WO2005109481A1 - Composition de polissage et procédé de polissage de substrat - Google Patents

Composition de polissage et procédé de polissage de substrat Download PDF

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Publication number
WO2005109481A1
WO2005109481A1 PCT/JP2005/008518 JP2005008518W WO2005109481A1 WO 2005109481 A1 WO2005109481 A1 WO 2005109481A1 JP 2005008518 W JP2005008518 W JP 2005008518W WO 2005109481 A1 WO2005109481 A1 WO 2005109481A1
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WO
WIPO (PCT)
Prior art keywords
polishing
substrate
polishing composition
semiconductor substrate
composition according
Prior art date
Application number
PCT/JP2005/008518
Other languages
English (en)
Japanese (ja)
Inventor
Hiroki Katoh
Hiroyuki Nakano
Katsuyuki Shirai
Masashi Teramoto
Naoki Matsumoto
Kikurou Takemoto
Yoshiki Miura
Original Assignee
Nitta Haas Incorporated
Sumitomo Electric Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitta Haas Incorporated, Sumitomo Electric Industries, Ltd. filed Critical Nitta Haas Incorporated
Priority to JP2006513029A priority Critical patent/JP5116305B2/ja
Publication of WO2005109481A1 publication Critical patent/WO2005109481A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

Definitions

  • the present invention relates to a polishing composition mainly used for polishing a gallium nitride-based compound semiconductor substrate used for a blue light emitting diode or a blue-violet semiconductor laser, and a method for polishing a substrate using the polishing composition.
  • the present inventors have proposed a wet polishing method for precisely finishing a large-diameter gallium nitride substrate (Japanese Patent Application No. 2003-100373).
  • the metal platen is polished with a padded platen from the exposed surface, and the final polishing is polished with composite abrasive grains without using the conventional chlorine gas etching! ⁇ ⁇
  • the present inventor has conducted intensive studies on a polishing method that does not generate a surface damage layer and has no pits.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2001-322899
  • the polishing composition proposed in the above-mentioned application is polished in a pH range of an alkaline range even with a neutral force of pH 6.0 or more, the polishing is performed in a state where generation of scratches such as latent scratches and scratches is suppressed. Although it could be polished, it was not possible to suppress the small pits (pits) generated corresponding to the crystal defect accumulating sites on the gallium nitride substrate.
  • the crystal defect accumulating portion in the gallium nitride substrate has a brittle structure, and is subjected to an alkaline attack during polishing, so that it is preferentially cut off from a sound portion, resulting in V and even pits remaining. Things. If it is possible to make the polishing rate of a healthy part and that of a defective part the same by preventing the Al force and the re-attack on such a crystal defect gathering part and suppressing the polishing rate, it is possible to make the fine dent and The effective area can be further increased, and significant cost reduction of products can be expected.
  • the present invention has been made in view of such circumstances, and can easily perform a polishing operation on a substrate having a crystal defect concentration site such as a gallium nitride-based compound semiconductor substrate.
  • An object of the present invention is to provide a polishing composition capable of performing favorable polishing while suppressing the influence of the crystal defect concentration site, and a method for polishing a substrate using the polishing composition.
  • the polishing composition according to the first invention of the present invention has a soft abrasive and a hard abrasive dispersed in water as a dispersion medium, and has a pH value of 1.5 or more and 5.0 or less. It is characterized by being adjusted to the range.
  • the soft guns grains preferably in the range of the gun grain hardness force 00 ⁇ 1000KgZmm 2 by Vickers hardness test instrument hard guns grains, the hardness 1300 ⁇ 6000KgZmm by Vickers hardness test 2 It is preferable to be a cannonball! / ,.
  • the polishing composition of the first invention of the present invention since the soft abrasive grains surround the hard abrasive grains, the aggregation of the hard abrasive grains is suppressed. Problems such as the occurrence of scratches can be suppressed.
  • the pH value is adjusted to be in a range of 1.5 or more and 5.0 or less, an alkali attack on a crystal defect concentration portion of the object to be polished is avoided, and a normal portion of the object to be polished and the crystal defect concentration portion are separated. Polishing can be performed at the same polishing rate, and as a result, the region where crystal defects are concentrated is not preferentially polished. it can.
  • the pH value of the polishing composition according to the first invention of the present invention is more preferably in the range of pH 2.0 to pH 3.0.
  • the polishing composition according to the first invention of the present invention preferably contains a bactericide and a polishing inhibitor.
  • the presence of the disinfectant can prevent bacteria from proliferating in the polishing composition, so that problems such as impairment of the flowability of the polishing composition due to bacterial growth can be avoided and polishing can be prevented.
