas outlet side of the ceramic sleeve 61A is the same as that of the ceramic sleeve 61, and 1 mm or more is preferable.

By using the ceramic sleeve 61A, in addition to the effect obtained when the ceramic sleeve 61 is used, the corrosion resistance of the plasma on the inner wall of the gas discharge hole 40 can be improved, and the resistance to the plasma can also be improved. Gas The corrosion resistance. In addition, in order to insert the ceramic sleeve 61A, it is not necessary to form an anodized aluminum film on the wall surface of the through hole provided in the base 60.

However, a yttrium oxide sleeve made of yttrium oxide may be used as the ceramic sleeve 61 instead of the alumina sleeve. In this case, as long as the base film 62 is formed, it is preferable to use an yttrium oxide base film made of the same material. In addition, when the plasma-resistant yttrium oxide film is formed as the plasma-resistant film 63, the base film 62 may not be formed.

FIG. 7(a) is a cross-sectional view showing a fourth structural example of the gas discharge hole 40 provided in the shower head 22. As shown in FIG. The fourth structural example is compared with the first structural example (FIG. 3). A SUS sleeve 71 made of stainless steel is used instead of the ceramic sleeve 61. The base film 62 is not provided, and the film forming surface of the substrate 60 is directly formed The plasma resistant film 63 is different from the first structural example in this point. Hereinafter, these differences will be explained.

The shape of the SUS sleeve 71 can be set to be equivalent to the shape of the ceramic sleeve 61. The SUS sleeve 71 is inserted into the recess provided in the base 60, and is bonded using a silicon dioxide-based adhesive or the like. The SUS sleeve 71 is processed by sandblasting, for example, to make the surface a predetermined surface roughness, thereby improving the adhesion between the plasma resistant film 63 and the plasma resistant film 63 when the plasma resistant film 63 is formed by the spray method. Therefore, when the SUS sleeve 71 is used, the base film 62 is not required. In addition, the coefficient of linear expansion of stainless steel is similar to that of aluminum. Therefore, even if the outer diameter of the SUS sleeve 71 is increased, cracks are unlikely to occur at the joint boundary with the base 60, and the shower head 22 exhibits excellent durability against thermal cycles caused by plasma treatment.

Plasma resistant film 63, in addition to plasma resistant alumina film, In addition to the plasma yttrium oxide film, a plasma resistant SUS film can also be used. The plasma-resistant SUS film is the same as the plasma-resistant alumina film and the plasma-resistant yttrium oxide film, and can be formed by the APS spray method, and its thickness is 50 μm to 400 μm, preferably 100 μm to 200 μm.

Since the manufacturing sequence of the shower head 22 with the gas ejection hole 40 provided with the SUS sleeve 71 is based on the manufacturing sequence of the shower head 22 described in the first structural example (FIG. 3), except for the point that the base film 62 is not formed. Therefore, the description is omitted. The shower head 22 using the SUS sleeve 71 exerts the same effect as the shower head 22 using the ceramic sleeve 61. Moreover, since the shower head 22 using the SUS sleeve 71 does not need to form the base film 62, there is an advantage that the manufacturing process can be shortened.

As shown in Fig. 4, the SUS sleeve 71 shows the high adhesion of plasma-resistant alumina film, plasma-resistant yttrium oxide coating, and plasma-resistant SUS film. Therefore, by using the SUS sleeve 71, plasma-resistant The degree of freedom of selection of the film 63 becomes greater.

FIG. 7(b) is a cross-sectional view showing a fifth structural example of the gas discharge hole 40 provided in the shower head 22. As shown in FIG. The fifth structural example is that a through hole is formed in the base 60, and a SUS sleeve 71A is inserted into the through hole. The structure is bonded with a silica-based adhesive or the like. This point is similar to the fourth structural example (Figure 7(a)) is different, but the other configuration is the same as the fourth structural example.

