JP2007036197A - Constitutional member of semiconductor manufacturing apparatus and semiconductor manufacturing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve durability of a constitutional member constituting a semiconductor manufacturing apparatus or corrosion resistance against a corrosive gas by forming a deposited film on the surface of the constitutional member. <P>SOLUTION: A material gas and a reaction gas are alternately supplied to a surface, contacting the processing gas, of a constituent member selected from among a processing container, a part to be provided in the processing container, piping for supplying the processing gas to the processing container, a gas supply apparatus connected to the piping, and an exhaust pipe, and the gas is deposited. In this way, a deposit film containing any one of aluminum, hafnium, zirconium and yttrium is formed on the surface contacting the processing gas. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a technique for forming a deposited film on the surface of a constituent member constituting a semiconductor manufacturing apparatus.

  A semiconductor manufacturing apparatus used in a semiconductor manufacturing process of a semiconductor device or an LCD substrate, for example, a film forming processing apparatus, an oxidation processing apparatus, an etching processing apparatus, etc. A processing container for performing a predetermined process such as a film forming process using a processing gas, a processing gas supply source for supplying a processing gas to the processing container via a processing gas supply pipe, and the processing container. And an exhaust means for exhausting through the exhaust pipe.

  The constituent members such as the processing vessel, the processing gas supply pipe, and the exhaust pipe are usually made of stainless steel electrolytic polished product or metal such as aluminum. Moreover, the metal structural member is contained also in the inside of a processing container. For metal components constituting these semiconductor manufacturing apparatuses, for example, in order to improve the corrosion resistance when corrosive gas is used, the surface of the region in contact with the corrosive gas, that is, the processing gas supply pipe and the exhaust A predetermined surface treatment may be applied to the inner surface of the tube, the inner wall of the processing container, or the surface of the constituent members inside the processing container.

As the surface treatment, there are various methods such as a fluoride film forming process, an ozone passivation process (film forming process), a SiO ₂ coating process, a ceramic sprayed film forming process, an anodizing process, and a CVD (Chemical Vapor Deposition) process. However, in the past, since the semiconductor manufacturing apparatus is assembled after individually purchasing the components that have been subjected to such surface treatment, the components become expensive and the total cost of the semiconductor manufacturing apparatus is increased. There is a problem that the manufacturing cost increases.

Further, each surface treatment method has the following problems. In other words, in the above-mentioned fluoride film forming treatment, if bending is performed at the time of assembling the apparatus on the surface-treated pipe, the passivated film (surface treatment film) in the bent region is broken and peeled off. It becomes a factor of contamination and particle generation. In the oxide film forming process or the anodic oxidation process, it is difficult to form a sufficiently thick oxide film, and the corrosion resistance is poor. In the SiO ₂ coating process, when the inner diameter of the pipe to be processed is small, the process is impossible and it is not suitable for a fluorine atmosphere. In the ceramic sprayed film forming process, the coating film has a porous structure and the surface is rough, so that film peeling occurs during the process, which causes generation of particles. In a CVD (Chemical Vapor Deposition) process, a dense and good film can be formed, but since the temperature is high, the object of film formation is limited, and it is difficult to apply to aluminum components.

In addition, an aluminum processing container (film formation chamber) may be subjected to surface treatment with a sprayed film having high corrosion resistance, for example, sprayed with yttria (Y ₂ O ₃ ) or alumina (Al ₂ O ₃ ). If the corrosiveness of the material is strong or the plasma treatment is performed and the time of exposure to plasma is long, the sprayed film has a porous structure. In some cases, re-spraying must be performed.

  By the way, in patent document 1, in the heat processing apparatus provided with the processing gas introduction pipe part which introduces processing gas, and the exhaust pipe part which leads to an exhaust system, it is on the gas contact surface of the metal member exposed to the furnace environment of a processing furnace. Techniques for coating a chromium oxide film or coating a fluororesin film on the gas contact surface of a pipe are described. However, as described above, it is difficult to form the chromium oxide film to a thickness for ensuring sufficient corrosion resistance, and the fluororesin film tends to peel off when the pipe is bent, It becomes a factor of metal contamination and particle generation.

  Patent Document 2 suggests a technique for performing surface treatment by a CVD method. However, in the CVD method, it is necessary to heat to a high temperature of 400 ° C. to 500 ° C. or higher, and aluminum is melted in a component made of aluminum. Also, stainless steel pipes are usually heated by winding a tape heater around the outer surface of the pipe, but with such a technique, it is difficult to heat to a high temperature of 400 ° C. to 500 ° C. or higher. In fact, the surface treatment by the CVD method cannot be realized.

JP 2002-222807 A JP 2000-290785 A

  The present invention has been made under such circumstances, and an object thereof is to form a deposited film on the surface of the base material of the constituent member constituting the semiconductor manufacturing apparatus, thereby improving the durability of the constituent member. It is to provide a technology for improvement.