  • the polishing rate can be adjusted to an appropriate state.
  • the hard abrasive grains are selected from any one of diamond, nitride, and oxide having an average particle diameter of 50 nm or more and 100 nm or less. preferable. In this case, the polishing rate and the like can be made appropriate.
  • the soft abrasive grains have an average particle diameter in the range of 1Z20 or more and 2Z3 or less of the hard cannonballs. Further, it is preferable that the average particle diameter of the soft cannonball is in the range of 1Z20 to 1Z3 of the hard cannonball.
  • the soft abrasive grains are easily arranged so as to surround the hard abrasive grains, whereby aggregation of the hard abrasive grains can be prevented, and occurrence of defects such as scratches due to the aggregated hard abrasive grains can be suppressed.
  • the weight ratio of the soft cannonball to the hard cannonball is such that the soft cannonball 1 has a soft cannonball weight of 0.7 or more and 10.0 or more. It is preferable to be in the following range.
  • the soft abrasive grains are easily arranged so as to surround the hard abrasive grains, whereby aggregation of the hard cannonballs can be prevented and defects such as scratches caused by the aggregated hard cannonballs can be suppressed. .
  • the bactericide is preferably at least one of hydrogen peroxide and organic amine.
  • the organic amine is at least one of piperazine, TMAH (tetramethylammonium hydroxide), ethylenediamine, and diethylenetriamine. It is preferably one.
  • the polishing inhibitor may be a monosalt. It preferably contains at least one of a basic acid, a dibasic acid and a tribasic acid.
  • the polishing composition according to the first invention of the present invention is characterized in that, as the hard cannonball, 0.2% by weight or more and 3.0% by weight or less of diamond and 0.2% by weight or more of the soft cannonball 20. It is preferable that the polishing inhibitor be 0.1% by weight or less and 5.0% by weight or less, the disinfectant be 0.02% by weight or more and 2% by weight or less, and the balance be pure water. In this case, if the ratio of diamond, which is a hard abrasive, is lower than 0.2% by weight, the polishing rate becomes extremely low, and the productivity becomes worse. If the ratio of diamond is higher than 2.0% by weight, the polishing rate becomes extremely low.
  • the soft cannon can be used in an amount sufficient to completely disperse the diamond particles. If the ratio is less than 0.2% by weight, the diamond particles may not be sufficiently dispersed. This is not preferable because the occurrence of aggregation causes the occurrence of scratches. Conversely, if the ratio is more than 2% by weight, the polishing rate is extremely reduced, which is not preferable.
  • the method for polishing a substrate according to the first invention of the present invention is a method for polishing a semiconductor substrate, preferably a gallium nitride-based compound semiconductor substrate, using the polishing composition according to the first invention of the present invention. It is characterized by the following.
  • the soft cannonball of the polishing composition becomes hard cannonball.
  • aggregation of the hard abrasive grains can be suppressed, so that generation of scratches and the like due to the aggregated hard abrasive grains can be suppressed.
  • the pH value of the polishing composition to a range of 1.5 or more and 5.0 or less, an alkali attack on a crystal defect concentration site in a semiconductor substrate to be polished is avoided. Defect concentration sites can be prevented from being preferentially polished. As a result, the generation of minute pits (pits) caused by preferentially polishing the crystal defect concentration site can be eliminated.
  • the method for polishing a substrate according to the first invention of the present invention includes a polishing surface opposing a surface to be polished of a semiconductor substrate, and rotating around an axis along the opposing direction.
  • polishing load on said semiconductor substrate of the polishing tool to be 50 gf / cm 2 or more 900 gf / cm 2 or more
  • the moving speed at the outer periphery of the polishing surface of the polishing tool is 25mZmin or more 250m
  • the polishing composition is used in a temperature range of 10 ° C. or more and 80 ° C. or less during polishing.
  • a semiconductor substrate is polished by using the polishing composition in a state where a polishing pad is attached to a polishing platen. Good.
  • the polishing pad when polishing the semiconductor substrate, preferably has a compression ratio of 1. Ovol% or more and 20 vol% or less. No.
  • the substrate polishing method according to the first invention of the present invention is characterized in that the polished surface of the polished surface of the semiconductor substrate has an arithmetic average roughness (Ra) of 20 angstroms or less. Further, the thickness variation (TTV: Total Thickness Variation) of the surface to be polished is preferably 20 ⁇ m or less.
  • the composite abrasive grains are polished in an acidic region with a low alkaline attack, and as a result, not only scratches and latent scratches but also fine depressions The generation of (pits) has also been suppressed, and a polished surface with high precision flatness can be obtained.
