Patent Publication Number: US-2016225586-A1

Title: Plasma treating apparatus, substrate treating method, and method of manufacturing a semiconductor device

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This U.S. non-provisional patent application is a divisional application of U.S. patent application Ser. No. 14/693,873, filed Apr. 23, 2015, which claims priority under 35 U.S.C. §119 to Korean Patent Application No. 10-2014-0107130, filed on Aug. 18, 2014, the entire contents of each of which are hereby incorporated by reference. 
    
    
     BACKGROUND 
     The present disclosure herein relates to a plasma treating apparatus and a substrate treating method. 
     Plasma is generated by high temperature, an intense electric field, or an RF electromagnetic field, and includes an ionized gas state comprised of ions, electrons, radicals or the like. In a semiconductor device fabrication process, deposition and etching processes may be performed by using a material in the plasma state. Also, in the semiconductor device fabrication process, an annealing process may be performed by using the material in the plasma state. 
     Like this, the processes using the plasma state material are performed by collisions of particles in an ionized state or a radical state with a substrate. When particles colliding with the substrate have excessively high energy, damage to the substrate may be incurred. 
     SUMMARY 
     The present disclosure provides a plasma treating apparatus and a substrate treating method for efficiently treating a substrate. 
     Embodiments of the inventive concept provide plasma treating apparatuses including: a process chamber having an inner space that is formed therein; a microwave applying unit configured to excite a gas of the inner space into plasma; a first nozzle formed in an inner wall of the process chamber, the first nozzle structured to direct a first process gas toward an upper portion of the inner space; and a second nozzle formed in the inner wall of the process chamber, the second nozzle structured to direct a second process gas toward a lower portion of the inner space. 
     In other embodiments of the inventive concept, substrate treating methods include: disposing a substrate on a platform in a lower portion of an inner space of a process chamber; directing a first process gas upward from a first nozzle formed at an inner wall of the process chamber into an upper portion of the inner space, the first process gas being an inert gas and wherein the first nozzle is an obliquely upward-oriented nozzle structured to direct the first process gas upward; and directing a second process gas downward from a second nozzle formed at an inner wall of the process chamber into a lower portion of the inner space, the second process gas being hydrogen gas and wherein the second nozzle is an obliquely downward-oriented nozzle structured to direct the second process gas downward; and applying a microwave to the upper portion of the inner space to excite the first process gas and the second process gas into plasma, and then treating the substrate. 
     In other embodiments, a method includes: placing a substrate on a platform in an inner space of a process chamber; directing a first process gas upward from an inner wall of the process chamber into an upper portion of the inner space, the first process gas being an inert gas and the inner wall being structured to direct the first process gas obliquely upward; directing a second process gas downward from the inner wall of the process chamber into a lower portion of the inner space where the substrate is located, the second process gas being hydrogen gas and the inner wall being structured to direct the second process gas obliquely downward; applying a microwave to the upper portion of the inner space to excite the first process gas and the second process gas into plasma; and processing the substrate in the plasma environment. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The accompanying drawings are included to provide a further understanding of the inventive concept, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the inventive concept and, together with the description, serve to explain principles of the inventive concept. In the drawings: 
         FIG. 1  is a view illustrating a plasma treating apparatus according to one embodiment of the inventive concept; 
         FIG. 2  is an enlarged view illustrating a gas supply unit in a plasma treating apparatus in  FIG. 1 ; 
         FIG. 3  is a cross-sectional view taken along line A-A′ of  FIG. 2 , according to one embodiment; 
         FIG. 4  is a cross-sectional view taken along line B-B′ of  FIG. 2 , according to one embodiment; 
         FIG. 5  is an enlarged view illustrating a gas supply unit according to another embodiment of the inventive concept; 
         FIG. 6  is a cross-sectional view illustrating a first nozzle in a gas supply unit according to a further embodiment of the inventive concept; 
         FIG. 7  is a cross-sectional view illustrating a second nozzle in a gas supply unit according to one embodiment of the inventive concept; 
         FIG. 8  is a view illustrating an inner surface of a process chamber in which a first spray part and a second spray part are formed, according to one embodiment; 
         FIG. 9  is a side view illustrating a first spray part and a second spray part overlapping each other, according to one embodiment; 
         FIG. 10  is a cross-sectional view illustrating a first nozzle in a gas supply unit according to another embodiment of the inventive concept; 
         FIG. 11  is a cross-sectional view illustrating a second nozzle in a gas supply unit according to one embodiment of the inventive concept; and 
         FIG. 12  is a view illustrating an inner surface of a process chamber in which a first spray part and a second spray part are formed, according to one embodiment. 
