Substrate processing method, manufacturing method, and substrate processing apparatus

Abstract

The invention discloses a substrate processing method, a manufacturing method and a substrate processing device. Specifically disclosed is a method of processing a substrate, the method including: an etchant supply operation of supplying an etchant to remove a film on the substrate; and a removal liquid supply operation of supplying a removal liquid having a conductivity within a set range to remove impurities adhering to the substrate after the etchant supply operation is performed.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2023 - 0167957, filed with the Korean Intellectual Property Office on November 28, 2023, the entire content of which is incorporated herein by reference. Technical Field

[0003] The present invention relates to a substrate processing method, a manufacturing method, and a substrate processing apparatus. Background Art

[0004] To manufacture semiconductor devices, various processes (such as photolithography, deposition, etching, and ion implantation) are performed on a substrate (such as a wafer).

[0005] Among them, the etching process is a process of removing a film formed on a substrate. The etching process may include a narrow - sense etching process of removing a film by using a mask or the like, and a broad - sense etching process including an ashing process of removing a mask remaining on the substrate after performing the etching process.

[0006] The etching process includes a dry - etching process of removing a film on a substrate by using plasma or the like, and a wet - etching process of removing a film on a substrate by supplying an etchant to the substrate. The wet - etching process is performed by supplying an etchant to a rotating substrate. However, in this case, process by - products generated during the wet - etching process may be redeposited on the substrate. This problem may occur more frequently when the etchant used for performing the wet - etching process is recycled. Summary of the Invention

[0007] The present invention is dedicated to providing a substrate processing method, a substrate manufacturing method, and a substrate processing apparatus capable of effectively processing a substrate.

[0008] The present invention is also dedicated to providing a substrate processing method, a substrate manufacturing method, and a substrate processing apparatus capable of effectively supplying an etchant to a substrate and improving the efficiency of removing a film on the substrate.

[0009] The present invention is also dedicated to providing a substrate processing method, a substrate manufacturing method, and a substrate processing apparatus capable of effectively removing process by - products that may re - attach to the substrate.

[0010] The problems to be solved by the present invention are not limited to the above problems, and those skilled in the art will clearly understand the problems not mentioned from the following description.

[0011] Exemplary embodiments of the present invention provide a method for processing a substrate, the method comprising: an etchant supply operation that supplies an etchant to remove a film on the substrate; and a removal liquid supply operation that supplies a removal liquid after the etchant supply operation to remove impurities attached to the substrate, wherein the removal liquid has a conductivity within a set range.

[0012] According to an exemplary embodiment, the etchant may be prepared by mixing a reused etchant and an unused etchant.

[0013] According to an exemplary embodiment, the removal liquid may be a low-concentration ammonia water having a concentration of 1.5 to 58 ppm.

[0014] According to an exemplary embodiment, the removal liquid may be a liquid having a conductivity of 5 to 40 μS / cm.

[0015] According to an exemplary embodiment, the film may be formed of a material including any one selected from the following: TiN, Co, Cu, AlO, AlN, tungsten-doped carbon, and combinations thereof.

[0016] According to an exemplary embodiment, the method may further include: a wetting liquid supply operation that supplies a wetting liquid for heating the substrate to the upper part of the substrate before supplying the etchant.

[0017] According to an exemplary embodiment, compared with the etchant, the polarity of the film may be more similar to the polarity of the wetting liquid.

[0018] According to an exemplary embodiment, the film may be formed of a material containing TiN, and the wetting liquid may be isopropyl alcohol.

[0019] According to an exemplary embodiment, the wetting liquid supply operation may further include supplying a lower wetting liquid to the lower part of the substrate to heat the substrate.

[0020] According to an exemplary embodiment, the lower wetting liquid may be deionized water or isopropyl alcohol.

[0021] According to an exemplary embodiment, the etchant may be a liquid containing an aqueous hydrogen peroxide solution, an organic chemical, a nucleophilic reducing agent, a pH regulator, a metal precipitation inhibitor, a chelating agent, and an organic solvent.

[0022] Another exemplary embodiment of the present invention provides a manufacturing method, which includes: an etchant supply operation that supplies an etchant to remove a TiN film formed on a wafer; and a removal liquid supply operation that supplies a removal liquid to remove impurities adhering to a metal surface that can be exposed (exposable) in the case of removing the TiN film, the impurities being included in the etchant, the removal liquid supply operation being performed immediately after the etchant supply operation, wherein the impurities are electrostatically attached to the metal surface, and the removal liquid has a conductivity within a set range to remove static electricity and separate the impurities from the metal surface.

[0023] According to the exemplary embodiment, the set range may be 5 to 40 μS / cm.

[0024] According to the exemplary embodiment, the removal liquid may be a low-concentration ammonia water having a concentration of 1.5 to 58 ppm.

[0025] According to the exemplary embodiment, the method may further include: a wetting liquid supply operation that heats the wafer before or after the etchant supply operation and forms a liquid film mixed with the etchant.

[0026] Another exemplary embodiment of the present invention provides an apparatus for processing a substrate, the apparatus including: a substrate support chuck for supporting and rotating the substrate; a cup-shaped member surrounding at least a part of the substrate support chuck and recovering the liquid supplied to the substrate support chuck; a liquid supply unit including an etchant nozzle and a removal liquid nozzle, the etchant nozzle for supplying an etchant to the top surface of the substrate placed on the substrate support chuck to remove the film on the substrate; the removal liquid nozzle for supplying a removal liquid to the top surface of the substrate placed on the substrate support chuck, the removal liquid removing the impurities electrostatically attached to the substrate; and a circulation unit for supplying the etchant to the etchant nozzle, wherein the circulation unit includes: a recovery pipeline for recovering the regenerated etchant recovered from a drain line connected to the cup-shaped member; a recovery tank connected to the recovery pipeline and connected to a storage pipeline for supplying unused etchant; a sub-tank for receiving the etchant including a mixture of the regenerated etchant and the unused etchant from the recovery tank and adjusting the temperature of the etchant to a set temperature; and a main tank for receiving the etchant adjusted to the set temperature from the sub-tank and supplying the etchant to the etchant nozzle.

[0027] According to an exemplary embodiment, the apparatus may further include: a three-way valve, wherein the three-way valve is connected to a discharge line, a recovery line, and a discharge line, and the discharge line is configured to discharge at least a portion of the etchant discharged through the discharge line to the outside of the apparatus.

[0028] According to an exemplary embodiment, the apparatus may further include: a controller configured to control the liquid supply unit and the etchant circulation unit, wherein the controller is configured to generate control signals to control the liquid supply unit and the substrate support chuck to perform: an etchant supply operation of supplying etchant to a substrate placed on the substrate support chuck through an etchant nozzle; and a removal liquid supply operation of supplying removal liquid to the substrate placed on the substrate support chuck through a removal liquid nozzle.

[0029] According to an exemplary embodiment, the controller may be configured to generate a control signal to control the three-way valve such that a portion of the etchant supplied through the etchant nozzle is discarded through the discharge line and another portion is recycled to a recovery tank through the recovery line.