  • the present inventors have conducted intensive studies to provide a higher-quality semiconductor substrate, in particular, a gallium nitride-based compound semiconductor substrate. As a result, the following polishing composition and substrate of the second invention of the present invention were obtained. A polishing method was found.
  • the polishing composition according to the second invention of the present invention is a polishing composition used for further polishing the semiconductor substrate after polishing the semiconductor substrate using the polishing composition according to the first invention.
  • the soft cannonball is dispersed in water as a dispersion medium and the pH value is adjusted to a range of 1.5 or more and 5.0 or less.
  • a semiconductor substrate polished using the polishing composition according to the first invention can be used by using the polishing composition according to the second invention. Further polishing is performed to polish the surface of the semiconductor substrate, particularly, the surface of the gallium nitride-based compound semiconductor substrate. The distortion is further improved.
  • the pH value of the polishing composition according to the second invention is more preferably in the range of pH 3.0 to pH 5.0.
  • the polishing composition according to the second invention of the present invention preferably contains a bactericide and a polishing inhibitor.
  • a disinfectant bacteria can be prevented from growing in the polishing composition, so that it is possible to avoid problems such as deterioration of the flowability of the polishing composition due to bacterial growth, and
  • the polishing rate can be adjusted to an appropriate state.
  • the bactericide is preferably at least one of hydrogen peroxide and organic amine.
  • the organic amine is at least one of piperazine, TMAH (tetramethylammonium hydroxide), ethylenediamine, and diethylenetriamine. It is preferably one.
  • the polishing inhibitor preferably contains at least one of a monobasic acid, a dibasic acid and a tribasic acid. preferable.
  • the average particle diameter of the soft cannonball is in the range of 20 nm to 200 nm.
  • the concentration of the soft cannonball is preferably in the range of 0.1% by weight to 50% by weight, more preferably 9% by weight. More preferably, it is in the range of not less than 19% by weight.
  • the method for polishing a substrate according to the second invention of the present invention is directed to a first polishing method for polishing a semiconductor substrate, preferably a gallium nitride-based compound semiconductor substrate, using the polishing composition according to the first invention. And a second polishing step of polishing the semiconductor substrate using the polishing composition according to the second invention after the first polishing step.
  • the semiconductor substrate that has been primarily polished in the first polishing step using the polishing composition according to the first invention is subjected to the second invention. Since the secondary polishing is performed in the second polishing step using the polishing composition according to the above, the polishing strain on the surface of the semiconductor substrate, particularly, the surface of the gallium nitride-based compound semiconductor substrate is further improved.
  • the second polishing step includes a polished surface facing the polished surface of the semiconductor substrate and faces the polished surface.
  • polishing load with respect to the semiconductor substrate of the polishing tool is rotated about the axis along the direction is at 50GfZcm 2 or 900 gf / cm 2 or less, you Keru moving speed on the outer periphery of the polishing surface of the polishing tool is less 250mZmin more 20mZmin It is preferred that
  • the polishing composition according to the second invention is used in a temperature range of 10 ° C to 80 ° C during polishing. preferable.
  • the polishing according to the second invention is performed in a state where a polishing pad is attached to a polishing platen.
  • the semiconductor substrate is polished using a composition.
  • the compression rate of the polishing pad is 1. Ovol% or more and 20vol or less. % Or less! / ,.
  • the surface roughness of the polished surface of the semiconductor substrate after being polished in the second polishing step is an arithmetic average roughness (Ra).
  • the thickness variation (TTV) of the surface to be polished is preferably 20 ⁇ m or less.
  • the polishing composition and the method for polishing a substrate according to the first invention of the present invention as a result of performing the composite abrasive polishing in an acidic region having a small alkali attack, the polishing of the gallium nitride-based compound semiconductor substrate is performed.
  • the polishing rate at the crystal defect gathering portion can be made equal to the polishing speed at the normal crystal portion.
  • the polishing rate could be kept the same as before. In this way, the generation of not only scratches and latent scratches but also micro-pits (pits) has been suppressed, and a polished surface having high precision flatness can be obtained.
  • the semiconductor substrate primarily polished in the first polishing step using the polishing composition according to the first invention is used.
  • FIG. 1 is a side view schematically showing a state of polishing using the polishing composition according to the first invention of the present invention.
  • FIG. 2 is a graph showing the relationship between the pH value of a polishing composition and the number of pits on a substrate after polishing as an example of the present invention.