For this reason, this invention is a structural member used for a semiconductor manufacturing apparatus,
The base material of the component member is placed in a first source gas atmosphere containing an element selected from the group consisting of aluminum, hafnium, zirconium, and yttrium, and the first source gas is adsorbed on the surface of the base material. Then, the atmosphere is switched to the atmosphere of the second source gas that reacts with the first source gas to form a compound layer that is a compound of the element, and thus the atmosphere in which the substrate is placed is changed to the first source material. By alternately switching between the gas atmosphere and the second source gas atmosphere a number of times, a deposited film that is a stack of compound layers containing the element is formed on the surface of the base material. Features. As the base material, for example, aluminum or stainless steel is used.

  In addition, the component performs processing on the substrate in the processing container by supplying the processing gas into the processing container via the gas supply path, and the processing gas is a corrosive gas or is processed after the substrate processing. A component used in a semiconductor manufacturing apparatus that supplies a cleaning gas, which is a corrosive gas, into the container to clean the inside of the processing container. Specifically, the processing container, parts provided in the processing container, corrosive gas Is selected from a pipe for supplying the gas to the processing container, a gas supply device connected to the pipe, or an exhaust pipe. Further, the constituent member may be a constituent member of a semiconductor manufacturing apparatus including a plasma processing step.

  Further, a sprayed film may be formed between the base material of the component member and the deposited film, and as the sprayed film, boron, magnesium, aluminum, silicon, gallium, chromium, yttrium, zirconium, germanium, tantalum, Those containing any of neodymium are formed. Furthermore, the constituent member may be a member in which a base film is subjected to alumite treatment and a deposited film is formed thereon.

  The present invention also provides a process for processing a substrate in a processing container by supplying the processing gas into the processing container via a gas supply path, and the processing gas is a corrosive gas or the processing container after the substrate processing. A semiconductor manufacturing apparatus that supplies a cleaning gas, which is a corrosive gas, to clean the inside of a processing container, and is a semiconductor manufacturing apparatus that includes a constituent member on which a deposited film is formed as described above. To do.

  Furthermore, the present invention is a semiconductor manufacturing apparatus including a plasma processing step, and includes a constituent member on which a deposited film is formed as described above.

  In the present invention, the atmosphere in which the base material is placed on the surface of the base material of the constituent member of the semiconductor manufacturing apparatus is alternately changed into a gas atmosphere containing the source gas of the film to be deposited and a gas atmosphere containing oxygen atoms. By switching the number of times, a dense deposited film containing an element selected from the group consisting of aluminum, hafnium, zirconium, and yttrium is formed by a method of forming a deposited film by stacking extremely thin films in multiple layers. The durability of the constituent member can be improved.

  Further, in the semiconductor manufacturing apparatus for introducing the corrosive gas into the processing container, the compound layer which is a compound of the element is deposited on the surface of the constituent member of the semiconductor manufacturing apparatus to form the deposited film. The surface is covered with a dense film having high corrosion resistance, and the corrosion resistance of the constituent member can be improved. For this reason, even if it introduces a corrosive gas into a processing container and performs processing, corrosion of a constituent member is controlled and generation of particles which cause this corrosion is controlled.

  In addition, by purchasing an inexpensive component member that has not been surface-treated and then performing the surface treatment to form the deposited film, the corrosion resistance of the component member can be improved. A manufacturing apparatus can be manufactured, and the total manufacturing cost of the semiconductor manufacturing apparatus can be reduced.

  Further, by forming the deposited film on the surface of the component on which the sprayed film is formed, the deposited film is formed so as to enter the hole portion of the sprayed film having a porous structure. Therefore, the deposited film is originally formed on the sprayed film having high corrosion resistance. The dense deposited film is formed, the surface of the constituent member can be covered with a stronger film, and a greater corrosion resistance against the corrosive gas can be ensured.

  The present invention improves the durability of the structural member and the corrosion resistance against corrosive gas by forming a deposited film on the surface of the structural member used in the semiconductor manufacturing apparatus. The semiconductor manufacturing apparatus includes not only a semiconductor device but also a flat panel display manufacturing apparatus. For example, an apparatus that uses a corrosive gas as a processing gas, and a cleaning gas that is a corrosive gas is supplied into a processing container after processing a substrate. Thus, an apparatus that cleans the inside of the processing container, an apparatus that performs processing using plasma, and the like can be given.

Next, constituent members of the semiconductor manufacturing apparatus to be subjected to the surface treatment will be briefly described using the apparatus shown in FIG. In this apparatus, a wafer W is mounted on a mounting table 11 provided in the processing container 10, and a gas supply unit (gas shower head) 12 provided in the processing container 10 so as to face the mounting table 11. For example, a corrosive processing gas is supplied to the wafer W on the mounting table 11 from the lower surface member 13 in which a large number of gas holes 13a are formed. A processing gas is supplied into the processing container 10 from the processing gas supply pipe 14 through the gas supply unit 12, and the processing container 10 is exhausted through an exhaust pipe 15 by exhaust means (not shown). ing. Further, this apparatus is provided with a baffle plate 16 formed so that, for example, a plurality of gas exhaust ports 16 a are annularly arranged around the mounting table 11 around the mounting table 11. Is performed almost uniformly from the periphery of the mounting table 11 in the circumferential direction. In the drawing, reference numeral 17 denotes a mechanical chuck for mechanically pressing the periphery of the wafer W and holding the wafer W on the mounting table 11.
Here, in the apparatus shown in FIG. 1, the constituent member to be surface-treated according to the present invention is roughly divided into a first constitution in which the inner surface is in contact with the processing gas and the inner surface is a constituent member to be surface-treated. There is a member 21 and a second constituent member 22 whose inner and outer surfaces are in contact with the processing gas, and whose inner and outer surfaces are constituent members to be surface-treated.

