Patent Publication Number: US-11380537-B2

Title: Method of manufacturing a semiconductor device and a cleaning composition for an adhesive layer

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This U.S. non-provisional patent application is a continuation of and claims priority to U.S. patent application Ser. No. 15/841,946 filed on Dec. 14, 2017, now U.S. Pat. No. 10,332,740, which claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2016-0170557, filed on Dec. 14, 2016, in the Korean Intellectual Property Office, the disclosure of each of these applications being hereby incorporated by reference in its entirety. 
    
    
     BACKGROUND 
     Embodiments of the inventive concepts relate to a method of processing a substrate, a method of cleaning a substrate, and a cleaning composition for an adhesive layer. 
     The number of electrode terminals of a semiconductor device has been increased and a pitch of the electrode terminals has been reduced. Thus, various methods of highly integrating semiconductor devices are being studied. A semiconductor substrate may be processed to reduce a thickness of the semiconductor substrate. However, it may be beneficial to maintain electrical characteristics of the semiconductor substrate during the processing of the semiconductor substrate. 
     SUMMARY 
     Embodiments of the inventive concepts may provide a method of processing a substrate, which is capable of improving a yield, and a cleaning composition used in the same. 
     In an aspect, a method of processing a substrate may include preparing a semiconductor substrate to which an adhesive layer adheres, removing the adhesive layer from the semiconductor substrate, and applying a cleaning composition to the semiconductor substrate to remove a residue of the adhesive layer. The cleaning composition may include a solvent including a ketone compound and having a content that is equal to or greater than 40 wt % and less than 90 wt %, quaternary ammonium salt, and primary amine. 
     In an aspect, a cleaning composition for an adhesive layer may include a solvent including a ketone compound and having a content that is equal to or greater than 40 wt % and less than 90 wt %, quaternary ammonium salt, and primary amine. 
     In an aspect, a method of processing a substrate may include preparing a semiconductor substrate to which an adhesive layer adheres; and applying a cleaning composition to the semiconductor substrate to remove the adhesive layer. The cleaning composition comprises: quaternary ammonium salt; and primary amine. 
     In an aspect, a method of processing a substrate may include providing a semiconductor substrate having a through-via, a pad, and a solder ball, wherein an adhesive layer adheres on a first surface of the semiconductor substrate and the solder ball; providing a cleaning composition on the semiconductor substrate; and removing an adhesive layer from the first surface of the semiconductor substrate and the solder ball with the cleaning composition. The cleaning composition comprises: a polar solvent including a ketone compound and having a content that is equal to or greater than 40 wt % and less than 90 wt %; quaternary ammonium salt; and primary amine. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The inventive concepts will become more apparent in view of the attached drawings and accompanying detailed description. 
         FIGS. 1 to 5, 6A, 7A, and 9  are cross-sectional views illustrating a method of processing a substrate, according to some embodiments of the inventive concepts. 
         FIG. 6B  is an enlarged view of a region ‘A’ of  FIG. 6A . 
         FIG. 7B  is an enlarged view of a region ‘A’ of  FIG. 7A . 
         FIGS. 8A to 8C  are schematic views illustrating a cleaning process according to some embodiments of the inventive concepts. 
         FIG. 10  is a cross-sectional view illustrating a semiconductor device according to some embodiments of the inventive concepts. 
     
    
    
