Abstract:
The method of polishing a copper layer of a substrate is capable of improving a stock removal rate, etc. The method comprises the steps of: supplying a substrate onto an polishing pad of an polishing plate with a copper layer facing the polishing pad; pressing the substrate onto the polishing pad, with a backing pad, by a press head; relatively rotating the press head with respect to the polishing plate, with supplying polishing slurry onto the polishing pad. The backing pad is made of a material whose Asker C hardness is 75-95 and whose compressibility is 10% or less. The polishing slurry includes a chelating agent for chelating copper, an etching agent for etching the surface of copper layer, an oxidizing agent for oxidizing the surface of copper layer, and water.

Description:
BACKGROUND OF THE INVENTION  
         [0001]    The present invention relates to a method of polishing a copper layer of a substrate, e.g., a build-up substrate, a semiconductor wafer.  
           [0002]    Some multi-layered circuit boards, on which electronic parts, e.g., semiconductor chips, etc. will be mounted, are made by a build-up method.  
           [0003]    The build-up method will be explained.  
           [0004]    Firstly, as shown in FIG. 9, an insulating resin layer  12  is formed on lower cable patterns  11 , then via-holes  13  are formed so as to expose a part of each lower cable pattern  11 .  
           [0005]    Next, as shown in FIG. 10, a copper layer  14  is formed in the via-holes  13  and a surface of the insulating resin layer  12  by non-electrolytic plating and electrolytic plating. In some cases, the copper layer  14  fills an inner space of each via-hole  13 . The copper layer  14  formed by plating is apt to be thick in the vicinity of edges of the insulating resin layer  12 . Therefore, parts of the copper layer  14  corresponding to the via-holes  13  are projected upward, so that flatness of the surface of the copper layer  14  must be low.  
           [0006]    To make the surface of the copper layer  14  flat, firstly the surface of the copper layer  14  is removed by a roll-buff. Then, the copper layer  14  is etched to form into prescribed cable patterns (upper cable patterns). With this method, the upper cable patterns are electrically connected to the lower cable patterns  11 . This method will be repeated prescribed times to form the multi-layered circuit board.  
           [0007]    In the case of forming circuits on a semiconductor wafer, connecting terminals, e.g., copper bumps, are formed in the wafer after the circuits are formed therein. The copper bumps are formed by the steps of: forming a resist mask having opening sections, which correspond to the copper bumps, on the wafer; plating parts of circuit sections exposed in the opening sections with copper; and removing the resist mask. With this method, the copper bumps can be projected from the surface of the wafer. Note that, the wafer hiving the copper bumps will be cut and divided into a plurality of semiconductor chips. Each of the semiconductor chips will be electrically connected to a circuit board by the copper bumps as terminals.  
           [0008]    In some cases, copper bumps are formed in a circuit board so as to electrically connect a semiconductor chip(s) to the circuit board.  
           [0009]    However, the above described conventional methods have following disadvantages.  
           [0010]    The roll-buff is made of hard abrasive grains, which are bound by binders and formed into a cylindrical shape. The roll-buff is rolled on the surface of the copper layer so as to remove the projected parts of the copper layer. The projections can be removed by the roll-buff, but waviness in a wide area cannot be removed by the roll-buff, so that it is difficult to form the copper layer having uniform thickness. Further, the surface of the copper layer is scratched by the roll-buff, so that reliability of an electric element must be lower.  
           [0011]    On the other hand, height of the copper bumps must be equal so as to securely connect the copper bumps. It is effect to remove the copper bumps to make their height equal, but there are no effective methods.  
         SUMMARY OF THE INVENTION  
         [0012]    The present invention has invented to solve the problems of the conventional methods.  
           [0013]    An object of the present invention is to provide a method of polishing a copper layer of a substrate, which is capable of improving an stock removal rate, forming a copper layer having uniform thickness, restricting scratches on a surface of the copper layer, and forming copper bumps having equal height.  
