TW201237130A - Polishing composition for semiconductor wafer, method for manufacturing the same, and polishing method - Google Patents

Abstract

A polishing composition for semiconductor wafers is provided, in which haze or pits, ''abrasive residues'' in particular, are hardly generated on a flat portion of a wafer during a process of polishing the flat and edge portions of device wafers, etc. The polishing composition for semiconductor wafers in the disclosure contains colloidal silicon dioxide produced from using active silicic acid as a raw material in the presence of potassium ions. The polishing composition for semiconductor wafers is characterized as follows: the colloidal silicon dioxide contains potassium ions and a group of nonspherical deformed silicon dioxide particles with a major to minor axis ratio of 1.2 to 10 being observed through a transmission electron microscope. By using the polishing composition for semiconductor wafers in the disclosure, a mirror grinding process of the flat and edge portions of semiconductor wafers can be efficiently carried out.

Description

[Technical Field] The present invention relates to a wafer polishing composition and a method of fabricating the same, in which a metal film, an oxide film, or a nitride is formed on a wafer or a surface thereof The flat surface and the edge portion of the semiconductor wafer such as a semiconductor device substrate such as a film (hereinafter referred to as a metal film) are subjected to polishing processing. Further, the present invention relates to a polishing method for mirror-finishing a plane and an edge portion of a semiconductor wafer using the above-described composition for polishing a wafer. [Prior Art] A built-in circuit (1C), a large scale integration (LSI), or a very large scde integration (Super LSI) using a semiconductor material such as a germanium single crystal as a material. The electronic component is manufactured on the basis of a small-sized semiconductor element wafer in which a plurality of fine circuits are divided and formed by cutting a single crystal ingot of tantalum or other compound semiconductor into a thin circular plate shape. . The wafer obtained by slicing the ingot is subjected to lapping, etching, and further polishing (hereinafter sometimes referred to as polishing), and is processed into a flat surface and the edge surface is finished as a decoration. Mirrored mirror wafer. In the subsequent process, the wafer is gradually formed into a fine circuit on the mirror-finished surface. At present, in terms of the speed of LSI, the wafer is transferred to the following wiring forming process: the wiring material is previously The A1 is changed to a lower resistance Cu' wiring film is changed from a stone oxide film to a low dielectric constant film having a lower dielectric constant, and further has a gap between Cu and a low dielectric constant film to prevent A structure in which a Cu is diffused into a low dielectric constant film or a barrier film of nitrided 201237130 1 ·»·袅夏钽. In order to form and integrate the wiring structure as described above, the planarization of the interlayer insulating film, the formation of a metal connection portion (plug) between the upper and lower layers of the multilayer wiring, or the formation of buried wiring are repeated and frequently performed. Grinding step. In the polishing of the flat surface, the semiconductor wafer is placed on a fixed plate on which a polishing cloth including a synthetic resin foam or a suede-style synthetic leather is spread, and the polishing composition is quantitatively supplied while being rotated. The solution is processed. In the inner edge surface, the metal film or the like is stacked irregularly. The step of supporting the transfer of the wafer to the semiconductor element wafer in the state in which the wafer is held in the first disk shape is supported. When the outer peripheral side edge of the crystal is irregular in shape at the time of conveyance, fine particles are generated due to contact with the conveyance = fine particles are generated. The fine particles generated in the subsequent step ^ are dissipated to contaminate the surface on which the precision processing is performed, and have a large influence on the yield or quality of the product. In order to prevent contamination of the fine particles, it is necessary to perform mirror polishing of the edge portion of the semiconductor wafer after forming a metal film or the like. In the above-mentioned edge polishing, a polishing machine including a synthetic resin foam, a synthetic leather, or a non-woven fabric is attached to the surface of the polishing cloth support, and the edge portion of the semiconductor wafer is pressed while being supplied with oxidizing. A polishing composition solution containing a polishing abrasive as a main component is obtained by rotating a polishing cloth support and a wafer or either. As the abrasive for the polishing composition used at this time, colloidal silica or fumedsiUca, ceria, alumina, or the like is proposed. In particular, colloidal silica dioxide 201237130 ^luipir is therefore easy to obtain a smooth mirror or smoked nitric oxide. Because it is a fine particle, the surface is therefore of concern. Such a polishing composition is also referred to as described above. Excited j (slurry), the following has A test eighty-four fine grinding Lai secret is usually package j: The principle of completion is to check the chemical action of component (10), , body and g, will be the oxidation (four) or metal film The table is used in combination with the mechanical grinding action of the dioxide (four) material. Specifically, the second is: ^ The side of the ship, in the crystal, the surface of the workpiece is formed into a thin soft eclipse layer 1 _ by the micro-abrasive particles of the mechanism of the dip (four) 'considering the steps such as New Zealand: ^ Add: After the polishing, a cleaning step is performed to remove the cerium oxide abrasive or the lye from the surface to be processed and the portion. In the far, 彖 step, the problem of residual abrasive on the surface of the wafer has been pointed out. The pure residual surface of the round surface can be greatly improved by the grinding conditions or the cleaning method. However, the other side may be accompanied by a large drop in the polishing rate and a complicated cleaning method, so that the problem cannot be solved. Further, the miniaturization of the device wiring has become remarkable year by year, and as the wiring width of the device is advanced, the surface of the cast wafer is required to be cleaned after the polishing. A polishing abrasive for grinding a semiconductor crystal_abrasive agent having a particle diameter of about several tens of nanometers as described above. Previously, since the particle size of the abrasive was sufficiently small with respect to the width of the wiring, the residual of the abrasive generated on the surface of the semiconductor wafer did not become a major problem. However, due to the miniaturization of the device wiring, the particle size of the abrasive and the wiring width of the device 201237130 [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 6U(10)% (Patent 5) [2] Japanese Patent Laid-Open No. 2, No. 2, No. 2, pp. [Patent Document 5] Japanese Patent Laid-Open No. Hei 8-83780 (Patent No. 5-^9_i93〇〇4^ Patent Scope) 'Patent Document η 曰 专利 专利 专利 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ 专利 专利(7th page) [Patent Document 8] Japanese Patent Special Publication _ Brain 4 () Bulletin Page) (Application (Japanese Patent No. 9) Japanese Patent Special Publication No. 1 (Japanese Patent No. 11) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 349 (Patent Application Scope) Since the prior art, a variety of grinding methods have been proposed for mirror polishing of semiconductor wafers. For example, Patent Document i discloses the inclusion of carbonic acid. The best body of oxidation and oxidation W - oxidized stone eve. Patent Document 2 revealed A colloidal oxidized granule containing ethylenediamine is shown. Patent Document 3 discloses the use of a cerium-shaped cerium particle formed into a bismuth shape. Patent Document 4 discloses the use of a microparticle containing ethylene·diamine·phthalic acid and dioxane. A method for polishing a wafer of water by a powder. Patent Document 