     DETAILED DESCRIPTION 
     The present disclosure now will be described more fully hereinafter with reference to the accompanying drawings, in which various embodiments are shown. The invention may, however, be embodied in many different forms and should not be construed as limited to the example embodiments set forth herein. 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. 
     In the drawings, like numbers refer to like elements throughout. Though the different figures show various features of exemplary embodiments, these figures and their features are not necessarily intended to be mutually exclusive from each other. Rather, certain features depicted and described in a particular figure may also be implemented with embodiment(s) depicted in different figure(s), even if such a combination is not separately illustrated. Referencing such features/figures with different embodiment labels (e.g. “first embodiment”) should not be interpreted as indicating certain features of one embodiment are mutually exclusive of and are not intended to be used with another embodiment. 
     Unless the context indicates otherwise, the terms first, second, third, etc., are used as labels to distinguish one element, component, region, layer or section from another element, component, region, layer or section (that may or may not be similar). Thus, a first element, component, region, layer or section discussed below in one section of the specification (or claim) may be referred to as a second element, component, region, layer or section in another section of the specification (or another claim). 
     It will be understood that when an element is referred to as being “connected,” “coupled to” or “on” another element, it can be directly connected/coupled to/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, or as “contacting” or “in contact with” another element, there are no intervening elements present. 
     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 positional relationship relative to another element(s) or feature(s) as illustrated in the figures. It will be understood that such 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. Thus, a device depicted and/or described herein to have element A below element B, is still deemed to have element A below element B no matter the orientation of the device in the real world. 
     Embodiments may be illustrated herein with idealized views (although relative sizes may be exaggerated for clarity). It will be appreciated that actual implementation may vary from these exemplary views depending on manufacturing technologies and/or tolerances. Therefore, descriptions of certain features using terms such as “same,” “equal,” and geometric descriptions such as “planar,” “coplanar,” “cylindrical,” “square,” etc., as used herein when referring to orientation, layout, location, shapes, sizes, amounts, or other measures, encompass acceptable variations from exact identicality, including nearly identical 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 emphasize this meaning, unless the context or other statements indicate otherwise. 
     Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill consistent with their meaning in the context of the relevant art and/or the present application. 
     Embodiments of the inventive concepts will be described hereinafter in detail. 
       FIGS. 1 to 5, 6A, 7A, and 9  are cross-sectional views illustrating a method of processing a substrate, according to some embodiments of the inventive concepts.  FIG. 6B  is an enlarged view of a region ‘A’ of  FIG. 6A .  FIG. 7B  is an enlarged view of a region ‘A’ of  FIG. 7A . 
     Referring to  FIG. 1 , a semiconductor substrate  100  may be provided. The semiconductor substrate  100  may have a first surface  100   a  and a second surface  100   b  which are opposite to each other. For example, the semiconductor substrate  100  may include silicon or germanium. The semiconductor substrate  100  may be a wafer-level substrate. The semiconductor substrate  100  may include a plurality of semiconductor chips  101 . For example, in a later process, the semiconductor substrate  100  may be divided into a plurality of semiconductor chips  101  as shown in  FIG. 9 . 
     The semiconductor substrate  100  may include a circuit layer  110 , solder balls  120 , pads  130 , and through-vias  140 . The circuit layer  110  may be provided on the first surface  100   a  of the semiconductor substrate  100 . The circuit layer  110  may include an integrated circuit. For example, the circuit layer  110  may include a memory circuit, a logic circuit, or a combination thereof. The through-vias  140  may penetrate at least a portion of the semiconductor substrate  100  from the first surface  100   a  of the semiconductor substrate  100 . In some embodiments, the through-vias  140  may be spaced apart from the second surface  100   b  of the semiconductor substrate  100 . 
     The solder balls  120  may be provided on the first surface  100   a  of the semiconductor substrate  100 . The solder balls  120  may be electrically connected to the through-vias  140  and/or the integrated circuit of the circuit layer  110 . The solder balls  120  may include tin, silver, copper, or any alloy thereof. The pads  130  may be disposed between the solder balls  120  and the through-vias  140 , respectively. The pads  130  may include a metal such as copper or aluminum. 