  • FIG. 3 is a metal micrograph ( ⁇ 50) showing a polishing result of a gallium nitride substrate polished using the polishing composition of the comparative example for comparison with the example of the present invention.
  • FIG. 4 is a metal micrograph ( ⁇ 50) showing the result of polishing a gallium nitride substrate polished with the polishing composition according to the present invention, in an example according to the present invention.
  • FIG. 5 is a side view schematically showing a state of polishing using the polishing composition according to the second invention of the present invention.
  • FIG. 1 there is schematically shown a polishing apparatus 1 for polishing a gallium nitride compound semiconductor substrate using the polishing composition according to the first invention of the present invention.
  • the polishing apparatus 1 is provided with a small-diameter disk-shaped holding-side surface plate 5 for holding an object to be polished 3 via a backing film 4 in a state facing above a large-diameter disk-shaped metal surface plate 2.
  • a polishing pad 6 is attached on the metal platen 2 to form a polishing tool.
  • the polishing pad 6 is made of a resin whose surface is processed in a suede tone.
  • the holding surface plate 5 is driven around a vertical axis by a driving motor 11 connected to a rotating shaft 9 and a belt 10, and the metal surface plate 2 is driven around a rotating shaft 12 and a belt 13 to be driven. , Each of which is rotationally driven around the vertical axis.
  • a desired polishing load is applied to the workpiece 3 through the holding surface plate 5.
  • a gallium nitride-based compound semiconductor substrate, which is the object to be polished 3, is held on a holding platen 5 by a backing film 4.
  • the polishing device 1 is provided with a supply device 8 that supplies a polishing slurry 7 as the polishing composition according to the first invention dropwise to a polishing position.
  • the supply device 8 collects the polishing slurry 7 used for polishing and circulates it so that it can be supplied again to the polishing location.
  • the polishing slurry 7 is a polishing composition according to the first invention of the present invention, in which hard cannonballs and soft abrasive grains are dispersed in pure water as a dispersion medium, and a polishing inhibitor and a sterilizing agent are further dispersed. It is composed by mixing agents. Fine diamond particles are used as hard abrasive particles, and colloidal silica is used as soft abrasive particles.
  • nitrides such as indium nitride and silicon nitride, and oxide nitrides such as alpha alumina, aluminum oxide and zirconium oxide are used. It may be.
  • the soft cannonball at least one of fumed silica, colloidal alumina, fumed alumina, beta alumina, fumed titania and the like may be used in addition to colloidal silica.
  • the specific resistance of the pure water used in the polishing slurry 7 is preferably at least 1 ⁇ 'cm.
  • polishing slurry 7 it is preferable to use one of hydrochloric acid and phosphoric acid as the polishing inhibitor.
  • dibasic acids such as sulfuric acid may be used in addition to hydrochloric acid as a monobasic acid and phosphoric acid as a tribasic acid. Further, a plurality of these acids may be combined to form a polishing inhibitor.
  • monobasic acids and dibasic acids may be those represented by the chemical formulas (R'COOM) and (R '(COOM)), wherein R is a linear alkyl group,
  • M means, for example, a metal element.
  • nitric acid, acetic acid and the like may be used as the polishing inhibitor in addition to the above.
  • the polishing inhibitor also adjusts the pH value of the polishing composition to a predetermined range. Therefore, by adjusting the pH value, the pH value of the polishing composition is set in a range from 1.5 to 5.0.
  • the disinfectant is at least one of hydrogen peroxide, piperazine, a kind of organic amine, TMAH (tetramethylammonium hydroxide), ethylenediamine, and diethylenetriamine. It is preferable to use them. Since these organic amines tend to coordinate with metal ions taken into the polishing slurry during polishing to form a complex, the organic amine not only has a sterilizing effect but also suppresses metal ion contamination of the gallium nitride-based compound semiconductor substrate. Also contributes.
  • TMAH tetramethylammonium hydroxide
  • the polishing composition according to the first invention of the present invention has a composition in which the average particle diameter of diamond is in the range of 50 nm or more and 100 nm or less, whereas the colloidal silica of soft cannonball has an average particle diameter of It is preferably in the range of 35 nm or more and 130 nm or less, and the particle size of the colloidal silica is preferably in the range of 1Z20 to 2Z3 in terms of the diamond particle size in order to suppress aggregation of the diamond abrasive particles by the colloidal silica abrasive particles. That is, if the particle size of the colloidal silica is too large, the possibility of concealing the diamond particles increases.
  • the polishing rate is extremely reduced, which is not preferable.
  • the particle diameter of the colloidal silica is too small, the diamond particles are exposed, and immediately with such exposed diamond particles, the aggregation of the diamond particles easily occurs. Scratch is likely to occur during polishing.