5 discloses a method for polishing a water-soluble (tetra) semiconductor wafer containing a fine powder of lanolin, nitrogen peroxide, benzotriazine, and oxidized oxime. In the literature 6 towel, the TprfSKQjj aqueous solution towel is dispersed with an abrasive having a mean particle diameter of 5 nm and 30 nm, and a method for preparing the same. In Patent Document 7, the grinding of the colloidal cerium oxide for removing sodium by cation exchange is carried out. The slurry is proposed to have an amine added as a polishing accelerator and a fourth-grade lye which is added as a bactericide. The singular use of 8 towels is used. In Patent Document 9, 'the use of tetrahydrocarbyl hydroxide is used instead of sodium hydroxide. As the alkali agent used in the particle growth step of the colloidal cerium oxide, colloidal cerium oxide is produced, and the high-purity colloidal cerium oxide for polishing which is substantially free of sodium is contained in the patent document 10 A combination of acid and strong test, weak acid and weak test or weak acid and weak test to prepare a cerium oxide colloidal solution adjusted with a buffer solution having a buffering value between pH 8 7 and 1 〇 6. Patent Literature η In the case of using a colloidal cerium oxide as in the case of the above-mentioned Patent Document 1 and Patent Document 2, an impurity is added to the ruthenium-containing ruthenium oxide. The colloidal cerium oxide is produced by using sodium citrate as a raw material, and contains a relatively large amount of an alkali metal such as sodium, which is a material which easily causes abrasive residue. The zirconia granules of the shape of the shape of the patent document 3 201237130 Since the organic ruthenium compound is produced as a raw material, it has high purity and is excellent in that it does not contain a metal test. However, the lack of the ruthenium dioxide particles is due to the fact that the polishing rate is low due to softness. Patent Document 4 and Patent Document $ are excellent in that they do not contain metal. However, since the use of the fine powder of the dioxide pin has been disclosed, the use of smoked silica dioxide has a high polishing rate, but it is easy to produce a mark on the polished surface. Patent Document 6 is (4) produced by (10) dioxotomy, and has a high polishing rate. However, it is easy to cause scratches on the polished surface, and a K〇H aqueous solution is not used. The low-nano colloidal silica dioxide disclosed in detail 7 is as detailed on page 7 of the document, and the grinding promotes (4) as an amine, and the tetra-salt is added as a grinding-promoting effect. EXAMPLES The use of amine ethyl b- and _ as amines is described. Recently, amines have formed a chelate due to their chelates, and they have become the cause of crystal contamination. In addition, in this document, = 〇Η is described, and the reduction of the amount of sodium is a problem. Patent Document 8 describes the risk of wafer contamination caused by acetamidine. Patent Document No. 9 is an excellent study of ruthenium oxide because it does not exist in the water phase and on the surface of the particles or inside the particles. However, if the value fluctuates greatly 'by the dioxin in the atmosphere = == Γ (4), the lap is obtained. The purpose of the ΐ 明 明 在于 在于 在于 在于 在于 在于 在于 明 明 明 明 明 明 明 明 明 明 明 明 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Further, another object of the present invention is to provide a mirror polishing method for a flat surface and an edge portion of a semiconductor wafer using the polishing composition of 201237130, 1 υιριι. The inventors of the present invention have found that a composition for polishing a semiconductor wafer containing a colloidal dioxygen (tetra) manufactured by using active tannic acid in the presence of potassium ions is used by using a semiconductor wafer polishing composition: ^ The semiconductor wafer polishing composition is characterized in that the colloid has potassium ions and contains non-spherical shaped cerium oxide particles having a length to diameter ratio of 1.2 to 1 Å observed by a penetrating (four) submicroscope. The group can efficiently perform mirror polishing processing of the semiconductor crystal plane and the edge portion, thereby completing the present invention. The compound which is a source of the potassium ion source is preferably potassium, and more preferably the semiconductor wafer polishing composition preferably has a riding value (pKa) of 8 g which is a reciprocal of the 25 = acid dissociation constant. A weak buffer of ~i2 5 is a buffer solution with a buffering effect between pH 8 u. The composition for polishing the conductor wafer is preferably an aqueous dispersion having a oxygen cut concentration of from 1 Gg% to 5 g% by weight relative to the colloidal solution. The 〇/2' feed conductor wafer is preferably ground for every 1 weight. The conductivity of a Weizi at 25 ° C is 15 mS/m or more. whole. The conductivity is newly added by the salt of the fourth-class ship or the salt of the i== level bond is preferably the fourth grade of sulfuric acid, and the fourth grade of 201237130. The anion forming the weak acid is preferably carbonate ion and At least 1#' of the bicarbonate ions and the fourth order are at least the species of the test ion, the tetradecyl bond ion, and the tetraethylammonium towel. Lin is a generic term for trimethyl (ethyl) ammonium. Further, it is preferable that the colloidal dioxide dioxins in the semiconductor wafer polishing composition have a mean short diameter of 5 nm to 1 〇 nm as observed by a transmission electron microscope. Further, the second invention of the present invention is a method for producing a semiconductor wafer polishing composition, characterized in that a lion (four)_ and a cation exchange resin are used, and a _sub (4) active tree aqueous solution is removed, followed by an active mechanical aqueous solution. Adding a supply source of potassium ions and a test material, so that the positive = become 曲 8 〜 1 卜 is heated to grow the colloidal particles, and then the ultrafiltration is used to make the smear concentration of the cerium oxide 1 〇 wt%~ 5 〇 wt% = oxygen ~ chemistry 2, body 2, adjusted to 2% of oxidative pain 2, while adding a weak acid and a quaternary ammonium base in a buffer composition. A third invention of the present invention is a polishing method, which is characterized in that: Table 1 is a rotatable fixing plate and a wafer to which a polishing cloth is attached: a semiconductor wafer polishing composition and/or a semiconductor wafer are supplied by a touch. Rotating to grind the flat edge of the semiconductor wafer to make the disk The fourth invention of the present invention is a polishing method, and the shape of the drum having the polishing cloth on the surface is studied by grinding the member and the semiconductor wafer : having a circular arc pressure, and supplying the semiconductor wafer polishing circle portion to the opposite side, and forming a material, and grinding the edge of the semiconductor wafer while polishing the 201237130 member and/or the semiconductor wafer. When the semiconductor wafer polishing composition of the present invention is used, it is difficult to cause pits or haze in the planar portion during polishing of a semiconductor wafer or the like, and a high polishing rate is obtained, so that it is difficult to cause abrasive residue ( The following is an excellent effect of "abrasive residue". The term "abrasive residue" means that the abrasive component of the polishing composition is fixed to the flat portion of the wafer during the grinding, and the abrasive remains in the flat portion after the cleaning. According to the present invention, it is possible to obtain an abrasive residue in a flat portion where the previous countermeasures are insufficient, and to obtain a polishing composition having excellent polishing force and durability in the mirror polishing process of the wafer. The effect is great. [Embodiment] Hereinafter, the present invention will be described in detail. The semiconductor wafer polishing composition of the present invention contains colloidal cerium which is produced by using activated citric acid as a raw material in potassium ions. The colloidal oxidized granule is characterized in that it contains Nazi and contains a non-spherical chemi-type