     The semiconductor substrate  100  may be provided on a carrier substrate  300 . At this time, the first surface  100   a  of the semiconductor substrate  100  may face the carrier substrate  300 . The carrier substrate  300  may include glass. Alternatively, the carrier substrate  300  may include silicon. An adhesive layer  200  may be provided between the semiconductor substrate  100  and the carrier substrate  300 . The adhesive layer  200  may cover the first surface  100   a  of the semiconductor substrate  100  and the solder balls  120 . The semiconductor substrate  100  may be adhered to the carrier substrate  300  by the adhesive layer  200 . The adhesive layer  200  may include a hardened insulating resin. For example, the adhesive layer  200  may be hardened after the adhesive layer  200  is disposed between the semiconductor substrate  100  and the carrier substrate  300 . For example, the adhesive layer  200  may be disposed on either the semiconductor substrate  100  or the carrier substrate  300 , and then the other substrate may be disposed on the adhesive layer  200  before hardening the adhesive layer  200 . The adhesive layer  200  may include a compound having a carbonyl group. For example, the adhesive layer  200  may include acrylic polymer. Unlike  FIG. 1 , the adhesive layer  200  may include a plurality of layers. In this case, the plurality of layers may include the closest layer to the semiconductor substrate  100 , and the closest layer may include acrylic polymer. 
     Referring to  FIG. 2 , a portion of the semiconductor substrate  100  may be removed to thin the semiconductor substrate  100 . The process of thinning the semiconductor substrate  100  may include a polishing process, a grinding process or an etching process, which is performed on the second surface  100   b  of the semiconductor substrate  100 . The polishing process may include a chemical mechanical polishing (CMP) process. The thinning process of the semiconductor substrate  100  may expose the through-vias  140  at the second surface  100   b  of the semiconductor substrate  100 . A conductive pad  150  may be formed on the second surface  100   b  of the semiconductor substrate  100  so as to be connected to a through-via  140 . When the semiconductor substrate  100  is processed, the thinned semiconductor substrate  100  may be easily handled by the carrier substrate  300 . For example, the carrier substrate  300  may inhibit the semiconductor substrate  100  from being damaged by an external impact. For example, the carrier substrate  300  may protect the semiconductor substrate  100  from damage so that the carrier substrate  300  may help processing the semiconductor substrate  100  in the following steps of process or manufacture. 
     Referring to  FIG. 3 , a crack  250  may be formed in the adhesive layer  200 . The crack  250  may be formed to remove the adhesive layer  200  in a subsequent process which will be described below with reference to  FIG. 5 . In some embodiments, light  400  may be irradiated to the adhesive layer  200  to form the crack  250 . The light  400  may include ultraviolet. In certain embodiments, a physical impact may be applied to the adhesive layer  200  to form the crack  250 . For example, in certain embodiments, a physical impact and/or a light energy (e.g., laser) may be applied to the adhesive layer  200  to form a crack  250  and/or to separate the semiconductor substrate  100  and the carrier substrate  300  from each other. 
     Referring to  FIG. 4 , the carrier substrate  300  may be removed from the semiconductor substrate  100  and/or the adhesive layer  200 . For example, the carrier substrate  300  may be removed from the semiconductor substrate  100  and/or the adhesive layer  200  by a physical method, e.g., by a physical force. When the carrier substrate  300  is removed from the adhesive layer  200 , the crack  250  may further propagate in the adhesive layer  200 . For example, the crack  250  may propagate between the adhesive layer  200  and the carrier substrate  300 . 
     Referring to  FIG. 5 , the adhesive layer  200  may be removed from the semiconductor substrate  100 . The adhesive layer  200  may be removed from the semiconductor substrate  100  by a physical method, e.g., by a physical force. For example, a rolling tape  500  may be provided on the adhesive layer  200 . The adhesive layer  200  may be adhered to the rolling tape  500 . Due to the crack  250 , an adhesive strength between the adhesive layer  200  and the rolling tape  500  may be stronger than an adhesive strength between the adhesive layer  200  and the semiconductor substrate  100 . The rolling tape  500  may horizontally move, e.g., on the adhesive layer  200 . The rolling tape  500  may move to separate the adhesive layer  200  from the semiconductor substrate  100 . 
     Referring to  FIGS. 6A and 6B , a portion of the adhesive layer  200  may remain on the semiconductor substrate  100  and the solder balls  120  to form a residue  201 . For example, the residue  201  may leave on the first surface  100   a  of the semiconductor substrate  100  and the solder balls  120 . The residue  201  may include the same material as the adhesive layer  200 . 
     Referring to  FIGS. 7A and 7B , a cleaning process may be performed on the semiconductor substrate  100  to remove the residue  201 . In the cleaning process, a cleaning composition may be provided on the first surface  100   a  of the semiconductor substrate  100 . The cleaning composition may include a solvent, quaternary ammonium salt, and primary amine. 