  • the weight ratio of the soft abrasive grains to the hard abrasive grains in the polishing composition is preferably set in the range of 0.7 to 10.0 of the soft cannon particles with respect to the hard abrasive grains 1.
  • the weight ratio in the polishing composition is preferably such that colloidal silica is in the range of 0.9 or more to 2.7 or less with respect to 1 diamond particle. .
  • the specific force of each composition in the polishing slurry 7 is not less than 0.2% by weight and not more than 2.0% by weight of diamond as hard cannonball, and not less than 0.2% by weight of 20.0% by weight of colloidal silica as soft cannonball.
  • a polishing composition having a composition in which the polishing inhibitor is 0.1% by weight or more and 5.0% by weight or less, the disinfectant is 0.02% by weight or more and 2% by weight or less, and the balance is pure hydraulic power is preferred.
  • the amount of diamond, which is a hard globule is less than 0.02% by weight, the polishing rate becomes extremely low, and the productivity is deteriorated.
  • the content is more than 2.0% by weight, the cost of polishing is increased because diamond is expensive, which is not preferable.
  • Soft cannonballs are not preferred, as long as the amount is sufficient to completely disperse the diamond particles, and if the amount is too large, the polishing rate is extremely reduced. If it is too small, it will not disperse completely and cause scratches.
  • the fungicide should be at least 0.02% by weight is necessary. If the amount is too small, the bacteria in the polishing slurry 7 cannot be completely sterilized.
  • the polishing load is 50 gfZcm 2 or more and 900 gfZcm 2 or less
  • the moving speed on the outer periphery of the polished surface of the metal platen 2 (Peripheral speed) is preferably 20 mZmin or more and 250 mZmin or less.
  • the moving speed at the outer periphery of the polished surface of the metal platen 2 is more preferably 20 mZmin or more and 30 mZmin or less, more preferably 25 mZmin or more and 30 mZmin or less.
  • the temperature at which the polishing slurry 7 is supplied to the polishing surface is preferably in the range of 10 ° C to 80 ° C. Setting the temperature within this range is preferable in terms of the polishing rate. Further, the compression rate of the polishing pad 5 during the polishing is preferably in the range of 1. Ovol% to 20 vol%. It is preferable to set the compression ratio within this range in that the surface roughness and the occurrence of latent scratches can be suppressed.
  • the surface roughness of the polished surface of the object to be polished after polishing in this manner is such that the arithmetic average roughness (Ra) is 20 ⁇ or less, and the thickness variation of the polished surface ( (TTV) can be reduced to 20 ⁇ m or less, which eliminates the need for the RIE process and enables precision finishing only by the wet polishing process.
  • the present inventor prepared a polishing slurry as the polishing composition according to the first invention of the present invention and a polishing slurry as a comparative example, and performed a polishing test using these polishing slurries.
  • the explanation is given below.
  • polishing load 300gfZcm 2 Polishing time 60 minutes or more and 80 minutes or less, surface plate rotation speed 60rpm or more and 80rpm or less (peripheral speed of the surface plate 20mZmin or more and 30mZmin or less), polishing slurry flow rate 20mlZmin or more and 30mlZmin or less, precision polishing pad A suede for finishing A polishing pad made of resin preparation (Whitex RG-S, manufactured by Yutta Haas Co., Ltd.) was used.
  • the object to be polished is a gallium nitride-based compound semiconductor substrate (wafer).
  • the composition of the polishing slurry is as follows: diamond abrasive grains (particle diameter 500 nm), colloidal silica (particle diameter 70 nm), pure water (specific resistance 1 M ⁇ ⁇ cm or more), HC1 (hydrochloric acid) as a polishing inhibitor, and A bactericide, HO (peroxydani hydrogen) was used. As comparative examples, pH values were adjusted to 9, 11, and 12.
  • the adjusted polishing slurry was adjusted to the alkali side by using potassium hydroxide instead of hydrochloric acid as a polishing inhibitor. Further, the polishing slurry of the comparative example having a pH value of 7 was adjusted to be neutral.
  • the pH value was adjusted to 2, 3, and 5 by adjusting to 0.0008% by weight.
  • the rest is pure water.
  • the polishing slurry of Comparative example adjusted to the alkaline side for the polishing slurry one comparative example of a pH of 7, the composition is colloidal silica 1.0 wt%, the diamond 0.9 wt 0/0, HO is 0.03% by weight, and the concentration of the potassium hydroxide is 0.0043% by weight.
  • the balance is pure water.
