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WO2012071286A1 - Method for shaping and slicing ingots using an aqueous phosphate solution - Google Patents

Method for shaping and slicing ingots using an aqueous phosphate solution Download PDF

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Publication number
WO2012071286A1
WO2012071286A1 PCT/US2011/061539 US2011061539W WO2012071286A1 WO 2012071286 A1 WO2012071286 A1 WO 2012071286A1 US 2011061539 W US2011061539 W US 2011061539W WO 2012071286 A1 WO2012071286 A1 WO 2012071286A1
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Prior art keywords
workpiece
polyphosphate
solution
tripolyphosphate
wire saw
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PCT/US2011/061539
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French (fr)
Inventor
Mark Jonathan Beck
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FONTANA Technology
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FONTANA Technology
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28DWORKING STONE OR STONE-LIKE MATERIALS
    • B28D5/00Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor
    • B28D5/0058Accessories specially adapted for use with machines for fine working of gems, jewels, crystals, e.g. of semiconductor material
    • B28D5/0076Accessories specially adapted for use with machines for fine working of gems, jewels, crystals, e.g. of semiconductor material for removing dust, e.g. by spraying liquids; for lubricating, cooling or cleaning tool or work
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/10Salts
    • C11D7/16Phosphates including polyphosphates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67011Apparatus for manufacture or treatment
    • H01L21/67017Apparatus for fluid treatment
    • H01L21/67028Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/6704Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
    • H01L21/67051Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/22Electronic devices, e.g. PCBs or semiconductors
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40Specific cleaning or washing processes
    • C11D2111/46Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

  • silicon ingots are used for silicon wafer fabrication.
  • silicon ingots When used for photovoltaic applications, silicon ingots can be both polycrystalline and monocrystalline. In either case, the ingot needs to be further sawn or shaped into the desired shape after either crystal pulling (monocrystalline) or after solidification from the molten state (polycrystalline) into a block.
  • the ingot coming out from the crystal pulling operation is usually cylindrical in shape and has a circular cross section. This cylindrical shape needs to be converted into a near or quasi -square shape by an operation called "squaring.”
  • a wire saw cuts ends of the cylindrieally shaped ingot in order to end up with a near square ingot. Traditionally this has been done with steel wires together with a slurry that contains an abrasive, such as silicon carbide (SiC).
  • SiC silicon carbide
  • the new wire saw comprises a diamond coated steel wire, where the diamond bits are embedded on the steel wire with a nickel coating.
  • a machine that can be adapted to use the new diamond coated steel wire cutting technology is commercially available from the Swiss company MB Wafertec, under the product designations DS 271 and DS 264.
  • diamond wire saws An advantage of the new wire saws (called “diamond wire” saws or DW saws) is that the slurry does not need to contain the abrasive, because the diamond on the wire functions as the abrasive.
  • DW saws diamond wire saws
  • the new solution does not need to contain an abrasive and the new solution should be more environmentally friendly with respect to waste treatment and disposal issues than the ethylene glycol solutions used previously.
  • the present invention comprises a method for slicing a workpiece into wafers in which an aqueous polyphosphate solution is applied to the workpiece during the slicing process.
  • the method comprises the steps of positioning the workpiece, such as a silicon ingot, in the vicinity of a wire saw that can cut through workpiece without the use of an abrasive slurry; causing an aqueous polyphosphate solution to contact the workpiece; and causing the wire saw to cut into the workpiece while the polyphosphate solution is in contact with the workpiece.
  • the polyphosphate solution is rinsed off of the wafers.
  • the wire saw used in this method is a diamond wire saw.
  • the polyphosphate solution used in the present invention is effective at keeping small particles and debris from the cutting operation in suspension, thereby reducing the build-up of abraded particles on both the wafers and the equipment used in the slicing process. Additionally, the polyphosphate solution does not contain an abrasive and is more environmentally friendly with respect to waste treatment and disposal issues than is an ethylene glycol solution.
  • FIG. 1 is a schematic illustration of a prior art slicing apparatus that uses a wire Saw
  • FIG. 2 is a schematic illustration of a prior art wire saw cutting surface
  • FIG. 3 is a schematic illustration of a prior art workpiece sliced into sections.
  • FIG. 4 is a schematic illustration of the particle repulsion effect exhibited by the water-soluble phosphates of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Fig. 1 illustrates a slicing apparatus 10 for cutting a workpiece 14 used in the prior art.
  • the apparatus 10 comprises a feed spool 16, first reel 18, a second reel 22, a wire 26 and a take-up spool 28.
  • a first dispensing means 30, a second dispensing means 34, and a third dispensing means 38, are positioned to dispense a fluid 42 that contacts at least a region of the wire 26 and at least a region on the workpiece 14.
  • a commercially available machine that can function as the apparatus 10 is available from the Swiss company MB Wafertec under the product designations DS 271 and DS 264.
  • the fluid 42 comprises an aqueous polyphosphate solution as is described below.
  • the fluid 42 typically comprises either a slurry comprised of an abrasive material suspended in a liquid such as ethylene glycol, or simply deionized water without an abrasive material.
  • the wire 26 is one long continuous wire that is wrapped around the reels 18 and 22.
  • the feed spool 16 delivers the wire 26 to the reels 18 and 22, while the take-up spool 28 collects the wire 26 after it has passed around the reels 18 and 22, In use, the wire 26 is accelerated from the feed spool 16 to the take-up spool 28.
  • the wire decelerates, reverses direction and then moves in the opposite direction ⁇ i.e. from the take-up spool 28 to the feed spool 16).
  • the wire 26 is accelerated, the fluid 42 is sprayed onto the wire 26 and the workpiece 14 is lowered onto the wire 26, The motion of the wire 26 as it moves from the feed spool to the take-up spool and vice versa, slices the workpiece 14 into sections.
  • a cutting surface 46 is comprised of a plurality of cutting sections 50 of the wire 26 formed when the wire 26 is wrapped around the first reel 18 and the second reel 22 many times (for example, thousands of times).
  • the plurality of the cutting sections 50 are each accelerated from the first reel 18 to the second reel 22 (i.e. through the cutting surface 46) when the wire 26 is accelerated from the feed spool 16 to the take-up spool 28, When the feed spool comes near to the end of the wire, the wire decelerates, reverses direction and then moves in the opposite direction (i.e. from the take-up spool to the feed spool).
