Abstract:
Provided is a method and apparatus for treating a substrate with a liquid. The substrate treating method comprises a pre-treating step for supplying the treatment liquid containing hydrogen fluoride (HF) to the substrate and treating the substrate before the surface modification step and a surface modification step for supplying an alkene-based chemical onto a substrate to change the surface of the substrate to a hydrophobic state. As a result, the surface of the substrate is uniform, and generation of particles can be reduced when the substrate is removed.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    A claim for priority under 35 U.S.C. §119 is made to Korean Patent Application No. 10-2016-0065843 filed May 27, 2016, in the Korean Intellectual Property Office, the entire contents of which are hereby incorporated by reference. 
       BACKGROUND OF THE INVENTION 
       [0002]    The present invention disclosed herein relates to a method and a apparatus for treating substrate with liquid. 
         [0003]    In order to manufacture a semiconductor device or a liquid crystal display, various processes such as photolithography, ashing, etching, ion implantation, thin film deposition, and cleaning are performed on the substrate. From this kind of substrate treating process, a pattern may be formed on the substrate, and the formed pattern may be collapsed by the atmosphere or water. In order to prevent the collapse of the pattern, a step of changing the surface of the substrate from hydrophilic to hydrophobic (hereinafter, surface modification step) is performed. 
         [0004]    Generally, in the surface modification process, a substrate having a hydrophilic surface is bonded to a silyl or hydroxyl group to modify the surface to be hydrophobic. Such a surface modification step should be performed sequentially in a first rinsing step, a first replacement step, a surface modification step, a second replacement step, a second rinsing step, and a drying step. 
         [0005]    This requires rinsing and replacement steps before and after the surface modification step, respectively, and it takes a lot of time since the rinsing step and the replacement step are repeated. In addition, when the surface of a substrate is modified with a chemical containing a silyl or hydroxyl group, the surface of the substrate is uneven, and when removing this, a large amount of particles are generated. 
       SUMMARY OF THE INVENTION 
       [0006]    Embodiments of the inventive concept described herein relate to a method and apparatus capable of uniformly modifying the surface of a substrate. 
         [0007]    Embodiments of the inventive concept described herein relate to a method and apparatus for minimizing the generation of large quantities of particles during hydrophilic modification of a hydrophobic surface of a substrate. 
         [0008]    Embodiments of the inventive concept described herein relate to a method and apparatus for treating a substrate with a liquid. The substrate treating method comprises a surface modification step for supplying an alkene-based chemical onto a substrate to change the surface of the substrate to a hydrophobic state. 
         [0009]    The substrate treating method further comprises a pre-treating step for supplying the treatment liquid containing hydrogen fluoride (HF) to the substrate and treating the substrate before the surface modification step. In the surface modification step, the chemical may be radically reacted with the surface of the substrate. The radical reaction may be generated by irradiating the substrate with ultraviolet light. 
         [0010]    The radical reaction may be generated by heating the substrate. 
         [0011]    The temperature of the substrate may be 200° C. or less, and the treating time of the surface modification step may be within 2 minutes. A rinsing step for supplying a rinsing liquid to the substrate and treating the substrate after the surface modification step and a replacement step for supplying an organic solvent to the substrate after the rinsing step to replace the rinsing liquid remaining on the substrate may be further comprised. 
         [0012]    The substrate treating apparatus further comprises a substrate support unit for supporting the substrate and a liquid supply unit for supplying the substrate support unit with liquid, wherein the liquid supply unit includes a chemical nozzle for supplying an alkene series chemical onto a substrate so that the surface of the substrate is changed to be hydrophobic. 
         [0013]    The liquid supply unit further comprises a pretreatment nozzle for discharging a treatment liquid containing hydrogen fluoride (HF), and a controller for controlling the chemical nozzle and the treatment nozzle, wherein the controller may control the chemical nozzle and the treatment nozzle to supply a treatment liquid onto the substrate and then supply the chemical. The liquid supply unit may further include a heater for heating the substrate supported by the substrate support unit. The liquid supply unit may further include a lamp for irradiating ultraviolet (UV) light onto the substrate supported by the substrate support unit. 
         [0014]    According to an embodiment, the surface modification process of the substrate is performed by treating the substrate with a treatment liquid containing hydrogen fluoride (HF), and thereafter modifying the surface of the substrate to a hydrophobic property with an alkene series chemical. As a result, the surface of the substrate is uniform, and generation of particles can be reduced when the substrate is removed. 