  Examples of the first constituent member 21 include the metal processing container 10, a processing gas supply pipe 14 that is a pipe for supplying a processing gas into the processing container 10, and the processing container 10. Exhaust pipe 15, a valve provided in the pipe, a measuring device such as a flow rate adjustment unit, a pressure gauge, and the metal pipe such as a gas supply unit in which these valves, the flow rate adjustment unit, and a filter are integrated In addition, a gas supply device whose inner surface is in contact with the processing gas is included, and the surface treatment is performed on the surface in contact with the processing gas.

  Further, as the second component member 22, for example, a lower surface member 13 of the gas supply unit (gas shower head) 12 shown in FIG. 1, a part provided inside the processing container 10 such as a baffle plate 16 and a mechanical chuck 17. A surface treatment is performed on the surface that is included and contacts these treatment gases.

Next, embodiments of the present invention will be described. FIG. 2 shows an example of a surface treatment apparatus in which the surface treatment method of the present invention is carried out. Al ₂ which is a compound containing aluminum (Al) as a deposited film on the surface of a component to be subjected to the surface treatment below. A case where surface treatment for forming an O ₃ film is performed will be described as an example.

In the drawing, reference numeral 31 denotes a supply source (first source gas supply source) of trimethylaluminum (TMA: Al (CH ₃ ) ₃ ) which is a first source gas, and the first source gas supply source 31 It has a TMA gasification mechanism. In the figure, reference numeral 32 denotes a supply source (second source gas supply source) of ozone (O ₃ ) gas that is the second source gas, and downstream of these first and second source gas supply sources 31 and 32. Is provided with a connecting portion 33. The first and second source gas supply sources 31, 32 are, for example, first source flow channels including first and second on-off valves V1, V2 and first and second mass flow controllers M1, M2. The connection part 33 is connected via a path 41.

  The downstream side of the connecting portion 33 is connected to a vacuum exhaust means such as a vacuum pump 5 via a second raw material flow path 42 provided with an opening / closing valve V3, and is branched from the first raw material flow path 41. And, it is connected to the film-forming container 6 for surface treatment used when the surface treatment is performed on the second component member 22 through the third raw material flow path 43 provided with the opening / closing valve V4. . The film forming container 6 is connected between the open / close valve V3 of the second raw material flow path 42 and the vacuum pump 5 through a fourth raw material flow path 44 having an open / close valve V5. .

  When the surface treatment target is the first component member 21, the connection portion 33 connects the first component member 21 to the first raw material flow channel 41 and the second raw material flow channel 42. It is a part to be connected. In this connection portion 33, for example, these raw material flow channels 41, 42 are provided at the end of the first raw material flow channel 41 and the second raw material flow channel 42 on the connection side of the first component member 21. Connector members 34 and 35 for connecting the constituent pipes and the connecting ends on both sides of the first constituent member 21 are provided.

  The connector members 34 and 35 are used when the sizes of the opening portions of the connection ends of the raw material passages 41 and 42 and the first constituent member 21 are different, and the raw material passage is provided at one end side. The first constituent member 21 is connected to the flow path 41 (42) and the other end side, respectively, and a flow path for the source gas is formed inside.

  For example, when the first component member 21 is a metal pipe such as the processing gas supply pipe 14 or the exhaust pipe 15, as shown in FIG. 3, first raw material passages are provided at both ends of the metal pipe. 41 and the second raw material flow path 42 are connected via the connector portions 34 and 35. In the figure, reference numeral 36 denotes a tape heater that forms a heating means, for example. When the metal pipe is connected to the connection portion 33, the tape heater 36 is wound around the outer surface of the pipe, for example, and the pipe is heated. It is like that.

  A plurality of the connector members 34 and 35 are prepared in accordance with, for example, the opening at the connection end of the first component member 21. Further, when the diameters of the connecting portions between the first constituent member 21 and the pipes constituting the raw material passages 41 and 42 are substantially the same size, for example, each pipe without using the connector parts 34 and 35. You may make it connect these directly by connecting the flange parts provided in these connection ends.

