WO2001071788A1 - Eau pour le stockage de plaquettes de silicium et procede de stockage - Google Patents
Eau pour le stockage de plaquettes de silicium et procede de stockageInfo
- Publication number
- WO2001071788A1 WO2001071788A1 PCT/JP2001/001903 JP0101903W WO0171788A1 WO 2001071788 A1 WO2001071788 A1 WO 2001071788A1 JP 0101903 W JP0101903 W JP 0101903W WO 0171788 A1 WO0171788 A1 WO 0171788A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- storage
- storage water
- wafer
- storing
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 235000012431 wafers Nutrition 0.000 title claims abstract description 110
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 38
- 239000010703 silicon Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000000694 effects Effects 0.000 claims abstract description 38
- 150000007524 organic acids Chemical class 0.000 claims abstract description 23
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000003860 storage Methods 0.000 claims description 132
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 239000004094 surface-active agent Substances 0.000 claims description 53
- 238000005498 polishing Methods 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 150000005215 alkyl ethers Chemical class 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 230000006866 deterioration Effects 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 12
- 238000004140 cleaning Methods 0.000 abstract description 12
- 239000010419 fine particle Substances 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract 2
- 239000013522 chelant Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 20
- -1 polyoxyethylene Polymers 0.000 description 18
- 230000003746 surface roughness Effects 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 238000011109 contamination Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 7
- 230000002950 deficient Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
Definitions
- the present invention relates to a storage water and a storage method used for storing silicon wafers (sometimes simply referred to as wafers), particularly wafers immediately after etching or polishing, in water.
- silicon wafers sometimes simply referred to as wafers
- a silicon wafer manufacturing method includes a slicing step of slicing a single-crystal ingot to obtain a wafer in the form of a thin disk, cracking of a wafer obtained by the slicing step, A chamfering process for chamfering the outer periphery to prevent chipping, a lapping process for flattening the wafer, and an etch for removing machining distortion remaining in the chamfered and wrapped wafer.
- a polishing step for polishing the wafer surface to a mirror surface (polishing), and a cleaning step for cleaning the polished wafer and removing abrasives and foreign substances adhering thereto.
- the above steps show the main steps.Other steps such as a heat treatment step are added, and the order of the steps is changed. Storage may be required and must be done in a manner appropriate for the condition of the silicon.
- the wafer after the polishing step A has a cleaning step C in the next step, and is stored in water (in pure water) during the waiting time before it is sent to this step.
- Tank storage B is usually used. This is because if the wafer is left in the air, the slurry caused by the drying of the polishing slurry This is because it is difficult to remove the wafer by cleaning in the next process ( and the wafer surface after polishing is very unstable. There is a problem in that the fine particles containing metal tend to adhere, and the wafer surface is easily etched by an alkali component in the polishing agent, which lowers the wafer quality after cleaning, particularly the oxide film breakdown voltage. This is a major factor.
- the applicant of the present application has proposed a technique for regulating the concentration of metal, particularly Cu, in storage water in order to prevent the oxide film breakdown voltage from being deteriorated due to metal contamination (Japanese Patent Laid-Open No. 11-191943). ) And a technology in which a chelating agent was added to water for storage (Japanese Patent Publication No. Hei 11-243703).
- Japanese Patent Application Laid-Open No. 11-191943 Japanese Patent Application Laid-Open No.
- an oxide film formed on the surface of the wafer by hydrogen peroxide or ozone is used for the purpose of preventing the attachment of fine particles (Japanese Patent Application Laid-Open No. Hei 7-246304, Kaihei 8-8 3 7 8 3 Publication).
- the wafer with the oxide film formed thereon can prevent particles, it still has the problem that the surface roughness of the ⁇ : -8 surface is generated.
- the present invention has been made in view of the above-described problems, and reduces the adhesion of metal-containing fine particles to a wafer surface, prevents the surface of the wafer from being etched by an alkali component in an abrasive, Storage water and storage for silicon wafers to prevent deterioration of wafer quality, especially oxide film breakdown voltage after cleaning, or deterioration of haze (HAZE) and adhesion of particles.
- the aim is to provide a method.
- a first aspect of the present invention is a storage water used for storing silicon wafers in water, which has a chelating effect. It is characterized by adding an organic acid to pure water and being weakly acidic to neutral.