     
    
    
     DETAILED DESCRIPTION 
     Hereinafter, embodiments of the inventive concept will be described in detail with reference to accompanying drawings. The invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Like numbers may refer to like elements throughout. 
     These example embodiments are just that—examples—and many implementations and variations are possible that do not require the details provided herein. It should also be emphasized that the disclosure provides details of alternative examples, but such listing of alternatives is not exhaustive. Furthermore, any consistency of detail between various examples should not be interpreted as requiring such detail—it is impracticable to list every possible variation for every feature described herein. The language of the claims should be referenced in determining the requirements of the invention. 
     The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items and may be abbreviated as “/”. 
     It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. Unless indicated otherwise, these terms are only used to distinguish one element from another, for example as a naming convention. For example, a first chip could be termed a second chip, and, similarly, a second chip could be termed a first chip without departing from the teachings of the disclosure. 
     It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof. 
     It will be understood that when an element is referred to as being “connected” or “coupled” to or “on” another element, it can be directly connected or coupled to or on the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between,” “adjacent” versus “directly adjacent,” etc.). However, the term “contact,” as used herein refers to direct contact (i.e., touching) unless the context indicates otherwise. 
     Embodiments described herein will be described referring to plan views and/or cross-sectional views by way of ideal schematic views. Accordingly, the exemplary views may be modified depending on manufacturing technologies and/or tolerances. Therefore, the disclosed embodiments are not limited to those shown in the views, but include modifications in configuration formed on the basis of manufacturing processes. Therefore, regions exemplified in figures may have schematic properties, and shapes of regions shown in figures may exemplify specific shapes of regions of elements to which aspects of the invention are not limited. 
     Spatially relative terms, such as “beneath,” “below,” “lower,” “above,” “upper” and the like, may be used herein for ease of description to describe one element&#39;s or feature&#39;s relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. 
     Terms such as “same,” “planar,” or “coplanar,” as used herein when referring to orientation, layout, location, shapes, sizes, amounts, or other measures do not necessarily mean an exactly identical orientation, layout, location, shape, size, amount, or other measure, but are intended to encompass nearly identical orientation, layout, location, shapes, sizes, amounts, or other measures within acceptable variations that may occur, for example, due to manufacturing processes. The term “substantially” may be used herein to reflect this meaning. 
     Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and/or the present application, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. 
       FIG. 1  is a view illustrating a plasma treating apparatus according to one embodiment of the inventive concept. 
     Referring to  FIG. 1 , a plasma treating apparatus includes a process chamber  100 , a support member  200 , a microwave applying unit  300  and a gas supply unit  400 . 
     The process chamber  100  has an inner space  101  that is formed therein, and the inner space  101  is provided in a space where a substrate W treating process is performed. An opening  110  may be formed on one sidewall of the process chamber  100 . The opening  110  is provided as an entrance through which the substrate W is loaded and unloaded into and from the process chamber  100 . The opening  110  is opened and closed by a door  111 . 
     The support member  200  is disposed, in one embodiment, on a center of a lower portion in the process chamber  100  to support the substrate W. The support member  200 , also referred to herein as a support structure, includes, for example, a susceptor  210  and an electrostatic chuck  220 . The support structure may include a platform or stage on which the substrate W is placed. For example, the chuck  220  may constitute a platform or stage. 
     The susceptor  210  provides a framework for the support member  200 . The susceptor  210  may be provided, for example, in a barrel shape of which an upper surface is flat. The susceptor  210  may be provided as a conductor. In certain embodiments, the susceptor  210  is electrically connected to a radio frequency (RF) power source  211 . For example, a lower surface of the susceptor  210  may be connected to a support rod  212 , and the support rod  212  may be connected to the RF power source  211 . Also, a matching unit  213  may be disposed between the support rod  212  and the RF power source  211 . The support rod  212  is provided as a conductor having a cylinder, a polygonal column or a hollow barrel shape. The RF power source  211  supplies electric energy for controlling energy of ions used in treating the substrate W. The matching unit  213  performs an impedance matching between the RF power source  211  and a load. 