     For example, the quaternary ammonium salt may include tetramethylammonium phosphate, tetramethylammonium chloride, tetramethylammonium nitrate, dicyclohexylamine nitride, dicyclohexylammonium nitride, or any combination thereof. The primary amine may include 2-aminoethanol, benzylamine, ethylene diamine, butyldiethanolamine, butylamine, cyclohexylamine, methylamine hydrochloride, 2-aminoethyl dihydrogen phosphate, methoxyamine hydrochloride, 2-aminoethyl hydrogen sulfate, 3-chloroproplyamine hydrochloride, or any combination thereof. 
     The cleaning composition according to some embodiments and the cleaning process using the same will be described hereinafter in more detail. 
       FIGS. 8A to 8C  are enlarged views of the residue to illustrate the cleaning process according to some embodiments of the inventive concepts. The descriptions of the same features as the ones mentioned above will be omitted for the purpose of ease and convenience of explanation. The cleaning process will be described with reference to  FIGS. 6A, 6B, 7A, and 7B  as well as  FIGS. 8A to 8C . 
     Referring to  FIG. 8A , the residue  201  may include an insulating resin. For example, the residue  201  may include acrylic polymer. The residue  201  may have a chain or net structure. 
     Referring to  FIG. 8B , the cleaning composition may be provided on the residue  201 . As described above, the cleaning composition may include the solvent, the quaternary ammonium salt, and the primary amine. The solvent may have polarity. The solvent may permeate into the residue  201 , and thus the residue  201  may swell. A content of the solvent in the cleaning composition may be equal to or greater than 40 wt % and less than 90 wt %. If the content of the solvent in the cleaning composition is less than 40 wt %, the residue  201  may not sufficiently swell. The solvent may include a ketone compound. For example, the ketone compound may include acetone, diacetonealcohol, acetophenone, cyclohexanone, methylethylketone, butylethylketone, heptylmethylketone, hexylmethylketone, or any combination thereof. The solvent may further include an acetate-based compound. The ketone compound and the acetate-based compound may have polarities. The acetate-based compound may include alkyl acetate or vinyl acetate. For example, the acetate-based compound may include at least one of methyl acetate, butyl acetate, ethyl acetate, pentyl acetate, octyl acetate, amyl acetate, heptyl acetate, n-decyl acetate, dodecyl acetate, pentin acetate, isobutyl acetate, vinyl acetate, isopropyl acetate, or ethylhexyl acetate. The acetate-based compound may not have toxicity. 
     The cleaning composition may further include an inorganic acid. The inorganic acid may include phosphoric acid, nitric acid, hydrofluoric acid, hydrochloric acid, iodic acid, bromic acid, acetic acid, perchloric acid, silicic acid, boric acid, fluoroboric acid, hexafluorophosphoric acid, or any combination thereof. The inorganic acid may adjust a pH of the cleaning composition. For example, the pH of the cleaning composition may be adjusted by adjusting a content of the inorganic acid. For example, the inorganic acid may have a content of 15 wt % or less in the cleaning composition. For example, the content of the inorganic acid in the cleaning composition may range from 1 wt % to 15 wt %. For example, the content of the inorganic acid in the cleaning composition may be greater than 2 wt % and equal to or less than 15 wt %. The pH of the cleaning composition may range from 7 to 8. The solder balls  120  and/or the pads  130  may be damaged by an alkaline or acidic solution. However, according to some embodiments of the inventive concepts, the pH of the cleaning composition may be adjusted to prevent or inhibit the solder balls  120  and/or the pads  130  (in  FIGS. 6A and 6B ) from being damaged. For example, a semiconductor manufacturing apparatus (not shown) may be damaged (e.g., corroded) by an alkaline solution. In this case, the pH of the cleaning composition may be adjusted to prevent or inhibit the semiconductor manufacturing apparatus from being damaged. 
     The cleaning composition may further include a hydroxy-benzene-based compound. The hydroxy-benzene-based compound may prevent or inhibit the solder balls  120  and/or the pads  130  from corroding during the cleaning process. The hydroxy-benzene-based compound may include at least one of phenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-aminophenol, 2-fluorophenol, 4-aminophenol, 4-amino-2-nitrophenol, 2,4-dinitrophenol, 4-hydroxybenzenesulfonic acid, catechol, hydroquinone, pyrogallol, gallic acid, methylgallate, ethylgallate, n-propylgallate, or n-butylgallate. A content of the hydroxy-benzene-based compound may range 0.1 wt % to 20 wt % of the cleaning composition. 
     The cleaning composition may further include an amine compound. The amine compound may be different from the quaternary ammonium salt and the primary amine. For example, the amine compound may include 1,6-hexanediamine, triethanolamine, triethylamine, diisopropyl amine, trimethylamine hydrochloride, or any combination thereof. 
     In certain embodiments, the cleaning composition may not include at least one of the acetate-based compound, the inorganic acid, the hydroxy-benzene-based compound, or the amine compound. 
     Referring to  FIG. 8C , the quaternary ammonium salt  601  and the primary amine  602  may be provided into the residue  201 . The quaternary ammonium salt  601  and the primary amine  602  may function as a remover of the residue  201 . The residue  201  may react with the quaternary ammonium salt  601  and the primary amine  602  as the following chemical formula 1, and thus the residue  201  may be decomposed into imine. 
     