- organic acid examples include water-soluble organic acids having 10 or less carbon atoms and containing two or more carboxyl groups, such as oxalic acid, citric acid, tartaric acid, lingic acid, malonic acid, benzenetetracarboxylic acid, and the like.
- oxalic acid citric acid, tartaric acid, lingic acid, malonic acid, benzenetetracarboxylic acid, and the like.
- citric acid is preferred.
- a surfactant may be further added to the storage water.
- the pH of the storage water is preferably 3 or more and 7 or less, but more preferably pH 4 or more and 7 or less.
- the amount of the organic acid added is preferably 0.0001 to 0.01%, more preferably 0.0001 to 0.05%. In this specification, when the addition amount or the concentration of the organic acid is simply expressed by%, it means mass%.
- an alkaline abrasive containing an alkaline component is generally used, and the wafer is often stored in storage water immediately after polishing, but has a chelating effect. If the wafer is stored with water for storage of an organic acid, for example, citric acid or an acidic solution to which cunic acid and a surfactant have been added, (4) It also has the effect of neutralizing the residual component adhering to the wafer surface, prevents excessive etching by alkali, and keeps the surface condition of the wafer surface in good condition.
- an organic acid for example, citric acid or an acidic solution to which cunic acid and a surfactant have been added
- the storage water after polishing gradually changes to an alkaline property with an increase in the number of times of use, but from an organic acid having a chelating effect such as citric acid or an acid containing cunic acid and a surfactant to a medium acid. If stored in a neutral solution, the change to alkaline will be prevented. Further, it is not preferable that the storage water for the silicon wafer has an effect of etching the silicon wafer. This is because, since the storage time is not constant, if the etching effect is present, there is a problem that the surface state of the wafer differs depending on the batch. To reduce the etching effect, the storage water should be based on pure water, and an organic acid having a chelating effect, for example, citric acid should be added thereto, and if necessary, a surfactant or the like may be added.
- an organic acid having a chelating effect for example, citric acid should be added thereto, and if necessary, a surfactant or the like may be added.
- a second embodiment of the storage water for silicon wafers of the present invention is storage water used for storing silicon wafers in water, characterized by adding a nonionic surfactant.
- the wafer By keeping the wafer in storage water containing such a nonionic surfactant, it can be stored for a long time (regardless of time) in the same surface condition (without surface roughness). be able to.
- the wafer surface exists in a bare silicon state.
- the storage water contains dissolved oxygen, which reacts with the silicon surface to form a thin oxide film on the silicon surface.
- this oxide film is considered to elute in the storage water and cause surface roughness.
- a surfactant is added to prevent the oxide film from forming on the silicon surface, and even if formed, it does not elute into the storage water, and acts to protect the wafer surface. This is the eye of the present invention.
- Storage of the present invention The concentration of the surfactant in the working water is preferably at least 0.01%. In the present specification, when the amount or concentration of the surfactant is simply expressed in%, it means% by volume.
- surfactants added to protect the surface of the wafer include: ⁇ ⁇ uniformly dispersed on the surface, and ⁇ prevent adhesion to the surface of the wafer against external contamination. Those free of contamination are preferred.
- surfactant examples include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylen ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene.
- Nonionic surfactants such as sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene glyceride, and alkyl alcohol amide are used.
- polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers and / or polyoxyethylene polyoxypropylene ethers are high-purity surfactants that do not contain metal impurities that lower the oxide film breakdown voltage. It is preferred.
- the pH of the storage water is not on the alkaline side. That is, the pH is preferably 7 or less. Also in alkaline, it can not sufficiently improve despite the effect of preventing the Re surface roughness, since the quality deterioration of Ueha surface would occur, like the storage toward neutral to acidic correct ( From this point of view, surfactants are more cationic surfactants than anionic surfactants, and preferably nonionic surfactants are more preferable for preventing deterioration of the wafer surface. Some have low pH 4 like higher alcohol non-ionic surfactants such as polyoxyalkylene alkyl ethers.By adding such surfactants, pH can be controlled at about 4 to 7 .
- a greater effect is observed when the concentration of dissolved oxygen in the storage water of the present invention is 3 mg / L or more.