  • the plurality of the cutting sections 50 are accelerated, the fluid 42 is sprayed onto selected regions of the cutting surface 46 and/or the workpiece 14, and the workpiece 14 is lowered onto the cutting surface 46.
  • the motion of the cutting surface 46 as the plurality of the cutting sections 50 move from the first reel 18 to the second reel 22 and vice versa slices the workpiece into a plurality of thin sections.
  • Fig. 3 illustrates that after the slicing operation by the apparatus 10, the workpiece 14 is divided into a plurality of thin sections or wafers 54.
  • n number of cutting sections 50 produces n + 1 number of sections 54 after slicing.
  • Each of the individual sections 54 are a cross section of the workpiece 14. Therefore, if the workpiece 14 is shaped so that it has a square cross section, the individual sections 54 will each have at least one square face 58.
  • the workpiece 14 comprises a photovoltaic semiconductor material, meaning a semiconductor material that can convert solar radiation into direct current electricity.
  • a photovoltaic semiconductor material include monocrystalline silicon, polycrystaliine silicon and amorphous silicon.
  • a workpiece comprised of polycrystaliine silicon is the most preferred material for use in the present invention.
  • Other photovoltaic materials such as cadmium telluride can also be used.
  • the workpiece 14 can have various shapes, but frequently in the photovoltaic industry, ingots of polycrystaliine silicon have a brick shape that is cuboid in nature.
  • the shape of the workpiece 14 could be a rectangular cuboid or a square cuboid.
  • the workpiece 14 is illustrated as having a square cuboid shape.
  • a workpiece comprised of polycrystaliine silicon and having a square cuboid shape is the most preferred configuration for the workpiece 14 in the present invention.
  • other shapes can be used for the workpiece 14, including cylindrically shaped workpieces.
  • a workpiece such as the workpiece 14 is sliced into one or more sections by positioning the workpiece in the vicinity of a wire saw, such as the wire 26; by causing a polyphosphate solution to contact the workpiece, such as by spraying the polyphosphate solution onto the wire 26 and workpiece 14 (Fig. 1 ); and by causing the wire saw to cut into the workpiece while the polyphosphate solution is in contact with the workpiece, such as by lowering the workpiece 14 onto the wire saw (Figs. 1 and 2).
  • the polyphosphate solution is removed from the sections 54, such as by rinsing the sections with water.
  • rinsing the sections with water.
  • DI deionized
  • the water can be sprayed on the sections 54, or other methods of rinsing can be used, such as dipping the sections in a rinse tank.
  • the method of the present invention can be used in forming the workpiece 14.
  • a wire saw is used to cut the ends off of a cylindrically shaped ingot in order to end up with a near square (i.e., a rectangular cuboid or a square cuboid) ingot that can be used as the workpiece 14.
  • the polyphosphate solution of the present invention can be used in "shaping" procedures of this type.
  • the wire 26 is a wire that can cut or slice the workpiece 14 Without the use of an abrasive material in the fluid 42.
  • the wire 26 comprises a wire, usually comprised of steel, which has diamond pieces attaehed to its surface.
  • the diamonds can be either natural or synthetic diamonds and are usually held on the steel wire by a nickel coating.
  • the fluid 42 comprises a polyphosphate solution.
  • the polyphosphate solution comprises an aqueous solution of any of the water-soluble polyphosphates.
  • linear polyphosphates having the following formula are used:
  • X + H + , Na ⁇ K + , NH 4 + , R 3 NH + .
  • X + can be a combination of these cations or it can be a single cation chosen from this list repeated on each location of the polyphosphate where X + is annotated.
  • K potassium (K)
  • K-tripolyphosphate is preferred.
  • the K-tripolyphosphate structure is as follows:
  • trimetaphosphoric acid is as follows:
  • the most preferred polyphosphates are the
  • tripolyphosphates typically either Na-tripolyphosphate or ⁇ -tripolyphosphate is used or a penta-ammonium tripolyphosphate may be used.
  • Other tri-polyphosphates can be used as well, such as, but not limited to, triethanolamine tripolyphoshate or the tripolyphosphoric acid.
  • the tripolyphosphate in the concentrated source solution is typically between 0.5% and 200%-w and preferably between 2% and 150%-w and most preferably between 5% and 100%-w as a ratio by weight of polyphosphate to added liquid (typically H?0).
  • the maximum concentration is typically determined by the solubility limit of the tripolyphosphate.
  • the solubility of the K -tripolyphosphate is much higher than the solubility of the Na-tripolyphosphate. E.g. the Na-tripolyphosphate solubility is only about 20%-w.
  • the K -tripolyphosphate on the other hand is much more soluble and can be dissolved even up to about 150%-w concentrations.
  • the penta ammonium tripolyphosphate is also very soluble, but is not so widely available. After dilution of the source solution at point-of-use, the final concentration of tripolyphosphate for cleaning the substrates is preferably 0.2%- 15%.
  • tripolyphosphate and preferably the K- or the penta ammonium
  • tripolyphosphate can be used by itself, it can be used combined and it can also be combined with potassium or ammonium hydroxide. Potassium or ammonium hydroxide is typically added to increase the pH of the solution. Surfactants and chelating agents can also be added.
  • the tripolyphosphate in a concentrated source solution is typically between 0.5% and 200% and preferably between 2% and 150% and most preferably between 5% and 100% relative to the H?0 in the solution.
  • ammonium hydroxide is added to the concentrated source solution, it can be added in a concentration range of 1%-28%-w (weight of NH 3 ) to make a source solution consisting of ammonium hydroxide and ammonium polyphosphate. Potassium hydroxide can be added to the K -tripolyphosphate in the source solution in a range of 0.001%-45% (weight of KOH).
  • the final concentration of polyphosphate for shaping and slicing the ingots is preferably 0.2%-l 5% by weight in the solution.
  • the source solution will be diluted between 5 and 50 times with DI water in the fab to make up the ingot slicing/shaping solution, preferably 7 to 25 times, and most preferably 9 to 15 times.
  • the source solution may also contain from 0.01% to 20% of an organic amine.