[0030] According to an exemplary embodiment, a plurality of discharge lines may be provided. When the etchant supply operation and the removal liquid supply operation are performed in an overlapping manner, the controller generates a control signal to control the three-way valve to discard the etchant and the removal liquid through the discharge line, and when the etchant supply operation and the removal liquid supply operation are not performed in an overlapping manner, the controller controls a lifting driver to lift and lower a cup-shaped member so as to discharge the etchant and the removal liquid from the cup-shaped member through different discharge lines.

[0031] According to an exemplary embodiment of the present invention, a substrate can be effectively processed.

[0032] Furthermore, according to an exemplary embodiment of the present invention, the etchant can be effectively supplied onto the substrate and the efficiency of removing the film on the substrate can be improved.

[0033] Furthermore, according to an exemplary embodiment of the present invention, process by-products reattached to the substrate can be effectively removed.

[0034] The effects of the present invention are not limited to the foregoing effects, and those skilled in the art can clearly understand the effects not mentioned from this specification and the appended drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 A top plan view of a substrate processing apparatus according to an exemplary embodiment of the present invention.

[0036] Figure 2 Shown as being provided in Figure 1Cross-sectional view of a substrate processing apparatus in a process chamber.

[0037] Figure 3 Schematic diagram showing a liquid supply unit for supplying an etchant to Figure 1 and a circulation unit for recycling the used etchant.

[0038] Figure 4 Flowchart showing a substrate processing method according to an exemplary embodiment of the present invention.

[0039] Figure 5 Schematic diagram showing features formed on a substrate processed by a substrate processing method through Figure 4

[0040] Figure 6 Schematic diagram of a process chamber performing a wetting liquid supply operation for Figure 4

[0041] Figure 7 Schematic diagram of a process chamber performing an etchant supply operation for Figure 4

[0042] Figure 8 Schematic diagram showing features formed on a substrate after an etchant supply operation has been performed for Figure 4

[0043] Figure 9 Schematic diagram of a process chamber performing a removal liquid supply operation for Figure 4

[0044] Figure 10 Schematic diagram showing features formed on a substrate after a removal liquid operation has been performed for Figure 4

[0045] Figure 11 Schematic diagram of a process chamber performing a wetting liquid supply operation according to another exemplary embodiment of the present invention.

[0046] Figures 12 to 15 Flowchart showing a substrate processing method according to another exemplary embodiment of the present invention.

[0047] The various features and advantages of the non-limiting exemplary embodiments of this specification will become apparent upon review of the detailed description in conjunction with the accompanying drawings. The accompanying drawings are provided for illustrative purposes only and should not be construed as limiting the scope of the claims. Unless otherwise specified, the drawings are not considered to be drawn to scale. For clarity and ease of understanding, various dimensions in the figures may be exaggerated. Detailed Description ​​​​​​

[0048] Example embodiments will now be described more fully with reference to the accompanying drawings. The example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that the example embodiments may be embodied in many different forms and that the specific details should not be construed as limiting the scope of the present disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies have not been described in detail.

[0049] The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. Unless the context clearly dictates otherwise, the singular forms “a,” “an,” and “the” are intended to include the plural forms. The terms “comprises,” “comprising,” “including,” and “having” are inclusive and thus specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or combinations thereof. The method steps, processes, and operations described herein are not to be construed as necessarily performed in the particular order discussed or illustrated, unless specifically identified as an order of performance. It should also be understood that additional or alternative steps may be employed.

[0050] When an element or layer is referred to as being “on,” “engaged to,” “connected to,” or “coupled to” another element or layer, it can be directly on, engaged directly to, connected directly to, or coupled directly to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly engaged to,” “directly connected to,” or “directly coupled to” another element or layer, there may be no intervening elements or layers. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” relative to “directly between,” “adjacent” relative to “directly adjacent,” etc.). As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0051] Although the terms "first", "second", "third", etc. may be used herein to describe different elements, components, regions, layers, and / or sections, these elements, components, regions, layers, and / or sections should not be limited by these terms unless otherwise specified. These terms may be used merely to distinguish one element, component, region, layer, and / or section from another. When used herein, terms such as "first", "second", and other numerical terms do not imply an order or sequence unless the context clearly indicates otherwise. Thus, the first element, first component, first region, first layer, or first section discussed below may be referred to as a second element, second component, second region, second layer, or second section without departing from the teachings of the exemplary embodiments.

[0052] For ease of description, spatial relative terms, such as "inner", "outer", "beneath", "below", "lower", "above", and "upper", etc., may be used herein to describe the relationship of one element or feature shown in the drawings to another (other) element or feature. Spatial relative terms are intended to cover different orientations of the device in use or operation in addition to the orientation depicted in the drawings. For example, if the device in the figures is flipped, an element described as "below" or "beneath" another element or feature will then be oriented "above" the other element or feature. Thus, the exemplary term "below" can cover both an orientation above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatial relative descriptors used herein are to be interpreted accordingly.

[0053] When the terms "same" or "identical" are used in the description of the exemplary embodiments, it should be understood that there may be some imprecision. Thus, when an element or value is referred to as being the same as another element or value, it should be understood that the element or value is the same as other elements or values within the manufacturing or operating tolerances (e.g., ±10%) thereof.

[0054] When the term "about" or "substantially" is used in conjunction with a numerical value, it should be understood that the associated numerical value includes the manufacturing or operating tolerances around the stated value (e.g., ±10%). In addition, when the words "generally" and "substantially" are used in reference to a geometry, it should be understood that exactness of the geometry is not required, but the latitude of the shape is within the scope of the present disclosure.

[0055] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the exemplary embodiments belong. It should be further understood that terms, including those defined in commonly used dictionaries, should be interpreted as having a meaning consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0056] Hereinafter, a manufacturing method, a substrate processing method, and a substrate processing apparatus according to an exemplary embodiment of the present invention will be described in detail. The manufacturing method may be a method of manufacturing a semiconductor device. The substrate processing method may be a process corresponding to some of the various processes required for manufacturing a semiconductor device. Further, the substrate processing apparatus may be an apparatus that implements the above-described substrate processing method for processing a substrate W (such as a wafer). Further, the substrate processing apparatus may correspond to a semiconductor device manufacturing apparatus that can perform a process corresponding to some of the various processes required for manufacturing the above-described semiconductor device.

[0057] Hereinafter, reference will be made to Figures 1 to 15 describe the exemplary embodiments of the present invention in more detail.

[0058] Figure 1 is a top plan view of a substrate processing apparatus according to an exemplary embodiment of the present invention.

[0059] Referring to Figure 1 , the substrate processing apparatus includes an index module 100, a process processing module 200, and a controller 900. The index module 100 includes a load port 120 and a transfer frame 140. The load port 120, the transfer frame 140, and the process processing module 200 are arranged in a row in this order. Hereinafter, the direction in which the load port 120, the transfer frame 140, and the process processing module 200 are arranged is referred to as a first direction 12, and when viewed from above, the direction perpendicular to the first direction 12 is referred to as a second direction 14, and the direction perpendicular to the plane including the first direction 12 and the second direction 14 is referred to as a third direction 16.