  Next, the film forming container 6 for performing the surface treatment of the second component member 22 will be described with reference to FIG. For example, the inner surface of the film forming container 6 is formed of an alumina sprayed film, and a gas supply unit 61 is provided on the upper side. The gas supply section 61 is connected to the other end of the third material flow path 43, and a plurality of material gas supply holes 61a are formed on the lower surface. A support base 62 is provided on the lower side inside the film forming container 6 so as to face the gas supply unit 61, for example, and the second component member 22 to be surface-treated is placed on the support base 62. It is supposed to be placed. For example, the contact surfaces of the gas supply unit 61 and the support table 62 with the surface treatment source gas are made of aluminum, for example. Further, a heater 63 made of, for example, a resistance heating element is provided on the wall portion of the film forming container 6. Further, an exhaust port 64 is formed at the bottom of the film forming container 6, and the exhaust port 64 is connected to the vacuum pump 5 via the fourth raw material flow channel 44 and the second raw material flow channel 42.

  Next, the surface treatment method of the present invention will be described with reference to FIGS. This surface treatment is performed, for example, before assembling the apparatus or during maintenance. First, the case where the surface treatment for forming the deposited film is performed on the processing gas supply pipe 14 and the exhaust pipe 15 as the first constituent member 21 will be described. At this time, for example, when the processing gas supply pipe 14 and the exhaust pipe 15 are made of a metal base material such as stainless steel or aluminum, a deposited film is formed on the surface of the metal base material.

  First, as shown in FIG. 3, metal pipes such as the processing gas supply pipe 14 and the exhaust pipe 15 are connected to the connecting portion 33 as described above (step S1). For example, while heating to about 150 ° C., the valves V1, V2, V4, and V5 are closed, the valve V3 is opened, and the inside of the metal pipe is evacuated to, for example, about 133 Pa (1 Torr) by the vacuum pump 5.

  Next, the valve V3 is closed, the valve V1 is opened, and the TMA gas as the first source gas is supplied into the metal pipe for about 1 second at a flow rate of about 100 ml / min, for example. Thereby, TMA gas is adsorbed on the inner surface of the metal pipe that is the target of the surface treatment (step S2).

Subsequently, the valve V1 is closed, the valve V3 is opened, and the inside of the metal pipe is evacuated for about 2 seconds (step S3). As a result, the first source gas remaining in a state of floating inside the metal pipe without being adsorbed on the inner face of the metal pipe is discharged. Next, the valve V3 is closed, the valve V2 is opened, and O ₃ gas as the second source gas is supplied into the metal pipe for about 1 second at a flow rate of about 1000 ml / min. As a result, the O ₃ gas reacts with the liquid TMA adsorbed on the metal pipe to produce a reaction product (solid phase) represented by the chemical formula of Al ₂ O _3. For example, the film thickness is about 0.1 nm. A very thin compound layer (oxide layer) made of Al ₂ O ₃ is formed (step S4).

Subsequently, the valve V2 is closed, the valve V3 is opened, and the inside of the metal pipe is evacuated for about 2 seconds, and the O ₃ gas remaining inside the metal pipe is exhausted (step S5). Then, by repeating the steps S2 to S5, for example, several hundred times, a deposited film having a film thickness of, for example, 30 nm is formed (step S6).

  Thus, in the present invention, as described above, the metal base material to be treated is placed in the atmosphere of the first source gas, and the first source gas is adsorbed on the surface of the base material, Next, by switching the atmosphere to the atmosphere of the second source gas that reacts with the first source gas, for example, a compound layer having a film thickness of about 0.1 nm is formed, and thus the atmosphere in which the substrate is placed is changed to the first source gas. By alternately switching between the atmosphere of the source gas and the atmosphere of the second source gas many times, a deposited film, which is a laminated film of compound layers, is formed on the surface of the base material.

Further, this process will be described with reference to FIG. 6. This FIG. 6 shows the timing of supplying / disconnecting the TMA gas and the O ₃ gas which are the raw material gases in time series. As shown in FIG. TMA gas and O ₃ gas are alternately supplied into the constituent member 21, and the inside of the metal pipe is pulled out, for example, every 2 seconds during each gas supply (time t 2 to t 3 and time t 4 to t 5). As a result, an extremely thin Al ₂ O ₃ film is formed on the inner surface of the metal pipe. When each step from time t1 to time t5 is one cycle, for example, by repeating several hundred cycles, a deposited film made of an Al ₂ O ₃ film having a thickness of, for example, 30 nm is formed on the inner surface of the metal pipe.

  For example, when the first component member 21 is a metal processing vessel 10, for example, the processing vessel 10 has a base material made of aluminum, a sprayed film formed on the surface of aluminum, or yttria spraying. Since the film is formed of a film, a deposited film is formed on the surface of the aluminum, the sprayed aluminum film on which the sprayed film is formed, or the surface of the yttria sprayed film. Examples of the sprayed film include boron (B), magnesium (Mg), aluminum (Al), silicon (Si), gallium (Ga), chromium (Cr), yttrium (Y), zirconium (Zr), and tantalum (Ta). ), Germanium (Ge), neodymium (Nd) and the like are formed.