     A sealing member  214  is disposed outside the support rod  212 . The sealing member  214  may be provided, for example, in a barrel shape, and opposite ends thereof may be connected to the process chamber  100  and the matching unit  213 , respectively. 
     The electrostatic chuck  220  may be disposed on an upper surface of the susceptor  210 . The electrostatic chuck  220  may be formed, for example, of an insulating material, and include an electrode  221  therein. The electrode  221  is connected to a power source  223  through an electric wire  222 . When a switch  224  disposed on the electric wire  222  is turned on, and then electric power is applied to the electrode  221 , the substrate W may be adsorbed to the electrostatic chuck  220  by a coulomb force. 
     A focus ring  230  disposed outside the electrostatic chuck  220  in a radial direction thereof, may be provided on an upper surface of the susceptor  210 . An upper surface of the focus ring  230  may be stepped such that an outer portion  231  is higher than an inner portion  232 . In one embodiment, the inner portion  232  of the upper surface of the focus ring  230  is disposed at the same height as an upper surface of the electrostatic chuck  220 . The inner portion  232  of the upper surface of the focus ring  230  supports an edge region of the substrate W, which is disposed outside the electrostatic chuck  220 . The outer portion  231  of the focus ring  230  is provided so as to surround the edge region of the substrate W. 
     A coolant path  216  may be formed in the susceptor  210 . The coolant path  216  is connected to a pipe line so that coolant is circulated through the coolant path  216 . The support member  200  and the substrate W disposed on the support member  200  may be controlled in temperature by coolant circulated through the coolant path  216 . 
     A supply path  226  is formed in the support member  200 , and is connected to an upper surface of the support member  200  The supply path  226  supplies a heat transfer medium between a lower surface of the substrate W and an upper surface of the support member  200 . The heat transfer medium may be, for example helium. 
     The susceptor  210  may be supported by a support part  240  so as to be spaced apart from a bottom of the process chamber  100 . The support part  240  may be formed, for example of an insulator. An auxiliary support part  250  may be provided on an outer circumference of the support part  240 . The auxiliary support part  250  may extend in a barrel shape from the bottom of the process chamber  100  in an upward direction. The auxiliary part  250  may be formed, for example of a conductive material. 
     A discharge path  260  is formed between an inner wall of the process chamber  100  and the auxiliary support part  250 . A baffle plate  261  having a ring shape may be disposed on an upper end or upper portion of the discharge path  260 . 
     At least one discharge hole  262  is formed on a lower portion of a sidewall or lower wall of the process chamber  100 . The discharge hole  262  is connected to a pump  263 . A valve  264  is provided between the discharge hole  262  and the pump  263 . An inside pressure of the process chamber  100  may be reduced to a desired vacuum level through the pump  263 . Also, a reaction by-product generated during a process and a gas remaining in the process chamber  100  may be discharged outside the process chamber  100  through the pump  263 . 
     A microwave applying unit  300  is configured to apply and applies a microwave to an inside of the process chamber  100 . In one embodiment, the microwave applying unit  300  includes a microwave power source  310 , a waveguide  320 , a coaxial converter  330 , an antenna member  340 , a dielectric block  351 , a dielectric plate  370 , and a cooling plate  380 . 
     The microwave power source  310  is configured to generate and generates a microwave. In an example, a microwave generated in the microwave power source  310  may be in a transverse electric mode (TE mode) having a frequency of 2.3 GHz to 2.6 GHz. The waveguide  320  is disposed on one side of the microwave power source  310 . The waveguide  320  is provided in a tube shape of which a cross-section is a polygon or a circle. An inner surface of the waveguide  320  is formed, for example of a conductor. In an example, the inner surface of the waveguide  320  may be formed of gold or silver. The waveguide  320  provides a passage through which a microwave generated in the microwave power source  310  is transferred. 
     The coaxial converter  330  is disposed inside the waveguide  320 . The coaxial converter  330  is disposed on an opposite side of the microwave power source  310 . One end of the coaxial converter  330  is fixed to an inner surface of the waveguide  320 . In one embodiment, the coaxial converter  330  may be provided in a cone shape of which a cross-section area of a lower end is smaller than that of an upper end. A microwave transferred through an inner space  321  of the waveguide  320  is converted in mode in the coaxial converter  330  and is transmitted in a downward direction. In an example, the microwave may be converted from a transverse electric mode (TE mode) to a transverse electromagnetic mode (TEM mode). 