[0060] A carrier 130 that houses the substrate W is installed on the load port 120. A plurality of load ports 120 are provided and the plurality of load ports are arranged in a line in the second direction 14. The number of load ports 120 may be increased or decreased according to the process efficiency of the process processing module 200 and the floor area requirements. The carrier 130 is formed with a plurality of slots (not shown) for receiving the substrate W in a horizontal position relative to the ground. A Front Opening Unified Pod (FOUP) may be used as the carrier 130.

[0061] The process module 200 includes a buffer unit 220, a transfer chamber 240, and a process chamber 260. The transfer chamber 240 can be arranged such that its longitudinal direction is parallel to the first direction. The process chamber 260 can be disposed at the opposite side of the transfer chamber 240. On one side of the transfer chamber 240 and on the other side of the transfer chamber 240, the process chamber 260 is symmetrically arranged with respect to the transfer chamber 240. On one side of the transfer chamber 240, a plurality of process chambers 260 are provided. Some of the process chambers 260 can be arranged along the longitudinal direction of the transfer chamber 240. Further, some of the plurality of process chambers 260 can be arranged to be stacked on top of each other. That is, the plurality of process chambers 260 can be arranged in an A×B layout at one side of the transfer chamber 240. Here, "A" is the number of process chambers 260 arranged in a line along the first direction 12, and "B" is the number of process chambers 260 arranged in a line along the third direction 16. When four or six process chambers 260 are provided at one side of the transfer chamber 240, the process chambers 260 can be arranged in a 2×2 or 3×2 layout. The number of process chambers 260 can be increased or decreased. Different from the foregoing, the process chamber 260 can be provided only on one side of the transfer chamber 240. In addition, the process chamber 260 can be provided as a single layer on one side and both sides of the transfer chamber 240.

[0062] The buffer unit 220 is disposed between the transfer frame 140 and the transfer chamber 240. The buffer unit 220 can provide a space in which the substrate W stays before being transferred between the transfer chamber 240 and the transfer frame 140. Slots (not shown) for placing the substrate W are provided inside the buffer unit 220. A plurality of slots (not shown) can be provided to be spaced apart from each other along the third direction 16. The surface of the buffer unit 220 facing the transfer frame 140 and the surface of the buffer unit 220 facing the transfer chamber 240 can be open.

[0063] The transfer frame 140 transfers the substrate W between the carrier 130 installed at the loading port 120 and the buffer unit 220. The indexing rail 142 and the indexing robot 144 are provided on the transfer frame 140. The longitudinal direction of the indexing rail 142 is parallel to the second direction 14. The indexing robot 144 is mounted on the indexing rail 142 and linearly moves along the indexing rail 142 in the second direction 14. The indexing robot 144 has a base 144a, a body 144b, and an indexing arm 144c. The base 144a is mounted to be movable along the indexing rail 142. The body 144b is coupled to the base 144a. The body 144b is arranged to be movable along the third direction 16 on the base 144a. Further, the body 144b is arranged to be rotatable on the base 144a. The indexing arm 144c is coupled to the body 144b and is arranged to be movable forward and backward relative to the body 144b. A plurality of indexing arms 144c are arranged to be individually driven. The indexing arms 144c are arranged to be stacked in a state of being spaced apart from each other along the third direction 16. When the substrate W is transferred from the process module 200 to the carrier 130, some of the indexing arms 144c can be used, and when the substrate W is transferred from the carrier 130 to the process module 200, some of the plurality of indexing arms 144c can be used. This can prevent particles generated from the substrate W before processing from adhering to the substrate W after processing during the loading and unloading of the substrate W by the indexing robot 144.

[0064] The transfer chamber 240 transfers the substrate W between the buffer unit 220 and the process chamber 260, and between the process chambers 260. The guide rail 242 and the main robot 244 are provided in the transfer chamber 240. The guide rail 242 is arranged such that its longitudinal direction is parallel to the first direction 12. The main robot 244 is mounted on the guide rail 242 and linearly moves along the first direction 12 on the guide rail 242. The main robot 244 includes a base 244a, a body 244b, and a main arm 244c. The base 244a is mounted to be movable along the guide rail 242. The body 144b is coupled to the base 244a. The body 244b is arranged to be movable along the third direction 16 on the base 244a. Further, the body 244b is arranged to be rotatable on the base 244a. The main arm 244c is coupled to the body 244b and is arranged to be movable forward and backward relative to the body 244b. A plurality of main arms 244c are arranged to be individually driven. The main arms 244c are arranged to be stacked in a state of being spaced apart from each other along the third direction 16.

[0065] The process chamber 260 performs a liquid processing process on the substrate W. The liquid processing process can be a wetting process (pre-processing process) in which the substrate W is heated and / or wetted. Further, the liquid processing process can be an etching process for removing some features formed on the substrate W. The liquid processing process can also be a cleaning process (or post-processing process) for removing impurities on the substrate W. Depending on the type of liquid processing process performed, the process chamber 260 can have different structures. Alternatively, each of the process chambers 260 can have the same structure. Optionally, the process chambers 260 can be divided into multiple groups such that the process chambers 260 belonging to the same group can be set to have the same structure, while the process chambers 260 belonging to different groups can be set to have different structures.

[0066] The controller 900 can control the configuration of the substrate processing apparatus 10. The controller 900 can control the indexing module 100 and the process processing module 200. Further, the controller 900 can be configured to control the substrate processing apparatus provided in the process chamber 260.

[0067] Further, the controller 900 can include: a process controller composed of a microprocessor (computer) that executes the control of the substrate processing apparatus 10; a user interface composed of a keyboard in which an operator performs command input operations and the like to manage the substrate processing apparatus 10; a display for visualizing and displaying the operating status of the substrate processing apparatus 10; and a storage unit that stores a control program for executing the process performed in the substrate processing apparatus 10 under the control of the process controller, or stores a program (i.e., a processing recipe) for executing the process in each component according to various data and processing conditions. Further, the user interface and the storage unit can be connected to the process controller. The processing recipe can be stored in a storage medium in the storage unit, and the storage medium can be a hard disk, a portable disk (such as a CD-ROM or a DVD), or a semiconductor memory (such as a flash memory).

[0068] Figure 2 To show the Figure 1 cross-sectional view of the substrate processing apparatus in the process chamber, and Figure 3 To show the Figure 1 schematic diagram of the liquid supply unit for supplying the etchant to

[0069] Referring to Figure 2 and Figure 3。The process chamber 260 may be provided with a substrate processing apparatus for liquid processing of the substrate W. The process chamber 260 may include a substrate support chuck 310, a first liquid supply unit 320, a second liquid supply unit 330, a cup 340, a discharge line 350, a lift actuator 360, and a circulation unit 370.

[0070] The substrate support chuck 310 may support and rotate the substrate W. The substrate support chuck 310 may include a chuck body 312, support pins 314, a rotation shaft 315, and a hollow motor 316.