           [0014]    Namely, the method of the present invention comprises the steps of:  
           [0015]    supplying a substrate having a copper layer onto an polishing pad on a polishing plate with the copper layer facing the polishing pad;  
           [0016]    pressing the substrate onto the polishing pad, with a backing pad, by a press head;  
           [0017]    relatively rotating the press head with respect to the polishing plate, with supplying polishing slurry onto the polishing pad, so as to polish the copper layer,  
           [0018]    wherein the backing pad is made of a material whose Asker C hardness is 75-95 and whose compressibility is 10% or less,  
           [0019]    and the polishing slurry includes a chelating agent for chelating copper, an etching agent for etching the surface of copper layer, an oxidizing agent for oxidizing the surface of copper layer, and water.  
           [0020]    Copper bumps formed in the substrate can be effectively removed by the invention. Step height of the copper bumps can be reduced effectively, and the surface of the substrate can be uniformly polished.  
           [0021]    Further, a copper layer formed in a build-up substrate can be effectively polished by the invention, too.  
           [0022]    In the method of the present invention, the hard and low compressible backing pad, whose Asker C hardness is 75-95 and compressibility is 10% or less, is used.  
           [0023]    Therefore, the substrate is held by the press head and the backing pad contacts a back side of the substrate when the copper layer (a front side) of the substrate is polished.  
           [0024]    In this case, if the backing pad is too soft, a pressing force applied to projections in the front side or a counter force from the polishing pad is transmitted to the backing pad and the backing pad is depressed by the projections. Namely, the parts of the substrate, which correspond to the projections, are berried in the backing pad, so that it is difficult to remove the projections in the front side of the substrate and the copper layer cannot be uniformly polished.  
           [0025]    On the other hand, if the backing pad is too hard e.g., Asker C hardness is 96-100, the back side of the substrate becomes a standard face for the polishing. If there are small projections in the back side of the substrate, the projections are not berried in the backing pad, so that the projections badly influence to the polishing. Uniformity of the polished copper layer must be lower.  
           [0026]    In the method of the present invention, the backing pad has said hardness and compressibility, so that projections and concaves in the rear face of the substrate can be absorbed by the backing pad, and the backing pad is not badly influenced by projections in the copper layer. Therefore, the copper layer can be polished uniformly, and the copper layer having uniform thickness can be produced.  
           [0027]    In the method, the backing pad may be made of polyurethane foam.  
           [0028]    Further, the polishing slurry used in the method is capable of increasing the stock removal rate without scratching the surface of the copper layer, so that manufacturing efficiency can be improved. Namely, the polishing slurry includes a chelating agent for chelating copper, an etching agent for etching the surface of the copper layer,  
           [0029]    an oxidizing agent for oxidizing the surface of the copper layer, and water. The copper layer is chemically etched by the etching agent.  
           [0030]    The chelating agent catches copper grains, which are removed and separated by the etching agent and the abrasive grains in the case of the polishing slurry includes abrasive grains,  
           [0031]    and acts as the accelerator of the polishing.  
           [0032]    Further, the chelating agent prevents the surface of the copper layer from scratching by copper grains, so that no surface defects are formed on the surface of the copper layer.  
           [0033]    In the method, the chelating agent may be organic carboxylic acid. For example, it may be at least one selected from a group comprising: amino acid; quinoline-2-carboxylic acid (quinaldic acid); 2-pyridine carboxylic acid; 6-pyridine carboxylic acid; and quinine. Preferably, amino acid is selected due to good environmental conditions and high stock removal rate. Further, the chelating agent may be at least one amino acid selected from a group comprising: neutral amino acid, such as glycine, α-alanine, β-alanine, valine, leucine, L-isoleucine, D-isoleucine, L-alloisoleucine, D-alloisoleucine, serine, L-threonine, D-threonine, L-allothreonine, D-allothreonine, cysteine, methionine, phenylalanine, tryptophan, tyrosine, proline, cystine; and basic amino acid, such as lysine, arginine, histidine. Especially, the preferable chelating agent is at least one selected from a group comprising: glycine, α-alanine and β-alanine due to high stock removal rate.  
           [0034]    Amount of the chelating agent in the slurry should be 0.015-2.5 mol/l. If it is less than 0.015 mol/l, the stock removal rate must be low; if it is more than 2.5 mol/l, some chelating agents are deposited. Attention is highly required.  
           [0035]    Preferable amount of the chelating agent in the slurry is 0.03-2.0 mol/l; further preferably, 0.05-1.8 mol/l.  
           [0036]    The etching agent chemically etches the surface of the copper layer. It further accelerates the mechanical polishing, in which the slurry including abrasive grains is used.  