     The antenna member  340  transmits the microwave converted in mode in the coaxial converter  330  in a downward direction. The antenna member  340 , also referred to as an antenna structure, includes an outer conductor  341 , an inner conductor  342 , and an antenna  343 . The outer conductor  341  is disposed on a lower portion of the waveguide  320 . A space  341   a  connected to an inner space of the waveguide  320  is formed inside the outer conductor  341  in a downward direction. 
     The inner conductor  342  is disposed inside the outer conductor  341 . In one embodiment, the inner conductor  342  is provided in a rod having a cylinder shape, and a longitudinal direction thereof is parallel to a vertical direction. An outer circumference of the inner conductor  342  is spaced apart from an inner surface of the outer conductor  341 . 
     An upper end of the inner conductor  342  is fixed (e.g., attached) to a lower end of the coaxial converter  330 . The inner conductor  342  extends in a downward direction, and a lower end thereof is disposed inside the process chamber  100 . The lower end of the inner conductor  342  is fixedly coupled to a center of the antenna  343 . The inner conductor  342  is vertically disposed on an upper surface of the antenna  343 . 
     The antenna  343  is provided in a plate shape. In an example, the antenna may be provided in a thin circular plate. The antenna  343  is disposed so as to be opposed to the susceptor  210 . A plurality of slot holes are formed in the antenna  343 . 
     The dielectric plate  370  is disposed on an upper portion of the antenna  343 . The dielectric plate  370  is formed of a dielectric such as alumina, quartz or the like. A microwave transmitted in a vertical direction from the microwave antenna  343  is transmitted in a radial direction of the dielectric plate  370 . The microwave transmitted to the dielectric plate  370  is compressed in wavelength to be resonated. The resonated microwave is transmitted into the slot holes of the antenna  343 . The microwave passing through the antenna  343  may be converted from the transverse electromagnetic mode (TEM) to a plane wave. 
     A cooling plate  380  is provided on an upper portion of the dielectric plate  370 . The cooling plate  380  cools the dielectric plate  370 . The cooling plate  380  may be formed of an aluminum material. The cooling plate  380  may allow a cooling fluid to flow into a cooling path  381  formed therein to cool the dielectric plate  370 . A cooling type may be a water cooling type or an air cooling type, for example. 
     The dielectric block  351  is provided on a lower portion of the antenna  343 . An upper surface of the dielectric plate  351  may be spaced a predetermined gap from a lower surface of the antenna  343 . Unlike this, the upper surface of the dielectric plate  351  may contact the lower surface of the antenna  343 . The dielectric plate  351  is formed of a dielectric such as alumina, quartz or the like. The microwave passing through the slot holes of the antenna  343  is emitted to an upper space  101   a  via the dielectric block  351 . The microwave has a gigahertz frequency. Therefore, in certain embodiments, the microwave has a low transmittance, so it does not reach a lower space  102 . 
       FIG. 2  is an enlarged view illustrating a gas supply unit in the plasma treating apparatus in  FIG. 1 , according to one exemplary embodiment. 
     Referring to  FIG. 2 , a gas supply unit  400  includes a first gas nozzle  410 , a second gas nozzle  420 , a first supply member  430  and a second supply member  440 . 
     The nozzles  410  and  420  are disposed so as to be embedded in a sidewall of the process chamber  100 . The first nozzle  410  may be disposed on a sidewall of a central portion of the process chamber  100 , which is spaced apart from an upper surface of the support member  200  and a lower surface of the dielectric block  351 . For example, from a vertical perspective, the nozzles  410  and  420  may be located in a sidewall of the process chamber  100  at a central portion vertically between a lower surface of the dielectric block and an upper surface of the support member  200  (e.g., if the vertical space is divided into thirds, the nozzles  410  and  420  can be substantially within the middle third). However, other configurations may be used. In one embodiment, the first nozzle  410  supplies a first process gas to the upper space  101   a  of the inner space. The first process gas may be an inert gas. For example, the first process gas may be one of an argon (Ar) gas, a neon (Ne) gas, a helium (He) gas, a xenon (Xe) gas or the like. Also, the first process gas may be a gas in which at least two gases of the above gases are mixed with each other. 
       FIG. 3  is a cross-sectional view taken along line A-A′ of  FIG. 2 . 