         [0015]    According to an embodiment, in the surface modification step of the substrate, heating or ultraviolet rays are irradiated, and the degree of hydrophobicity can be controlled by controlling the temperature and the process time of the substrate. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0016]      FIG. 1  is a plan view showing a substrate treating apparatus according to an embodiment of the present invention. 
           [0017]      FIG. 2  is a cross-sectional view showing the substrate treating apparatus of  FIG. 1 . 
           [0018]      FIG. 3  is a flowchart illustrating a process of treating a substrate using the substrate treating apparatus of  FIG. 2 . 
           [0019]      FIGS. 4 to 7  are views illustrating a process of treating a substrate using the liquid supply unit of  FIG. 2 . 
       
    
    
     DETAILED DESCRIPTION 
       [0020]    Various example embodiments will be described more fully hereinafter with reference to the accompanying drawings, in which some example embodiments are shown. The present invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art. Therefore, features of the drawings are exaggerated to emphasize definite explanation. 
         [0021]    In the embodiment, a process of cleaning a hydrophobic film formed on a substrate will be described as an example. Hereinafter, an example of the present invention will be described in detail with reference to  FIGS. 1 to 7 . 
         [0022]      FIG. 1  is a plan view showing a substrate treating apparatus according to an embodiment of the present invention. Referring to  FIG. 1 , a substrate treating apparatus  1  comprises an index module  10  and a process treating module  20 . The index module  10  have a load port  120  and a transfer frame  140 . The load port  120 , the transfer frame  140 , and the process treating module  20  are sequentially arranged in a row. Hereinafter, a direction where the load port  120 , the transfer frame  140 , and the process treating module are arranged is referred to as a first direction  12 . And a direction perpendicular to the first direction  12  is referred to as a second direction  14 , when view from a top side, and a direction perpendicular to a plane including the first direction  12  and the second direction  14  is referred to as a third direction  16 . 
         [0023]    A carrier  18  where a substrate W is stored is seated on the load port  120 . The load port  120  is provided as a plurality of numbers and they are arranged in a row along the second direction  14 . The number of load ports  120  may be increased or decreased depending on a requirement like process efficiency and a footprint of the process treating module  20 . The carrier  18  is formed with a plurality of slots (not shown) for accommodating the substrates W horizontally with respect to the plane surface. A front opening unified pod (FOUP) may be used as the carrier  18 . 
         [0024]    The process treating module  20  comprises a buffer unit  220 , a transfer chamber  240 , and a process chamber  260 . The transfer chamber  240  is provided such that the lengthwise direction thereof is parallel with the first direction  12 . Process chambers  260  are disposed on both sides of the transfer chamber  240 , respectively. On both sides of the transfer chamber  240 , the process chambers  260  are positioned symmetrically with respect to the transfer chamber  240 . Some of the process chambers  260  are placed along the lengthwise direction of the transfer chamber  240 . Also, some of the process chambers  260  are placed vertically stacked to each other. That is, in one side of the transfer chamber  240 , the process chambers  260  may be arranged in A×B array. Herein, A is the number of the process chambers  250  which are provided along the first direction  12 , and B is the number of process chambers  260  which are provided along the third direction  16 . When four or six process chambers  260  are provided on one side of the transfer chamber  240 , the process chambers  260  may be arranged in 2×2 or 3×2 arrays. The number of the process chamber  260  may be increased or decreased. 
         [0025]    Selectively, the process chamber  260  may be provided only on one side of the transfer chamber  240 . Also, the process chamber  260  may be provided as a single layer at both sides of the transfer chamber  240 . 
         [0026]    The buffer unit  220  is arranged between the transfer frame  140  and the transfer chamber  240 . The buffer unit provides a space for the substrate W to stay temporarily before transferring the substrate W between the transfer chamber  240  and the transfer frame  140 . The slot (not described) where the substrate places is provided inside (e.g., inner wall) of the buffer unit  220 , and the slots (not described) are provided with a plurality of numbers spaced apart from each other along the third direction  16 . One side of the buffer unit  220  facing the transfer frame  140 , and the other side of the buffer unit  220  facing the transfer chamber  240  are opened. 