       
         
         
             
             
         
       
     
     In the chemical formula 1, each of “R 1 ”, “R 2 ”, “R 3 ”, “R 4 ”, “R 5 ”, and “R 6 ” may be independently selected from a group consisting of an alkyl group, an alkene group, an alkyne group, and an aromatic group. “A − ” may be a negative ion. For example, A −  may be an anion present in the quaternary ammonium salt  601 . For example, the quaternary ammonium salt  601  may include an ionic bond between a quaternary ammonium cation and an anion A − . 
     The residue  201  may swell, and thus the quaternary ammonium salt  601  and the primary amine  602  may easily and quickly react with the residue  201 . A sum of a content of the quaternary ammonium salt  601  and a content of the primary amine  602  may range 1 wt % to 30 wt % in the cleaning composition. If the sum of the contents of the quaternary ammonium salt  601  and the primary amine  602  is less than 1 wt %, the residue  201  may not be removed well. If the sum of the contents of the quaternary ammonium salt  601  and the primary amine  602  is greater than 30 wt %, the content of the solvent may be reduced. A weight ratio of the quaternary ammonium salt  601 :the primary amine  602  may range from 3:1 to 1:3. 
     Since the solvent has polarity, the decomposed residue (e.g., imine) may be dissolved in the solvent. The decomposed residue may be exhausted to the outside through the solvent. For example, the decomposed residue may be removed from the semiconductor substrate  100  into the solvent. If the content of the solvent is less than 40 wt % in the cleaning composition, the decomposed residue may not be exhausted to the outside but may be re-adsorbed on the semiconductor substrate  100 . For example, some of the decomposed residue may be re-attached on the semiconductor substrate  100  when the content of the solvent is not enough. If the content of the solvent is equal to or greater than 90 wt % in the cleaning composition, the contents of the quaternary ammonium salt  601  and the primary amine  602  may be reduced. 
     Referring again to  FIGS. 7A and 7B , the residue  201  of  FIGS. 6A and 8C  may be removed by the cleaning process. At this time, the solder balls  120  may not be damaged (e.g., corroded) by the cleaning composition. 
     Referring to  FIG. 9 , the semiconductor substrate  100  may be sawed to separate the plurality of semiconductor chips  101  from each other. The sawing process may be performed along a scribe lane (not shown) of the semiconductor substrate  100 . 
       FIG. 10  is a cross-sectional view illustrating a semiconductor device according to some embodiments of the inventive concepts. Hereinafter, the descriptions of the same technical features as the ones mentioned above will be omitted or mentioned briefly for the purpose of ease and convenience of explanation. 
     Referring to  FIG. 10 , a semiconductor device  1  may include a package substrate  700 , a first semiconductor chip  102 , a second semiconductor chip  103 , a third semiconductor chip  104 , and a molding layer  800 . The first semiconductor chip  102  and the second semiconductor chip  103  may be manufactured as described with reference to  FIGS. 1 to 9 . In some embodiments, the package substrate  700  may include a printed circuit board (PCB) or a semiconductor chip. A solder  710  may be provided on a top surface of the package substrate  700 . An external terminal  720  may be provided on a bottom surface of the package substrate  700 . 
     The first semiconductor chip  102  may be mounted on the package substrate  700 . The first semiconductor chip  102  may include a first circuit layer  112 , a first solder ball  122 , a first pad  132 , a first through-via  142 , and a first conductive pad  152 . The first circuit layer  112 , the first solder ball  122 , the first pad  132 , the first through-via  142 , and the first conductive pad  152  may be the same as the circuit layer  110 , the solder ball  120 , the pad  130 , the through-via  140 , and the conductive pad  150  described with reference to  FIGS. 1 to 9 , respectively. The first semiconductor chip  102  may be disposed on the package substrate  700  in such a way that the first solder ball  122  is aligned with the solder  710 . A reflow process may be performed on the first solder ball  122  and the solder  710  to form a connection terminal  750 . The connection terminal  750  may electrically connect the package substrate  700  and the first semiconductor chip  102  to each other. If the residue  201  remains on the first solder ball  122 , electrical characteristics of the connection terminal  750  may be deteriorated. However, according to embodiments of the inventive concepts, the residue  201  may be removed by the cleaning process described with reference to  FIGS. 8A to 8C , and thus the first semiconductor chip  102  may be stably electrically connected to the package substrate  700 . Since the first solder ball  122  is not damaged in the cleaning process, electrical characteristics of the semiconductor device  1  may be improved. In addition, a manufacture yield of the semiconductor device  1  may be improved. 
     The second semiconductor chip  103  may include a second circuit layer  113 , a second solder ball  123 , a second pad  133 , a second through-via  143 , and a second conductive pad  153 . The second circuit layer  113 , the second solder ball  123 , the second pad  133 , the second through-via  143 , and the second conductive pad  153  may be the same as the circuit layer  110 , the solder ball  120 , the pad  130 , the through-via  140 , and the conductive pad  150  described with reference to  FIGS. 2 to 9 , respectively. The second semiconductor chip  103  may be electrically connected to the first semiconductor chip  102  through the second solder ball  123  and the first conductive pad  152 . In certain embodiments, an additional connection solder (not shown) may be formed between the second solder ball  123  and the first conductive pad  152 , and a reflow process may be performed on the second solder ball  123  and/or the additional connection solder. The third semiconductor chip  104  may be mounted on the second semiconductor chip  103 . The third semiconductor chip  104  may include a third circuit layer  114  but may not include a through-via. In certain embodiments, the third semiconductor chip  104  may include a through-via. 
     Hereinafter, the method of cleaning a substrate using the cleaning composition will be described with reference to experimental examples of the inventive concepts and comparative examples. 
     Manufacture of Cleaning Composition and Cleaning of Substrate 
     Comparative Examples 
     Cleaning compositions represented in the following tables 1 and 2 were manufactured. An adhesive layer was adhered to a semiconductor substrate. At this time, an acrylic polymer adhesive tape was used as the adhesive layer. The adhesive layer was removed from the semiconductor substrate. Each of the cleaning compositions was provided to the semiconductor substrate, and the semiconductor substrate was left at an environment of a temperature of 25 degrees Celsius to 50 degrees Celsius for a time of 1 minute to 30 minutes. Thereafter, the semiconductor substrate was cleaned using isopropyl alcohol and deionized water for 1 minute to remove a residue. A nitrogen gas was supplied to the semiconductor substrate to dry the semiconductor substrate. A removal rate of the residue was measured. 
     