     Referring to  FIGS. 2 and 3 , the first nozzle  410  is formed on the sidewall of the process chamber  100  along a circumferential direction of the process chamber  100 . When an inner wall of the process chamber  100  has a circular shape, the first nozzle  410  is formed in a ring shape on the inner wall of the process chamber  100 . The first nozzle  410  is formed to be inclined upward as going from an outside of the process chamber  100  to an inside. Therefore, the process gas sprayed from the first nozzle  410  is sprayed in a ring shape toward the upper space  101   a  of the process chamber  100 . 
     The first nozzle  410  is connected to the first supply member  430  through a first line  431 . In one embodiment, the first supply member  430  includes a storage tank storing the first process gas. Also, the first supply member  430  may include a mass flow controller (MFC) controlling a flux of the first process gas that is supplied to the first nozzle  410 . A first valve  432  opening and closing the first line  431  may be provided on the first line  431 . An end of the first line  431  connected to the first nozzle  410  may be provided to be inclined upward in the same direction as the first nozzle  410 . 
     In certain embodiments, the first line  431  includes a plurality of outlets, which may also be described as a plurality of lines, around the circumference of the process chamber  100  to evenly release gas through the ring-shaped nozzle  410  into the process chamber  100 . For example, in one embodiment, a first supply member  430  connects through a valve  432  to a first line  431  split into a plurality of lines (e.g., after the valve), to introduce gas into the process chamber  100 . Each of the split lines may be angled as shown, for example, in  FIG. 2 . The first supply member  430  combined with the valve  432  and the first line  431  (e.g., including a plurality of split lines) may be referred to herein as a first gas supply device. 
       FIG. 4  is a cross-sectional view taken along line B-B′ of  FIG. 2 . 
     Referring to  FIGS. 2 and 4 , the second nozzle  420  may be disposed on a sidewall of a central portion of the process chamber  100 , which is spaced apart from an upper surface of the support member  200  and a lower surface of the dielectric block  351 . The second nozzle  420  is disposed above the first nozzle  410 . The second nozzle  420  supplies a second process gas to a lower space  101   b  of the inner space. The second process gas may be, for example, a hydrogen gas. 
     The second nozzle  420  is formed on a sidewall of the process chamber  100  along a circumferential direction of the process chamber  100 . When an inner wall of the process chamber  100  has a circular shape, an end of the second nozzle  420  is formed in a ring shape on the inner wall of the process chamber  100 . 
     The second nozzle  420  is formed to be inclined upward as going from an outside of the process chamber  100  to an inside. Therefore, the second process gas sprayed from the second nozzle  420  intersects with the first process gas to be sprayed in a ring shape toward the lower space  101   b  of the process chamber  100  in which the support member  200  is disposed. 
     The second nozzle  420  is connected to the second supply member  440  through a second line  441 . In one embodiment, the second supply member  440  includes a storage tank storing the second process gas. Also, the second supply member  440  may include a mass flow controller (MFC) controlling a flux of the second process gas that is supplied to the second nozzle  420 . A second valve  442  opening and closing the second line  441  may be provided on the second line  441 . An end of the second line  441  connected to the second nozzle  420  may be provided to be inclined upward in the same direction as the second nozzle  420 . 
     In certain embodiments, the second line  441  includes a plurality of outlets, which may also be described as a plurality of lines, around the circumference of the process chamber  100  to evenly release gas through the ring-shaped nozzle  420  into the process chamber  100 . For example, in one embodiment, a second supply member  440  connects through a valve  442  to a second line  441  split into a plurality of lines (e.g., after the valve), to introduce gas into the process chamber  100 . Each of the split lines may be angled as shown, for example, in  FIG. 2 . The second supply member  440  combined with the valve  442  and the second line  441  (e.g., including a plurality of split lines) may be referred to herein as a second gas supply device. 
     The first and second nozzles  410  and  420  may be formed, for example, as first and second respective openings in the sidewall of the process chamber  100 . In certain embodiments, an additional component may be placed in the openings for spraying the gas, but in either case, a nozzle is formed. However, one benefit of using the sidewall of the process chamber  100  itself as the nozzle instead of using a separate component, is that it simplifies the manufacturing process and can reduce the number of parts that may need maintenance. 
     In certain embodiments, as shown, the openings in the sidewall of the process chamber  100  may have an angled direction with respect to a line perpendicular to the sidewall in a horizontal direction. In certain embodiments, openings in the sidewall of the process chamber  100  are structured such that gas exiting the nozzle is directed in a direction angled with respect to a line perpendicular to the side wall in a horizontal direction. For example, the different nozzles may be configured to either spray gas in an upward direction (with respect to that perpendicular line) or a downward direction. 