oxidized particle group having a long diameter/short view of 丨.2~1() by a microelectron microscope. . The average short diameter of the dielectrically cut dioxo particles of the domestic trioxide is observed as follows: 5 nm~1〇nm ° The long diameter/short diameter ratio in the present invention is the obtained colloidal silica. On the epoch of the penetrating electron microscope photograph, the scale is attached (the selected one. The dioxins are used to determine the oxidized record). The most 12, 201237130, the shortest side b, 々 use this value (a^a2, .. , al00 and bl, b2, and blOO) to calculate the long-axis/short-diameter ratio (ai/b, ·, alOO/blGG) of each particle'. The arithmetic mean of the values of the five points on the minimum side is limited. And the arithmetic mean value of the value of 5 points on the maximum value side is taken as the lower limit 1 and the average value of the so-called long diameter/short diameter ratio in the month means the penetration type of the obtained colloid-emulsified stone The electron micrograph is attached with 100 particles randomly selected from the scale to measure the shortest side b of the longest edge oxide particles of the cerium oxide particles, and this value is used (a, a2, a3 to al00: ) =, b2, b3 To blOO) to calculate the long diameter/short diameter ratio of each particle, Bo /l = 2 ' _ to al_GG) ' and the value of 5 points except the maximum side and the small value side The arithmetic mean of 9〇 points. In the composition for polishing a semiconductor wafer of the present invention, the solubility of the solution is 2% by weight to 5 == The second step of the second political solution is to improve the polishing composition. H) weight: 25% by weight and further 'in the present invention', in order to maintain the net grinding force in the actual polishing process, it is preferred to keep the pH of the solution as a whole at 8 to ^. If the pH is less than /, the polishing rate is lowered. There is a practical van = r. When the pH value exceeds 1 Å, the etching other than the polishing portion becomes strong; the haze or the pit is generated or the other dioxin particles are opened * = the net is formed, so that the stability of the polishing composition is lowered. The scope of the situation. In addition, the pH of the child is better, and the pH value of the child is preferably not due to friction, sputum, sputum contact or the mixed county of the financial domain is (4), corrected = 13 201237130. Especially in edge grinding, the polishing composition is used as a circulating stream. That is, the semiconductor wafer polishing composition supplied from the slurry storage tank to the polishing portion is used to return to the slurry storage tank. When the composition for polishing a semiconductor wafer containing only an alkali agent is used, the value is lowered in a short time. This is because the fluctuation of the polishing rate caused by the dissolution of the object to be polished or the incorporation of the washing water causes the polishing rate to be insufficient or the excessive polishing due to excessive polishing. In order to keep the pH of the polishing composition of the present invention constant, it is preferably 25. (The logarithmic value (pKa) of the reciprocal of the acid dissociation constant is 8 〇~12.5, and the quaternary ammonium base is combined to form a buffer solution. It is also preferred to have a buffer between pH 8 and 11 at this time. Preferably, the anion forming a weak acid is a carbonate ion and/or hydrogen carbonate, an ion, and the cation constituting the quaternary ammonium strong base is at least at least a choline ion, a tetramethyl 2 or a tetraethyl lining. - Other four-level recording: preferably comprising a carbon number of 4 or less or a carbon number of 4 or less of a heterogeneous group, the base is a sulfhydryl group, an ethyl group, a propyl group, a butyl group, and a silk. 2 is a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group. Specifically, a tetrazole ion, a tetrabutylammonium ion, an f-based tricentric group, and a triethylamine-ethyl group The sub-transfer is secret, so it is better. Further, it is preferable because it is obtained as another y = y-dimethyl dimethyl ion or a phenyl trimethyl group ion. According to the type of organic base, the grade _ sub-synthesis can be different for the rot and the recording of the ruthenium, and the pure cleansing property is also the same as the appropriate choice. Therefore, it is better to use a plurality of combinations. 201237130 S.〇^TTn::H^7?^4(PKa)^ %因) This is not good. In the case where the acid dissociation (pKa) is more than 12.5, the value is difficult: (4) Value: stable buffer with a large buffering solution pH = less than 8% of the liquid is less than 20% of the buffering effect of the grinding The weakness of the composition solution is preferably (4) (pKa = 6 35 ), hydrogen carbonate 1 〇 · 33), and can be listed (pKa = 9.24), phosphoric acid (pKa ^ i5, 72 〇, 1 ^. 35) and A water-soluble organic acid or the like may also be a mixture thereof. In addition, it is strongly tested to use a quaternary ammonium hydroxide. The buffer solution described in the present invention is a solution which is formed by the above combination and which is dissociated in the form of a valence weak acid as a valence ion, or a _ state and an untouched state, and is characterized in that even a small amount of acid or In the test, there is also little change in the positive value. In the present invention, the polishing rate can be improved by increasing the conductivity of the semiconductor wafer polishing composition solution. The electric conductivity is a numerical value indicating the ease of electrical circulation in a solution, and is a reciprocal value of the value per unit length. In the present invention, the numerical value (micro.Siemens) of the electrical conductivity per unit length is expressed by a numerical value converted into cerium oxide per i% by weight. In the present invention, when the conductivity at 25 t is 15 mS/m/l%-SiO 2 or more, the polishing processing speed is preferably improved, and if it is 20 mS/m/l%-Si〇2 or more, Especially good. The addition of salts reduces the stability of the colloid. Therefore, there is an upper limit to the addition. The upper limit differs depending on the particle size of the second & fossil eve, which is approximately 6 〇 mS/m/l% _Si 〇 2 or so. 15 201237130 As mentioned above, this processing is an application, in particular the application of oxidized pins or gold; That is, the corrosive property of the alkali is utilized, and the workpiece is immersed in a soft and etched layer. By gradual removal of the surface of the workpiece by mechanical action, the oxidation reaction is carried out, and the metal surface is passively transferred from the film of the deposited film to the solution in the solution. The conductivity must be high. There are two methods for rushing ~ one is to increase the concentration of the buffer bath, and the other is to add a salt. In order to raise the concentration of the buffer solution, it is only necessary to increase the ^ degree without changing the molar ratio of the acid to the test. The salt used in the method of adding a salt includes an acid and a test group: '酉夂 can be any of a strong acid and a weak acid, and a mineral acid, an organic acid, or a Wei compound can be used. Compared to the four-reduced hydroxide of the water. In the case where it is added by a combination of a weak acid and a strong base, a test, a weak acid, and a weak base, since the pH of the buffer solution is changed, a large amount of addition is not preferable. The above two methods can also be used in combination. The salt of the strong acid and the quaternary ammonium base is preferably at least one of quaternary ammonium sulfate, quaternary ammonium nitrate, and vaporized quaternary ammonium. The cation constituting the quaternary ammonium base is preferably at least one of a cholesteric ion, a tetrakisyl ammonium ion, and a tetraethylammonium ion. Other quaternary ammonium ions are used. Further, the semiconductor wafer polishing composition of the present invention is also preferably a chelating agent containing a water-insoluble chelating compound with steel. For example, the chelating agent is preferably a saliva such as stupid and tris beta or a linalool 201237130