- the wafer surface immediately after polishing is easily oxidized due to the effect of dissolved oxygen dissolved in storage water (pure water). It is important to avoid such reactions as much as possible, since oxidation tends to cause surface roughness. Therefore, it is necessary to take measures to minimize the dissolved oxygen in the pure water.However, add a surfactant to the pure water and store the wafer in pure water with the wafer coated in advance with the surfactant. By doing so, it can be stored without worrying about the effects of dissolved oxygen.
- a surfactant has a sufficient effect even when the dissolved oxygen concentration is relatively high, 3 mg / L or more, and can prevent surface roughness and particle adhesion.
- the upper limit of the dissolved oxygen concentration is not particularly specified, but the effect can be obtained up to the saturated dissolved oxygen concentration at the operating temperature of the storage water.
- the storage water of the present invention exhibits its function sufficiently even if it is composed only of a surfactant and pure water.
- a first aspect of the method for storing a silicon wafer according to the present invention is characterized in that the wafer is stored using the storage water of the present invention described above.
- a surfactant is directly added to the storage water.
- the surface of the wafer is coated with a non-ionic surfactant. It is characterized by comprising a coating step and a storage step of storing the coated wafer in pure water. In the storage step, it is also effective to store the pure water in storage water obtained by adding an organic acid having a chelating effect such as citric acid.
- the wafer surface can be properly protected and deterioration of the wafer surface can be prevented.
- the storage of the air is usually performed immediately after the etching step and / or the polishing step.
- the concentration of the surfactant is preferably 0.01% or more. More specifically, the concentration may be higher than the critical micelle concentration. Also, wastewater containing surfactants cannot be discharged directly to the outside and requires special treatment. This makes the more difficult the surfactant, the more difficult it is to treat.
- FIG. 1 is a flowchart showing a first embodiment of the method for storing a silicon wafer according to the present invention.
- FIG. 2 is a flowchart showing a second embodiment of the silicon wafer storage method of the present invention.
- FIG. 3 is a flowchart showing a conventional method of storing silicon wafers. BEST MODE FOR CARRYING OUT THE INVENTION
- Cuenic acid suitably used as the organic acid having a chelating effect in the first embodiment of the storage water of the present invention has a chelating property and a short-term potential property. Due to the chelating properties of citric acid, it forms compounds with metals in storage water. Also, due to the zeta potential characteristic of citric acid, the repulsion between the surface and metal-containing particles (silicone dust, silica particles used in abrasives, particles in liquid, etc.) This prevents the metal in the storage water from adhering to the surface of the evaporator.
- organic acids having a chelating effect include other organic acids having properties similar to citric acid, such as oxalic acid, which are water-soluble at room temperature and whose carboxyl groups are far apart. No organic acids can be used.
- a concentration range with a small washing and jetting effect For example, in the case of citric acid, a concentration of about 0.0001 to 0.01% is preferable, and more preferably 0.00%. The concentration is preferably 0.1 to 0.005%. When the concentration of citrate is lower than 0.001%, the chelating effect is weakened and the effect of preventing metal contamination is reduced. Also, as the concentration of citrate increases, the cost of chemicals and the load on wastewater treatment increase, so it is necessary to keep the concentration below 0.01%. Wastewater treatment of citrate is easier than chelating agents, but at too high a concentration the cost cannot be ignored.
- pH is preferably greater than 3 and about 7, more preferably pH 4 to pH 7.
- a nonionic surfactant is particularly preferred.
- the nonionic surfactants those listed above are used.
- ether nonionics such as polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene ether are used.
- Surfactants are preferred.
- the addition amount of this surfactant is preferably in the range of 0.01% to 0.1%, and the pH of the storage water after addition of the surfactant is preferably 7 or less. A greater effect is observed when the concentration of dissolved oxygen in the storage water is 3 mg / L or more.
- FIG. 1 is a flowchart showing a first embodiment of the method for storing silicon wafers of the present invention.
- the polishing step A and the next step (cleaning) C are the same as the conventional steps.
- the difference between the pit tank storage B1 in Fig. 1 and the conventional process is that the storage water (pure water) filled in the bit tank contains an organic acid and / or surfactant that has a chelating effect. Is a point.