The fifth structural example is the same as the above-mentioned third structural example (Figure 6(b)). The center hole of the SUS sleeve 71A is formed as a gas discharge 孔40. By using the SUS sleeve 71A, the corrosion resistance to the plasma of the inner wall of the gas discharge hole 40 can be improved, and the corrosion resistance to the gas used can also be improved.

8(a) and (b) are cross-sectional views showing a sixth structural example of the gas discharge hole 40 provided in the shower head 22. FIG. In the first to fifth structural examples described above, the gas discharge hole 40 is provided with a step in the longitudinal direction (the direction in which the processing gas flows) by the sleeve. For example, when a processing gas composed of a plurality of gas streams is used, the squeezing effect caused by the step difference can improve the uniformity of the processing gas. However, the step difference in the gas ejection hole 40 does not necessarily have to be orthogonal to the longitudinal direction of the gas ejection hole 40.

Fig. 8(a) shows an example of a structure using a ceramic sleeve 61B with an inclined (push-pull type) provided in the center hole. A structure other than the ceramic sleeve 61B is used, which is the same as the first structure example (Fig. 3) The composition is the same. In addition, Fig. 8(b) shows an example of the structure using a SUS sleeve 71B with a slope in the center hole. A structure other than the SUS sleeve 71B is used, which is similar to the fifth structure example (Fig. 7(b)). )the same.

In addition, in the same way, the step provided on the inner circumference of the ceramic sleeve 61A may also be inclined, or the central hole of the SUS sleeve 71 may be provided with a push-pull shape. Also, although the gas ejection hole 40 does not necessarily have a step inside it, even when the step is not provided, the wall thickness in the radial direction of the sleeve on the side of the plasma generation space S must be set in order to obtain The desired durability of plasma.

Above, although the above-mentioned embodiment is used to explain about the present invention However, the present invention is not limited to the above-mentioned embodiment. For example, in the above-mentioned embodiment, although the plasma resistant film 63 is composed of only yttrium oxide or aluminum oxide, it may be composed of a mixed material. However, when the plasma-resistant film 63 is composed of yttrium oxide alone, the plasma-resistant film 63 has improved plasma resistance (hereinafter referred to as "plasma resistance"), but the yttrium oxide has an acid resistance (hereinafter referred to as "plasma resistance"). "Acid resistance") is low. Therefore, during the maintenance of the plasma processing device 11, the chamber 20 is opened to the atmosphere. When the moisture in the atmosphere reacts with the attachments (deposits) or the chlorides of the gas remaining in the chamber 20, hydrochloric acid (HCl) In the case of acids such as ), the plasma resistant film 63 may be damaged by the acid. Corresponding to this, although it is also considered to mix acid-resistant aluminum oxide with yttrium oxide to improve the acid resistance of the plasma resistant film 63, in this case, the alumina or yttrium oxide is directly present in the plasma resistant film in a granular form. 63 and the grain boundary is generated, so the plasma resistance is reduced. However, when silicon (Si) is melted and contained in the mixed material, the structure of the mixed material is deteriorated and densified into vitreous, making it difficult to produce grain boundaries. Therefore, for the purpose of improving acid resistance, when the plasma resistant film 63 is formed of a mixed material containing alumina, in order to suppress the occurrence of grain boundaries, it is preferable to add a silicon compound such as silicon oxide or silicon nitride to the mixed material.

FIG. 9 is a graph showing the result of evaluating the plasma resistance of the plasma resistance film 63 when the constituent material is changed. The plasma resistant film 63 is formed by the APS spray method even in any of the constituent materials. As the constituent materials, alumina (hereinafter referred to as "alumina spray") and yttrium oxide (hereinafter referred to as "Yttria spraying"), or using a mixed material of aluminum oxide, yttrium oxide and silicon oxide (SiO ₂ ) (hereinafter referred to as "hybrid spraying A") and aluminum oxide, yttrium oxide, silicon oxide and silicon nitride (Si ₃ N ₄ ) mixed material (hereinafter referred to as "hybrid spray B"). In addition, as the plasma, a plasma _{generated from a mixed gas of bromine chloride (BCl 3} ) and chlorine (Cl ₂ ) was used to evaluate the amount of removal of each plasma resistant film 63 after exposing the plasma to the plasma for a fixed period of time . In addition, the amount of removal of the plasma resistant film 63 of the yttrium oxide spray was set to 1, and the amount of removal of each plasma resistant film 63 was standardized.