[0071] The chuck body 312 may have the shape of a disk. The chuck body 312 may have an opening formed in its central region. In the opening formed in the chuck body 312, some configurations of the second liquid supply unit 330 described later may be inserted. The chuck body 312 may be configured to be rotatable.

[0072] The support pins 314 may be mounted on the chuck body 312. The support pins 314 may be mounted on the top of the chuck body 312. The support pins 314 may be configured to support the lateral portion and the bottom of the substrate W. The support pins 314 may be configured to support the edge region of the substrate W. The top end of the support pin 314 may be configured to include a first surface for supporting the bottom surface of the substrate W and a second surface for supporting the lateral portion of the substrate W.

[0073] The support pins 314 may be movable horizontally by a mechanical mechanism, which may include a motor, a track, etc. (not shown) as needed.

[0074] The rotation shaft 315 may be connected to the lower portion of the chuck body 312. The rotation shaft 315 may rotate the chuck body 312. The rotation shaft 315 may be provided as a hollow shaft. The rotation shaft 315 may be configured to have an inner diameter equal to or greater than the inner diameter of the opening formed in the central region of the chuck body 312. The inside of the rotation shaft 315 may be provided with a liquid supply shaft 336 for inserting the second liquid supply unit 330 described later.

[0075] The upper end of the rotation shaft 315 may be connected to the lower portion of the chuck body 312, and the lower end of the rotation shaft 315 may be connected to the hollow motor 316. The hollow motor 316 may rotate the rotation shaft 315. The hollow motor 316 may rotate the rotation shaft 315 to rotate the chuck body 312, and the chuck body may rotate the substrate W placed on the support pins 314. As will be described later, the rotational force generated by the hollow motor 316 may not be transmitted to the liquid supply shaft 336. That is, the second liquid supply unit 330 described later may be independent of the rotation of the chuck body 312.

[0076] The first liquid supply unit 320 may supply a processing liquid to the top surface of the substrate W. The second liquid supply unit 320 may supply a processing liquid to the top surface of the substrate W to perform an etching process to remove a part of the features formed on the substrate W. Further, the first liquid supply unit 320 may be configured to effectively process the substrate W by supplying a wetting liquid and a removing liquid before and after the etching process, respectively. The first liquid supply unit 320 may be an upper liquid supply unit that supplies a processing liquid to the top surface of the substrate W.

[0077] The first liquid supply unit 320 may include a first upper nozzle 321, a second upper nozzle 325, and a third upper nozzle arm 326. Although not shown, the first upper nozzle 321, the second upper nozzle 325, and the third upper nozzle 326 may be configured to be movable in the vertical and horizontal directions, respectively, above the substrate W. For example, the first upper nozzle 321, the second upper nozzle 325, and the third upper nozzle 326 may each be coupled to one end of a separate nozzle arm (not shown). The other end of the arm receives a rotational force from a motor or the like. That is, when viewed from above, the first upper nozzle 321, the second upper nozzle 325, and the third upper nozzle 326 may be arranged to change their positions in a virtual circular arc with the other end of the arm as the axis of rotation. The first upper nozzle 321, the second upper nozzle 325, and the third upper nozzle 326 may each be arranged to change their positions between a process position (where the processing liquid is supplied to the center of the substrate W) and a standby position (a position above a nozzle standby cup (not shown)).

[0078] However, the present invention is not limited thereto, and the first upper nozzle 321, the second upper nozzle 325, and the third upper nozzle 326 may all be mounted on a single arm, or may be distributed and mounted on two arms. In addition, the positions of the first upper nozzle 321, the second upper nozzle 325, and the third upper nozzle 326 may be configured to be movable in a linear direction by means of a linear motion LM guide or the like, rather than being limited to changing their positions in a virtual circular arc.

[0079] The first upper nozzle 321 may supply a wetting liquid to the substrate W. The first upper nozzle 321 may receive the wetting liquid from a first upper liquid supply source 322 through a first upper liquid supply line 323. The first upper liquid supply line 323 may be equipped with a liquid heating heater 324 capable of heating the wetting liquid. The liquid heating heater 324 may be provided as a line heater that is arranged to wind around the outer side of the first upper liquid supply line 323. The liquid heating heater 324 may be arranged to heat the wetting liquid supplied by the first upper nozzle 321, so that a wetting liquid at a higher temperature may be supplied to the substrate W.

[0080] The wetting liquid is formed on the substrate W described above and may have a polarity similar to that of the film to be removed. The wetting liquid may have a polarity closer to that of the film to be removed than the above-described etchant. For example, the etchant may be hydrophilic, and the wetting liquid may be hydrophobic. For example, the TiN film formed on the substrate W and to be removed may be hydrophobic. The wetting liquid may also be hydrophobic.

[0081] The wetting liquid may be an organic solvent. For example, the wetting liquid may be an ethanol-containing organic solvent. The wetting liquid may be isopropyl alcohol (IPA).

[0082] The second upper nozzle 325 may supply the etchant to the substrate W. The etchant may be configured to remove the film to be removed from the features formed on the substrate W. The etchant may be formulated to include an aqueous hydrogen peroxide solution, an organic chemical, a nucleophilic reducing agent, a pH regulator, a metal precipitation inhibitor, a chelating agent, and an organic solvent. The etchant may be provided as various etchants capable of removing metal-containing metal thin films.

[0083] Further, the second upper nozzle 325 may be connected to a supply line 379 of a circulation unit 370 to be described later. The second upper nozzle 325 may supply the etchant supplied by the circulation unit 370 to the substrate W that is supported and rotated on the substrate support chuck 310. The etchant supplied by the second upper nozzle 325 may be an etchant in which a regenerated etchant that has been used for processing the substrate W and an unused etchant newly added by a reservoir line 373 of the circulation unit 370 to be described later are mixed.

[0084] The third upper nozzle 326 may supply a removal liquid to the substrate W. The removal liquid may be a processing liquid for removing impurities attached to the substrate W (e.g., attached to the features formed on the substrate W). The removal liquid may be configured to remove impurities attached to the substrate W by static electricity. The removal liquid may be configured to have a conductivity within a set range. The removal liquid may be a liquid having a conductivity of 5 to 40 μS / cm. For example, the removal liquid may be a liquid having a conductivity of 10 μS / cm. In addition, the removal liquid may be a low-concentration ammonia water. The low-concentration ammonia water may be provided at a concentration of 1.5 to 58 ppm. For example, the low-concentration ammonia water may be provided at a concentration of 3 ppm.

[0085] The third upper nozzle 326 may receive the removal liquid from a third upper liquid supply source 328 through a third upper liquid supply line 327. The third upper nozzle 326 may receive the removal liquid from the third upper liquid supply source 328 and supply the removal liquid to the substrate W.

[0086] The second liquid supply unit 330 may supply a processing liquid to the lower portion of the substrate W. The second liquid supply unit 330 may be a lower liquid supply unit. The second liquid supply unit 330 may include a lower nozzle 332, a second liquid supply line 333, a second liquid supply source 334, a cover 335, a liquid supply shaft 336, and a bearing 337.