A well-known compound such as HllOipu (quinoiinol) or quinaldine (quinoline derivative). The phthalocyanine = physical properties of the abrasive composition, surfactant, dispersant, and anti-falling inhibitor Etc. Organic matter, inorganic layered compound = 2 ί List of water-soluble grinding group money m material invention material conductor wafers two == colloidal oxidation error and other abrasives, inspection, additives, f This ==! The body wafer polishing composition is obtained by the following method: =: _ contact with the cation exchange resin, removal of the nano-distribution = the method of making the dioxo-cut into the buffer by the ultra-salt And =================================================================================================== The amount of potassium ions is preferably such that the ratio of active enthalpy is 3 G Γ Γ 与 与 与 与 与 与 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 1 effect, if the potassium ion is less than the range, it is easy to generate spherical cerium oxide When the cerium oxide particles are grown, potassium ions added during the formation of the cerium oxide particles may be added, and potassium ions may or may not be added. When potassium ions are added, the amount of potassium ions may be increased. The cerium oxide particles are formed less frequently, and preferably have a molar ratio of cerium oxide/potassium ions of 200. If the amount of potassium ions in the growth of the cerium oxide particles is decreased, the impurities of the two particles are close to each other. The _ sub is reduced by the discharge of the water and the water. Therefore, the amount of potassium ions of the finally obtained gel-fossil eve is several tens of ppm to several thousand ticks. Further, the present invention The molar ratio of the so-called (9) potassium ion of the towel is the molar number of the potassium ion added to the aqueous solution of the active I. citrate solution obtained from the dioxide dioxide of the aqueous active acid solution. Calculated. (4) Colloids containing a non-spherical shaped 7-particle group of particles: refers to cerium oxide particles having an egg shape, a peanut shape, a scorpion shape, a rod shape, a bent shape, and different shapes. Specifically, it contains as shown in Figure 1 and Figure 2. Shape:; oxygen tr colloidal dioxotomy. The long diameter / range of the dioxins. The non-spherical part of the dioxide w also has spherical spheroidal dioxide. The cerium oxide particles are exemplified by the production bar, and the oxidized dioxin dicing particles of the present invention account for a majority of the cerium dioxide particles in the colloidal dioxotomy of the present invention. The cerium oxide source is used in the particle formation step using 201237130 ions and the test material. The particle growth step is characterized by: adding an active aqueous solution of the aqueous solution of the sulphuric acid, testing the material and the potassium material, or adding the aqueous solution of the living (tetra) acid and testing the material. As the material, a metal hydroxide such as sodium hydroxide, quaternary ammonium hydroxide or the like can be used. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and triamyl-2-ethylammonium hydroxide (same as hydrogen hydroxide). As long as potassium hydroxide is used as the alkaline material, it is not necessary to add another compound which is a supply source of potassium ions. First, an aqueous solution of citric acid and alkali used as a raw material is usually suitably used as an aqueous solution called water glass (water glass No. 1 to water glass No. 4). Such an aqueous sodium citrate solution is relatively inexpensive and can be easily obtained. The nano-ion semiconductor towel preferably uses (4) an aqueous sodium acid solution and uses (4) a potassium aqueous solution as a raw material. There is also a method of preparing a water-soluble solution (4) in the form of a body-like sulphuric acid, which is subjected to a test. The decanting step is to produce 'there is a small amount of impurities. The 7-acid aqueous solution is used by diluting with water as needed. 阳离子 The cation exchange resin used in the present invention can be appropriately selected and used, and is not particularly limited. The contacting step of the aqueous solution with the cation exchange resin can be carried out, for example, by dissolving the water in the test, diluting with water to a concentration of 3% by weight to 1% by weight, and then performing a test with a strong acid cation exchange resin. According to the need of the tray h, the strong test _ child exchange _ fat turn off the _ sub. By this step to prepare the active (four) aqueous solution. The details of the contact conditions have been raised from the previous In the present invention, it is also possible to use the above-mentioned known method to form a dioxogranule particle 19 in the presence of a scorpion. 201237130 41 Jilpit ==2 Adding a compound which is a supply source of potassium ions is carried out by the method of the method. For example, by adding a rotor recording material at a pH value, the cerium oxide particles can be heated to form 24UC to form (two = _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Steps: The sol with a letter value of 8 or higher is heated to 6 〇t~2 thief, so that it can be added to the active Wei aqueous solution, add potassium active ion _, or add active acid acid aqueous solution and test material. In this case, the dioxane nm can be used, and the particle shape is long (four) into particles having an average purity of less than 5 Hm, more preferably 5 ^ 〇 nm. If the average short diameter exceeds 1 〇, the particles gradually form a tilt. And the gel obtained by the particle growth (4) === Concentration of colloidal dioxygenation can be performed as needed. The dioxide dioxide and the concentration can be the evaporation and concentration of water, but it is advantageous in terms of energy to overtake. Super 遽 遽 二 二 二 二 二 二 二The film is said to be separated by the ultra-transition membrane. The particles of nm to several micrometers are used as the pair, but the dissolved polymer material is the target. Therefore, the amount of H in the nano-region is expressed as _ degrees. In the invention, a super-removal film having a cut-off amount of 15' GGO or less can be suitably used. When a film of this range is used, particles having a particle size of 1 nm or more can be used, and it is particularly preferable to use a molecular weight cutoff of 3 〇〇〇, 000. Super; consider the film. If the molecular weight of the film is less than 3, the film of 〇〇〇 is over; if the resistance k is too large, the treatment time becomes long and uneconomical, if the molecular weight is too high.