  • Suitable organic amine compounds may be selected from alkanolamines (e.g. primary alkanolamines: monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyl diethanolamine, secondary alkanolamines: diethanolamine, diisopropanolamine, 2- (methylamineo)ehtano, morpholine, ternary alkanolamines: triethanolamine, tri- isopropylamine), alkylamines (e.g. primary alkylamines, monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylam ine,
  • alkanolamines e.g. primary alkanolamines: monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyl diethanolamine
  • secondary alkanolamines diethanolamine, diisoprop
  • alkyleneamines e.g.
  • primary alkylene amines ehtylenediamine, propylenediamine, triethylenetetramine), and mixtures thereof.
  • Preferred examples of such materials include monoethanolamine, ethylenediamine, triethylenetetramine and mixtures thereof. The most preferred is monoethanolamine.
  • the amount of the organic amine preferably ranges from 0.01 % to 20%, and most preferably from 0.2% to 2%.
  • the source solution may also contain a biocide such as 2-Methyl-4-isothiazolin- 3 -one (MIT) or 2-Methyl-4-lsothiazolin-3-one Hydrochloric acid (C 4 H 4 NOS, HCl, (M 1HCA).
  • a biocide such as 2-Methyl-4-isothiazolin- 3 -one (MIT) or 2-Methyl-4-lsothiazolin-3-one Hydrochloric acid (C 4 H 4 NOS, HCl, (M 1HCA).
  • the concentration of the biocide is preferably from 1 ppm to 100 ppm, and most preferably from 30-70 ppm. Other biocides may be used as well.
  • Surfactants can also be added. Typically non-ionic surfactants are preferred. Preferred surfactants are the ethylene oxide type surfactants with a general structure CnH 2n+1 O(C2H 4 O) m H. Ideally the number of carbon atoms in the hydrocarbon chain n is 1 .5 or less times the number of oxyethylene groups m. Ideally the number of carbon atoms n is more than 0.5 of the number of oxyethylene groups m. A good non-ionic surfactant isC 12 H 25 O(C 2 H 4 O) 1 1 H. The concentration of the surfactant in the concentrated solution will be between 0.1% and 5%. Preferred concentrations are around 0.5% for the concentrated source solution.
  • the concentration after dilution with water and when used for cleaning the surfaces will be preferably between 0.0001 to 0.5% by weight. This is between 1 ppm and 5000 ppm by weight. More preferably, the concentration after dilution will be between 10 ppm and 500 ppm.
  • Sequestering agents or compiexing agents can also be added.
  • Preferred sequestering or compiexing or chelating agents are the nitrogen-containing carboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and
  • DTPA diethylenetriaminepentaacetic acid
  • EDDHA ethylenediaminedi-o-hydroxyphenylacetic acid
  • concentration of the sequestering agent in the concentrated solution will be between 0.1% and 5%. Preferred concentrations are around 0.5%.
  • concentration of the sequestering agent after dilution with water and when used for cleaning the surfaces will be preferably between 10 ppm and 500 ppm.
  • tripolyphosphate for the clarity of this invention, in the remainder of this invention, we will mostly talk about tripolyphosphate, even though other suitable water-soluble polyphosphates can be used as explained earlier.
  • the ammonium polyphosphate is preferred when no alkali metals are allowed, but for the clarity of this invention, in the remainder of this invention, we will mostly talk about the tripolyphosphate.
  • the K -tripolyphosphate is preferred. The K in the solution can be rinsed off the surface very effectively, since it does not bind with the surface of the silicon ingots or sliced wafers and is extremely soluble in DI water.
  • a spray rinse can be a regular water spray or an aerosol spray.
  • a regular water spray is effective; preferably a flow in excess of IL/min per substrate is very effective.
  • the temperature of the rinse water can be any temperature from 0 degrees C to 100 °C, but a room temperature rinse is preferred because of its ease and economical advantage.
  • the polyphosphate solutions of the present invention provide advantages in the shaping/slicing process at the point-of-use, i.e. during the process in which the workpiece 14 is being sliced by the wire 26. Another advantage of the polyphosphate solutions is that they can be manufactured in concentrated form off-site and then can be diluted on-site around the time they are needed for a point-of-use operation.
  • the initial preparation of concentrated solutions provides economic benefits, such as reduced shipping and transportation costs. For purposes of illustration, representative examples for the composition of concentrated polyphosphate solutions are described below, along with representative dilutions for the point-of-use polyphosphate solutions.
  • Example 1 Typical source polyphosphate solutions are made up off-site by mixing a polyphosphate with Dl-water to a high concentration. A typical composition of a simple concentrated solution according to the invention is shown in Table 1 :
  • KOH potassium hydroxide
  • NH4OH NH4OH
  • monoethanolamine a substance that can be added to increase the pH further.
  • High pH is useful for increasing the repulsion effect between the abraded particles as is described below.
  • the pH is typically preferably adjusted to be between 9 and 14 and more preferably between 10 and 13 and most preferably between 1 1 and 12.
  • This solution in concentrated form can be transported to the point of use.
  • the concentrated form of the polyphosphate solution is referred to as a source solution and the concentration of the polyphosphate in this source solution is about 50% by weight (i.e. 1 OOOg polyphosphate per 1 OOOg water equals 50%).
  • this source solution can be diluted with DI water before use as a shaping/slicing solution.
  • the source solution can be diluted in a ratio of 10: 1 DI watensource solution of example 1.
  • the 10: 1 diluted solution of example 1 yields a pH of about 9.5 without any KOH added.
  • Example 2 Typical alkali free polyphosphate source solutions are made up off- site by mixing a polyphosphate with Di-water to a high concentration.
  • This solution in concentrated form can be transported to the point of use. At the point of use, this solution can be diluted with DI water before use as a shaping/slicing solution.
  • the concentrated source solution can be diluted in a ratio of 10: 1 DI watensouree solution.
  • other substances can be used to increase the pH of the diluted solution, such as TMAH and choline.
  • the shaping/slicing step is completed, a thorough rinsing of the newly cut sections of the workpiece 14 is required.
  • a spray rinsing with high flow spray of water is preferred method of rinsing. Typical spray flows of 1 L/min to 4 L/min per nozzle are preferred. Also an aerosol atomized and accelerated spray can be used.