[0087] The lower nozzle 332 may be mounted on the cover 335 to face the bottom center region of the substrate W. The cover 335 may prevent the processing liquid supplied to the substrate W from entering the rotating shaft 315 or the liquid supply shaft 336 through the hollow portion formed in the chuck body 312. The lower nozzle 332 may be disposed inside the liquid supply shaft 336 and may be connected to the second liquid supply line 333. The second liquid supply line 333 may be connected to the second liquid supply source 334, and the second liquid supply source may supply the processing liquid supplied by the second liquid supply source 334 to the lower nozzle 332. The processing liquid supplied by the second liquid supply source 334 may be an organic solvent (such as isopropyl alcohol (IPA) or deionized water (DI water)). The second liquid supply source 334 may also heat the processing liquid and supply the heated processing liquid to the lower nozzle 332.

[0088] In addition, the bearing 337 may be disposed between the liquid supply shaft 336 and the chuck body 312. The outer surface of the liquid supply shaft 336 and the chuck body 312 may be spaced apart by the bearing 337. Further, the rotational force provided by the hollow motor 316 through the bearing 337 may not be transmitted to the liquid supply shaft 336. That is, the second liquid supply unit 330 may be independent of the rotation provided by the hollow motor 316.

[0089] The cup-shaped member 340 may be provided to surround the substrate support chuck 310. The cup-shaped member 340 may be configured to recover the processing liquid supplied to the substrate W by the first liquid supply unit 320 and the second liquid supply unit 330.

[0090] The cup-shaped member 340 may include a first cup-shaped member 341, a second cup-shaped member 342, and a third cup-shaped member 343. The first cup-shaped member 341 may be an inner cup-shaped member. The first cup-shaped member 341 may define a first discharge space 341a, a second discharge space 341b, and a third discharge space 341c. The first discharge space 341a, the second discharge space 341b, and the third discharge space 341c may be spaces for recovering the processing liquid supplied to the substrate W and sputtered. For example, the first discharge space 341a may be a space for recovering an etchant. Further, the second discharge space 341b may be a space for recovering an etchant. Further, the third discharge space 341c may be a space for recovering a wetting liquid and a removing liquid.

[0091] The first discharge space 341a may be located adjacent to the chuck 310, the second discharge space 341b may be located farther from the chuck 310 than the first discharge space 341a, and the third discharge space 341c may be located farther from the chuck 310 than the second discharge space 341b.

[0092] In addition, the discharge pipeline 350 may discharge the liquid collected in the above discharge spaces 341a and 341c to the outside. The discharge pipeline 350 may include a first discharge pipeline 351 connected to the first discharge space 341a, a second discharge pipeline 352 connected to the second discharge space 341b, and a third discharge pipeline 353 connected to the third discharge space 341c.

[0093] The first discharge pipeline 351 may be connected to the first valve DV1. The first valve DV1 may be a three-way valve. The first valve DV1 may be connected to the first discharge pipeline DL1 and the first recovery pipeline RE1. The recovered processing liquid may be discharged to the outside of the substrate processing apparatus through the first discharge pipeline DL1, and the processing liquid may be circulated to the circulation unit 370 through the first recovery pipeline RE1 for reuse of the recovered processing liquid.

[0094] The second discharge pipeline 352 may be connected to the second valve DV2. The second valve DV2 may be a three-way valve. The second valve DV2 may be connected to the second discharge pipeline DL2 and the second recovery pipeline RE2. The recovered processing liquid may be discharged to the outside of the substrate processing apparatus through the second discharge pipeline DL2. The recovered processing liquid may be circulated to the circulation unit 370 through the second recovery pipeline RE1 for reuse of the recovered processing liquid.

[0095] The first recovery pipeline RE1 and the second recovery pipeline RE2 may be connected to the main recovery pipeline 371 of the circulation unit 370 described later.

[0096] The third discharge pipeline 353 may be connected to the third valve DV3. The third valve DV3 may be a two-way valve. The third valve DV3 may be connected to the third discharge pipeline DL3. The recovered processing liquid may be discharged to the outside of the substrate processing apparatus through the third discharge pipeline DL3.

[0097] The second cup-shaped member 342 may be an intermediate cup-shaped member. The third cup-shaped member 343 may be an outer cup-shaped member. The first cup-shaped member 341 may define a first recovery path D1 corresponding to the first discharge space 341a. The first cup-shaped member 341 and the second cup-shaped member 342 may be combined with each other to define a second recovery path D2 corresponding to the second discharge space 341b. The second cup-shaped member 342 and the third cup-shaped member 343 may be combined with each other to define a third recovery path D3.

[0098] The lifting driver 360 can lift the cup-shaped members 340. The lifting driver 360 can lift the first cup-shaped member 341, the second cup-shaped member 342, and the third cup-shaped member 343 independently of each other. The lifting driver 360 can include a first lifting driver 361 for lifting the first cup-shaped member 341, a second lifting driver 362 for lifting the second cup-shaped member 342, and a third lifting driver 363 for lifting the third cup-shaped member 343. The lifting driver 360 can adjust the heights of the cup-shaped members 351, 352, and 353 to adjust the heights of the above-mentioned recovery paths D1 and D2 and the gaps between the recovery paths D1 and D2.

[0099] The circulation unit 370 can circulate the processing liquid supplied to the substrate W. The circulation unit 370 can supply the processing liquid to the first liquid supply unit 320. The circulation unit 370 can recover the etchant supplied by the second upper nozzle 325 and circulate the recovered etchant.

[0100] Hereinafter, the etchant supplied by the second upper nozzle 325 is referred to as the supplied etchant. In addition, the etchant recovered by the cup-shaped member 340 is referred to as the regenerated etchant. In addition, the newly added etchant through the reservoir pipeline 373 described later is referred to as the unused etchant. The supplied etchant can be a mixture of the regenerated etchant and the unused etchant.

[0101] The circulation unit 370 can include a main recovery pipeline 371, a recovery tank 372, a reservoir pipeline 373, a first connection pipeline 374, a sub-tank 375, a second connection pipeline 376, a main tank 378, and a supply pipeline 379.

[0102] The main recovery pipeline 371 can be connected to the first recovery pipeline RE1 and the second recovery pipeline RE2. The main recovery pipeline 371 can recover the processing liquid recovered by the cup-shaped member 340. The main recovery pipeline 371 can recover the used supplied etchant through the cup-shaped member 340.

[0103] The main recovery pipeline 371 can be connected to the recovery tank 372. The recovery tank 372 recovers the regenerated etchant. The recovery tank 372 can have a space for recovering the processing liquid. Further, the recovery tank 372 can be equipped with a concentration measurement sensor for measuring the concentration of the etchant and a temperature measurement sensor for measuring the temperature of the etchant. In addition, the recovery tank 372 can be connected to the reservoir pipeline 373 for supplying the unused etchant (new etchant). Further, the recovery tank 372 can be equipped with a heater for controlling the temperature of the etchant.