     Since certain nozzles are described herein as having a ring shape, those nozzles may be referred to as ring nozzles. For example, each individual ring nozzle shown for example in  FIGS. 3 and 4  extends around the circumference of the process chamber. 
     An annealing process using plasma (e.g., a plasma environment) may be performed with respect to the substrate W for improving roughness. In an example, a transistor may be formed on the substrate W. A channel among elements constituting the transistor accounts for a greatest proportion of total resistance of the transistor. An increase of a scattering on a surface of the substrate W according to roughness generated in treating the substrate W, reduces mobility of carriers. The roughness of the surface of the substrate W may be reduced through an annealing process. 
     The annealing process using plasma may use a gas in a radical state. In an example, when hydrogen in a radical state operates on the surface of the substrate W, mobility of atoms on the surface of the substrate W is increased, so that atoms on a protrusion portion may be moved toward a lower portion. In a state where only a hydrogen gas is introduced into the process chamber  100 , when the hydrogen gas is excited to a plasma state, the plasma state may be in an unstable state. Therefore, an inert gas together with the hydrogen gas is introduced for stability of the plasma state. 
     The inert gas introduced into the process chamber is also excited into an ion or the like. The inert gas has a mass greater than that of hydrogen. Also, the ion into which the inert gas is excited, has straightness. Like this, the ion into which the inert gas is excited, operates on the surface of the substrate W, and on the contrary, the surface of the substrate W may be damaged to worsen an operation property of the transistor included on the substrate W. 
     In the plasma treating apparatus according to an embodiment of the present disclosure, the first process gas that is an inert gas, is supplied to the upper space  101   a  of the process chamber  100 . The first process gas is excited into a plasma state by the microwave applying unit  300 . 
     The first process gas excited into the plasma state, operates on the second process gas located in the lower space  101   b.  The second process gas is excited into the plasma state by the first process gas to then operate on the substrate W. The substrate W is annealed by the second process gas in the plasma state. At this time, the first process gas is prevented from moving toward the lower space by the second process gas, so that an amount of the first process gas moving toward the substrate W disposed on the susceptor  210 , may be minimized. Therefore, the first process gas in the plasma state operates on the substrate W, thereby preventing damage to the substrate W. 
     For example, in one embodiment, hydrogen gas may be injected in an obliquely downward direction toward the substrate, using an obliquely downward-oriented nozzle that directs the hydrogen gas obliquely downward, while inert gas that provides stability for the plasma state is introduced to the chamber in a slantingly upward direction (e.g., obliquely upward) away from the substrate and toward the microwave applying unit  300 , using an obliquely upward-oriented nozzle that directs the inert gas obliquely upward. As a result, the injected inert gas may be separated from the substrate while the hydrogen gas is adjacent to the substrate. 
       FIG. 5  is an enlarged view illustrating a gas supply unit according to another embodiment of the inventive concept. 
     Referring to  FIG. 5 , a plasma supply unit  401  includes a first nozzle  410   a,  a second nozzle  420   a,  a first supply member  430   a  and a second supply member  440   a.    
     The first nozzle  410   a  is disposed above the second nozzle  420   a.    
     Configurations of the first supply member  430   a  and the second supply member  440   a,  and connection relations thereof with the first nozzle  410   a  and the second nozzle  420   a  other than disposition relations of the first nozzle  410   a  and the second nozzle  420   a,  may be provided in the similar or same manner as the gas supply unit  400  of  FIG. 1 . As such, in the embodiment of  FIG. 5 , hydrogen gas and an inert gas may be supplied to the process chamber  100  without crossing each other, such that one gas (e.g., an inert gas) may be supplied from an upper nozzle in an upward direction toward a microwave applying unit, and a second gas (e.g., hydrogen) may be supplied from a lower nozzle in a downward direction toward the substrate. 
       FIG. 6  is a cross-sectional view illustrating a first nozzle in a gas supply unit according to another embodiment of the inventive concept, and  FIG. 7  is a cross-sectional view illustrating a second nozzle in a gas supply unit according to this additional embodiment. 
     Referring to  FIGS. 6 and 7 , a gas supply unit  402  includes a first nozzle  410   b,  a second nozzle  420   b,  a first supply member  430   b  and a second supply member  440   b.    