20 201237130 Full 〇: The degree of purification is reduced. _Materials are viscous, polyacrylonitrile, sintered metal, ceramic, carbon, etc. ~~ i#. Use any one. In terms of heat resistance, filtration type, tubular type, hollow fiber type, etc., it may be in the form of a spiral compact or a compact one. Hollow fiber type membranes. Potassium ions are washed out and removed. In addition, in the super-twisting step, the removal of f is reduced by ~ degrees, and then pure water is added, and the potassium ion removal rate of IT is further washed out. Preferably, in this step, 1 oxygen is used, and thus, the colloidal dioxygen trimming is reformed === two 5 double weights; %' is simultaneously added as a buffering composition to add tannic acid and four wafer polishing compositions. It is in its water, and the salt used to adjust the conductivity. The rider is detached. Hereinafter, a polishing method using the semiconductor conductor wafer of the present invention will be described. In the case of the surface polishing of the composition for the circular polishing, the polishing composition obtained by dispersing in water is quantitatively supplied, such as a foam or a suede-like synthetic leather {a surface contact of the leather, etc. The surface is ground. The force 1 machine used in the present invention is, for example, a device manufactured by SpeedFam Co., Ltd., which is represented by a single-side polishing device, a FAM-20B double-face polishing device, or the like. 21 201237130 4H3lPif In the case of edge grinding, it is usually carried out as follows: ^The rotating material of the grinding material is a grinding machine that contains a polishing cloth such as a blister foam, a σ leather or a non-woven fabric. On the other hand, the workpiece (the workpiece) is chamfered (de-streaked (the edge portion (four) of the Shishi wafer, etc. - the side is tilted and slanted... The so-called edge polishing processing machine used in the present invention is, for example, a coffee/bump/bend edge (four) wire (four), comprising a rotatable polishing cloth support having a polishing cloth attached to the surface thereof, and Holding the portion of the workpiece attached to the miscellaneous portion and pressing the edge portion of the workpiece attached to the miscellaneous portion to the polishing cloth support, the semiconductor wafer is subjected to the inspection of the semiconductor crystal of the present invention. Both the edge red member and the polishing cloth support are rotated to perform mirror polishing processing on the edge portion of the workpiece. That is, on the side-rotation-edge-difficult to rise or fall and gradually change the position of the rubbing support dragon, - Edge of the workpiece __ edge (10) The semiconductor wafer polishing short product of the present invention is dropped to a processing: P-knife, edge-cutting, and polishing. The semiconductor wafer® polishing method using the semiconductor wafer polishing composition of the present invention is used. In addition, the device is not limited to the above description, and any device described in, for example, Japanese Patent Laid-Open No. Hei. No. 2002-36079, and the like can be used. Hereinafter, the present invention will be further described in detail by way of examples. The measurement in the examples uses the following apparatus: 22 201237130 (1) Transmission Electron Microscope (TEM) observation: use of the (stock) manufacturing facility Transmissive electron microscope model H-7500. (2) Analysis of metal elements: Inductively Coupled Plasma (ICP) luminescence analyzer ULTIMA2 was used. (Production Example 1) (Active citric acid aqueous solution Preparation) Add 2.1 kg of sodium sulphate No. 3 to 13 kg of deionized water (SiO 2 : 28.8 wt%, Na20: 9.7 wt%, h20: 61.5 wt %), uniformly mixed to prepare a diluted sodium cerate having a cerium oxide concentration of 4% by weight. The diluted sodium citrate is passed through a H-type strongly acidic cation exchange resin (0rgano c〇rp〇rati〇) which is regenerated by using hydrochloric acid in advance. n (share) manufactured