  Also in this case, as in the case of the metal pipe, in the connection portion 33, the processing gas supply port 14a (see FIG. 1) that is the connection portion with the processing gas supply pipe 14 of the processing container 10 is connected to the first portion. The raw material flow path 41 is connected via the connector portion 34, and the second raw material flow path 42 is connected to the exhaust port 15 a (see FIG. 1) that is a connection portion with the exhaust pipe 15 of the processing container 10. The surface treatment for forming a deposited film on the inner surface of the processing vessel 10 is performed according to the process shown in FIG.

  Further, for example, as shown in FIG. 8, a dedicated apparatus for surface-treating the inner surface of the processing container 10 may be provided, and the processing may be performed by this apparatus. This apparatus is the surface treatment apparatus shown in FIG. 2, in which the processing container 10 is disposed between the first raw material flow path 41 and the second raw material flow path 42. The downstream end and the upstream end of the second raw material flow path 42 are provided as dedicated connection ends for connecting to the processing gas supply port 14a and the exhaust port 15a, respectively. This apparatus is configured in the same manner as the apparatus shown in FIG. 2 except that the film forming container 6 and the third and fourth raw material flow paths 43 and 44 are not provided, and the first and second raw material flow paths. When the processing container 10 that is a surface treatment target is connected between 41 and 42, for example, a heating unit made of, for example, a resistance heating element 37 is provided around the side wall of the processing container 10, and the processing container 10 is heated. It is like that. In addition, in the case of surface treatment of the inner surface of the processing container 10, the processing may be performed with the gas supply unit 12 disposed in the processing container 10, or the processing may be performed without the gas supply unit 12 being attached. Alternatively, the gas supply unit 12 that has been subjected to the separate surface treatment may be disposed in the processing container 10.

  Next, a case where surface treatment is performed on the second component member 22 will be described. At this time, since the second constituent member 21, for example, the lower surface member 13 of the gas supply unit 12, the baffle plate 16, and the base material of the mechanical chuck 17 are made of metal such as stainless steel or aluminum, these A deposited film is formed on the surface.

  In this case, as shown in FIGS. 4 and 7, the first raw material flow channel 41 and the second raw material flow channel 42 are directly connected to each other at the connection portion 33 to form the second constituent member 22. It mounts on the support stand 62 inside the container 6 (step S11). For example, the heater 63 heats the inner surface of the film forming container 6 to, for example, about 150 ° C., closes the valves V 1, V 2, V 3, V 4, opens the valve V 5, and opens the valve V 5 to the inside of the film forming container 6. Is evacuated to about 133 Pa (1 Torr), for example.

  Next, the valve V5 is closed, the valves V1 and V4 are opened, and the TMA gas that is the first source gas is supplied into the film forming container 6 at a flow rate of, for example, about 100 ml / min for about 1 second. The first material gas is adsorbed on the contact surface (step S12). Subsequently, the valves V1 and V4 are closed, the valve V5 is opened, and the inside of the film formation container 6 is evacuated for about 2 seconds, and the remaining TMA gas is exhausted (step S13).

Next, the valve V5 is closed, the valves V2 and V4 are opened, and the O ₃ gas as the second source gas is supplied into the film forming container 6 at a flow rate of about 1000 ml / min for about 1 second. An extremely thin compound layer (oxide layer) made of Al ₂ O _{3 of} about 0.1 nm is formed (step S14). Subsequently, the valves V2 and V4 are closed, the valve V5 is opened, and the inside of the film forming container 6 is evacuated for about 2 seconds to exhaust the remaining O ₃ gas (step S15). Then, by repeating the steps S12 to S15, for example, several hundred times, a deposited film made of an Al ₂ O ₃ film having a thickness of, for example, about 30 nm is formed on the surface of the second component member 22 (step S16). Here, since the deposited film is formed at a temperature of, for example, room temperature to 200 ° C., heating by the tape heater 36, the resistance heating element 37, and the heater 63 may not be performed.

  Further, in the surface treatment method described above, when the inside of the object to be treated (in the above example, the metal pipe and the film forming container 6) is evacuated as shown in Step 3 and Step 13, purge gas is introduced into the object to be treated. A certain nitrogen (N2) gas may be supplied to purge the inside of the processing object. Thus, by introducing nitrogen gas at the time of evacuation, the TMA gas remaining in the state of being floated inside the processing object can be efficiently exhausted.

  Further, in step 3 and step 13, when the inside of the processing object is evacuated, if the pressure inside the processing object is higher than the above value, the amount of adsorption of TMA on the inner surface of the processing object increases. The film thickness formed by one reaction can be made thicker. On the other hand, when the inside of the processing object is set to a pressure lower than the above value, the film thickness formed by one reaction can be made thinner.

  When this process is performed at the time of manufacturing the semiconductor manufacturing apparatus, after performing a surface treatment for forming a deposited film on the contact surfaces of the first component member 21 and the second component member 22 with the process gas, The semiconductor manufacturing apparatus is manufactured by assembling the first structural member 21 and the second structural member 22. In addition, when this processing is performed periodically or as necessary during maintenance of the semiconductor manufacturing apparatus, first, the constituent member to be surface-treated is removed from the semiconductor manufacturing apparatus and deposited on the contact surface of the constituent member with the processing gas. After the surface treatment for forming the film is performed, this constituent member is attached to the semiconductor manufacturing apparatus.