  • the state of the formation of the fine dents on the polished surface of the gallium nitride-based compound semiconductor polished using each of these polishing slurries an image of each surface was taken at a magnification of 50 times using a metallographic microscope. Based on the imaging results, the state of occurrence of the micro pits was numerically evaluated (pit index).
  • the pit index is an evaluation visually perceived to be a depression rather than a groove width and a shadow width.
  • the polishing rate at this time was 1.4 mZhr.
  • the degree of rawness is in the range of 2 to 4 in terms of the pit index, it is determined that polishing has been performed well.
  • the degree of generation of micro-pits (pits) was determined by the above pit index.
  • Fig. 3 shows a photograph of the surface of a gallium nitride-based compound semiconductor substrate polished according to No. 7) taken with a metallographic microscope at 50x magnification.
  • the depth of the stripe-shaped depression corresponding to the minute depression was larger than the desired depth value serving as a reference for determining a non-defective product.
  • the depth of the stripe-shaped micro dent is shallower than that of the comparative example of FIG. 3, and the flatness in which the generation of the micro dent is suppressed is suppressed. It was determined that excellent polishing was performed.
  • the surface of the semiconductor substrate polished by the method for polishing a substrate according to the first invention using the polishing composition according to the first invention of the present invention as described above is subjected to reflection high-energy electron diffraction (RHEED). ) Method was used to evaluate the outermost surface structure.
  • RHEED reflection high-energy electron diffraction
  • the semiconductor substrate polished (primary polishing) using the polishing composition according to the first invention is further polished (secondary polishing).
  • the polishing composition used for the secondary polishing is the polishing composition according to the second invention, and the method for polishing a substrate according to the second invention is provided with the primary and secondary polishing steps.
  • the polishing composition and the method for polishing a substrate according to the second invention of the present invention will be described.
  • the first invention not only generation of scratches and latent scratches but also generation of minute pits (pits) is suppressed. Since a polished surface having high-precision flatness can be obtained, the second invention may be implemented as needed.
  • FIG. 5 is a schematic configuration diagram of a polishing apparatus 1 for explaining a polishing composition and a method of polishing a substrate according to the second invention of the present invention, and a portion corresponding to FIG.
  • the same reference numerals are given and the description is omitted.
  • the gallium nitride based compound semiconductor substrate, which is the object to be polished 3 ′, is held on a holding platen 5 by a backing film 4.
  • the gallium nitride-based compound semiconductor substrate, which is the object to be polished 3 ', is polished in the first polishing step using the polishing slurry 7, which is the polishing composition according to the first invention, as described above. This is the semiconductor wafer after completion.
  • the supply device 8 supplies the polishing slurry 7 ′, which is the polishing composition according to the second invention, to the polishing position in place of the polishing slurry 7, which is the polishing composition according to the first invention. It is a thing.
  • the other configurations of the polishing apparatus 1 are the same as those of the method for polishing a substrate using the polishing composition according to the first aspect of the present invention, and a description thereof will be omitted.
  • the polishing slurry 7 ' which is the polishing composition according to the second invention of the present invention, is configured by dispersing soft abrasive grains in pure water as a dispersion medium, and further mixing a polishing inhibitor and a disinfectant. It is a thing.
  • Colloidal silica is used as the soft abrasive.
  • As the soft abrasive at least one of fumed silica, colloidal alumina, fumed alumina, beta alumina, fumed titania, and the like may be used in addition to colloidal silica.
  • the average particle size of the soft cannonball is preferably in the range of 20 nm or more and 200 nm or less, more preferably in the range of 35 nm or more and 130 nm or less.
  • the concentration of the soft cannonball is preferably in the range of 0.1% by weight to 50% by weight, and more preferably in the range of 9% by weight to 19% by weight. It is preferable that the specific resistance of the pure water used for the polishing slurry 17 ′ is 1 ⁇ ′cm or more.
  • polishing slurry 7 ' it is preferable to use either hydrochloric acid or phosphoric acid as the polishing inhibitor. That's right.
  • dibasic acids such as sulfuric acid may be used in addition to hydrochloric acid as a monobasic acid and phosphoric acid as a tribasic acid. Further, a combination of a plurality of these acids may be used as a polishing inhibitor.
  • monobasic acid or dibasic acid those represented by the chemical formulas (R'COOM) and (R '(COOM)) may be used, where R is a linear alkyl group.
  • M means, for example, a metal element.
  • nitric acid, acetic acid and the like may be used as the polishing inhibitor in addition to the above.