  • the shaping/slicing step is stopped by various methods, such as by lifting the workpiece 14 off of the wire 26 or cutting surface 46. Alternatively, the motion of the wire 26 can be stopped, or both of these steps can be taken together.
  • the polyphosphate solutions of the present invention work in the following manner.
  • abraded particles are generated. These abraded particles are comprised of whatever material the workpiece 14 is made of. For example, in the preferred embodiment, abraded particles would be particles of polycrystalline silicon.
  • the water- soluble phosphates in the fluid 42 interact with the abraded particles by putting an additional electrostatic charge on the abraded particles and providing for an increased electrostatic repulsive force between the particles and the surface of the sliced workpiece 14.
  • a medium 60 has an adhered particle 62 on its surface.
  • the medium 60 could correspond, for example, to one of the sections 54 illustrated in Fig. 3, to the workpiece 14 or to the equipment that is used in the apparatus 10.
  • the water-soluble phosphates put a plurality of negative charges 66 on both the surface of the medium 60 and the surface of the particle 62. The repulsion between these negative charges means that the particle 62 and the surface of the medium 60 are repelled and hence the particle can be suspended. Only the charges which are relevant for the repulsion of the particle 62 are shown.
  • the solution of this invention with water-soluble phosphates is very effective for shaping and slicing silicon ingots with a diamond coated wire.
  • the main function of the fluid 42 is for cooling and lubrication during the process in which the wire 26 slices the workpiece 14. Water is good for both of these purposes, so an aqueous based fluid 42 is desirable.
  • pure water will not prevent the abraded silicon from depositing on either the cut wafers or on many of the parts of the apparatus 10. This is because water evaporates easily and leaves all the abraded silicon hard baked on many of the parts of the apparatus 10. Also, water does not prevent the abraded silicon from depositing on the cut wafers.
  • the polyphosphate solution is superior to pure water because it prevents the abraded silicon from depositing on the cut wafers by keeping the abraded silicon in solution as was described previously. Additionally, polyphosphates are hygroscopic and prevent the water from easily evaporating when the cut solution ends up on the parts of the apparatus 10.

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Abstract

A method for slicing a workpiece (14) into wafers (54) in which a polyphosphate solution is applied to the workpiece during the slicing process. The method comprises the steps of positioning the workpiece, such as a silicon ingot, in the vicinity of a wire saw (26) that can cut through the workpiece without the use of an abrasive slurry; causing an aqueous polyphosphate solution to contact the workpiece; and causing the wire saw to cut into the workpiece while the polyphosphate solution is in contact with the workpiece. After the workpiece has been cut into wafers, the polyphosphate solution is rinsed off of the wafers. Preferably, the wire saw used in this method is a diamond wire saw.

Description

METHOD FOR SHAPING AND SLICING INGOTS USING AN AQUEOUS PHOSPHATE SOLUTION
BACKGROUND ART
As presently practiced, silicon ingots are used for silicon wafer fabrication.
When used for photovoltaic applications, silicon ingots can be both polycrystalline and monocrystalline. In either case, the ingot needs to be further sawn or shaped into the desired shape after either crystal pulling (monocrystalline) or after solidification from the molten state (polycrystalline) into a block. In the case of monocrystalline pulling, the ingot coming out from the crystal pulling operation is usually cylindrical in shape and has a circular cross section. This cylindrical shape needs to be converted into a near or quasi -square shape by an operation called "squaring." During the squaring operation a wire saw cuts ends of the cylindrieally shaped ingot in order to end up with a near square ingot. Traditionally this has been done with steel wires together with a slurry that contains an abrasive, such as silicon carbide (SiC).
Similarly for the polycrystalline case, so called silicon "bricks" have to be cut with a wire saw from the block of silicon that results the solidification process. After the ingot shaping operations, the ingot needs to be sliced into wafers. This is also done with a wire saw. As was described previously, conventional wire saws for all these operations comprise steel wires that are used with a slurry that contains the abrasive. The slurry medium in which the abrasive is dissolved is usually ethylene glycol.
However, currently a new type of wire saw is being introduced into the process. The new wire saw comprises a diamond coated steel wire, where the diamond bits are embedded on the steel wire with a nickel coating. For example, a machine that can be adapted to use the new diamond coated steel wire cutting technology is commercially available from the Swiss company MB Wafertec, under the product designations DS 271 and DS 264.
An advantage of the new wire saws (called "diamond wire" saws or DW saws) is that the slurry does not need to contain the abrasive, because the diamond on the wire functions as the abrasive. When using diamond wire saws, there is a need for a new solution that can keep the abraded silicon that is generated during the sawing operation, in solution so that the abraded silicon does not contaminate the photovoltaic substrates or build up on the machinery used with the diamond wire saw. Additionally, the new solution does not need to contain an abrasive and the new solution should be more environmentally friendly with respect to waste treatment and disposal issues than the ethylene glycol solutions used previously. SUMMARY OF THE INVENTION
Briefly, the present invention comprises a method for slicing a workpiece into wafers in which an aqueous polyphosphate solution is applied to the workpiece during the slicing process. The method comprises the steps of positioning the workpiece, such as a silicon ingot, in the vicinity of a wire saw that can cut through workpiece without the use of an abrasive slurry; causing an aqueous polyphosphate solution to contact the workpiece; and causing the wire saw to cut into the workpiece while the polyphosphate solution is in contact with the workpiece. After the workpiece has been cut into wafers, the polyphosphate solution is rinsed off of the wafers. Preferably, the wire saw used in this method is a diamond wire saw.
The polyphosphate solution used in the present invention is effective at keeping small particles and debris from the cutting operation in suspension, thereby reducing the build-up of abraded particles on both the wafers and the equipment used in the slicing process. Additionally, the polyphosphate solution does not contain an abrasive and is more environmentally friendly with respect to waste treatment and disposal issues than is an ethylene glycol solution.
BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a schematic illustration of a prior art slicing apparatus that uses a wire Saw;
FIG. 2 is a schematic illustration of a prior art wire saw cutting surface;
FIG. 3 is a schematic illustration of a prior art workpiece sliced into sections; and
FIG. 4 is a schematic illustration of the particle repulsion effect exhibited by the water-soluble phosphates of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS
Fig. 1 illustrates a slicing apparatus 10 for cutting a workpiece 14 used in the prior art. The apparatus 10 comprises a feed spool 16, first reel 18, a second reel 22, a wire 26 and a take-up spool 28. A first dispensing means 30, a second dispensing means 34, and a third dispensing means 38, are positioned to dispense a fluid 42 that contacts at least a region of the wire 26 and at least a region on the workpiece 14. A commercially available machine that can function as the apparatus 10 is available from the Swiss company MB Wafertec under the product designations DS 271 and DS 264. In the present invention, the fluid 42 comprises an aqueous polyphosphate solution as is described below. In the prior art, the fluid 42 typically comprises either a slurry comprised of an abrasive material suspended in a liquid such as ethylene glycol, or simply deionized water without an abrasive material.
Typically, the wire 26 is one long continuous wire that is wrapped around the reels 18 and 22. The feed spool 16 delivers the wire 26 to the reels 18 and 22, while the take-up spool 28 collects the wire 26 after it has passed around the reels 18 and 22, In use, the wire 26 is accelerated from the feed spool 16 to the take-up spool 28. When the feed spool 16 senses that it is near the end of the wire 26, the wire decelerates, reverses direction and then moves in the opposite direction {i.e. from the take-up spool 28 to the feed spool 16). During a slicing procedure, the wire 26 is accelerated, the fluid 42 is sprayed onto the wire 26 and the workpiece 14 is lowered onto the wire 26, The motion of the wire 26 as it moves from the feed spool to the take-up spool and vice versa, slices the workpiece 14 into sections.
Generally, using only a single section of the wire 26 to cut the workpiece 14 is not practical because it would only result in one cut in the workpiece 14. While this could be useful in some situations, it is typically more useful to utilize a plurality of cutting surfaces to make a plurality of simultaneous cuts in the workpiece 14. in the apparatus 10, this is accomplished by forming a cutting surface 46. Fig. 2 illustrates that the cutting surface 46 is comprised of a plurality of cutting sections 50 of the wire 26 formed when the wire 26 is wrapped around the first reel 18 and the second reel 22 many times (for example, thousands of times).
The plurality of the cutting sections 50 are each accelerated from the first reel 18 to the second reel 22 (i.e. through the cutting surface 46) when the wire 26 is accelerated from the feed spool 16 to the take-up spool 28, When the feed spool comes near to the end of the wire, the wire decelerates, reverses direction and then moves in the opposite direction (i.e. from the take-up spool to the feed spool). During a slicing procedure, the plurality of the cutting sections 50 are accelerated, the fluid 42 is sprayed onto selected regions of the cutting surface 46 and/or the workpiece 14, and the workpiece 14 is lowered onto the cutting surface 46. The motion of the cutting surface 46 as the plurality of the cutting sections 50 move from the first reel 18 to the second reel 22 and vice versa, slices the workpiece into a plurality of thin sections.
Fig. 3 illustrates that after the slicing operation by the apparatus 10, the workpiece 14 is divided into a plurality of thin sections or wafers 54. Generally, n number of cutting sections 50 produces n + 1 number of sections 54 after slicing. Each of the individual sections 54 are a cross section of the workpiece 14. Therefore, if the workpiece 14 is shaped so that it has a square cross section, the individual sections 54 will each have at least one square face 58.
In the preferred embodiments, the workpiece 14 comprises a photovoltaic semiconductor material, meaning a semiconductor material that can convert solar radiation into direct current electricity. Preferable photovoltaic semiconductor materials include monocrystalline silicon, polycrystaliine silicon and amorphous silicon. A workpiece comprised of polycrystaliine silicon is the most preferred material for use in the present invention. Other photovoltaic materials such as cadmium telluride can also be used.
The workpiece 14 can have various shapes, but frequently in the photovoltaic industry, ingots of polycrystaliine silicon have a brick shape that is cuboid in nature. For example, the shape of the workpiece 14 could be a rectangular cuboid or a square cuboid. In Figs. 1 and 2, the workpiece 14 is illustrated as having a square cuboid shape. A workpiece comprised of polycrystaliine silicon and having a square cuboid shape is the most preferred configuration for the workpiece 14 in the present invention. However, other shapes can be used for the workpiece 14, including cylindrically shaped workpieces.
In the method of the present invention, a workpiece, such as the workpiece 14 is sliced into one or more sections by positioning the workpiece in the vicinity of a wire saw, such as the wire 26; by causing a polyphosphate solution to contact the workpiece, such as by spraying the polyphosphate solution onto the wire 26 and workpiece 14 (Fig. 1 ); and by causing the wire saw to cut into the workpiece while the polyphosphate solution is in contact with the workpiece, such as by lowering the workpiece 14 onto the wire saw (Figs. 1 and 2).
Additionally, after the workpiece has been sliced into two or more of the sections 54, and the slicing has been stopped, the polyphosphate solution is removed from the sections 54, such as by rinsing the sections with water. Preferably, deionized (DI) water is used in this step, but other rinse solutions could be used. The water can be sprayed on the sections 54, or other methods of rinsing can be used, such as dipping the sections in a rinse tank.
In addition to forming the sections or wafers 54 shown in Fig. 3, the method of the present invention can be used in forming the workpiece 14. For example, in the "squaring" operation discussed earlier, a wire saw is used to cut the ends off of a cylindrically shaped ingot in order to end up with a near square (i.e., a rectangular cuboid or a square cuboid) ingot that can be used as the workpiece 14. The polyphosphate solution of the present invention can be used in "shaping" procedures of this type.
In the preferred embodiments, the wire 26 is a wire that can cut or slice the workpiece 14 Without the use of an abrasive material in the fluid 42. Most preferably, the wire 26 comprises a wire, usually comprised of steel, which has diamond pieces attaehed to its surface. The diamonds can be either natural or synthetic diamonds and are usually held on the steel wire by a nickel coating.
In the present invention, the fluid 42 comprises a polyphosphate solution. The polyphosphate solution comprises an aqueous solution of any of the water-soluble polyphosphates. Preferably, linear polyphosphates having the following formula are used:
Figure imgf000006_0001
Where n=0, 1 ,2,3,... 1000 and X+= H+, Na\ K+, NH4 +, R3NH+. X+ can be a combination of these cations or it can be a single cation chosen from this list repeated on each location of the polyphosphate where X+ is annotated.