Amberlite (registered trademark) IR12〇B) 4 〇〇〇ml of the column was subjected to a test, and 15 kg of an active acid aqueous solution having a pH of 29 was obtained at a concentration of 3.5% by weight of the cerium oxide. (the production of the seed sol), and then the confession of ', the secret of the second, the live (four) acid cutting liquid towel added silk potassium ion u compound, and then added _ and become the test, the twisting, knife 5'000 g, in After adding an aqueous potassium carbonate solution under stirring for 4 Torr, a solution of ^f was added to bring the pH to 8, and the mixture was heated, and then cooled in sodium water. The obtained (10) dihydrogen cut (transfer) is reduced by about 20 r% and is about 4 wt% due to evaporation of water 23 201237130 ^luipif. In addition, potassium ion infiltration penetrating type of thunder; weight%. The obtained colloidal silica dioxide was confirmed to have an average minor diameter of 5 nm to 6 H observed by a penetration electron microscope (TEM), and the main f/train ratio was in the range of h5 to 6, and the long diameter/short diameter A non-spherical shaped cerium oxide particle group having a flat value of 4. (Growth of oxidized hair particles) (biTd and 'the method of reheating the above-mentioned sol to the boot and adopting the layering =P)', adding 1G for 2 hours, and 活性g of active sodium sulphate In the case of an aqueous acid solution, '5% by weight of hydrogen peroxide was simultaneously added. The value of the average short diameter of the observation mirror (TEM) is about 1 Gnm, the long diameter is 3 liters, and the average of the long diameter/short diameter ratio is 6: the solar particle group. In addition, the molar ratio of the dioxide ions was 120. The TEM photograph is shown in the drawing. About (concentration of colloidal cerium oxide) (Mlcroza (registered and deleted) manufactured by Asahi Kasei (4), the obtained hetero-diglyoxide pump t is pressurized, and the concentration of the dioxide dioxide _ 2G liquid will be obtained. The properties of the colloidal cerium oxide are shown on the surface of the surface. ;: 031% by weight, so the conversion in terms of oxide is 0. 037% by weight. In addition, the molars of 'dioxane potassium ions 24 201237130 "fiuipir 210 (Production Example 2) (Preparation of seed sol) In the above production example i, colloidal silica was synthesized in the same manner except that the molar ratio of the cerium oxide/potassium ion was changed to 80. Dioxide 7 (seed sol) is reduced by evaporation of water, and the concentration of sulphur dioxide is about 4% by weight. In addition, the concentration of nitrite is about 0.033% by weight. By means of a transmission electron microscope (M), the average short diameter of 5 ca ~ 6 nm, the long diameter / short warp ratio in the range of ^ and the long diameter / short diameter ratio of the average shape of cerium oxide particles Group. ^状" (The growth of the oxidized particles of the oxidized stone in the eve of the ί: In the same manner as in the above Production Example 1, the dioptric oxidation of the same body was confirmed to contain pits of .3, and the observation by a transmission electron microscope (TEM) was about 丨. The aspect ratio of her was 2 to 4" = group: will be: non-spherical shaped hydrogen dioxide-particles (concentration of colloidal dioxide 11) (Xuyu uses a hollow fiber type super-membrane with a molecular weight cutoff of 6,000 (two ingenuity SIP-1013 manufactured by Asahi Kasei (4)), The obtained U-volume UF pull group adds a secret and concentrates to - the liquid colloidal dioxygenity obtained by the pump circulation is 2 or more. The trait of the evening is shown in the table. The potassium ion concentration is about 25 201237130 41131pif is α〇4ΐ, and %′ 0 is converted into oxide by the concentration of 0.049% by weight. The ratio of 'the dioxide/potassium ion' is calculated to be 330. [Table 1] Table 1 Manufacturing Example Colloidal silica dioxide obtained in the evening _&__ specific gravity (25 ° C) Si02 ft #%) χτ« r\ / -ϋ- ^ [------- -- Manufacturing Example 1_ 9.8 ------- Manufacturing Example 2 ' - 9.8 1.136 ---20.5 20.8 — INd2\J , 3⁄4 / κ2ο (% by weight) --_0·24 0.23 L 0.037 LZ 0.049 [Comparative Manufacturing Example 1] A colloidal ceria was produced in the same manner as in the particle formation step of Production Example 1, except that a compound which is a supply source of potassium ions was added. The obtained colloidal ceria was contained by an average observed by a transmission electron microscope (TEM). Colloidal silica dioxide with spherical cerium oxide particles having a particle size of 7 nm. Then, the obtained colloidal cerium oxide was again heated to 1 Torr, and 1 G, _ g of the active Wei water solution was added by a layering method for 2 hours. When the active aqueous solution of citric acid was added, a 5 wt% aqueous sodium hydroxide solution was simultaneously added so that the pH became a range of 95 to 1 Torr 5 . In the step of growing the carbon dioxide particles, a compound which is a supply source of potassium ions is not added. At the same time, the addition was completed, and the mixture was aged for 10 hours under y>c, and then allowed to cool. Then, a hollow fiber type filter membrane having a molecular weight of 6 and a ruthenium was used (Microza manufactured by L-forming) (registered trademark) uf II SIP-1013), subjected to pressure filtration by pump circulation, concentrated to dioxane