In the above, as the deposited film, in addition to the Al ₂ O ₃ film formed by the above-described method, Al (T—OC ₄ H ₉ ) ₃ gas is used as the first source gas, and H _{2 is used} as the second source gas. Al ₂ O ₃ formed using O gas, HfCl ₄ gas as the first source gas, HfO ₂ formed using O ₃ gas as the second source gas, Hf (N (CH ₃ ) (C ₂ H ₅ )) ₄ gas, HfO ₂ formed using O ₃ gas as the second source gas, Hf (N (C ₂ H ₅ ) ₂ ) ₄ as the first source gas Gas, HfO ₂ formed using O ₃ gas as the second source gas, ZrCl ₄ gas used as the first source gas, ZrO ₂ formed using O ₃ gas as the second source gas, first as the raw material gas _{Zr (T-OC 4 H 9} ) Gas, ZrO _2, YCl ₃ gas as a first source gas, _Y 2 _O 3, which is formed using _{O 3} gas as the second source gas that is formed using _{O 3} gas as the second source gas, Aluminum (Al), hafnium (Hf), zirconium (such as Y (C ₅ H ₅ ) ₃ gas as the first source gas and Y ₂ O ₃ formed using O ₃ gas as the second source gas) Zr), a compound having a shape surrounded by a binder organic containing yttrium (Y), or a compound such as chloride containing aluminum (Al), hafnium (Hf), zirconium (Zr), yttrium (Y), or the like. Things are formed.

  In such an embodiment, in the case of the first component member 21, the raw material gas is supplied into the first component member 21, and in the case of the second component member 22, the film is formed. Since the constituent member 22 is placed in the container 6 and the raw material gas is supplied into the film forming container 6, the compound layers are laminated to form a thin film. The deposited film can be uniformly formed on the entire inner surfaces of the constituent members 21 and 22, and the durability of the constituent members 21 and 22 can be increased.

  In other words, the deposited film formed by this deposition method is formed by laminating extremely thin compound layers, so that the formed film is a dense film and has high corrosion resistance against durable and corrosive processing gases. . In addition, since a film with high surface flatness is formed, there is no possibility of film peeling due to surface roughness.

  At this time, in the present invention, the surface treatment is performed by supplying the raw material gas in the same manner as the processing gas such as the corrosive gas to the structural member to be surface treated. The source gas can be supplied to the contact area, and therefore, a surface treatment can be performed on the inner surface of the component member 21 in contact with the processing gas to form a deposited film.

  Further, since the deposited film is formed by a vacuum process, the contact surface with the processing gas inside the valve and the flow rate adjusting unit provided inside the pipe constituting the first component 21, and the second component Even in the case of the 22 complex shapes, the raw material gas is distributed to the details, and the deposited film can be formed up to the region. At this time, since the deposited film is formed by stacking very thin layers one by one as described above, it is desired to control the number of repetitions of steps S2 to S5 (steps S12 to S15) as described above. Therefore, the thickness of the deposited film can be easily adjusted according to the surface treatment target, for example. By performing surface treatment with a thin deposited film on a complex shape part such as a gas supply device unit provided with a large number of pipes and valves, flow meters, filters and the like connected together by this, For example, the corrosion resistance against corrosive gas can be enhanced without hindering the gas flow.

  In addition, since evacuation is performed between the supply of the first raw material gas and the second raw material gas and the second raw material gas is supplied in a state where the first raw material gas does not remain, The reaction between the first source gas and the second source gas inside the film forming container 6 is suppressed, and the generation of particles due to the generation of the reaction product can be suppressed.

  In this way, since a dense film can be formed on the entire contact surface of the constituent member with the processing gas, the corrosion resistance of the constituent member 21 to the corrosive processing gas can be improved. It is possible to suppress the generation of particles caused by corrosion.

  At this time, the deposited film is formed at a temperature of, for example, room temperature to about 200 ° C., and is processed at a lower temperature than the CVD method. Therefore, for example, for aluminum or a processing container in which a sprayed film is formed on aluminum. However, the surface treatment can be performed without causing dissolution of aluminum. Here, when forming a deposited film on the sprayed film, the deposited film is formed with the compound layer entering a large number of holes in the porous sprayed film, so that a stronger film can be formed. become. Therefore, it is possible to increase the corrosion resistance by forming a dense deposited film on the originally sprayed film having high corrosion resistance, and to cover the weak point of the sprayed film having a porous structure and a rough surface. Even when a corrosive processing gas is used, the occurrence of film peeling during processing can be suppressed.

  In addition, when the surface treatment is performed on the metal pipe, the deposited film is treated at a low temperature as described above, so that the first source gas and the second source gas are heated by the tape heater 36. The reaction can proceed sufficiently, and the treatment can be carried out by a simple heating method, which is effective.