[0104] The controller 900 can generate control signals to control the circulation unit 370 to supply unused etchant through the storage pipeline 373, and control the temperature of the etchant through the heater, so that the concentration and temperature of the etchant measured by the concentration measurement sensor and the temperature measurement sensor reach the preset concentration and temperature.

[0105] In addition, the recovery tank 372 can be equipped with a filter to filter process by-products that the regenerated etchant may contain. However, the present invention is not limited thereto, and the filter can be installed in the main recovery pipeline 371, or can be installed in both the recovery tank 372 and the main recovery pipeline 371.

[0106] The etchant supplied as a mixture of the regenerated etchant and the unused etchant can be transported from the recovery tank 372 to the sub-tank 375 through the first connection pipeline 374. In the sub-tank 375, the temperature of the supplied etchant can be precisely controlled. The sub-tank 375 can be equipped with a temperature sensor for measuring the temperature of the etchant and a heater for controlling the temperature of the etchant.

[0107] Since the recovery tank 372 can continuously supplement the unused etchant and the regenerated etchant, it may be difficult to precisely control the temperature of the etchant. Therefore, in the present invention, a separate sub-tank 375 is provided to precisely control the temperature of the etchant.

[0108] The temperature-controlled etchant can be transported to the main tank 378 through the second connection pipeline 376. In the main tank 378, a constant temperature can be maintained for the supplied etchant. The main tank 378 can be equipped with a temperature sensor for measuring the temperature of the etchant and a heater for controlling the temperature of the etchant. In the sub-tank 375, the temperature of the supplied etchant can fluctuate as the temperature of the supplied etchant is controlled. Therefore, when the etchant is directly transported from the sub-tank 375 to the second upper nozzle 325, the substrate W may be transported with the etchant at the temperature during the temperature fluctuation rather than at the desired temperature.

[0109] In an exemplary embodiment of the present invention, a separate main tank 378 is provided to precisely maintain the temperature of the etchant, and the etchant with precisely maintained temperature is supplied to the substrate W.

[0110] The supplied etchant maintained at the desired temperature in the main tank 378 can be transported to the second upper nozzle 325 through the supply pipeline 379.

[0111] Figure 4 A flowchart showing a substrate processing method according to an exemplary embodiment of the present invention, and Figure 5 is a schematic diagram showing features formed on a substrate processed by the Figure 4 substrate processing method.

[0112] Reference Figure 4 and Figure 5 According to an exemplary embodiment of the present invention, the substrate processing method S10 may include removing a film of a feature formed on a substrate W.

[0113] The feature may include an anti-reflection film (etch stop layer (ESL)), a porous insulating film (porous ultra-low k (ULK)), and a TiN film. In addition, a metal film (i.e., a Cu film) may be formed on the porous insulating film, and an AlO x film may be formed on the surface of the Cu film, wherein the Cu film is tungsten-doped. The TiN film and the porous insulating film may respectively have TiN residues and sidewall residues attached thereto. The substrate processing method S10 according to an exemplary embodiment of the present invention aims to effectively remove (etch) the TiN film, the residues, and the AlO x .

[0114] According to an exemplary embodiment of the present invention, the substrate processing method S10 may include a wetting liquid supply operation S11, an etchant supply operation S12, and a removal liquid supply operation S13.

[0115] Figure 6 FIG. is a schematic diagram of a process chamber for performing Figure 4 the wetting liquid supply operation.

[0116] Reference Figure 4 and Figure 6 According to an exemplary embodiment of the present invention, the wetting liquid supply operation S11 may include supplying a heated wetting liquid HIPA to the top surface of a rotating substrate W, and supplying a heated lower wetting liquid HDIW to the lower surface of the substrate W. The wetting liquid HIPA and the lower wetting liquid HDIW may be different types of processing liquids. For example, the wetting liquid HIPA may be heated isopropyl alcohol, and the lower wetting liquid HDIW may be heated deionized water. The wetting liquid HIPA and the lower wetting liquid HDIW may be heated to a temperature capable of increasing the temperature of the substrate W and supplied. For example, the wetting liquid HIPA and the lower wetting liquid HDIW may be heated to a temperature higher than that of an etchant ETC described later and supplied to the substrate W. The wetting liquid HIPA may be supplied by a first upper nozzle 321, and the lower wetting liquid HDIW may be supplied by a lower nozzle 332. The wetting liquid HIPA and the lower wetting liquid HDIW may be recovered through a third recovery path D3 and discharged to the outside of the apparatus through a third discharge line DL3.

[0117] In addition, the wetting liquid HIPA may have a polarity similar to that of the TiN film formed on the substrate W. The TiN film is hydrophobic. Therefore, when the etchant ETC is immediately supplied without supplying the wetting liquid HIPA, it may be difficult to supply the etchant ETC uniformly onto the substrate W.

[0118] Accordingly, the present invention provides a hydrophobic wetting liquid HIPA (i.e., having a polarity similar to that of the TiN film compared to the etchant ETC), and first uniformly supplies the wetting liquid HIPA onto the substrate W. Since the wetting liquid HIPA has a polarity similar to that of the TiN film, the wetting liquid HIPA can be uniformly supplied onto the substrate W. In a state where the wetting liquid HIPA is uniformly supplied, the etchant ETC described later is supplied in a case of being mixed with the wetting liquid, so that the etchant ETC can be uniformly supplied onto the substrate W. In addition, increasing the temperature of the substrate W by the wetting liquid HIPA and the lower wetting liquid HDIW can increase the reactivity of the film with the etchant ETC. Therefore, the film removal efficiency (etching efficiency) of the substrate W can be further improved.

[0119] Figure 7 FIG. shows the execution of Figure 4 a schematic diagram of a process chamber for an etchant supply operation.

[0120] Referring to Figure 4 and 7 , the etchant supply operation S12 may include supplying the etchant ETC to the upper surface of the rotating substrate W to remove the film on the substrate. The etchant ETC may be supplied by the second upper nozzle 325. The etchant ETC may be recovered through the second recovery path D2 and / or the third recovery path D3.

[0121] Not all of the etchant ETC delivered to and used on the substrate W is delivered to the circulation unit 370. Some may be discarded through the discharge pipelines DL1 and DL2, and some may be recovered through the recovery pipelines RE1 and RE2. The etchant ETC delivered to and used in the substrate W may have an elevated temperature, and in the case where other parts are regenerated, some of the used etchant ETC may be discarded. By discarding a part of the used etchant ETC, it is easier to adjust the temperature of the etchant ETC in the circulation unit 370. By reducing the amount of impurities that need to be filtered out from the circulation unit 370 and by supplying a new etchant via the reservoir pipeline 373, the degree of contamination of the etchant circulated through the circulation unit 370 can be maintained at a level suitable for processing the substrate W.