       
         
           
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                 Removal 
               
            
           
           
               
               
               
            
               
                   
                 Kind and Content (wt %) of Cleaning composition 
                 rate of 
               
            
           
           
               
               
               
               
            
               
                 Comparative 
                 Solvent 
                 Remover 
                 Residue 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 example 
                 DMSO 
                 EDG 
                 NMP 
                 BDG 
                 TMAH 
                 HDZ 
                 HDA 
                 (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 85 
                   
                   
                 5 
                 1.25 
                   
                 2.5 
                 10 
               
               
                 2 
                 40 
                   
                   
                 50 
                 1.25 
                   
                 2.5 
                 8 
               
               
                 3 
                   
                 20 
                   
                   
                   
                 2.4 
                 12 
                 15 
               
               
                 4 
                   
                 20 
                   
                   
                   
                 12 
                 24 
                 21 
               
               
                 5 
                   
                   
                 3 
                 20 
                 6 
                   
                 2.4 
                 13 
               
               
                 6 
                   
                   
                 3 
                 70 
                 6 
                   
                 2.4 
                 20 
               
               
                   
               
               
                 DMSO: Dimethyl sulfoxide 
               
               
                 EDG: Ethyl diglycol 
               
               
                 NMP: N-methylpyrrolidone 
               
               
                 BDG: Butyl di glycol 
               
               
                 TMAH: Tetramethylammonium hydroxide 
               
               
                 HDZ: Hydrazine 
               
               
                 HDA: Hydroxyl amine 
               
            
           
         
       
     
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2 
               
             
            
               
                   
                   
               
               
                   
                 Kind and Content (wt %) of Cleaning composition 
                   
               
            
           
           
               
               
               
            
               
                   
                 Remover 
                 Removal 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Solvent 
                   
                 Quaternary 
                   
                 rate of 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Comparative 
                 Ketone 
                 Acetate 
                 Hydroxy-benzene-based compound 
                 Inorganic 
                 Amine 
                 ammonium 
                 Primary 
                 Residue 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 example 
                 compound 
                 compound 
                 A 
                 B 
                 C 
                 acid 
                 compound 
                 salt 
                 amine 
                 (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 7 
                 53 
                 24 
                 — 
                 6 
                 — 
                 10 
                 — 
                 7 
                 — 
                 30 
               