As shown in FIG. 9, the scraping amount of the plasma resistant film 63 of the aluminum oxide spray is 9. For this, the scraping amount of the plasma resistant film 63 of the mixed spray A or the mixed spray B is 1. In other words, it can be seen that the hybrid spray A or the hybrid spray B has the same plasma resistance as the yttrium oxide spray. In addition, the structure of the plasma resistant film 63 of the hybrid spray A or the hybrid spray B was confirmed by SEM. As a result, no grain boundary was confirmed, but the structure was confirmed to be deteriorated and densified into vitreous. Therefore, it is known that the plasma resistant film 63 of the hybrid spray A or the hybrid spray B compensates for the decrease in the plasma resistance caused by the mixing of materials other than yttrium oxide through the densification of the structure.

FIG. 10 is a graph showing the result of evaluating the adhesion of the plasma resistant film 63 of the hybrid spray A and B using the combination of the ceramic sleeve 61 and the SUS sleeve 71 and the base film 62. In addition, the ceramic sleeve 61 here is an aluminum oxide sleeve or an yttrium oxide sleeve, and the base film 62 is an yttrium oxide base film.

The evaluation of the adhesion of the plasma-resistant film 63 in FIG. 10 is the same as the evaluation in FIG. 4, in that the jig is mounted on the plasma-resistant film 63 by an adhesive and the jig is drawn by a fixed force. The peeling of serous membrane 63 The ease of separation is determined. The "○" in the figure indicates the situation where high adhesion has been obtained.

When the plasma resistant film 63 of the mixed spray A and B is directly formed on the ceramic sleeve 61, there are problems with low adhesion and durability. However, when the plasma resistant film 63 of the mixed spray A and B was formed on the base film 62, it was confirmed that the plasma resistant film 63 had high adhesion. On the other hand, when the plasma resistant film 63 of the mixed spray A and B was formed on the SUS sleeve 71 directly or sandwiching the base film 62, it was confirmed that the plasma resistant film 63 had high adhesion.

From the above, it can be seen that as long as the plasma resistant film 63 is formed by mixing spraying A and B, not only the acid resistance can be ensured by the contained alumina, but also the denseness of the structure due to the contained silicon compound can be achieved. To ensure plasma resistance. Moreover, when forming the plasma resistant film 63 of the mixed spray A and B on the ceramic sleeve 61, it is preferable to form the base film 62 from the viewpoint of the adhesion of the plasma resistant film 63. On the other hand, when the plasma resistant film 63 of the mixed spray A and B is formed on the SUS sleeve 71, the base film 62 may or may not be formed.

Although the above-mentioned hybrid spray A contains silicon oxide, and the hybrid spray B contains silicon oxide and silicon nitride, the contribution of silicon is greater due to the densification of the structure (the deterioration of glass quality). Therefore, the plasma resistant film 63 As long as it contains any silicon compound, the structure can be densified. For example, even if the plasma resistant film 63 is composed of a mixed material of alumina, yttrium oxide and silicon nitride that does not contain silica, the structure can be densified.

In addition, the plasma resistant film is formed by mixing spray A and B At 63 o'clock, in order to densify the structure reliably, it is better to spray the granulated powder of alumina, yttrium oxide, silicon oxide or silicon nitride by spraying granulation method instead of oxidizing the granulated powder. Each powder of aluminum, yttrium oxide, silicon oxide or silicon nitride is mixed and directly sprayed.