           [0037]    Whatever materials which have an etching force against copper may be used.  
           [0038]    Copper can be etched by an acid etching agent and an alkaline etching agent. Preferably, the etching agent is at least one selected from a group comprising: ammonia; and ammonium salt due to synergism with the oxidizing agent. For example, the ammonium salt is at least one selected from a group comprising: inorganic ammonium salts, e.g., ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, ammonium nitrate, ammonium sulfate, ammonium chloride; and organic ammonium salts, e.g., ammonium lactate, ammonium citrate, ammonium malate, ammonium oxalate. Preferably, ammonium carbonate is selected due to good environmental conditions and high stock removal rate.  
           [0039]    Amount of the etching agent should be 5-25 wt % of the polishing slurry. If it is less than 5 wt %, the stock removal rate is too low; if it is more than 25 wt %, some etching agents are deposited. Attention is highly required.  
           [0040]    Preferable amount of the etching agent of the polishing slurry is 10-25 wt %, further preferably, 15-25 wt %.  
           [0041]    The etching agent may be added with high density, and it may be diluted when it is used. In the case of using ammonia (ammonia water) as the etching agent, preferably it is added immediately before the use due to stability of the polishing slurry.  
           [0042]    The oxidizing agent chemically oxidizes the surface of the copper layer. The chelating agent works to the oxidized copper layer, and in the case of the polishing slurry includes abrasive grains, the abrasive grains mechanically works thereto, so that the polishing is further accelerated. Namely, the oxidizing agent accelerates the polishing with the abrasive grains.  
           [0043]    Note that, the preferable oxidizing agent is hydrogen peroxide water due to oxidizing force and cost.  
           [0044]    Amount of the oxidizing agent should be 0.1-10 wt % of the slurry. If it is less than 0.1 wt %, the stock removal rate is too low; if it is more than 10 wt %, a container for storing the polishing slurry is expanded and stability of the polishing slurry is low.  
           [0045]    Preferable amount of the oxidizing agent of the polishing slurry is 0.5-8 wt %, further preferably, 1-5 wt %.  
           [0046]    The oxidizing agent of high density may be prepared, and it may be diluted with a solvent when it is used. Preferably, the oxidizing agent is added immediately before the use due to stability of the polishing slurry and prevention of natural dissolution.  
           [0047]    The water is used for dispersing and dissolving the agents. Preferably, the water is ion-exchanged water, which has been filtered to remove impurities, or distilled water.  
           [0048]    A pH value of the polishing slurry should be 7-10. If it is less than 7, the stock removal rate is too low; if it is more than 10, the slurry is formed into gel and the surface of the copper layer is made rough.  
           [0049]    In the method of the present invention, the polishing slurry may include abrasive grains which are made of at least one selected from a group comprising: silicon dioxide; aluminum oxide; cerium oxide; titanium oxide; silicon nitride; and zirconium oxide, and amount of the abrasive grains may be 0.1-50 wt % of the polishing slurry.  
           [0050]    In the case of the polishing slurry includes abrasive grains, the copper layer can be mechanically removed, too. Surface roughness of the polished copper layer can be improved, and further precise polishing can be executed. By the mechanical polishing, the amount of the etching agent can be reduced, so that influences of the chemical polishing can be reduced. Therefore, the surface roughness of the polished copper layer can be improved.  
           [0051]    If the amount of the abrasive grain is less than 0.1 wt %, the surface of the copper layer is made rough; if it is more than 50 wt %, mixture and dissolution of other agents are difficult. Preferable amount of the abrasive grains is 0.5-40 wt %, more preferably, 1-35 wt %.  
           [0052]    Note that, a preferable material of the abrasive grains is silicon dioxide, more preferably one is colloidal silica.  
           [0053]    Average diameter of the abrasive grains will be explained. In the case of the abrasive grains made of silicon dioxide, the preferable average diameter is 10-300 nm (measured by BET method), more preferably 30-100 nm. In the case of the abrasive grains made of cerium oxide, the preferable average diameter is 0.01-0.5 μm (observed by a scanning electron microscope), more preferably 0.05-0.45 μm. In the case of the abrasive grains made of other materials, the preferable average diameter is 0.01-2 μm (measured by a laser diffraction particle size analyzer LS-230 manufactured by Coulter Inc., USA), more preferably 0.05-1.5 μm.  