[0122] Figure 8 FIG. shows that after the execution of Figure 4Schematic diagram of features formed on a substrate after an etchant supply operation. The etchant ETC can remove the TiN film, AlO x film, and residues contained in the features formed on the substrate W, and remove the residues attached to the features. However, as described above, the etchant ETC supplied to the substrate W is prepared by mixing the regenerated etchant and the unused etchant. In other words, the etchant ETC includes the regenerated etchant. Most of the impurities in the regenerated etchant can be removed by a filter or the like in the circulation unit 370, but some may not be removed. In addition, these impurities may be TiN residues generated in the case of removing the TiN film.

[0123] When the etchant ETC is supplied, the TiN film, AlO x film, and residues on the substrate W can be removed. When the AlO x film is removed by the etchant ETC, the surface of the Cu film may be exposed to the outside. In this case, the TiN residues that may be contained in the etchant are electrostatically attached to the surface of the Cu film. Since these residues are electrostatically attached, it may be difficult to remove the residues by using ordinary deionized water. In addition, the supply of ordinary deionized water may cause oxidation and corrosion of the exposed surface of the Cu film.

[0124] Therefore, the substrate processing method S10 according to an exemplary embodiment of the present invention can perform the etchant supply operation S12 and then perform the removal liquid supply operation S13.

[0125] Figure 9 To show the execution of Figure 4 Schematic diagram of a process chamber for the removal liquid supply operation.

[0126] Referring to Figure 4 and Figure 9 , the removal liquid supply operation S13 can include supplying the removal liquid LN to the rotating substrate W through the third upper nozzle 326. The removal liquid LN can be recovered through the third recovery path D3. The removal liquid LN recovered through the third recovery path D3 can be discharged to the outside of the apparatus through the third discharge line DL3.

[0127] Figure 10 To show the features formed on the substrate after the Figure 4 removal liquid operation has been performed.

[0128] After performing the liquid supply removal operation S13, TiN residues adhering to the surface of the Cu film on the substrate W can be removed. This is possible because the removal liquid LN is a liquid having a conductivity within a set range. The removal liquid LN can have a conductivity of 5 to 40 μS / cm. For example, the removal liquid LN can have a conductivity of 10 μS / cm. The conductivity of the removal liquid LN can remove the static electricity of the adhering TiN residues, thereby effectively separating the TiN residues from the surface of the Cu film.

[0129] In addition, the removal liquid can be low-concentration ammonia water. For example, the removal liquid LN can be low-concentration ammonia water having a concentration of 1.5 to 58 ppm. For example, the removal liquid LN can be low-concentration ammonia water having a concentration of 3 ppm. When the concentration of the removal liquid LN is between 1.5 ppm and 58 ppm, the removal liquid LN can have a constant conductivity and can have a substantially neutral property. When the removal liquid LN is strongly acidic or strongly alkaline, the Cu film itself may be damaged during the process of removing the TiN residues adhering to the Cu film.

[0130] Through long-term experiments, the inventors of the present invention have confirmed that when the removal liquid LN is low-concentration ammonia water having a concentration of 1.5 to 58 ppm, and in particular, the removal liquid LN is low-concentration ammonia water having a concentration of 3 ppm, the removal liquid LN has a very good effect of removing the static electricity of the adhering TiN residues and does not damage the Cu film.

[0131] In the substrate processing method S10 according to an exemplary embodiment of the present invention, the substrate W is heated by supplying the wetting liquid HDIW. In addition, the wetting liquid HDIW can be supplied before the etchant ETC to form a liquid film on the TiN film, thereby solving the problem that the etchant ETC cannot effectively remove the TiN film due to the polarity difference between the etchant ETC and the TiN film. Since the liquid film formed by HDIW is a liquid, the liquid film can be effectively mixed with the ETC. This allows the ETC to be uniformly supplied to the TiN film.

[0132] In other words, the etchant ETC includes a regenerated etchant. Therefore, the etchant ETC can include process by-products (TiN residues) generated in the case of removing the TiN film. When AlO x is removed, the process by-products may be electrostatically attached to the exposed surface of the Cu film.

[0133] To remove the above process by-products, the present invention supplies a removal liquid LN, which is a low-concentration ammonia water. The removal liquid LN removes the above static electricity, thereby separating the process by-products from the surface of the Cu film. In addition, since the removal liquid LN is provided as low-concentration ammonia water, the removal liquid LN can have a substantially neutral property, thereby minimizing the damage to the externally exposed Cu film. To perform the above functions, the removal liquid LN can be provided as low-concentration ammonia water having a concentration of 1.5 to 58 ppm and a conductivity of 5 to 40 μS / cm, and preferably, the removal liquid LN can be provided as low-concentration ammonia water having a concentration of 3 ppm and a conductivity of 10 μS / cm.

[0134] Table 1 below shows the experimental etching rates and particle levels in the case of removing the film by supplying the etchant ETC and then supplying ordinary deionized water (comparative example) and in the case of removing the film by sequentially supplying the wetting liquid HIPA, the etchant ETC, and the removal liquid LN (example).

[0135] In the experiment, wafers with TiN, Co, Cu, AlO, AlN, and tungsten-doped carbon (WDC) as the films to be removed were used for substrate processing according to the comparative example and the example.

[0136] [Table 1]

[0137]

[0138] As shown in Table 1 above, it can be seen that, compared with the substrate processing method according to the comparative example, in the substrate processing method S10 according to an exemplary embodiment of the present invention, the etching rates for the TiN, Co, Cu, AlO, AlN, and tungsten-doped carbon (WDC) wafers are improved, and the particle level is also greatly improved from 24 to 18.

[0139] In the above example, the present invention has been described by taking as an example the case where deionized water is supplied to the lower part of the substrate W in the wetting liquid supply operation S11, but it is not limited thereto. For example, as Figure 11 shown, the wetting liquid supply operation S11 can also supply heated isopropyl alcohol (HIPA) to the lower part of the substrate W.

[0140] In addition, the inventors also conducted experiments on various process conditions related to the present invention, as shown in Table 2 below.

[0141] [Table 2]

[0142]

[0143] As shown in the above table, it can be seen that when low-concentration ammonia water is supplied after the supply of the etchant, no defects occur. Specifically, referring to Case 5 and Case 10, it can be seen that in order to prevent the occurrence of defects, it is most preferable to supply low-concentration ammonia water immediately after the supply of the etchant.

[0144] Referring to the above defect-free cases, the present invention can consider a substrate processing method according to other exemplary embodiments as Figures 12 to 15 shown.

[0145] For example, a substrate processing method S20 such as Figure 12 shown can sequentially perform an etchant supply operation S21 and a removal liquid supply operation S22.

[0146] Furthermore, a substrate processing method S30 such as Figure 13 shown can sequentially perform an etchant supply operation S31, a removal liquid supply operation S32, and a wetting liquid supply operation S33.

[0147] Furthermore, a substrate processing method S40 such as Figure 14 shown can sequentially perform a removal liquid supply operation S41, an etchant supply operation S42, a removal liquid supply operation S43, and a wetting liquid supply operation S44.