26 201237130

The value is 9; up to 2%. The obtained colloidal cerium oxide PH stone particles, junction micro-mirror (TEM) to observe the cerium oxide particles 腭 =,, 'has already contained spherical oxidized particles with an average particle diameter of bnm. cut. A TEM photograph is shown in Fig. 3. Production example of L additive A] Adding a test 95% sulfuric acid 37 5 kg to a 37.5 kg towel.

265 ^ &quot; 25% A aqueous solution of tetramethyl citrate. [Production Example of Additive B] to a pH of 7 and a state of kg [manufactured example of the additive B] was prepared by adding a emulsified stone to a pH of 8 4 to a l64 k 25% aqueous solution of tetradecyl ammonium hydroxide. 184 2 4 Norwegian hydrogen tetradecyl ammonium solution. A (4) kg of 25% oxygen oxytetramide solution was added thereto to prepare a 333 3 kg buffered tetradecyl ammonium solution. The tetrahydrocarbyl hydrogencarbonate is a salt which is a combination of a weak acid (pKa == i〇33) and a strong one. The addition (4) is a buffer solution of the present invention. Additive B is an additive for increasing electrical conductivity. (Example 1 and Example 2, Comparative Example 1) <Preparation of semiconductor wafer polishing composition of p Η value buffer composition> Colloidal oxidization produced by the production method of Production Example 2 and Comparative Production Example i In the 7 kg, the above-mentioned additive A and additive B were added in such a manner as to be in the level of Table i, respectively, and mixed for 24 hours. Thus, the 'having a pH buffering effect' produces a oxidizing hair concentration. 27 201237130 41131pif ί Semiconductor (5) A composition for round grinding. Three types of semiconductor wafers were developed and abbreviated as Examples 2 and Comparative Example 1 respectively, which are shown in Table 2. In addition, the conductivity "mS/m/l wt%-SiO 2" in the table is a value obtained by dividing the conductivity of each colloidal dioxotomy and dividing the measured value by the concentration of cerium oxide. [Table 2] Table 2

<Plane polishing test> The semiconductor wafer polishing composition of Table 2 was diluted with pure water to a concentration indicated by 3, and a polishing experiment was performed. An 8-inch etched wafer of a resistivity 〇〇ΐΩ·' crystal orientation <100> manufactured by the Czochralski method (CZ method) and a conductive type was used as a wafer. The results are shown in Table 3. The wafer polishing apparatus and polishing conditions used in the present invention are described. The polishing conditions were performed by mirror polishing using the following method.

Grinding device: sh_24 type manufactured by SpeedFam Co., Ltd. Fixed plate speed: 70RPM 28 201237130 ΤΙ 1 J ipii