           [0054]    As described above, undiluted solutions of said agents may be prepared with high density, and they may be mixed with proper rates and properly diluted by the water. With this manner, they can be easily and effectively stored and transported. Further, a high density mixture, which includes the chelating agent, water and the abrasive grains (in the case of the polishing slurry includes abrasive grains), may be previously prepared, and the etching agent (in the case of using ammonia water) and the oxidizing agent may be added, with prescribed rate, to the mixture, then the mixture may be further diluted with water so as to use as the polishing slurry. 
       
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0055]    Embodiments of the present invention will now be described by way of examples and with reference to the accompanying drawings, in which:  
         [0056]    [0056]FIG. 1 is a front view of an polishing machine;  
         [0057]    [0057]FIG. 2 is a partial sectional view of a press head;  
         [0058]    [0058]FIG. 3 is an explanation view of a substrate, in which a through-hole is formed;  
         [0059]    [0059]FIG. 4 is an explanation view of the substrate, in which a plated film is formed in the through-hole;  
         [0060]    [0060]FIG. 5 is an explanation view of the substrate, on which cable patterns are formed;  
         [0061]    [0061]FIG. 6 is an explanation view of the substrate, on which an insulating resin layer is formed;  
         [0062]    [0062]FIG. 7 is an explanation view of the substrate, in which a via-hole and a copper layer are formed;  
         [0063]    [0063]FIG. 8 is an explanation view of a substrate, in which copper bumps are formed;  
         [0064]    [0064]FIG. 9 is an explanation view of a substrate, in which a via-hole is formed; and  
         [0065]    [0065]FIG. 10 is an explanation view of the substrate, on which a copper layer is formed. 
     
    
     DETAILED DESCRIPTION OF THE EMBODIMENTS  
       [0066]    Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings.  
         [0067]    [0067]FIG. 1 is a front view of a polishing machine  20 , and FIG. 2 is a partial sectional view of a press head  22 .  
         [0068]    A polishing pad  24 , which is made of, for example, polyurethane foam, a hard nonwoven fabric, is adhered on an upper face of a polishing plate  23 .  
         [0069]    Shallow grooves (not shown), which are mutually crossed like a grid, or small holes (not shown) may be formed in an upper face of the polishing pad  24 . For example, a polishing pad SUBA800 (D52), which is manufactured by Rodel Nitta Company and whose grid size of the shallow grooves is 20 mm×20 mm, may be used as the polishing pad  24  as well as a polishing machine for polishing silicon wafers.  
         [0070]    The polishing plate  23  is rotated about a rotary shaft (not shown), by a known driving mechanism (not shown), in a horizontal plane.  
         [0071]    The press head  22  is fixed at a lower end of a shaft  26 , which can be rotated about its own axis, and rotated together with the shaft  26 . The shaft  26  is pierced through a block  25 , which is provided on an arm  27 , and capable of moving in the vertical direction.  
         [0072]    A cylinder unit  28  is provided on the arm  27 . A supporting block  30  is fixed at an upper end of a cylinder rod  29  of the cylinder unit  28 . The shaft  26  is rotatably held by the supporting block  30 . A rotary joint  31  is connected to an upper end of the shaft  26 .  
         [0073]    A rotary cylinder (not shown), in which a gear is provided on an outer circumferential face, is provided in the block  25 , and the shaft  26  is pierced through the rotary cylinder and capable of moving in the vertical direction. The rotary cylinder is connected with the shaft  26  by a key (not shown) and a key groove (not shown).  
         [0074]    The shaft  26  can be freely moved in the vertical direction with respect to the rotary cylinder, but the shaft  26  is compulsorily rotated if the rotary cylinder is rotated about its own axis. A motor  32  is provided on the arm  27 . A gear (not shown) is fixed to a motor shaft of the motor  32  and engaged with the gear of the rotary cylinder.  
         [0075]    The arm  27  is fixed on a movable table  34 , which is moved along rails  33 .  
         [0076]    A substrate  36  to be polished is held on a bottom face of the press head  22 .  
         [0077]    Polishing slurry is supplied by a nozzle  37 .  