     Configurations of the first supply member  430   b  and the second supply member  440   b,  and connection relations thereof with the first nozzle  410   b  and the second nozzle  420   b  may be provided in the similar or same manner as the gas supply unit  400  of  FIG. 1 . 
     The first nozzle  410   b  includes a plurality of first spray parts  411 . The first spray parts  411  are provided in a hole shape directed toward an inner wall of the process chamber  100 , and supply a first process gas to an inner space of the process chamber  100 . The first spray parts  411  are formed to be inclined upward as going from an outside of the process chamber  100  to an inside in the similar manner as the first nozzle  410  of  FIG. 2 . The first spray parts  411  may be arranged along a circumferential direction of an inner wall of the process chamber  100 . For example, the first spray parts  411  may form a plurality of repeated openings, rather than a single ring opening as in  FIG. 3 . Each of the repeated openings may be inclined upward in a similar manner as in  FIGS. 2 and 3 . Each individual opening may be referred to herein as a nozzle, or the entire set of repeated openings may be referred to as a nozzle. 
     The second nozzle  420   b  includes a plurality of second spray parts  421 . The second spray parts  421  are provided in a hole shape directed toward an inner wall of the process chamber  100 , and supply a second process gas to an inner space of the process chamber  100 . The second spray parts  421  are formed to be inclined upward as going from an outside of the process chamber  100  to an inside in the similar manner as the second nozzle  420  of  FIG. 2 . The second spray parts  421  may be arranged along a circumferential direction of an inner wall of the process chamber  100 . For example, the second spray parts  421  may form a plurality of repeated openings, rather than a single ring opening as in  FIG. 4 . Each of the repeated openings may be inclined upward in a similar manner as in  FIGS. 2 and 4 . Each individual opening may be referred to herein as a nozzle, or the entire set of repeated openings may be referred to as a nozzle. 
     In addition, a similar structure such as shown in  FIGS. 6 and 7  may be used in an embodiment such as depicted in  FIG. 5 . 
       FIG. 8  is a view illustrating an inner surface of a process chamber in which a first spray part (e.g., nozzle) and a second spray part (e.g., nozzle) are formed, and  FIG. 9  is a side view illustrating a first spray part and a second spray part overlapping each other. 
     Referring to  FIGS. 8 and 9 , the first spray part  411  and the second spray part  421  may be arranged so as not to overlap each other as viewed from above. Therefore, even when a spray direction of the first process gas and a spray direction of the second process gas intersect with each other, a mutual interference phenomenon may be minimized. 
     In the embodiment shown in  FIGS. 8 and 9 , ends (e.g., outlets) of the first spray part  411  and the second spray part  421  may be disposed at the same height on a sidewall of the process chamber  100 . As such, in one embodiment, the outlets for gas to be sprayed in an upward direction alternate with outlets for gas to be sprayed in a downward direction. 
     Also, the first spray part  411  may be disposed under the second spray part  421  in the similar manner as the gas supply unit  400  of  FIG. 2 , such that the outlets are at different levels, but mutual interference is still minimized. 
     Also, the first spray part  411  may be disposed above the second spray part  421  in the similar manner as the gas supply unit  401  of  FIG. 5 . 
       FIG. 10  is a cross-sectional view illustrating a first nozzle in a gas supply unit according to a further embodiment of the inventive concept, and  FIG. 11  is a cross-sectional view illustrating a second nozzle in a gas supply unit according to that embodiment. 
     Referring to  FIGS. 10 and 11 , a gas supply unit includes a first nozzle, a second nozzle, a first supply member and a second supply member. 
     Configurations of the first supply member  430   c  and the second supply member  440   c,  and connection relations thereof with the first nozzle  410   c  and the second nozzle  420   c  may be provided in the similar or same manner as the gas supply unit  400  of  FIG. 1 . 
     The first nozzle  410   c  includes a plurality of first spray parts  413 . The first spray parts  413  are provided in a hole shape directed toward an inner wall of the process chamber  100 , and supply a first process gas to an inner space of the process chamber  100 . The first spray parts  413  are formed to be inclined upward as going from an outside of the process chamber  100  to an inside in the similar manner as the first nozzle  410  of  FIG. 2 . The first spray parts  413  may be arranged along a circumferential direction of an inner wall of the process chamber  100 . Also, the first spray parts  413  may be formed to be inclined with respect to a direction directed toward a center of an inside of the process chamber  100  as viewed from above. This may be referred to as sideways-inclined, or sideways-obliquely oriented. Therefore, the first process gas sprayed from the first spray part  413  may be supplied in a spiral shape to the upper space  101   a  of the process chamber  100 , rather than concentrically toward a center of the process chamber  100 . 