Satisfactorily examples of polyphosphates that can be used in the present method include sodium tripolyphosphate (n= l , X+=Na+), potassium tripolyphosphate (n=l , X+=K+), ammonium tripolyphosphate (n=l, X+=NH4 +), triethanolamine tripolyphosphate (n=l , X+=triethanolamine cation), choline tripolyphosphate (n=l , X+=choline cation), Tetra Methyl Ammonium (TMA) tripolyphosphate
(n~l,X+=TMA+), tetrasodium, -potassium and -ammonium pyrophosphate (n=0, X+=Na+ or K+ or NH4 +), disodium dihydrogen pyrophosphate (n=0, X+=Na+ and H+), di-ammonium dihydrogen pyrophosphate (n=0, X+=NH4 + and H+) and ammonium polyphosphate (n=1-60, X+=NH4 +).
When potassium (K) can be used with the workpiece 14, the K-tripolyphosphate is preferred. The K-tripolyphosphate structure is as follows:
Figure imgf000007_0001
Although linear polyphosphates are preferred in the present invention, other water soluble polyphosphates can also be used, such as e.g. sodium, potassium or ammonium polymetaphosphate. Sod ium hexametaphosphate is a typical example of the po lymetaphosphates. The structure of the trimetaphosphoric acid is as follows:
Figure imgf000007_0002
In the present invention, the most preferred polyphosphates are the
tripolyphosphates. Typically either Na-tripolyphosphate or Κ-tripolyphosphate is used or a penta-ammonium tripolyphosphate may be used. Other tri-polyphosphates can be used as well, such as, but not limited to, triethanolamine tripolyphoshate or the tripolyphosphoric acid.
The tripolyphosphate in the concentrated source solution is typically between 0.5% and 200%-w and preferably between 2% and 150%-w and most preferably between 5% and 100%-w as a ratio by weight of polyphosphate to added liquid (typically H?0). The maximum concentration is typically determined by the solubility limit of the tripolyphosphate. The solubility of the K -tripolyphosphate is much higher than the solubility of the Na-tripolyphosphate. E.g. the Na-tripolyphosphate solubility is only about 20%-w. The K -tripolyphosphate on the other hand is much more soluble and can be dissolved even up to about 150%-w concentrations. The penta ammonium tripolyphosphate is also very soluble, but is not so widely available. After dilution of the source solution at point-of-use, the final concentration of tripolyphosphate for cleaning the substrates is preferably 0.2%- 15%.
The tripolyphosphate and preferably the K- or the penta ammonium
tripolyphosphate can be used by itself, it can be used combined and it can also be combined with potassium or ammonium hydroxide. Potassium or ammonium hydroxide is typically added to increase the pH of the solution. Surfactants and chelating agents can also be added. The tripolyphosphate in a concentrated source solution is typically between 0.5% and 200% and preferably between 2% and 150% and most preferably between 5% and 100% relative to the H?0 in the solution. When ammonium hydroxide is added to the concentrated source solution, it can be added in a concentration range of 1%-28%-w (weight of NH3) to make a source solution consisting of ammonium hydroxide and ammonium polyphosphate. Potassium hydroxide can be added to the K -tripolyphosphate in the source solution in a range of 0.001%-45% (weight of KOH).
After dilution in the fab the final concentration of polyphosphate for shaping and slicing the ingots is preferably 0.2%-l 5% by weight in the solution. Typically the source solution will be diluted between 5 and 50 times with DI water in the fab to make up the ingot slicing/shaping solution, preferably 7 to 25 times, and most preferably 9 to 15 times.
The source solution may also contain from 0.01% to 20% of an organic amine. Suitable organic amine compounds may be selected from alkanolamines (e.g. primary alkanolamines: monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyl diethanolamine, secondary alkanolamines: diethanolamine, diisopropanolamine, 2- (methylamineo)ehtano, morpholine, ternary alkanolamines: triethanolamine, tri- isopropylamine), alkylamines (e.g. primary alkylamines, monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylam ine,
cyclohexylamine, secondary alkylamines: dimethylamine), alkyleneamines (e.g.
primary alkylene amines: ehtylenediamine, propylenediamine, triethylenetetramine), and mixtures thereof. Preferred examples of such materials include monoethanolamine, ethylenediamine, triethylenetetramine and mixtures thereof. The most preferred is monoethanolamine. The amount of the organic amine preferably ranges from 0.01 % to 20%, and most preferably from 0.2% to 2%.
The source solution may also contain a biocide such as 2-Methyl-4-isothiazolin- 3 -one (MIT) or 2-Methyl-4-lsothiazolin-3-one Hydrochloric acid (C4H4NOS, HCl, (M 1HCA). The concentration of the biocide is preferably from 1 ppm to 100 ppm, and most preferably from 30-70 ppm. Other biocides may be used as well.
Surfactants can also be added. Typically non-ionic surfactants are preferred. Preferred surfactants are the ethylene oxide type surfactants with a general structure CnH2n+1O(C2H4O)mH. Ideally the number of carbon atoms in the hydrocarbon chain n is 1 .5 or less times the number of oxyethylene groups m. Ideally the number of carbon atoms n is more than 0.5 of the number of oxyethylene groups m. A good non-ionic surfactant isC12H25O(C2H4O)1 1H. The concentration of the surfactant in the concentrated solution will be between 0.1% and 5%. Preferred concentrations are around 0.5% for the concentrated source solution. The concentration after dilution with water and when used for cleaning the surfaces will be preferably between 0.0001 to 0.5% by weight. This is between 1 ppm and 5000 ppm by weight. More preferably, the concentration after dilution will be between 10 ppm and 500 ppm.
Sequestering agents or compiexing agents can also be added. Preferred sequestering or compiexing or chelating agents are the nitrogen-containing carboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and
diethylenetriaminepentaacetic acid (DTPA). Especially preferred from the standpoint of the cleaning effect is ethylenediaminedi-o-hydroxyphenylacetic acid (EDDHA). The concentration of the sequestering agent in the concentrated solution will be between 0.1% and 5%. Preferred concentrations are around 0.5%. The concentration of the sequestering agent after dilution with water and when used for cleaning the surfaces will be preferably between 10 ppm and 500 ppm.