  • the polishing inhibitor also adjusts the pH value of the polishing composition to a predetermined range. Therefore, by adjusting the pH value, the pH value of the polishing composition according to the second invention of the present invention is set in a range of 1.5 or more and 5.0 or less.
  • the germicide it is preferable to use at least one of hydrogen peroxide, piperazine which is a kind of organic amine, TMAH (tetramethylammonium hydroxide), ethylenediamine and diethylenetriamine.
  • the method for polishing a substrate according to the second invention of the present invention comprises a first polishing step using the above-described polishing composition according to the first invention, and a polishing composition according to the second invention. And a second polishing step using an object.
  • the first polishing step is the same as the substrate polishing method according to the first invention of the present invention.
  • the polishing load is 50GfZcm 2 or 500 gf / cm 2 or less, the polishing time, for example, It is preferably about one hour, but may be shortened or extended as necessary. It is preferable that the moving speed (peripheral speed) at the outer periphery of the polished surface of the metal platen 2 is not less than 20 mZmin and not more than 250 mZmin.
  • the moving speed at the outer periphery of the polished surface of the metal platen 2 is more preferably 20 mZmin or more and 30 mZmin or less, more preferably 25 mZmin or more and 30 mZmin or less.
  • the temperature at which the polishing slurry 7 is supplied to the polishing surface is preferably in the range of 10 ° C to 80 ° C. Setting the temperature within this range is preferable in terms of the polishing rate.
  • the compression rate of the polishing pad 5 during the polishing is preferably in the range of 1. Ovol% to 20 vol%. It is preferable to set the compression ratio in this range in that the surface roughness and the occurrence of latent scratches can be suppressed.
  • the present inventor prepared four types of polishing slurries as the polishing composition according to the second invention of the present invention, and performed a polishing test using these polishing slurries. The explanation is given below.
  • polishing load 300gfZcm 2 Polishing time 60 minutes or more and 80 minutes or less, surface plate rotation speed 60rpm or more and 80rpm or less (peripheral speed of the surface plate 20mZmin or more and 30mZmin or less), polishing slurry flow rate 20mlZmin or more and 30mlZmin or less, precision polishing pad A suede for finishing A polishing pad made of resin preparation (Whitex RG-S, manufactured by Yutta Haas Co., Ltd.) was used.
  • the object to be polished is a gallium nitride-based compound semiconductor substrate (Ueno), which has been polished using the polishing composition according to the first invention.
  • the composition of the polishing slurry is colloidal silica (particle size 70 nm), pure water (specific resistance 1 ⁇ or more), HC1 as a polishing inhibitor and HO (hydrogen peroxide) as a disinfectant.
  • the weight concentration of colloidal silica was set to 3, 9, 15, and 19% by weight for comparison.
  • the pH was 4, and the HC1 concentration was 0.0015% by weight.
  • Each of these polishing slurries was used to polish a gallium nitride-based compound semiconductor substrate that had already been polished using the polishing composition according to the first invention described above, and the polishing strain on the surface was improved.
  • Diffraction photographs were taken using reflection high-energy electron diffraction (RHEED), and the intensity of the Kikuchi line was compared numerically. Note that the surface of the gallium nitride-based compound semiconductor substrate polished before polishing with these polishing slurries, that is, polished using the polishing composition according to the first invention, was similarly quantified.
  • Reflection high-energy electron diffraction is a method of observing the surface structure by irradiating an electron beam horizontally on a substrate and projecting a diffraction pattern on a screen using the electron beam diffracted on the surface. . Since the electron beam enters the substrate horizontally, the entrance of the incident electron beam causes the surface force of the substrate to be limited to several atomic layers. Therefore, the outermost surface can be evaluated.
  • the reflection high-energy electron diffraction (RHEED) apparatus and measurement conditions used are as follows.
  • Electron beam acceleration voltage / current 30kV / 15mA
  • Table 2 shows the results of the 10-level evaluation using the Kikuchi line measured as described above.
  • the polishing distortion on the outermost surface of the semiconductor substrate is further improved.
  • the present invention relates to a polishing composition (polishing slurry) mainly used for polishing a gallium nitride-based semiconductor substrate, and is used, for example, for polishing a thin film of a substrate in various semiconductor manufacturing processes. It can be used for polishing slurries.
  • a polishing composition polishing slurry mainly used for polishing a gallium nitride-based semiconductor substrate, and is used, for example, for polishing a thin film of a substrate in various semiconductor manufacturing processes. It can be used for polishing slurries.