         [0027]    The transfer frame  140  transfers the substrate W between the buffer unit  220  and the carrier  18  seated on the load port  120 . In the transfer frame  140 , an index rail  142  and an index robot  144  are provided. The index rail  142  is provided such that the lengthwise direction is parallel to the second direction  14 . The index robot  144  is installed on the index rail  142 , and move linearly along the index rail  142  to the second direction  14 . The index robot  144  comprises a base  144   a , a body  144   b , and an index arm  144   c . The base  133   a  is installed movably along the index rail  142 . The body  144   b  is coupled to the base  144   a . The body  144   b  is provided movably along the third direction  16  on the base  144   a . Also, the body  144   b  is provided rotatable on the base  144   a . The index arm  144   c  is coupled to the body  144   b , and is provided to move front and back to the body  144   b . The index arm  144   c  is provided with a plurality of numbers and they are driven independently. The index arms  144   c  are arranged vertically, i.e., spaced apart from each other along the third direction  16 . Some of the index arms  144   c  may be used when transferring the substrate W from the process treating module  20  to the carrier  18 , and some may be used when transferring the substrate W from the carrier  18  to the process treating module  200 . In this way, during the index robot  144  carries in or carries out the substrate W, particles that have come from a substrate before treating process may be prevented from adhering to a substrate after treating process. 
         [0028]    The transfer chamber  240  transfers the substrate W between process chambers  260  and the buffer unit  220  and between the process chambers  260 . A guide rail  242  and a main robot  244  are provided in the transfer chamber  240 . The guide rail  242  is places such that the lengthwise direction is parallel with the first direction  12 . The main robot  244  is installed on the guide rail  242 , and moves linearly along the first direction  12  on the guide rail  242 . The main robot  244  comprises a base  244   a , a body  244   b , and a main arm  244   c . The base  244   a  is installed movably along the guide rail  242 . The body  244   b  is coupled to the base  244   a . The body  244   b  is provided movably along the third direction  16  on the base  244   a . Also, the body  244   b  is provided rotatable on the base  244   a . The main arm  244   c  is coupled to the body  244   b , and is provided to move front and back to the body  244   b . The main arm  244   c  is provided with a plurality of numbers and they are provided to drive separately. The main arms  244   c  are arranged vertically, i.e., spaced apart from each other along the third direction  16 . 
         [0029]    In the process chamber  260 , a substrate treating apparatus  300  which performs a cleaning process to the substrate W is provided. The substrate treating apparatus  300  may have different structure based on kinds of cleaning process. The substrate treating apparatus  300  provided in each process chambers  240  may have the same structure. Selectively, the substrate treating apparatus  300  provided in the same group of the process chamber  260  may have the same structure, and the substrate treating apparatus  300  provided in different group of the process chamber  260  may have different structure. 
         [0030]    The substrate treating apparatus  300  performs a process of modifying and cleaning the surface of the substrate.  FIG. 2  is a cross-sectional view showing the substrate treating apparatus of  FIG. 1 . Referring to  FIG. 2 , the substrate treating apparatus  300  comprises a treatment container  320 , a spin head  340 , an elevating unit  360 , a liquid supply unit  370 , and a controller  500 . 
         [0031]    The treatment container  320  provides a treating space where a substrate treating process is performed. The treatment container  320  has open upper side. The treatment container  320  comprises an inner collecting container  322 , and an outer collecting container  326 . Each collecting containers  322 ,  324 ,  326  collects a treatment liquid that are different from each other among treatment liquids used in a process. The inner collecting container  322  is provided as a ring shape surrounding the spin head  340 . The outer collecting container  326  is provided as a ring shape surrounding the inner collecting container  322 . An inner space  322   a  of the inner collecting container  322  and an interspace  326   a  between the inner collecting container  322  and the outer collecting container  326  may function as a inlet where treatment liquid flows into the inner collecting container  322  and the outer collecting container  326 , respectively. According to an embodiment, each inlet  322   a ,  326   a  may be placed in different heights from each other. Collecting lines  322   b ,  326   b  are connected to the bottom side of inlets  322 ,  326  respectively. Treatment liquid that flew into each inlet  322 ,  326  may be reused through the collecting line  322   b ,  326   b  as treatment liquid regeneration system (not shown) of outside. 
         [0032]    The spin head  340  is provided as a substrate support unit  320  that rotates and supports the substrate W during process. The spin head  340  has a body  342 , a supporting pin  344 , a chuck pin  346 , and a supporting shaft  348 . When viewed from the top, the body  342  is generally provided such that an upper surface of the top body  342  is provided as a circular shape. The rotatable supporting shaft  348  is fixedly connected to the bottom side of the body  342  driven by a driving part  349 . 
         [0033]    The supporting pin  344  is provided as plurality number. The plurality of supporting pins  344  are provided and spaced apart from each other on edge of the upper surface of the body  342  and protrude upward from the body  342 . The supporting pins  344  are generally arranged to have a ring shape. The supporting pin  344  supports the back side of the substrate W to be spaced apart from the upper surface of the body  342 . 