- FIG. 2 is a flowchart showing a second embodiment of the method of storing silicon wafers of the present invention.
- the polishing step A and the next step (cleaning) C are the same as those in FIG. 1 and the conventional step.
- the process of FIG. 2 differs from the process of FIG. 1 and the conventional process in that the surface of the silicon wafer 18 is coated (coated) with a surfactant before the pit tank storage B.
- a nonionic surfactant is similarly used as a surfactant for coating the wafer.
- the concentration of the surfactant for coating is not particularly limited, but is preferably 10% or more. New When the concentration is about 10%, the surfactant can be coated on the surface of the wafer with an appropriate thickness.
- Sample wafer silicon wafer, p-type, crystal orientation 100>, 200 mm ⁇
- Polishing process The final finish polishing of Silicone A8 was performed under the polishing conditions of urethane foam resin polishing pad, colloidal sily abrasive, polishing load (25 O / cm 2 ) and polishing time (10 minutes). .
- the storage time of the sample ⁇ in the storage water was set to 2, 4, 8, and 12 hours.
- SC-1 cleaning solution liquid temperature: 80 ° C
- SC-2 washing solution liquid temperature: 80 ° C
- the quality was determined by the oxide film breakdown voltage (GOI; Gate Oxide Integrity).
- This oxide withstand voltage (GOI) evaluation is one of the most important parameters in evaluating the quality of the wafer (the reliability of the insulating film).
- GOI is one of the methods that can evaluate the amount of metal contamination in wafers. The evaluation results of GOI depend on the amount and distribution of metal contamination, and the quality of wafers can be judged.
- the oxide withstand voltage evaluation is performed by applying an electric field in a stepwise manner to the MOS capacity and measuring the breakdown electric field strength of the MOS capacity (electric field breakdown distribution: TZDB method; Time Zero Dielectric Breakdown). An electric field was applied, and the rate at which the MS capacity was destroyed over time was measured by changing the size of the electric field (time-dependent breakdown distribution: TDDB method; Time Dependent Dielectric Breakdown).
- the determination was performed at a current of 1 mA and a gate area of 8 mm 2 .
- Non mode also measurement of TDDB method produces an initial dielectric breakdown as well (defective), resulting in dielectric breakdown 5 C / cm 2 less than the range /? Mode one de (JunRyo products), no dielectric breakdown (Dielectric breakdown occurs at 5 C / cm 2 or more) Expressed as Amode (non-defective).
- the stress current value was 0.01 A / cm 2
- the measurement temperature was 100 ° C.
- the gate area was 4 mm 2 .
- storage water containing an organic acid having a chelating effect for example, citrate / decanoic acid + surfactant, is particularly preferable in view of the surface quality of the wafer, particularly the oxide film withstand voltage.
- Example 5 and 6 and Comparative Example 2 storage water, etc., may be mixed with metal for some effect, and at that time, the effect of metal contamination is likely to occur. Therefore, in order to confirm the effect in a severe environment, metal contamination (Cu) of about lpppp was intentionally performed on the same storage water as in Examples 1-2 and Comparative Example 1 above. Then, the battery was stored for 12 hours, and the breakdown voltage of the oxide film was evaluated. Table 3 shows the results of the evaluation.
- Example 5 is Example 1
- Example 6 is Example 2
- Comparative Example 2 is Comparative Example 1 and similar storage water.
- the specifications of sample A-8 used were the same as in Examples 1 to 4 and Comparative Example 1.
- the polishing conditions and the processing conditions before and after storage were the same as in Examples 1 to 4 and Comparative Example 1. Table 3
- the yield rate in the non-defective mode was able to be prevented in Examples 5 and 6, whereas the yield in the non-defective mode was significantly reduced only with pure water or the surfactant alone.
- the combination of citrate and a surfactant can further prevent the yield in the non-defective mode from decreasing.
- the effect of adding about 1% of cunic acid was effective.
- excessive addition was preferred, and the surface quality of the wafer was preferably 0.0001 to 0.01%.
- 0.0001 to 0.005% was particularly preferred.
- the problem is that the extracted components are problematic, and it is preferable to store them at a pH of 7 or less.
- the micro roughness of the wafer surface was evaluated to confirm the effect of the alkali component.