     The second nozzle  420   c  includes a plurality of second spray parts  423 . The second spray parts  423  are provided in a hole shape directed toward an inner wall of the process chamber  100 , and supply a second process gas to an inner space of the process chamber  100 . The second spray parts  423  are formed to be inclined upward as going from an outside of the process chamber  100  to an inside in the similar manner as the second nozzle  420  of  FIG. 2 . The second spray parts  423  may be arranged along a circumferential direction of an inner wall of the process chamber  100 . Also, the first spray parts  423  may be formed to be inclined with respect to a direction directed toward a center of an inside of the process chamber  100  as viewed from above. Therefore, the second process gas sprayed from the second spray part  423  may be supplied in a spiral shape to the lower space  101   b  of the process chamber  100 . A sideways-inclined direction of the second spray part  423  may be formed in the same direction to that of the first spray part  413 . Also, a sideways-inclined direction of the second spray part  423  may be formed in an opposite direction to that of the first spray part  413  as viewed from above. 
       FIG. 12  is a view illustrating an inner surface of a process chamber in which a first spray part and a second spray part are formed. 
     Referring to  FIG. 12 , a first spray part  413  is disposed under the second spray part  423 . In one embodiment, the first spray parts  413  direct sprayed gas upward and the second spray parts  423  direct sprayed gas downward. Also, an end of the first spray part  413  and an end of the second spray part  423  may be arranged so as not to overlap each other vertically. Therefore, even when a spray direction of a first process gas and a spray direction of a second process gas intersect with each other, a mutual interference phenomenon may be minimized. 
     Also, the first spray part  413  may be disposed above the second spray part  423  in the similar manner as the gas supply unit  401  of  FIG. 5 . 
     Further, the first spray part  413  and the second spray part  423  may be arranged such that the end of the first spray and the end of the second spray part  423  are disposed at the same height in the similar manner as the gas supply unit  402  of  FIG. 9 . Further, one or more of the different spray parts  421  and  423  may be sideways-inclined, as discussed in connection with  FIGS. 10 and 11 . 
     While it is described that the support member  200  supports the substrate W as well as the electrostatic chuck  220  in the aforementioned embodiment, unlike this, the support member  200  may support the substrate W in various manners. For example, the substrate support member  200  may provided in a vacuum chuck that vacuum-adsorbs the substrate W and maintains the substrate in the vacuum absorption state. Other variations in the different described features may be used without departing from the spirit and scope of the disclosed embodiments. 
     Also, while it is described that the annealing process is performed by using plasma in the aforementioned embodiment, the substrate treating process is not limited thereto, and may instead be applied to various substrate treating processes, for example, a depositing process, an ashing process, an etching process, a washing process and the like. 
     According to the various embodiments described herein, a substrate may be efficiently treated. 
     In addition, the substrate may be used as part of a semiconductor device. For example, in a method of manufacturing a semiconductor device according to certain embodiments, after providing a substrate in a process chamber  100  and performing one of more of the substrate treating processes described above using one of the nozzle embodiments described above in connection with  FIGS. 2-12  (e.g., for plasma treatment), the substrate may be formed into a semiconductor device such as an integrated circuit on a die (e.g., by performing various fabrication processes and singulating the die from a wafer that forms the substrate). The integrated circuit may form a semiconductor device such as a semiconductor chip, and the semiconductor chip may be packaged into a semiconductor device such as a semiconductor package (e.g., having a single chip on a package substrate, or multiple chips on a package substrate) or a package-on-package device. Also, the substrate may be processed to form a plurality of package substrates that form part of semiconductor devices such as packages. 
     The above detailed description exemplifies the present invention. Further, the above contents only illustrate and describe certain exemplary embodiments of the present invention and the various embodiments can be used under various combinations, changes, and environments. It will be appreciated by those skilled in the art that substitutions, modifications and changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the appended claims and their equivalents. The above-mentioned embodiments are used to describe a best mode in implementing the present invention. The present invention can be implemented in a other modes, however, such as modes not described herein or not described in the art. The detailed description of the present invention does not intend to limit the present invention to the disclosed embodiments.