         [0034]    The chuck pin  346  is provided as plurality number. The chuck pin  436  is arranged further apart from a center of the body  342  than the supporting pin  344 . The chuck pin  436  is provided as to protrude upward from the body  342 . The chuck pin  436  supports lateral part of the substrate W to make substrate W not deviate from a right position to a side direction when the spin head  340  is rotating. The chuck pin  346  is provided to move linearly between standby position and supporting position along a radius direction of the body  342 . The standby position is further apart from a center of the body  342  than the supporting position. When loading and unloading the substrate W from the spin head  340  the chuck pin  346  is placed on the standby position, and when processing the substrate W, the chuck pin  346  is placed on the supporting position. The chuck pin  346  on the supporting position is contacted with the lateral part of the substrate. 
         [0035]    The elevating unit  360  moves the treatment container  320  linearly up and down direction. As the treatment container  320  moves up and down direction, relative height of the treatment container  320  changes with respect to the spin head  340 . The elevating unit  360  has a bracket  362 , a moving shaft  364 , and a driver  366 . The bracket  362  is fixedly connected to an outer wall of the treatment container  320 , and the moving shaft  364  which moves to up and down direction by the driver  366  is fixedly connected to the bracket  362 . When the substrate is placed on the spin head  340  or when lifted from the spin head  340 , the treatment container  320  descends such that the spin head  340  protrudes upward from the treatment container  320 . Also, during processing, the height of the treatment container  320  are controlled such that treatment liquid flows into the predetermined collecting container  360  depending on a kind of treatment liquid supplied in substrate W. Selectively, the elevating unit  360  may move the spin head  340  up and down direction. 
         [0036]    The liquid supply unit  370  supplies treatment liquid to the substrate W. The liquid supply unit  370  includes a chemical member  380 , a pretreatment member  400 , a rinsing member  410 , a replacement member  420 , an irradiation member  450 , and a controller  500 . 
         [0037]    The chemical member  380  supplies the chemical on the substrate W. The chemical member  380  includes a nozzle moving member  381  and a chemical nozzle  390 . The nozzle moving member  381  moves the chemical nozzle  390  to the process position and the standby position. The process position is the position where the chemical nozzle  390  is opposed to the substrate W supported on the substrate support unit  340 , and the standby position is the position at which the chemical nozzle  390  is out of the process position. The nozzle moving member  381  includes a support shaft  386 , a support arm  382 , and a driving member  388 . The support shaft  386  is located on one side of the treatment container  320 . The support shaft  386  has a rod shape whose longitudinal direction faces the third direction. The support shaft  386  is provided to be rotatable by the driving member  388 . The support arm  382  is coupled to the upper end of the support shaft  386 . The support arm  382  extends vertically from the support shaft  386 . A chemical nozzle  390  is fixedly coupled to an end of the support arm  382 . As the support shaft  386  rotates, the chemical nozzle  390  is swingable with the support arm  382 . The chemical nozzle  390  can be swung and moved to the process position and the standby position. The chemical nozzle  390  may be positioned to coincide with the central axis of the substrate W in the process position. For example, the chemical may be an alkene-based liquid. The chemical may be 6 to 20 carbons (C) composed of double bonds. 
         [0038]    Alternatively, the support shaft  386  may be provided so as to be movable up and down. Also, the support arm  382  can be provided so as to be movable forward and backward in the longitudinal direction thereof. 
         [0039]    The pretreatment member  400  supplies the treatment liquid onto the substrate W. The pretreatment member  400  includes a nozzle moving member and a pretreatment nozzle  402 . The nozzle moving member of the pretreatment member  400  has the same shape as the nozzle moving member  381  of the chemical member  380  described above. Thereby, a detailed description thereof will be omitted. For example, the treatment liquid may be a liquid containing hydrogen fluoride (HF). 
         [0040]    The rinsing member  410  supplies the rinsing liquid onto the substrate W. The rinsing member  410  includes a nozzle moving member and a rinsing nozzle  412 . The nozzle moving member of the rinsing member  410  has the same shape as the nozzle moving member  381  of the chemical member  380  described above. A detailed description thereof will be omitted. For example, the rinsing liquid may be pure. 