- Microroughness was evaluated using a haze mode of LS-600 manufactured by Hitachi Electronics Engineering Co., Ltd., and a detection voltage of 900 V.
- the evaluation value (bit) of the micro roughness indicates that the larger the value is, the more rough the surface is.
- the deterioration of the wafer surface includes 10 (bit) in Example 7, 0 (bit) in Example 8, 93 (bit) in Comparative Example 3, and 256 (bit) in Comparative Example 4, including the aliasing component.
- bit 10
- 0 bit
- Comparative Example 3 93
- bit 256
- Comparative Example 4 including the aliasing component.
- the surface of ewa was significantly deteriorated.
- the storage water 1 to 5 used in the above experiment are as follows.
- a polyoxyethylene alkyl ether was used so as to be 10 wt% (Example 15) and 30 wt% (Example 16).
- the polished wafer was immediately immersed in a container containing the above surfactant, and then stored in pure water only. The storage time was 12 hours.
- Table 4 shows the haze (HAZE) and particle difference ( ⁇ ⁇ ⁇ and ALPD) before and after storage using the storage water of Examples 9 to 16 and Comparative Examples 5 to 7.
- the adhesion of the fine particles containing metal to the surface of the wafer is reduced, and the water due to the alkaline component in the abrasive is reduced. Etching on the surface of the wafer is prevented, and a great effect is achieved in that it is possible to prevent the deterioration of the wafer quality after cleaning, particularly the deterioration of the oxide film breakdown voltage.
- a surfactant as one component of the storage water of the silicone agent 8
- deterioration of haze (HAZE) and adhesion of particles are prevented.
- the addition of a surfactant can almost completely prevent the deterioration of haze (HA ZE) in pure water with a high amount of dissolved oxygen or storage water on the acidic side. Is done.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Weting (AREA)
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01912262A EP1189265A4 (en) | 2000-03-17 | 2001-03-12 | WATER FOR STORAGE OF SILICON PADS AND STORAGE METHOD |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-76490 | 2000-03-17 | ||
JP2000076490 | 2000-03-17 | ||
JP2000145444 | 2000-05-17 | ||
JP2000-145444 | 2000-05-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001071788A1 true WO2001071788A1 (fr) | 2001-09-27 |
Family
ID=26587826
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/001903 WO2001071788A1 (fr) | 2000-03-17 | 2001-03-12 | Eau pour le stockage de plaquettes de silicium et procede de stockage |
Country Status (5)
Country | Link |
---|---|
US (1) | US20030036570A1 (ja) |
EP (1) | EP1189265A4 (ja) |
KR (1) | KR100724883B1 (ja) |
TW (1) | TW526301B (ja) |
WO (1) | WO2001071788A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010034387A (ja) * | 2008-07-30 | 2010-02-12 | Sumco Corp | 半導体ウェーハの製造方法 |
WO2015029524A1 (ja) * | 2013-08-28 | 2015-03-05 | Sumco Techxiv株式会社 | 半導体ウェーハの研磨方法および研磨装置 |
JP2019117816A (ja) * | 2017-12-26 | 2019-07-18 | 花王株式会社 | シリコンウェーハ製造方法 |
JP2019121795A (ja) * | 2017-12-27 | 2019-07-22 | 花王株式会社 | シリコンウェーハの製造方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7078343B2 (en) * | 2001-03-06 | 2006-07-18 | Sumitomo Electric Industries, Ltd. | Method of manufacturing compound semiconductor wafer |
AU2003204558B2 (en) | 2002-10-29 | 2008-11-13 | Migun Medical Instrument Co., Ltd. | Heat Therapy Device and Heat Therapy System Using the Same |