         [0078]    When the movable table  34  is moved along the rails  33  by a driving mechanism (not shown), the press head  33  holding the substrate  36  is moved between a first position, which is outside of the polishing plate  23 , and a second position, which is above the polishing plate  23 .  
         [0079]    By moving the cylinder rod  29  of the cylinder unit  28  downward, the press head  22  is also moved downward, so that the substrate  36  contacts the polishing pad  24  of the polishing plate  23 . Further, the substrate  36  is pressed onto the polishing pad  24 , by a press mechanism (described later), with prescribed pressure, and the slurry is supplied onto the polishing pad  24  from the nozzle  37 . The polishing plate  23  and the press head  23  are respectively rotated about their own axes, so that the substrate  36  can be polished.  
         [0080]    The press head  22  will be explained in detail with reference to FIG. 2.  
         [0081]    A sectional shape of a body proper  40  of the press head  22  is formed into an inverted U-shape. A bottom face is opened, and a space  41  is formed in the body proper  40 . Symbols  40   a  indicate side wall sections of the body proper  40 .  
         [0082]    A plate  42 , which is made of, for example, ceramic, is provided in a lower part of the body proper  40  so as to close the space  41 . A diaphragm  44 , which is made of an elastic sheet, e.g., a rubber sheet, is fixed on an upper face of the plate  42 . An outer edge of the diaphragm  44  is fixed to a bottom face of a step section  43 . With this structure, the plate  42  is suspended by the diaphragm  44 . Further, the space  41  in the body proper  40  is divided by the diaphragm  44 .  
         [0083]    Compressed air is supplied into the space  41  via an air tube  46  provided in the shaft  26 . The compressed air is introduced to the air tube  46  from air supplying means (not shown), e.g., a compressor, via the rotary joint  31 .  
         [0084]    An O-ring  47  is provided between a step section formed on an outer circumferential face of the plate  42  and step sections formed in lower parts of the side wall sections  40   a.    
         [0085]    A backing pad  48  is exchangeably adhered on a bottom face of the plate  42  by, for example, an adhesive (not shown). Asker C hardness of the backing pad  48  is 75-95, and compressibility thereof is 10% or less. For example, a backing pad BP201 (compressibility 3.4%, compression elasticity 75%, Asker C hardness 84), which is manufactured by Fujiboseki Inc., may be used as the backing pad  48 . Further, polyurethane foam may be used as the backing pad  48 .  
         [0086]    A back side (an upper face) of the substrate  36  contacts a bottom face of the backing pad  48 , and the substrate  36  is held by the backing pad  48 . The substrate  36  is pressed onto the backing pad  48  including water so as to purge air left between the substrate  36  and the backing pad  48 . By purging the air, negative pressure is produced between the substrate  36  and the backing pad  48 , so that the substrate  36  can be held on the bottom face of the backing pad  48 . Preferably, a retainer ring (not shown), whose lower end is slightly projected downward from a lower end of the backing pad  48 , is provided on an outer circumferential face of the backing pad  48 . By providing the retainer ring, the substrate  36  never springs out during the polishing. The retainer ring presses the polishing pad  24  of a periphery of the substrate  36 , so that the upper face of the backing pad  48  is depressed and its level is made equal to that of a lower face (a front side) of the substrate  36 . With this function, over polishing of an edge of the substrate  36  can be prevented.  
         [0087]    By supplying the compressed air in the space  41  via the air tube  46 , the plate  42  and the substrate  36  held by the backing pad  48  can be pressed onto the polishing pad  24  with a prescribed force so as to polish the lower face of the substrate  36 .  
         [0088]    Next, an ordinary process of manufacturing a build-up substrate will be explained with reference to FIGS.  3 - 7 .  
         [0089]    Firstly, as shown in FIG. 3, a plurality of through-holes  51  (one of the through-holes is shown) are formed in a core substrate  50 , e.g., a plastic substrate including glass-cloth, whose both sides are covered with copper films by a drill or laser means. The through-holes  51  are arranged in a prescribed pattern.  
         [0090]    Then, copper layers are formed on the copper films and inner faces of the through-holes  51  by non-electrolytic copper plating and electrolytic copper plating (see FIG. 4).  
         [0091]    The copper layers are etched so as to form cable patterns  52   a  and  52   b  on the both faces of the core substrate  50  (see FIG. 5).  