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Abstract

[PROBLEMES] Fournir une composition de polissage pour polir facilement un substrat, possédant une partie de concentration de défauts cristallins, comme par exemple un substrat semi-conducteur de composé de nitrure de gallium, et pour effectuer un excellent polissage en supprimant les influences de la partie concentration de défauts cristallins, et proposer un procédé de polissage de substrat utilisant une telle composition de polissage. [MOYENS POUR RESOUDRE LES PROBLEMES] Il est prévu une composition de polissage possédant des grains abrasifs doux et des grains abrasifs durs dispersés dans de l’eau comme milieu de dispersion et possédant une valeur de pH ajustée dans la fourchette de 1,5 ou supérieure mais ne dépassant pas 5,0. Un substrat semi-conducteur est poli à l’aide d’une telle composition de polissage.
PCT/JP2005/008518 2004-05-11 2005-05-10 Composition de polissage et procédé de polissage de substrat WO2005109481A1 (fr)

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EP1897978A1 (fr) * 2006-09-05 2008-03-12 Sumitomo Electric Industries, Ltd. Procédé de fabrication de substrat de nitrures du groupe III, substrat de nitrures du groupe III, substrat de nitrures du groupe III avec une couche épitaxiale, dispositif à nitrures du groupe III, procédé de fabrication de substrat de nitrures du groupe III avec une couche épitaxiale, et procédé de fabrication de dispositif à nitrures du groupe III
JP2009034809A (ja) * 2007-07-10 2009-02-19 Panasonic Corp スラリー供給装置の洗浄方法およびスラリー供給装置
JP2011086656A (ja) * 2009-10-13 2011-04-28 Sumitomo Electric Ind Ltd 基板の研磨方法、基板および発光素子
JP2012519969A (ja) * 2009-03-13 2012-08-30 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド ナノダイヤモンドを用いた化学機械平坦化
JP2013117007A (ja) * 2011-11-01 2013-06-13 Crystal Kogaku:Kk 研磨材
JP2013201176A (ja) * 2012-03-23 2013-10-03 Mitsubishi Chemicals Corp ポリシングスラリー、及び第１３族窒化物基板の製造方法
JP2016169378A (ja) * 2015-03-11 2016-09-23 株式会社Adeka 硬質表面用除菌洗浄剤組成物及び硬質表面用除菌洗浄剤組成物セット
JP2019119776A (ja) * 2017-12-28 2019-07-22 花王株式会社 研磨液組成物

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JP6185274B2 (ja) * 2013-04-19 2017-08-23 株式会社フジミインコーポレーテッド 磁気ディスク基板用研磨組成物キット

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JP4322035B2 (ja) * 2003-04-03 2009-08-26 ニッタ・ハース株式会社 半導体基板用研磨組成物及びこれを用いた半導体基板研磨方法

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JPH11263968A (ja) * 1998-03-19 1999-09-28 Nec Kansai Ltd 研磨用スラリ及び研磨方法
JP2003347244A (ja) * 2002-05-29 2003-12-05 Mitsubishi Electric Corp 半導体ウエハの研磨方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1897978A1 (fr) * 2006-09-05 2008-03-12 Sumitomo Electric Industries, Ltd. Procédé de fabrication de substrat de nitrures du groupe III, substrat de nitrures du groupe III, substrat de nitrures du groupe III avec une couche épitaxiale, dispositif à nitrures du groupe III, procédé de fabrication de substrat de nitrures du groupe III avec une couche épitaxiale, et procédé de fabrication de dispositif à nitrures du groupe III
JP2009034809A (ja) * 2007-07-10 2009-02-19 Panasonic Corp スラリー供給装置の洗浄方法およびスラリー供給装置
JP2012519969A (ja) * 2009-03-13 2012-08-30 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド ナノダイヤモンドを用いた化学機械平坦化
JP2011086656A (ja) * 2009-10-13 2011-04-28 Sumitomo Electric Ind Ltd 基板の研磨方法、基板および発光素子
JP2013117007A (ja) * 2011-11-01 2013-06-13 Crystal Kogaku:Kk 研磨材
JP2013201176A (ja) * 2012-03-23 2013-10-03 Mitsubishi Chemicals Corp ポリシングスラリー、及び第１３族窒化物基板の製造方法
JP2016169378A (ja) * 2015-03-11 2016-09-23 株式会社Adeka 硬質表面用除菌洗浄剤組成物及び硬質表面用除菌洗浄剤組成物セット
JP2019119776A (ja) * 2017-12-28 2019-07-22 花王株式会社 研磨液組成物

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JPWO2005109481A1 (ja) 2008-03-21
TWI374929B (fr) 2012-10-21
TW200609336A (en) 2006-03-16

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