  As described above, in the present invention, durability treatment is performed by performing surface treatment to form a deposited film on an inexpensive component that is not subjected to surface treatment, such as a treatment container made of aluminum or stainless steel, piping, or a lower surface member. Since corrosion resistance against corrosive gas can be improved, a semiconductor manufacturing apparatus can be manufactured using inexpensive components without purchasing expensive components that have been surface-treated in advance. Cost reduction can be achieved.

  Moreover, if the apparatus shown in FIG. 2 is used as the apparatus for performing the surface treatment on the constituent members, the first pipe such as a metal pipe that performs the treatment by connecting to the connecting portion 33 by switching the opening / closing valve of the raw material supply path The surface treatment can be performed by selecting either the component member 21 or the second component member 22 which is carried into the film forming container 6 and performs the treatment. When the first constituent member 21 such as a metal pipe is connected to the connecting portion 33 and the second constituent member 22 is carried into the film forming container 6 and the source gas is supplied, the first and second members are used. When the raw material gas is supplied to both of the constituent members 21 and 22 and evacuated, both the first and second constituent members 21 and 22 are evacuated to thereby evacuate the first constituent member 21. And the second component 22 can be subjected to surface treatment at the same time. Thus, the surface treatment can be performed on one or both of the first component member 21 and the second component member 22 with one device, and the versatility of the device is high.

  However, as shown in the example of the processing container 10 in FIG. 8, the film forming container 6 is not provided with a metal pipe not provided with the film forming container 6, a surface treatment apparatus dedicated to the processing container 10, or the connection portion 33. The surface treatment device dedicated to the second component member 22 provided with only the surface treatment device may be provided, and the surface treatment may be performed on each component member by the dedicated device. In this case, a different treatment device may be used. Surface treatment can be performed in parallel on different components, and the throughput of the surface treatment can be increased.

  In addition, the constituent member to be a surface object of the present invention is a constituent member used in an apparatus for carrying out one step of a semiconductor manufacturing process, and is not only a metallic constituent member as described above but also an aluminum base material. Also included are structural members with alumite treatment on the surface, and members made of resin or quartz such as PEEK (polyether ketone) such as electrode plates, focus rings, and deposition shields. By performing a surface treatment for forming a deposited film on the members, the durability of these constituent members can be improved.

  In the present invention, after the second constituent member 22 is attached to the processing container 10, the inner surface of the processing container 10 and the second constituent member 22 may be simultaneously subjected to the surface treatment. . Further, in the present invention, when the surface treatment is performed on the inner surface of the processing container 10, the processing container 10 is connected to the connection portion of the film forming container 6 in FIG. The surface treatment may be performed.

  The second component member is an apparatus for performing one step of the semiconductor manufacturing process, such as the lower surface member 13 of the gas supply unit 12, the baffle plate 16, and the mechanical chuck 17 described above. All of the components provided in the processing container of the semiconductor manufacturing apparatus for introducing the processing gas into the processing container are included.

  Next, an experiment conducted for confirming the effect of the present invention will be described.

(Create sample)
A deposited film made of Al ₂ O ₃ was formed on the surface of the stainless steel substrate using the surface treatment apparatus shown in FIG. First, the stainless steel substrate placed on the support base 62 inside the film forming container 6 shown in FIG. 4 is heated to 200 ° C. by the heater 63 and the inside of the film forming container 6 is evacuated to about 133 Pa. Next, after TMA gas is supplied into the film formation container 6 at a flow rate of 100 ml / min for about 1 second, the film formation container 6 is evacuated for about 5 seconds. Next, water vapor is supplied into the film forming container 6 at a flow rate of 100 ml / min for about 1 second. These steps were repeated 100 times to form a deposited film on the stainless steel substrate. This stainless steel substrate is designated as sample 1.

After the surface of the stainless steel substrate is roughened with a blast material, a sprayed film made of Al ₂ O ₃ is formed on the substrate by plasma spraying, and the same processing method as that of sample 1 is applied to the sprayed film. A deposited film was formed. This stainless steel substrate is designated as sample 2.

(Adhesion test)
Samples 1 and 2 were tested for adhesion of the deposited film formed on the surface of the stainless steel substrate. As for the test method, when the adhesive tape is applied to the surface of the deposited film and the adhesive tape is peeled off, the adhesion strength of the deposited film and the stainless steel substrate is checked by checking the adhesion of the deposited film to the adhesive tape, and The adhesion strength between the deposited film and the sprayed film was evaluated. As a result of this test, when both the sample 1 and the sample 2 were peeled off the adhesive tape, no deposited film adhered to the adhesive tape, and there was no peeling of the deposited film. From this, it can be determined that there is no problem with any of the adhesion strength between the deposited film and the stainless steel substrate and the adhesion strength between the deposited film and the sprayed film.