KR100825528B1 (ko) * | 2002-12-27 | 2008-04-25 | 주식회사 실트론 | 실리콘웨이퍼의 연마 방법 및 연마 장치 |
EP2688688A4 (en) * | 2011-03-21 | 2014-12-31 | Basf Se | AQUEOUS CLEANING COMPOSITION WITHOUT NITROGEN, PREPARATION AND USE THEREOF |
JP6602720B2 (ja) * | 2016-04-04 | 2019-11-06 | グローバルウェーハズ・ジャパン株式会社 | 半導体基板の保護膜形成方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11191543A (ja) * | 1997-12-25 | 1999-07-13 | Shin Etsu Handotai Co Ltd | シリコンウエーハの保管用水及び保管する方法 |
JPH11243073A (ja) * | 1997-12-26 | 1999-09-07 | Shin Etsu Handotai Co Ltd | シリコンウエーハを液中で保管する方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2762230B2 (ja) * | 1994-03-25 | 1998-06-04 | 信越半導体株式会社 | シリコンウエーハの保管方法 |
DE19525521B4 (de) * | 1994-07-15 | 2007-04-26 | Lam Research Corp.(N.D.Ges.D.Staates Delaware), Fremont | Verfahren zum Reinigen von Substraten |
US5803956A (en) * | 1994-07-28 | 1998-09-08 | Hashimoto Chemical Company, Ltd. | Surface treating composition for micro processing |
US5944906A (en) * | 1996-05-24 | 1999-08-31 | Micron Technology Inc | Wet cleans for composite surfaces |
WO1998001896A1 (fr) * | 1996-07-03 | 1998-01-15 | Ultraclean Technology Research Institute | Appareil de lavage et procede de lavage |
US6296714B1 (en) * | 1997-01-16 | 2001-10-02 | Mitsubishi Materials Silicon Corporation | Washing solution of semiconductor substrate and washing method using the same |
US6593282B1 (en) * | 1997-10-21 | 2003-07-15 | Lam Research Corporation | Cleaning solutions for semiconductor substrates after polishing of copper film |
US6884721B2 (en) * | 1997-12-25 | 2005-04-26 | Shin-Etsu Handotai Co., Ltd. | Silicon wafer storage water and silicon wafer storage method |
US20040074518A1 (en) * | 2002-10-22 | 2004-04-22 | Texas Instruments Incorporated | Surfactants for post-chemical mechanical polishing storage and cleaning |
-
2001
- 2001-03-12 US US09/979,068 patent/US20030036570A1/en not_active Abandoned
- 2001-03-12 WO PCT/JP2001/001903 patent/WO2001071788A1/ja active Application Filing
- 2001-03-12 EP EP01912262A patent/EP1189265A4/en not_active Withdrawn
- 2001-03-12 KR KR1020017012085A patent/KR100724883B1/ko not_active IP Right Cessation
- 2001-03-16 TW TW090106259A patent/TW526301B/zh not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11191543A (ja) * | 1997-12-25 | 1999-07-13 | Shin Etsu Handotai Co Ltd | シリコンウエーハの保管用水及び保管する方法 |
JPH11243073A (ja) * | 1997-12-26 | 1999-09-07 | Shin Etsu Handotai Co Ltd | シリコンウエーハを液中で保管する方法 |
Non-Patent Citations (1)
Title |
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See also references of EP1189265A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010034387A (ja) * | 2008-07-30 | 2010-02-12 | Sumco Corp | 半導体ウェーハの製造方法 |
WO2015029524A1 (ja) * | 2013-08-28 | 2015-03-05 | Sumco Techxiv株式会社 | 半導体ウェーハの研磨方法および研磨装置 |
JP2015046488A (ja) * | 2013-08-28 | 2015-03-12 | Sumco Techxiv株式会社 | 半導体ウェーハの研磨方法および研磨装置 |
US10553420B2 (en) | 2013-08-28 | 2020-02-04 | Sumco Techxiv Corporation | Method and device for polishing semiconductor wafer |
JP2019117816A (ja) * | 2017-12-26 | 2019-07-18 | 花王株式会社 | シリコンウェーハ製造方法 |
JP7138432B2 (ja) | 2017-12-26 | 2022-09-16 | 花王株式会社 | シリコンウェーハ製造方法 |
JP2019121795A (ja) * | 2017-12-27 | 2019-07-22 | 花王株式会社 | シリコンウェーハの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1189265A4 (en) | 2007-04-25 |
EP1189265A1 (en) | 2002-03-20 |
KR20020001798A (ko) | 2002-01-09 |
US20030036570A1 (en) | 2003-02-20 |
KR100724883B1 (ko) | 2007-06-04 |
TW526301B (en) | 2003-04-01 |
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