         [0041]    The replacement member  420  supplies the organic solvent onto the substrate W. The rinsing liquid remaining on the substrate W can be replaced with an organic solvent. The replacement member  420  includes a nozzle moving member and a replacement nozzle  422 . The nozzle moving member of the replacement member  420  has the same shape as the nozzle moving member  381  of the chemical member  380  described above. A detailed description thereof will be omitted. For example, the organic solvent may be an isopropyl alcohol (IPA) solution. 
         [0042]    The irradiation member  450  induces a radical reaction between the substrate W and the chemical. The irradiation member  450  heats the substrate W. The irradiation member  450  includes a lamp  452  and a heater  454 . The lamp  452  irradiates light at the top of the substrate W. The lamp  452  is installed in the chemical nozzle  390 . The lamp  452  is located at one side of the chemical nozzle  390 . According to one example, the light may comprise ultraviolet (UV) radiation. 
         [0043]    The heater  454  heats the substrate W supported by the substrate support unit  340 . The heater  454  is positioned opposite to the non-treated surface of the substrate W. Herein, the non-treated surface of the substrate W corresponds to the bottom surface of the substrate W. The heater  454  is installed on the upper surface of the spin head  342 . For example, the heater  454  may generate heat at room temperature to 200° C. Alternatively, the heater  454  may be disposed on the other side of the chemical nozzle  390  and positioned opposite the upper surface of the substrate W. 
         [0044]    The controller  500  controls the pretreatment nozzle  402 , the chemical nozzle, the rinsing nozzle  412 , the replacement nozzle  422 , and the irradiation member  450  so that the pre-treating step S 10 , the surface modification step S 20 , the rinsing step S 30 , and the replacement step S 40  are sequentially performed. In the pretreatment step S 10 , the substrate W is treated with a treatment liquid, and in the surface modification step S 20 , the substrate W is treated with a chemical. In the rinsing step S 30 , the substrate W is treated with a rinsing liquid, and in the replacement step S 40 , the substrate W is treated with an organic solvent. The controller  500  irradiates light in the surface modification step S 20  and controls the irradiation member  450  so that the substrate W is heated. Selectively, the controller  500  may control to operate either the heating of the substrate W or the light irradiation in the surface modification step S 20 . 
         [0045]    A process of treating the substrate W using the above described substrate treating apparatus  300  will be described. As described above, the pre-treating step S 10 , the surface modification step S 20 , the rinsing step S 30 , and the replacement step S 40  are sequentially performed.  FIG. 3  is a flowchart illustrating a process of treating a substrate using the substrate treating apparatus of  FIG. 2 .  FIGS. 4 to 7  are views illustrating a process of treating a substrate using the liquid supply unit of  FIG. 2 . 
         [0046]    When the pre-treating step S 10  is performed, the pretreatment nozzle  402  is moved to the process position to supply the treatment liquid onto the substrate W. The surface of the substrate W is subjected to a reaction treatment with a treatment liquid containing hydrogen fluoride (HF). When the pre-treating step S 10  is completed, the pretreatment nozzle  402  is moved to the standby position, and the surface modification step S 20  is performed. 
         [0047]    As the surface modification step S 20  proceeds, the chemical nozzle is moved to the process position to supply the chemical on the substrate W. During the surface modification step S 20 , the substrate W is heated by the heater  454  and the surface of the substrate W is irradiated with light. Accordingly, the chemical reacts with the surface of the W by a radical reaction and forms a hydrophobic film on the upper surface of the substrate W. A degree of the hydrophobic film formed on the substrate W is proportional to the heating temperature and the processing time of the substrate W. That is, the degree of the hydrophobic film increases as the heating temperature is higher and the process time of the surface modification step S 20  is longer. When the surface modification step S 20  is completed, the chemical nozzle  390  is moved to the standby position and the rinsing step S 30  proceeds. According to an example, the surface modification step S 20  may be within 2 minutes. 
         [0048]    When the rinsing step S 30  is performed, the rinsing nozzle  412  is moved to the process position to supply the rinsing liquid onto the substrate W. The rinsing liquid rinses the chemical or particles remaining on the substrate W. When the rinsing step S 30  is completed, the rinsing nozzle  412  is moved to the standby position, and the replacement step S 40  proceeds. 
         [0049]    When the replacement step S 40  proceeds, the replacement nozzle  422  is moved to the process position to supply the organic solvent onto the substrate W. The rinsing liquid remaining on the substrate W is replaced with an organic solvent. When the replacement step S 40  is completed, a drying step for removing the organic solvent remaining on the substrate W may be further performed. In the drying step, an inert gas may be supplied onto the substrate W, or may be supercritically treated and dried.