               
                 8 
                 46 
                 24 
                 — 
                 6 
                 — 
                 10 
                 — 
                 14 
                 — 
                 55 
               
               
                 9 
                 53 
                 24 
                 — 
                 6 
                 — 
                 10 
                 — 
                 — 
                 7 
                 45 
               
               
                 10 
                 46 
                 24 
                 — 
                 6 
                 — 
                 10 
                 — 
                 — 
                 14 
                 70 
               
               
                 11 
                 68 
                 24 
                 — 
                 6 
                 — 
                 1 
                 — 
                 0.5 
                 0.5 
                 35 
               
               
                 12 
                 66 
                 24 
                 — 
                 6 
                 — 
                 2 
                 — 
                 1 
                 1 
                 40 
               
               
                 13 
                 6 
                 24 
                 — 
                 6 
                 — 
                 30 
                 — 
                 17 
                 17 
                 60 
               
               
                 14 
                 20 
                 24 
                 — 
                 6 
                   
                 10 
                   
                 20 
                 20 
                 60 
               
               
                 15 
                 — 
                 86 
                 2 
                   
                 — 
                 — 
                 12 
                 — 
                   
                 90 
               
               
                   
               
               
                 Ketone compound: Methyl ethyl ketone 
               
               
                 Acetate-based compound: Isopropyl acetate 
               
               
                 Hydroxy-benzene-based compound A: Propyl gallate 
               
               
                 Hydroxy-benzene-based compound B: Methyl gallate 
               
               
                 Hydroxy-benzene-based compound C: Catechol 
               
               
                 Inorganic acid: phosphoric acid 
               
               
                 Amine compound: Ethylenediamine 
               
               
                 Quaternary ammonium salt: Tetramethylammonium hydroxide 
               
               
                 Primary amine: 2-Aminoethanol 
               
            
           
         
       
     
     Experimental Examples 
     An adhesive layer was formed and removed by the same methods as the comparative examples. Thereafter, a residue was removed using a cleaning composition, and a removal rate of the residue was measured. However, in the experimental examples, cleaning compositions represented in the following table 3 were used. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 3 
               
             
            
               
                   
                   
               
               
                   
                 Kind and Content (wt %) of Cleaning composition 
                   
               
            
           
           
               
               
               
            
               
                   
                 Remover 
                 Removal 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Solvent 
                   
                 Quaternary 
                   
                 rate of 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Experimental 
                 Ketone 
                 Acetate 
                 Hydroxy-benzene-based compound 
                 Inorganic 
                 Amine 
                 ammonium 
                 Primary 
                 Residue 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 example 
                 compound 
                 compound 
                 A 
                 B 
                 C 
                 acid 
                 compound 
                 salt 
                 amine 
                 (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 50 
                 24 
                 2 
                 — 
                   
                 10 
                 — 
                 7 
                 7 
                 70 
               
               
                 2 
                 48 
                 24 
                 — 
                 4 
                 — 
                 10 
                 — 
                 7 
                 7 
                 80 
               
               
                 3 
                 46 
                 24 
                 — 
                 6 
                 — 
                 10 
                 — 
                 7 
                 7 
                 90 
               
               
                 4 
                 33 
                 24 
                 — 
                 6 
                   
                 10 
                   
                 13.5 
                 13.5 
                 80 
               
               
                 5 
                 46 
                 24 
                 — 
                 6 
                 — 
                 10 
                 — 
                 3.5 
                 10.5 
                 75 
               
               
                 6 
                 46 
                 24 
                 — 
                 6 
                   
                 10 
                   
                 10.5 
                 3.5 
                 80 
               
               
                 7 
                 64 
                 24 
                 — 
                 — 
                 6 
                 2.5 
                   
                 1.25 
                 1.25 
                 65 
               
               
                 8 
                 58 
                 24 
                 — 
                 — 
                 6 
                 5 
                   
                 3.50 
                 3.50 
                 75 
               
               
                 9 
                 16 
                 24 
                 — 
                 — 
                   
                 25 
                   
                 14.5 
                 14.5 
                 70 
               
               
                   
               
               