[0148] Furthermore, a substrate processing method S50 such as Figure 15 shown can sequentially perform a wetting liquid supply operation S51, an etchant supply operation S52, a removal liquid supply operation S53, and a wetting liquid supply operation S54.

[0149] In the above examples, the present invention has been described by taking as an example the case where the etchant supply operation S12 and the removal liquid supply operation S13 are performed without overlap, and the etchant ETC and the removal liquid LN are discharged from the cup-shaped member 340 through different discharge pipelines 350.

[0150] However, the present invention is not limited thereto, and the etchant supply operation S12 and the removal liquid supply operation S13 can be performed with partial overlap.

[0151] For example, the second upper nozzle 325 may move from the center of the substrate W in a scanning outward direction while supplying the etchant ETC, and the third upper nozzle 326 may supply the removal liquid LN to the center of the substrate W while the second upper nozzle 325 is moving. In this case, the etchant ETC and the removal liquid LN may be recovered into one or more recovery paths selected from the first to third recovery paths D1, D2, and D3 formed by the cup-shaped member 340. In this way, when the etchant supply operation and the removal liquid supply operation are performed in an overlapping manner, the processing liquid recovered during the overlapping operation may be discarded via the discharge pipelines DL1, DL2, and DL3 without being circulated to the circulation unit 370, thereby preventing the removal liquid LN from being circulated to the circulation unit 370.

[0152] It should be understood that the exemplary embodiments disclosed herein are and may have other variations. Each element or feature of a particular exemplary embodiment is generally not limited to that particular exemplary embodiment, but is interchangeable and, even if not specifically stated or described, may be used in a selected exemplary embodiment where applicable. Such modifications should not be regarded as departing from the spirit and scope of the present invention, and all modifications that are obvious to those of ordinary skill in the art are intended to be included within the scope of the appended claims.

Claims

1. A method for processing a substrate, the method comprising: an etchant supplying operation of supplying an etchant to remove a film on a substrate; as well as a removal liquid supplying operation of supplying a removal liquid after performing the etchant supplying operation to remove impurities attached to the substrate, Wherein, the removal liquid has an electrical conductivity within a set range.

2. The method according to claim 1, wherein: The etchant is prepared by mixing regenerated etchant and unused etchant.

3. The method according to claim 2, wherein: The removal liquid is a low-concentration ammonia water having a concentration of 1.5 to 58 ppm.

4. The method according to claim 2, wherein: The removal liquid is a liquid having an electrical conductivity of 5 to 40 μS / cm.

5. The method according to claim 1, wherein: The film is formed of a material including any of: TiN, Co, Cu, AlO, AlN, tungsten doped carbon, and combinations thereof.

6. The method according to claim 1, wherein: The method further comprises: A wetting liquid supplying operation of supplying a wetting liquid for heating the substrate to an upper portion of the substrate before supplying the etchant.

7. The method according to claim 6, wherein: The polarity of the film is more similar to the polarity of the wetting liquid than to the etchant.

8. The method according to claim 7, wherein: The film is formed of a material including TiN, and The wetting liquid is isopropyl alcohol.

9. The method according to claim 6, wherein: The wetting liquid supplying operation further includes supplying a lower wetting liquid to a lower portion of the substrate to heat the substrate.

10. The method according to claim 9, wherein: The lower wetting liquid is deionized water or isopropyl alcohol.

11. The method according to claim 1, wherein: The etchant is a liquid comprising an aqueous hydrogen peroxide solution, an organic chemical, a nucleophilic reducing agent, a pH adjuster, a metal precipitation inhibitor, a chelating agent, and an organic solvent.

12. A manufacturing method, comprising: an etchant supplying operation of supplying an etchant to remove a TiN film formed on the wafer; as well as a removal liquid supplying operation of supplying a removal liquid to remove impurities attached to a metal surface, the metal surface being exposed in the case of removing the TiN film, the impurities being included in the etchant, the removal liquid supplying operation being performed immediately after the etchant supplying operation, The impurities are attached to the metal surface by static electricity, and the removal liquid has an electrical conductivity within a set range to remove the static electricity and separate the impurities from the metal surface.

13. The manufacturing method according to claim 12, wherein: The setting range is 5 to 40 μS / cm.

14. The manufacturing method according to claim 12, wherein: The removal liquid is low-concentration ammonia water having a concentration of 1.5 to 58 ppm.

15. The manufacturing method according to claim 12, wherein: The method further comprises: A wetting liquid supplying operation heats the wafer and forms a liquid film mixed with the etchant before or after the etchant supplying operation.

16. An apparatus for processing a substrate, the apparatus comprising: A substrate support chuck, the substrate support chuck is used to support and rotate the substrate; a cup that surrounds at least a portion of the substrate support chuck and recovers liquid supplied to the substrate support chuck; a liquid supply unit including an etchant nozzle and a removal liquid nozzle, the etchant nozzle being used to supply an etchant to a top surface of the substrate placed on the substrate support chuck to remove a film on the substrate; the removing liquid nozzle is for supplying a removing liquid to a top surface of the substrate placed on the substrate supporting chuck, the removing liquid removing foreign matter electrostatically attached to the substrate; as well as a circulation unit for supplying the etchant to the etchant nozzle, Wherein, the circulation unit comprises: a recovery line for recovering the regenerated etchant recovered from the discharge line connected to the cup; a recovery tank connected to the recovery line and to a reservoir line supplying unused etchant; a sub-tank for receiving an etchant including a mixture of the regenerated etchant and the unused etchant from the recovery tank and adjusting a temperature of the etchant to a set temperature; and A main tank receives the etchant adjusted to the set temperature from the sub-tank and supplies the etchant to the etchant nozzle.

17. The apparatus according to claim 16, further comprising: Three-way valve, The three-way valve is connected to the discharge pipeline, the recovery pipeline and the exhaust pipeline, and the exhaust pipeline is used to discharge at least part of the etchant discharged through the discharge pipeline to the outside of the device.

18. The apparatus according to claim 17, further comprising: a controller, the controller being used to control the liquid supply unit and the etchant circulation unit, Wherein, the controller is configured to generate a control signal to control the liquid supply unit and the substrate supporting chuck to perform: an etchant supplying operation of supplying the etchant to the substrate placed on the substrate supporting chuck through the etchant nozzle; A removing liquid supplying operation of supplying the removing liquid to the substrate placed on the substrate supporting chuck through the removing liquid nozzle.

19. The device according to claim 18, wherein: The controller is configured to generate a control signal to control the three-way valve so that a portion of the etchant supplied through the etchant nozzle is discarded through the exhaust line and another portion is recovered to the recovery tank through the recovery line.

20. The device according to claim 18, wherein Provide a plurality of said discharge pipelines, When the etchant supply operation and the removal liquid supply operation are performed in an overlapping state, the controller generates a control signal to control the three-way valve to discard the etchant and the removal liquid through the exhaust line, and When the etchant supply operation and the removal liquid supply operation are performed without overlapping, the controller controls the elevating driver to elevate the cup so as to discharge the etchant and the removal liquid from the cup through the different discharge lines.

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