For the clarity of this invention, in the remainder of this invention, we will mostly talk about tripolyphosphate, even though other suitable water-soluble polyphosphates can be used as explained earlier. The ammonium polyphosphate is preferred when no alkali metals are allowed, but for the clarity of this invention, in the remainder of this invention, we will mostly talk about the tripolyphosphate. If alkali metals are allowed, the K -tripolyphosphate is preferred. The K in the solution can be rinsed off the surface very effectively, since it does not bind with the surface of the silicon ingots or sliced wafers and is extremely soluble in DI water.
In the present invention, after the shaping/slicing step with the wire 26 is finished, it is advantageous to follow up the shaping/slicing sequence with a DI water rinse, such as a rinse with a spray. A spray rinse can be a regular water spray or an aerosol spray. A regular water spray is effective; preferably a flow in excess of IL/min per substrate is very effective. The temperature of the rinse water can be any temperature from 0 degrees C to 100 °C, but a room temperature rinse is preferred because of its ease and economical advantage.
The polyphosphate solutions of the present invention provide advantages in the shaping/slicing process at the point-of-use, i.e. during the process in which the workpiece 14 is being sliced by the wire 26. Another advantage of the polyphosphate solutions is that they can be manufactured in concentrated form off-site and then can be diluted on-site around the time they are needed for a point-of-use operation. The initial preparation of concentrated solutions provides economic benefits, such as reduced shipping and transportation costs. For purposes of illustration, representative examples for the composition of concentrated polyphosphate solutions are described below, along with representative dilutions for the point-of-use polyphosphate solutions.
Example 1 : Typical source polyphosphate solutions are made up off-site by mixing a polyphosphate with Dl-water to a high concentration. A typical composition of a simple concentrated solution according to the invention is shown in Table 1 :
Figure imgf000011_0002
To this solution other substances can be added such as e.g. KOH, NH4OH and monoethanolamine. The addition of KOH can be used to increase the pH further. High pH is useful for increasing the repulsion effect between the abraded particles as is described below. Additionally, when using diamond coated wires where the diamonds are embedded with a nickel coating, it is important to bring the pH up to between 10 and 13, where nickel is quite stable. Hence, the pH is typically preferably adjusted to be between 9 and 14 and more preferably between 10 and 13 and most preferably between 1 1 and 12.
This solution in concentrated form can be transported to the point of use. The concentrated form of the polyphosphate solution is referred to as a source solution and the concentration of the polyphosphate in this source solution is about 50% by weight (i.e. 1 OOOg polyphosphate per 1 OOOg water equals 50%). At the point-of-use, this source solution can be diluted with DI water before use as a shaping/slicing solution. For example, the source solution can be diluted in a ratio of 10: 1 DI watensource solution of example 1. The 10: 1 diluted solution of example 1 yields a pH of about 9.5 without any KOH added.
Example 2: Typical alkali free polyphosphate source solutions are made up off- site by mixing a polyphosphate with Di-water to a high concentration.
A typical make-up of a simple concentrated solution according to the invention is shown in Tabel 2:
Figure imgf000011_0001
To this solution other substances can be added such as monoethanolamine, surfactants, sequestering agents and biocides. This solution in concentrated form can be transported to the point of use. At the point of use, this solution can be diluted with DI water before use as a shaping/slicing solution. For example, the concentrated source solution can be diluted in a ratio of 10: 1 DI watensouree solution. Additionally, other substances can be used to increase the pH of the diluted solution, such as TMAH and choline.
In the present invention, after the shaping/slicing step is completed, a thorough rinsing of the newly cut sections of the workpiece 14 is required. A spray rinsing with high flow spray of water is preferred method of rinsing. Typical spray flows of 1 L/min to 4 L/min per nozzle are preferred. Also an aerosol atomized and accelerated spray can be used. The shaping/slicing step is stopped by various methods, such as by lifting the workpiece 14 off of the wire 26 or cutting surface 46. Alternatively, the motion of the wire 26 can be stopped, or both of these steps can be taken together.
Without being bound by theory, it is thought that the polyphosphate solutions of the present invention work in the following manner. When the wire 26 cuts into the workpiece 14, abraded particles are generated. These abraded particles are comprised of whatever material the workpiece 14 is made of. For example, in the preferred embodiment, abraded particles would be particles of polycrystalline silicon. The water- soluble phosphates in the fluid 42 interact with the abraded particles by putting an additional electrostatic charge on the abraded particles and providing for an increased electrostatic repulsive force between the particles and the surface of the sliced workpiece 14.
This mechanism is illustrated in Fig. 4. In Fig. 4, a medium 60 has an adhered particle 62 on its surface. The medium 60 could correspond, for example, to one of the sections 54 illustrated in Fig. 3, to the workpiece 14 or to the equipment that is used in the apparatus 10. The water-soluble phosphates put a plurality of negative charges 66 on both the surface of the medium 60 and the surface of the particle 62. The repulsion between these negative charges means that the particle 62 and the surface of the medium 60 are repelled and hence the particle can be suspended. Only the charges which are relevant for the repulsion of the particle 62 are shown. The solution of this invention with water-soluble phosphates is very effective for shaping and slicing silicon ingots with a diamond coated wire. There are several other advantages to using polyphosphate solutions as the fluid 42. First, the main function of the fluid 42 is for cooling and lubrication during the process in which the wire 26 slices the workpiece 14. Water is good for both of these purposes, so an aqueous based fluid 42 is desirable. Second, when using diamond wire as the wire 26, there is no requirement for the fluid 42 to keep any abrasive in suspension. The diamonds on the wire do the action of cutting, so no abrasive is used in the fluid 42. However, pure water will not prevent the abraded silicon from depositing on either the cut wafers or on many of the parts of the apparatus 10. This is because water evaporates easily and leaves all the abraded silicon hard baked on many of the parts of the apparatus 10. Also, water does not prevent the abraded silicon from depositing on the cut wafers.
The polyphosphate solution is superior to pure water because it prevents the abraded silicon from depositing on the cut wafers by keeping the abraded silicon in solution as was described previously. Additionally, polyphosphates are hygroscopic and prevent the water from easily evaporating when the cut solution ends up on the parts of the apparatus 10.