Platen speed: 50RPM Grinding cloth: SUBA400 (manufactured by Nitta Haas) Load: 150g/cm2 Composition flow rate for semiconductor wafer polishing: 80 ml/min Grinding time: 1 〇min After the end of the plane polishing, replace the composition for semiconductor wafer polishing Flowing pure water, rinsing the semiconductor wafer polishing composition, taking out the wafer from the polishing column, and brushing with a 1% ammonia aqueous solution and pure water, and then performing a nitrogen blow - Rotate drying. The polishing rate is obtained from the difference in weight of the Shi Xi wafer before and after the polishing. The evaluation of the polished surface was carried out under the spotlight to visually observe the haze and the state of the pit. As is clear from the results shown in Table 3, the semiconductor wafer polishing compositions (Examples 1 and 2) containing the non-spherical cerium oxide particles of Production Example 2 and Production Example 2 contain spherical cerium oxide particles. In the semiconductor wafer polishing composition (Comparative Example 1), the polishing rate was higher, and haze or pits were not generated, and excellent polishing performance was exhibited. [Table 3] Table 3 + Conductor Wafer Research @Used Phase 1 --- cerium oxide concentration - (wt%) pits and haze on the polished surface __ 贯 ' Column I Actual wound 2 Comparative Example 1 2 4 2 4 2 4 Polishing speed (μπι/min) - 0.24 Heat 0.29 No 0.21 No 0.25 No 0.15 No 0.19 29 201237130 41131pif <Edge grinding test> The semiconductor wafer polishing composition of Table 2 was diluted with pure water to Table 4. The concentration of cerium oxide shown was subjected to the following grinding test. A 8 inch germanium wafer with a polycrystalline Si film was used as the germanium wafer. The results are shown in Table 4. The wafer edge polishing apparatus and polishing conditions used in the present invention are as follows. Grinding device: epd_2〇〇x type edge polishing device manufactured by SpeedFam Co., Ltd. Wafer rotation speed: 2000 times/min Grinding time: 60 seconds/piece Semiconductor wafer polishing composition Flow rate: 3 L/min Abrasive cloth: SUBA400 ( Nitta Haas Co., Ltd.) Load: 40 N/units were continuously ground for 10 wafers, and the 10th wafer was subjected to the following evaluation test. After the edge polishing is completed, pure semiconductor water is flowed instead of the semiconductor wafer polishing material, and the semiconductor wafer polishing composition is rinsed, the wafer is taken out from the polishing apparatus, and the brush is scraped with a 1% ammonia aqueous solution and pure water. After washing, spin drying was carried out while performing nitrogen gas blowing. For the wafer obtained above, the haze generated on the polished surface and the state of the pit and the grinding due to incomplete edge polishing are left to be visually observed under the spotlight, and 8 times of the entire circumference of the workpiece is performed. Microscopic observation. The polishing rate is determined based on the difference in weight of the device wafer before and after polishing. 201237130 τι 1^ipn [Table 4] Table 4 Example of semiconductor wafer polishing composition 1 1 f Example 2 Comparative Example 1 '-gasification degree (wt%) '2 — 4 2 4 2 4 Pit and haze are nothing, nothing, nothing, no? Nothing is not available. 4»No grinding speed (mg/min) 6.5 8.4 6.1 7.3 5.1 5.3 As shown by the results shown in Table 4, the semiconductor day containing non-diode (10) particles of Production Example 1 and Production Example 2 The composition for polishing the Japanese yen (Example 1 and Shell 2) is higher in the polishing rate than the composition for polishing the semiconductor wafer containing the spherical dioxo prior particles (Comparative Example 1), and the haze or pit is generated. , showing good grinding performance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a TEM photograph of colloidal cerium oxide obtained in Production Example 1. 2 is a TEM photograph of colloidal cerium oxide obtained in Production Example 2. Fig. 3 is a TEM photograph comparing the colloidal cerium oxide containing spherical cerium oxide particles obtained in Production Example 1. [Main component symbol description] Tuoba 31

Claims (1)

201237130 41131pif VII. Patent application scope: 1. A semiconductor crystal® polishing composition containing colloidal cerium oxide prepared by using active citric acid as a raw material in the presence of potassium ions, and a semiconductor semiconductor wafer polishing composition. The colloidal cerium oxide contains a smear ion and contains a non-spherical shaped cerium oxide particle group having a long warp/short diameter ratio of 1.2 to 10 as observed by a transmission electron microscope. 2. The semiconductor wafer polishing composition according to the above aspect of the invention, wherein the compound which is a source of the potassium ion is a potassium halide. 3. For the semiconductor wafer polishing composition of the above-mentioned item, the compound which is the source of the potassium ion is fluorinated. 4. The semiconductor wafer grinding material according to any one of the preceding claims, wherein the semiconductor wafer polishing composition comprises a reciprocal of an acid dissociation constant at 25 ° C. The logarithmic value (pKa) is a buffer solution of a combination of a weak acid of 8.0 to 12.5 and a quaternary ammonium base, and has a buffering effect at a pH of 8 to 11 at 25 C. 5. The semiconductor wafer polishing according to any one of the above-mentioned claims, wherein the composition for the semi-crystal phase polishing contains a salt of a strong acid and a quaternary ammonium base, and each The conductivity of the niobium cerium oxide particles at 25 ° C is 15 mS/m or more. The semiconductor wafer polishing composition according to Item 5, wherein the salt of the strong acid and the quaternary ammonium base is quaternary ammonium sulphate, quaternary ammonium sulphate or fluorinated quaternary ammonium. 7. The semiconductor wafer polishing group as described in claim 4 32 201237130 The composition 'the anion which constitutes the above weak acid is at least one of a carbonate ion and a biguanide hydrogen ion, and the above quaternary ammonium base is at least one of a choline ion sulfhydryl ion and a tetraethylammonium ion. 1 species. 8. The conductor wafer mortar composition according to any one of claims 1 to 7 wherein the colloidal dioxate is second. The average short diameter of the ruthenium particles observed by a transmission electron microscope was ~10 nm. 11111 Patent R = The manufacturing method of the composition for the polishing of the conductor, which is the composition for polishing the semiconductor wafer as described in the application, η is: the diluted sodium citrate and the cation exchange tree are touched' Remove the _ sub to prepare the active Wei water: pick up the stone, add the potassium ion supply source and the test material in the aqueous solution: and make the sulphur dioxide. The above-mentioned colloidal dioxide is oxidized to dioxane = ammonium by weight concentration. Adding weak acid and four grades in a light-punching manner. 10. Rotating (four) of a kind of grinding and earthing cloth. The surface of the patent is attached to the first item to the i-Semiconductor® contact, - The surface of the semiconductor wafer wafer to be coated, such as the composition for the application of the squeegee, is supplied. And/or the semiconductor wafer is rotated to grind the semi-conducting crucible. The drum-shaped grinding of the grinding-type abrasive cloth will be attached with a submerged member or a grinding surface having an arc-shaped working surface on the surface. 33 201237130 411Jlpif member The semiconductor wafer polishing composition according to any one of claims 1 to 8, wherein the polishing member and/or the semiconductor wafer are rotated while being pressed against the edge portion of the semiconductor wafer. While grinding the edge portion of the semiconductor wafer. 34