In addition, although the above-mentioned embodiment exemplified an inductively coupled plasma processing device as the plasma processing device 11, it is not limited to this. The plasma processing device 11 may also be provided by supplying high-frequency power to the nozzle 22 The method is a capacitively coupled plasma processing device that generates plasma in the plasma generating space S.

Moreover, although a plasma etching apparatus is mentioned as the plasma processing apparatus 11 for a substrate, it is not limited to this, It may be other plasma processing apparatuses, such as a film forming apparatus, an ashing apparatus, and an ion implantation apparatus. Moreover, although the glass substrate for FPD is mentioned as the board|substrate G, even if it is another board|substrate (for example, a semiconductor wafer), this invention can be applied.

40‧‧‧Gas vent hole

60‧‧‧Substrate

61‧‧‧Ceramic sleeve

62‧‧‧Basal membrane

63‧‧‧Plasma resistant film

64‧‧‧Silica-based adhesive

65‧‧‧Acid-resistant aluminum film

A‧‧‧Mixed spray

Claims (13)

A nozzle is a nozzle equipped with a plasma processing device, characterized in that the nozzle has: a base material, having: a gas ejection hole for ejecting processing gas; and a recess formed on the gas ejection port side of the gas ejection hole ; Cylindrical sleeve, made of stainless steel, fixed to the recess; and plasma resistant film covering the surface of the sleeve and the surface of the substrate where the sleeve is arranged, the plasma resistant film is alumina Film, yttrium oxide film or stainless steel film. A nozzle is a nozzle equipped with a plasma processing device, characterized in that the nozzle has: a base material, having: a gas ejection hole for ejecting processing gas; and a recess formed on the gas ejection port side of the gas ejection hole ; A cylindrical sleeve made of alumina and fixed to the recess; and a plasma resistant film covering the surface of the sleeve and the surface of the substrate where the sleeve is arranged, in the substrate and the sleeve Between the surface of the cylinder on the side of the plasma generating space and the aforementioned plasma resistant film, a base film made of aluminum or yttrium oxide is provided, The aforementioned plasma resistant film is an aluminum oxide film or an yttrium oxide film. A nozzle is a nozzle equipped with a plasma processing device, characterized in that the nozzle has: a base material, having: a gas ejection hole for ejecting processing gas; and a recess formed on the gas ejection port side of the gas ejection hole Cylindrical sleeve, made of stainless steel, fixed to the recess; and plasma resistant film covering the surface of the sleeve and the surface of the substrate where the sleeve is arranged, the plasma resistant film is made by mixing It is composed of a thermal spray film. The aforementioned hybrid thermal spray film contains at least one of silicon oxide and silicon nitride in addition to aluminum oxide and yttrium oxide. A nozzle is a nozzle equipped with a plasma processing device, characterized in that the nozzle has: a base material, having: a gas ejection hole for ejecting processing gas; and a recess formed on the gas ejection port side of the gas ejection hole ; A cylindrical sleeve made of alumina and fixed to the recess; and a plasma resistant film covering the surface of the sleeve and the surface of the substrate where the sleeve is arranged, in the substrate and the sleeve Between the plasma generation space side surface of the cylinder and the aforementioned plasma resistant film, a base skin made of aluminum or yttrium oxide is provided The film, the plasma resistant film, is composed of a hybrid spray film, and the hybrid spray film contains at least one of silicon oxide and silicon nitride in addition to aluminum oxide and yttrium oxide. A nozzle is a nozzle equipped with a plasma processing device. The nozzle is characterized in that the nozzle has: a substrate with a gas ejection hole for ejecting processing gas; a cylindrical sleeve made of stainless steel and fixed to the foregoing A gas discharge hole; and a plasma-resistant film covering the surface of the sleeve and the surface of the substrate where the sleeve is arranged. The sleeve has a fixed outer diameter and a difference in inner diameter. The gas of the gas discharge hole The wall thickness on the outlet side is thicker than the wall thickness on the gas inlet side. For example, the shower head according to any one of items 1 to 5 in the scope of the patent application, wherein the substrate is made of aluminum, and an acid-resistant aluminum film is formed on the wall surface where the gas discharge hole is formed. For example, the nozzle of any one of items 1 to 5 in the scope of patent application, wherein the aforementioned sleeve has an inner diameter of