                 Ketone compound: Methyl ethyl ketone 
               
               
                 Acetate-based compound: Isopropyl acetate 
               
               
                 Hydroxy-benzene-based compound A: Propyl gallate 
               
               
                 Hydroxy-benzene-based compound B: Methyl gallate 
               
               
                 Hydroxy-benzene-based compound C: Catechol 
               
               
                 Inorganic acid: phosphoric acid 
               
               
                 Amine compound: Ethylenediamine 
               
               
                 Quaternary ammonium salt: Tetramethylammonium hydroxide 
               
               
                 Primary amine: 2-Aminoethanol 
               
            
           
         
       
     
     Referring to the tables 1 to 3 and  FIGS. 6A, 6B, 7A, and 7B , the removal rates of the residues  201  of the experimental examples are higher than the removal rates of the residues  201  of the comparative examples. The cleaning compositions of the comparative examples 1 to 6 includes dimethyl sulfoxide (DMSO), ethyl diglycol (EDG), N-methylpyrrolidone (NMP), and/or butyl di glycol (BDG) as solvents. However, the cleaning compositions of the experimental examples includes ketone compounds and acetate compounds as solvents, and thus the removal rates of the residues  201  of the experimental examples were improved. 
     The cleaning compositions of the comparative examples 7 to 10 does not include one of quaternary ammonium salt and primary amine. However, each of the cleaning compositions of the experimental examples includes the quaternary ammonium salt and the primary amine, and thus the removal rates of the residue  201  were improved. 
     In the comparative examples 11 and 12, contents of the solvents were 90 wt % or greater in the cleaning compositions. When the content of the solvent is equal to or greater than 90 wt % in the cleaning composition, a content of the remover may be reduced, e.g., less than 10 wt %. However, the contents of the solvents were less than 90 wt % in the cleaning compositions of the experimental examples, and thus the removal rates of the residue  201  were improved. For example, for a better residue removal, it is beneficial that the solvent contents of the cleaning composition may be less than 90 wt % of the whole composition. 
     In the comparative examples 13 and 14, contents of removers were greater than 30 wt % in the cleaning compositions. Here, the remover includes the quaternary ammonium salt and the primary amine. However, contents of the removers were equal to or less than 30 wt % in the cleaning compositions of the experimental examples. Thus, the removal rates of the residue  201  were improved. 
     In the comparative example 13, a content of the solvent was less than 40 wt % in the cleaning composition. If the content of the solvent is less than 40 wt % in the cleaning composition, the residue may not sufficiently swell or the decomposed residue may be re-adsorbed on the semiconductor substrate  100 . However, since the contents of the solvents are equal to or greater than 40 wt % in the cleaning compositions of the experimental examples, the removal rates of the residue  201  may be improved. 
     The comparative example 15 showed a relatively high removal rate of the residue  201 . However, a semiconductor manufacturing apparatus was damaged by the cleaning composition of the comparative example 15. The cleaning composition of the comparative example 15 did not include the inorganic acid, and thus the cleaning composition of the comparative example 15 showed alkalinity. For example, a pH of the cleaning composition of the comparative example 15 was greater than 8. However, the cleaning compositions of the experimental examples included the inorganic acids, and thus each of the cleaning compositions of the experimental examples had a pH of 7 to 8. In the experimental examples, the semiconductor manufacturing apparatus was not damaged. For example, when the cleaning compositions of the experimental examples include inorganic acids, the semiconductor manufacturing apparatus may not be damaged. 
     The removal rates of the residues  201  of the comparative examples 7 to 15 are higher than the removal rates of the residues  201  of the comparative examples 1 to 6. The solvents of the comparative examples 7 to 15 include the ketone compound and/or the acetate compound. Thus, the removal rates of the comparative examples 7 to 15 may be higher than the removal rates of the comparative examples 1 to 6. For example, a cleaning composition including ketone compound and/or acetate compound may have higher removal rate of residue  201 . 
     Cleaning compositions according to embodiments of the inventive concepts may have high removal rates with respect to the residue of the adhesive layer. The cleaning compositions may quickly remove the residue of the adhesive layer. The cleaning compositions may not damage the solder ball and/or the pad of the semiconductor substrate. Thus, a processing yield of the semiconductor substrate may be improved. 
     While the inventive concepts have been described with reference to example embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirits and scopes of the inventive concepts. Therefore, it should be understood that the above embodiments are not limiting, but illustrative. Thus, the scopes of the inventive concepts are to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing descriptions.