         [0092]    Resin is applied to the both faces of the core substrate  50  so as to cover the cable patterns  52   a  and  52 , so that insulating resin layers  53   a  and  53   b  are formed (see FIG. 6). In some cases, surfaces of the insulating resin layers  53   a  and  53   b  may be polished to make flat. This polishing may be executed by the polishing machine shown in FIG. 1 with supplying proper polishing slurry.  
         [0093]    Then, as shown in FIG. 7, via-holes  54   a  and  54   b  are formed so as to partially expose the cable patterns  52   a  and  52   b . If the insulating resin layers  53   a  and  53   b  are made of photosensitive resin, the via-holes  54   a  and  54   b  can be formed by exposing and developing treatments; if the insulating resin layers  53   a  and  53   b  are made of non-photosensitive resin, they can be formed by, for example, laser means. Copper layers  55   a  and  55   b  are formed in the via-holes  54   a  and  54   b  and on the insulating resin layers  53   a  and  53   b . In some cases, the via-holes  54   a  and  54   b  may be filled with copper.  
         [0094]    In the present embodiment, the copper layers  55   a  and  55   b  of the substrate is polished to make flat. Firstly, the copper layer  55   a  is polished, then the substrate is inverted to polish the other copper layer  55   b . After the copper layers  55   a  and  55   b  are made flat, they are etched to make cable patterns. The above described process is repeated prescribed times to form a multi-layered build-up substrate.  
         [0095]    In the above described embodiment, the broad copper layers  55   a  and  55   b  are polished; in another embodiment, copper bums are polished.  
         [0096]    In FIG. 8, copper bumps  62 , which act as connecting terminals, are formed in a substrate  60 , e.g., a silicon wafer.  
         [0097]    The copper bumps  62  are made by the steps of: forming a resist mask having opening sections, which correspond to the copper bumps  62 , on the wafer  60 ; plating parts of circuit sections exposed in the opening sections with copper; and removing the resist mask. With this method, the copper bumps  62  can be projected from the surface of the wafer  60 .  
         [0098]    By the method of the present invention, copper bumps formed on a circuit board (a substrate) can be removed. The substrate is not limited to the plastic substrate; ceramic substrates, glass substrates, etc. can be polished.  
         [0099]    Results of experiments and comparative examples will be explained.  
       (Experiment 1)  
       [0100]    Copper layers of substrates were polished by the polishig machine shown in FIGS. 1 and 2 under following conditions:  
         [0101]    1. Polishing slurry  
         [0102]    Abrasive grains: colloidal silica,  
         [0103]    average grain diameter 35 nm, 10 wt %  
         [0104]    Chelating agent: glycine, 0.5 mol/l  
         [0105]    Etching agent: ammonia water (density 30%), 1 wt %  
         [0106]    Oxidizing agent: hydrogen peroxide water (density 31%),  
         [0107]    3 wt %  
         [0108]    Water: distilled water  
         [0109]    2. Backing pad  
         [0110]    BP201: Fujiboseki Inc., compressibility 3.4%  
         [0111]    Asker C hardness 84  
         [0112]    3. Polishing pad  
         [0113]    SUBA800 (D52): Rodel Nitta Company,  
         [0114]    grid size 20 mm×20 mm  
         [0115]    4. Pressure for polishing: 35.316 kPa  
         [0116]    5. Rotational speed of polishing plate: 70 rpm  
         [0117]    10 samples were polished, and the results were as follows:  
         [0118]    Stock removal rate: 8-9 μm/min.  
         [0119]    (target: 10 μm/min. or more)  
         [0120]    Uniformity polished layer: 0.15-0.47 μm  
         [0121]    (target: 0.75 μm or less)  
         [0122]    Average surface roughness (Ra): 0.05-0.19 μm  
         [0123]    (target: 0.5 μm or less)  
         [0124]    Note that, the uniformity of polished layer means uniformity of thickness of the copper layer, and it is standard deviation (1σ) of thickness of the copper layer measured at a center and eight points near edges.  
         [0125]    The average surface roughness (Ra) means roughness of the surface of the copper layer measured by the noncontacting measuring instrument.  
         [0126]    The stock removal rate was slightly less than the target, but the uniformity of the polished layer and the average surface roughness were sufficient.  