1mm~

2mm, outer diameter is 4mm~8mm, height is 3mm~5mm. For example, the nozzle of item 7 of the scope of patent application, wherein the wall thickness in the radial direction of the aforementioned sleeve is 1mm or more. A plasma processing device is provided with a substrate with a mounting substrate The mounting table on the mounting surface, the chamber that houses the mounting table in the interior, is arranged facing the substrate mounted on the mounting table, the shower head that supplies the processing gas to the chamber, and the chamber inside the chamber The plasma processing device for plasma generating means for treating plasma caused by gas applies the treatment by the plasma to the substrate placed on the mounting table, characterized in that the spray head has: a base material, It has: a gas ejection hole for ejecting the processing gas into the chamber; and a recess formed on the gas ejection port side of the gas ejection hole; a cylindrical sleeve made of stainless steel and fixed to the recess; and plasma resistant The film covers the surface of the sleeve and the surface of the substrate on which the sleeve is arranged, and the plasma resistant film is an aluminum oxide film, an yttrium oxide film, or a stainless steel film. For example, the plasma processing device of item 9 of the scope of patent application, wherein the aforementioned plasma resistant coating is composed of a mixed sprayed film, and the aforementioned mixed sprayed film contains alumina and yttrium oxide, and also contains silicon oxide and At least one of silicon nitride. A plasma processing apparatus is provided with a mounting table having a substrate mounting surface on which a substrate is mounted, a chamber in which the mounting table is housed, and arranged to face the substrate mounted on the mounting table. A shower head for supplying processing gas in the chamber and a plasma generating means for generating plasma caused by the processing gas in the interior of the chamber apply to the substrate placed on the mounting table The plasma processing apparatus for the plasma processing, characterized in that the shower head has: a base material having: a gas ejection hole for ejecting the processing gas into the chamber; and a recess formed in the gas ejection The gas outlet side of the hole; a cylindrical sleeve made of alumina and fixed to the recess; and a plasma resistant film covering the surface of the sleeve and the surface of the substrate on which the sleeve is arranged, Between the substrate and the surface of the sleeve on the plasma generation space side and the plasma resistant film, a base film made of aluminum or yttrium oxide is provided, and the plasma resistant film is an aluminum oxide film or an yttrium oxide film. A plasma processing apparatus is provided with a mounting table having a substrate mounting surface on which a substrate is mounted, a chamber in which the mounting table is housed, and arranged to face the substrate mounted on the mounting table. A nozzle for supplying processing gas in the chamber and a plasma generating means for generating plasma caused by the processing gas inside the chamber, and plasma treatment for applying the processing by the plasma to the substrate placed on the mounting table The device is characterized in that the shower head has: a base material having: a gas ejection hole for ejecting the processing gas into the chamber; and a recess formed on the gas ejection port side of the gas ejection hole; a cylindrical sleeve The barrel, made of alumina, is fixed in the aforementioned recess; And a plasma resistant film covering the surface of the sleeve and the surface of the substrate on which the sleeve is arranged, and between the substrate and the surface of the sleeve on the side of the plasma generation space and the plasma resistant film The base film is composed of aluminum or yttrium oxide, the aforementioned plasma resistant film is composed of a hybrid spray film, and the aforementioned hybrid spray film is made of aluminum oxide and yttrium oxide, but also silicon oxide and silicon nitride. At least one. For example, the plasma processing device of any one of items 10 to 12 in the scope of patent application, wherein the aforementioned sleeve has an inner diameter of

1mm~

2mm, outer diameter is 4mm~8mm, height is 3mm~5mm.

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