Third, even when the water finally evaporates, the polyphosphate will deposit together with the abraded silicon in a solid deposit on the various parts of the apparatus 10, This solid deposit is now a mix of polyphosphates and abraded silicon as opposed to solely abraded silicon. This mix of polyphosphate and abraded silicon will easily be dissolved in water when spraying or cleaning the equipment later with pure water.
Finally, the use of an aqueous polyphosphate solution in the wafer slicing process has environmental advantages over processes that use ethylene glycol in the fluid 42. Ethylene glycol is a solvent and is difficult to dispose of. Most countries regulate the quantity that can be disposed of in the waste water stream. The polyphosphate solution can simply be neutralized and can be disposed of in the waste stream. Additionally, ethylene glycol is used pure (that is, undiluted), whereas the polyphosphate would typically be used in at least a 10: 1 or more dilution. Hence, the volumes of chemicals that need to be transported to the cutting facility are at least 10 times smaller for polyphosphates than for ethylene glycol.
Although the present invention has been described in terms of the presently preferred embodiments, it is to be understood that such disclosure is not to be interpreted as limiting. Various alterations and modifications will no doubt become apparent to those skilled in the art after having read the above disclosure. Accordingly, it is intended that the appended claims be interpreted as covering all alterations and modifieations as fall within the true scope of the invention.

Claims

What is claimed is:
1. A method comprising:
a. positioning a workpiece in the vicinity of a wire saw that can cut through workpiece without the use of an abrasive slurry;
b. causing an aqueous polyphosphate solution to contact the workpiece; and c. causing the wire saw to cut into the workpiece while the polyphosphate solution is in contact with the workpiece.
2. The method of claim 1 further comprising:
d. rinsing the polyphosphate solution off of the workpiece.
3. The method of claim 1 wherein the workpiece comprises a semiconductor material.
4. The method of claim 3 wherein the semiconductor material is a photovoltaic material,
5. The method of claim 4 wherein the photovoltaic material comprises silicon.
6. The method of claim 4 wherein the photovoltaic material comprises an ingot of polysilicon having a rectangular cuboid or a square cuboid shape.
7. The method of claim 1 wherein the wire saw can cut through workpiece without the use of an abrasive slurry.
8. The method of claim 1 wherein the wire saw comprises a long wire comprised of a metal having diamonds attached to a surface of the wire.
9. The method of claim 1 wherein the polyphosphate solution comprises a polyphosphate having the formula:
Figure imgf000016_0001
wherein n = 0, 1 ,2,3, .. .1000 and X+ is chosen from the group of H+, Na+, K+, NH4+, R3NH+.
10. The method of claim 9 wherein the polyphosphate is chosen from the group consisting of sodium tripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate, triethanolamine tripolyphosphate, choline tripolyphosphate, TMA tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate and tetraammoniurn pyrophosphate, disodium dihydrogen pyrophosphate, and diammonium dihydrogen pyrophosphate.
1 1 The method of claim 1 wherein the aqueous polyphosphate solution comprises a polyphosphate having a concentration of between 0 2% and 15% by weight in the solution.
12. The method of claim 1 1 wherein the aqueous polyphosphate solution also includes a base.
13. The method of claim 12 wherein the base is chosen from the group consisting of KOH, NH4OH, TMAH and choline.
14. The method of claim 1 wherein the aqueous polyphosphate solution has a pH in the range of 9-14.
15. The method of claim 2 wherein the aqueous polyphosphate solution is rinsed off of the workpiece with a flow higher than 1 L/min.
16. A method for slicing a workpiece comprising:
a. positioning a workpiece in the vicinity of a diamond wire saw;
b. causing a polyphosphate solution comprised of a polyphosphate and water to contact the Workpiece;
c. causing the diamond wire saw to cut the workpiece into two or more sections while the polyphosphate solution is in contact with at least some of the workpiece and at least some of the two or more sections;
d. causing the diamond wire saw to stop cutting the workpiece; and e. rinsing the polyphosphate solution off of at least some of the two of more sections with a rinsing solution after the diamond wire saw has stopped cutting the workpiece.
17. The method of claim 16 wherein the workpiece comprises silicon.
18. The method of claim 16 wherein the polyphosphate comprises a tripolyphosphate.
19. The method of claim 16 wherein rinsing solution comprises water.
20. The method of claim 16 wherein the polyphosphate has a concentration of between 0.2% and 15% by weight in the polyphosphate solution.
PCT/US2011/061539 2010-11-22 2011-11-18 Method for shaping and slicing ingots using an aqueous phosphate solution Ceased WO2012071286A1 (en)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
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WO2009126922A2 (en) * 2008-04-11 2009-10-15 Iosil Energy Corp. Methods and apparatus for recovery of silicon and silicon carbide from spent wafer-sawing slurry
US20090308001A1 (en) * 2008-06-16 2009-12-17 Shaobing Wu Substrate and the application
WO2010009881A1 (en) * 2008-07-23 2010-01-28 Meyer Burger Ag Multi-wire cutting device with a revolving workpiece mount
JP2010074056A (en) * 2008-09-22 2010-04-02 Sumco Corp Semiconductor wafer and method of manufacturing same
WO2011044718A1 (en) * 2009-10-16 2011-04-21 Dow Global Technologies Llc Aqueous cutting fluid for use with diamond wiresaw

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Publication number Priority date Publication date Assignee Title
US4268404A (en) * 1978-11-20 1981-05-19 Hoechst Aktiengesellschaft Additive for use in metal working
US20080196742A1 (en) * 2007-02-08 2008-08-21 Mark Jonathan Beck Particle removal method and composition
WO2009126922A2 (en) * 2008-04-11 2009-10-15 Iosil Energy Corp. Methods and apparatus for recovery of silicon and silicon carbide from spent wafer-sawing slurry
US20090308001A1 (en) * 2008-06-16 2009-12-17 Shaobing Wu Substrate and the application
WO2010009881A1 (en) * 2008-07-23 2010-01-28 Meyer Burger Ag Multi-wire cutting device with a revolving workpiece mount
JP2010074056A (en) * 2008-09-22 2010-04-02 Sumco Corp Semiconductor wafer and method of manufacturing same
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