(Corrosion resistance test)
A corrosion test was performed on the stainless steel base material and sample 1 which were comparative samples not subjected to the treatment of the present invention. First, the comparative sample and the sample 1 are arranged in the chamber, fluorine (F ₂ ) gas is supplied into the chamber at a flow rate of 3 L / min, and nitrogen (N ₂ ) gas is supplied at a flow rate of 8 L / min. Was set to 50 kPa, and the comparative sample and Sample 1 were allowed to stand for 1 hour to evaluate the corrosion resistance of these sample surfaces. Thereafter, the comparative sample and Sample 1 were taken out from the chamber, and the depth profiles of these sample surfaces were measured with an X-ray electron spectroscopy (XPS) apparatus. In the profile of the comparative sample, it was observed that chromium (Cr) escaped from the surface of the deposited film, and the stainless steel substrate was corroded over time. On the other hand, in the profile of Sample 1, only the outermost surface of the deposited film was slightly aluminum fluoride (AlF ₃ ), and the film thickness was hardly changed. For this reason, forming a deposited film on the surface of the stainless steel base material can ensure a high corrosion resistance against corrosive gas, so that it can be understood that it is effective to form the deposited film on the stainless steel base material.

It is sectional drawing for demonstrating the semiconductor manufacturing apparatus used as the object of the surface treatment which forms the deposited film of this invention. It is a block diagram which shows an example of the surface treatment apparatus for performing the surface treatment which forms a deposited film with respect to the structural member of the said semiconductor manufacturing apparatus. In the said surface treatment apparatus, it is a block diagram which shows the case where a deposited film is formed with respect to metal piping. In the said surface treatment apparatus, it is a block diagram which shows the case where a deposited film is formed with respect to the structural member used in a processing container. In the said surface treatment apparatus, it is process drawing for demonstrating the case where a deposited film is formed with respect to metal piping. It is a block diagram which shows the mode of the supply / disconnection of source gas in the case of forming a deposited film with respect to the said metal piping. In the said surface treatment apparatus, it is process drawing for demonstrating the case where a deposited film is formed with respect to the structural member used in a processing container. It is a block diagram which shows an example of the surface treatment apparatus for performing the surface treatment which forms a deposited film with respect to the process container which is a structural member of the said semiconductor manufacturing apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor manufacturing apparatus 10 Processing container 11 Mounting stand 12 Gas supply part 13 Lower surface member 14 Process gas supply pipe 15 Exhaust pipe 16 Baffle plate 17 Mechanical chuck 31 1st source gas supply source 32 2nd source gas supply source 33 Connection part 41 First raw material supply path 42 Second raw material supply path 43 Third raw material supply path 44 Fourth raw material supply path 5 Vacuum pump 6 Deposition container

Claims (10)

A component used in a semiconductor manufacturing apparatus,
The base material of the component member is placed in a first source gas atmosphere containing an element selected from the group consisting of aluminum, hafnium, zirconium, and yttrium, and the first source gas is adsorbed on the surface of the base material. Then, the atmosphere is switched to the atmosphere of the second source gas that reacts with the first source gas to form a compound layer that is a compound of the element, and thus the atmosphere in which the substrate is placed is changed to the first source material. By alternately switching between the gas atmosphere and the second source gas atmosphere many times, a deposited film that is a laminated film of the compound layer containing the element is formed on the surface of the base material. A component of a semiconductor manufacturing apparatus.   2. The constituent member of a semiconductor manufacturing apparatus according to claim 1, wherein the substrate is made of aluminum or stainless steel.   The constituent member processes the substrate in the processing container by supplying the processing gas into the processing container through the gas supply path, and the processing gas is a corrosive gas or the processing container after the substrate processing. 3. A component of a semiconductor manufacturing apparatus according to claim 1, wherein the component is used for a semiconductor manufacturing apparatus for cleaning the inside of a processing container by supplying a cleaning gas which is a corrosive gas.   The constituent member is selected from a processing container, a part provided in the processing container, a pipe for supplying a corrosive gas to the processing container, a gas supply device connected to the pipe, or an exhaust pipe. The constituent member of the semiconductor manufacturing apparatus according to claim 3.   The constituent member of a semiconductor manufacturing apparatus according to claim 1, wherein the constituent member is a constituent member of a semiconductor manufacturing apparatus including a plasma processing step.   6. The component member of a semiconductor manufacturing apparatus according to claim 1, wherein a sprayed film is formed between a base material of the component member and a deposited film.   7. The component of a semiconductor manufacturing apparatus according to claim 6, wherein the sprayed film contains any one of boron, magnesium, aluminum, silicon, gallium, chromium, yttrium, zirconium, germanium, tantalum, and neodymium.   6. The component member of a semiconductor manufacturing apparatus according to claim 1, wherein the component member is obtained by subjecting a base material to an alumite treatment and having a deposited film formed thereon. The processing gas is supplied into the processing container through the gas supply path to process the substrate in the processing container, and the processing gas is a corrosive gas, or the corrosive gas in the processing container after the substrate processing. A semiconductor manufacturing apparatus for supplying a cleaning gas and cleaning the inside of a processing container,
A semiconductor manufacturing apparatus comprising the constituent member according to claim 1. A semiconductor manufacturing apparatus including a plasma processing step,
A semiconductor manufacturing apparatus comprising the constituent member according to claim 1.

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