       (Experiment 2)  
       [0127]    Copper layers of substrates were polished by the polishing machine shown in FIGS. 1 and 2. Only the polishing slurry was changed as follows:  
         [0128]    1. Polishing slurry  
         [0129]    Chelating agent: glycine, 0.7 mol/l  
         [0130]    Etching agent: ammonia water (density 30%), 1.25 wt %  
         [0131]    Oxidizing agent: hydrogen peroxide water (density 31%),  
         [0132]    3 wt %  
         [0133]    Water: distilled water  
         [0134]    10 samples were polished, the uniformity of the polished layer was appraised as well as Experiment 1, and the results were as follows:  
         [0135]    Stock removal rate: 8-9 μm/min.  
         [0136]    (target: 10 μm/min. or more)  
         [0137]    Uniformity of polished layer: 0.18-0.48 μm  
         [0138]    (target: 0.75 μm or less)  
         [0139]    Average surface roughness (Ra): 0.07-0.24 μm  
         [0140]    (target: 0.5 μm or less)  
         [0141]    The stock removal rate was slightly less than the target, but the uniformity of the polished layer and the average surface roughness were sufficient as well as Experiment 1. These were measured as well as Experiment 1.  
       (Experiment 3)  
       [0142]    Copper layers of substrates were polished by the polishing machine shown in FIGS. 1 and 2 under following conditions:  
         [0143]    1. Polishing slurry  
         [0144]    Abrasive grains: colloidal silica,  
         [0145]    average grain diameter 35 nm, 10 wt %  
         [0146]    Chelating agent: glycine, 0.04 mol/l  
         [0147]    Etching agent: ammonium carbonate,  
         [0148]    6.5 wt %  
         [0149]    Oxidizing agent: hydrogen peroxide water (density 31%),  
         [0150]    3 wt %  
         [0151]    Water: distilled water  
         [0152]    2. Backing pad  
         [0153]    BP201: Fujiboseki Inc., compressibility 3.4%  
         [0154]    Asker C hardness 84  
         [0155]    3. Polishing pad  
         [0156]    SUBA800 (D52+H5): Rodel Nitta Company,  
         [0157]    grid size 20 mm×20 mm  
         [0158]    hole diameter 5 mm  
         [0159]    4. Polishing pressure: 35.316 kPa  
         [0160]    5. Rotational speed of polishing plate: 110 rpm  
         [0161]    10 samples were polished, and the results were as follows:  
         [0162]    Stock removal rate: 10-12 μm/min.  
         [0163]    (target: 10 μm/min. or more)  
         [0164]    Uniformity polished layer: 0.45-0.50 μm  
         [0165]    (target: 0.75 μm or less)  
         [0166]    Average surface roughness (Ra): 0.07-0.24 μm  
         [0167]    (target: 0.5 μm or less)  
         [0168]    Note that, the uniformity of polished layer is standard deviation (1σ) of thickness of the copper layer evenly measured at 25 points.  
         [0169]    The average surface roughness was measured by the noncontacting measuring instrument as well as Experiment 1 and 2.  
         [0170]    The stock removal rate was slightly greater than the target and the uniformity of the polished layer and the average surface roughness were sufficient.  
       (Experiment 4)  
       [0171]    Copper layers of substrates were polished by the polishing machine shown in FIGS. 1 and 2 as well as Experiment 3. Only the polishing slurry was changed as follows:  
         [0172]    1. Polishing slurry  
         [0173]    Chelating agent: glycine, 0.07 mol/l  
         [0174]    Etching agent: ammonium carbonate, 8 wt %  
         [0175]    Oxidizing agent: hydrogen peroxide water (density 31%),  
         [0176]    3 wt %  
         [0177]    Water: distilled water  
         [0178]    10 samples were polished, and the results were as follows:  
         [0179]    Stock removal rate: 12-15 μm/min.  
         [0180]    (target: 10 μm/min. or more)  
         [0181]    Uniformity polished layer: 0.23-0.6 μm  
         [0182]    (target: 0.75 μm or less)  
         [0183]    Average surface roughness (Ra): 0.09-0.30 μm  
         [0184]    (target: 0.5 μm or less)  
         [0185]    The stock removal rate, the uniformity of the polished layer and the average surface roughness were highly sufficient. These were measured as well as Experiment 1.  
       (Experiment 5)  
       [0186]    Copper bumps of substrates were polished by the polishing machine shown in FIGS. 1 and 2 under following conditions:  
         [0187]    1. Polishing slurry  
         [0188]    Abrasive grains: colloidal silica,  
         [0189]    average grain diameter 35 nm, 10 wt %  
         [0190]    Chelating agent: glycine, 0.04 mol/l  
         [0191]    Etching agent: ammonium carbonate, 6.5 wt %  
         [0192]    Oxidizing agent: hydrogen peroxide water (density 31%),  
         [0193]    3 wt %  
         [0194]    Water: distilled water  
         [0195]    2. Backing pad  
         [0196]    BP201: Fujiboseki Inc., compressibility 3.4%  
         [0197]    Asker C hardness 84  
         [0198]    3. Polishing pad  
         [0199]    IC1000: Rodel Nitta Company,  
         [0200]    4. Polishing pressure: 3.43 kPa  
         [0201]    5. Rotational speed of polishing plate: 7 rpm  
         [0202]    10 samples were polished, and the results were as follows:  
         [0203]    Stock removal rate: 5-10 μm/min.  
         [0204]    Uniformity polished layer: 0.3-0.5 μm  
         [0205]    (target: 1 μm or less)  
         [0206]    Note that, in each substrate, nine copper bumps were formed at a center and at mid portions and outermost portions of four virtual lines radically extended from the center with regular angular separations. Height of the nine copper bumps of each substrate was measured. A difference between the highest bump and the lowest bump was calculated for each substrate. Thus, in the present experiment, a scattering range of said differences of 10 samples is considered as the uniformity of height of the polished copper bumps.  
         [0207]    The stock removal rate and the uniformity of height were highly sufficient.  
         [0208]    Note that, in Experiments 1-5, no scratches were observed in the polished surfaces of any copper layers and bumps.  
       COMPARATIVE EXAMPLE 1  
       [0209]    Copper layers of substrates were polished by the polishing machine shown in FIG. 1 under following conditions:  
         [0210]    1. Polishing slurry  
         [0211]    CMP slurry PLANERLITE-7101: Fujimi Inc.,  
         [0212]    2. Backing pad  
         [0213]    BP102: Fujiboseki Inc.,  
         [0214]    compressibility 18.8%, Asker C hardness 71  
         [0215]    3. Polishing pad  
         [0216]    SUBA800 (D52): Rodel Nitta Company,  
         [0217]    grid size 20 mm×20 mm  
         [0218]    4. Polishing pressure: 35.316 kPa  
         [0219]    5. Rotational speed of polishing plate: 70 rpm  
         [0220]    10 samples were abraded, and the results were as follows:  
         [0221]    Stock removal rate: 0.45-0.50 μm/min.  
         [0222]    Uniformity polished layer: 0.60-1.88 μm  
         [0223]    Average surface roughness (Ra): 0.06-0.10 μm  
         [0224]    The uniformity of polished layer and the average surface roughness were measured as well as Experiment 1.  
         [0225]    The results were insufficient.  
       COMPARATIVE EXAMPLE 2  
       [0226]    Copper bumps of substrates were polished by the polishing machine shown in FIG. 1 under following conditions:  
         [0227]    1. Polishing slurry  
         [0228]    POLIPLA-103: Fujimi Inc.,  
         [0229]    2. Backing pad  
         [0230]    BP201: Fujiboseki Inc.  
         [0231]    3. Polishing pad  
         [0232]    IC1000: Rodel Nitta Company,  
         [0233]    4. Polishing pressure: 3.43 kPa  
         [0234]    5. Rotational speed of polishing plate: 7 rpm  
         [0235]    10 samples were polished, the uniformity of height was appraised as well as Experiment 5, and the results were as follows:  
         [0236]    Stock removal rate: 1-3 μm/min.  
         [0237]    Uniformity polished layer: 0.60-1.88 μm  
         [0238]    The results were insufficient.  
         [0239]    The inventors confirmed that the stock removal rate, the uniformity polished layer and the average surface roughness of the Experiments 1-4 were superior to those of the Comparative Example 1; and the stock removal rate and the uniformity polished layer of the Experiments 5 were superior to those of the Comparative Example 2.  
         [0240]    The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by he foregoing description and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.