WO2019145486A9 - Procédé et dispositif pour nettoyer des surfaces gravées d'un substrat semi-conducteur - Google Patents

Procédé et dispositif pour nettoyer des surfaces gravées d'un substrat semi-conducteur Download PDF

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Publication number
WO2019145486A9
WO2019145486A9 PCT/EP2019/051875 EP2019051875W WO2019145486A9 WO 2019145486 A9 WO2019145486 A9 WO 2019145486A9 EP 2019051875 W EP2019051875 W EP 2019051875W WO 2019145486 A9 WO2019145486 A9 WO 2019145486A9
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Prior art keywords
cleaning
ozone
etching
medium
silicon substrate
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PCT/EP2019/051875
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German (de)
English (en)
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WO2019145486A1 (fr
Inventor
Maher Izaaryene
Mirza CORDA
Bianca WATTENBERG
Martin Max MENSCHICK
Benjamin MANDLMEIER
Jens Eckstein
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Singulus Technologies AG
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Singulus Technologies AG
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/137—Batch treatment of the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H10F77/703—Surface textures, e.g. pyramid structures of the semiconductor bodies, e.g. textured active layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0402—Apparatus for fluid treatment
    • H10P72/0418—Apparatus for fluid treatment for etching
    • H10P72/0422—Apparatus for fluid treatment for etching for wet etching
    • H10P72/0424—Apparatus for fluid treatment for etching for wet etching using mainly spraying means, e.g. nozzles
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/30—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for conveying, e.g. between different workstations
    • H10P72/32—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for conveying, e.g. between different workstations between different workstations
    • H10P72/3202—Mechanical details, e.g. rollers or belts
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/30—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for conveying, e.g. between different workstations
    • H10P72/33—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for conveying, e.g. between different workstations into and out of processing chamber
    • H10P72/3314—Continuous loading and unloading into and out of a processing chamber, e.g. transporting belts within processing chambers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method and apparatus for treating a surface of a textured silicon substrate. More particularly, the present invention relates to a method for cleaning etched surfaces of a semiconductor substrate, such as is applicable to photovoltaic modules. Exemplary embodiments relate to a process for the post-purification of multicrystalline diamant wire-sawn silicon substrates. Treatment of a textured silicon substrate may involve cleaning thereof, which may be done using, for example, an ozone-containing medium.
  • Semiconductor substrates can be textured during their further processing, which means that the surface of the semiconductor substrate can be treated, for instance to perform a roughening process. Texturing can be obtained, for example, by means of an acidic texture in the inline process. These are described, for example, in US 2010/0055398 A1 or EP 2 232 526 B1.
  • a texture can also be obtained by acid etching, as described for example in US 2015/0040983 A1.
  • Diamond wire sawn multicrystalline wafers can also be textured.
  • Texturing can also be achieved with acidic media using additive or organic compounds.
  • an etching mixture can be used to produce a textured surface on silicon substrates.
  • Such an etching mixture may comprise at least one polymer.
  • a polymer which is resistant to nitric acid and hydrofluoric acid and / or a hydrophilic polymer may be used.
  • Such a polymer used as thickener may be selected from the group consisting of cellulose, in particular methyl cellulose, polyvinyl alcohol and polyethylene oxide can be selected.
  • CN 103132079 A additives are described which consist of polyvinyl alcohol and polyethylene glycol alcohol.
  • FIG. 11 shows a schematic flow diagram of a method 1000 according to the prior art.
  • Step 1010 includes etching the semiconductor substrate to texure it.
  • the semiconductor substrate is rinsed in order to remove residues of substances or materials which have come into contact with the semiconductor substrate in step 1010.
  • a step 1030 an alkaline post-cleaning of the semiconductor substrate takes place.
  • step 1020 is executed again to rinse the semiconductor substrate.
  • a step 1040 an acid subsequent cleaning of the semiconductor substrate takes place.
  • purging 1020 is again performed to clean the semiconductor substrate of acid post-cleaning residues 1040.
  • the semiconductor substrate is dried.
  • a disadvantage of this method is that impurities can remain on the semiconductor substrate.
  • the object of the present invention is therefore to provide a method for treating a surface of a textured silicon substrate and an apparatus for carrying out such a method, which provide high-quality cleaned semiconductor substrates.
  • a finding of the present invention is that it has been recognized that, although some residues of the etching, in particular porous silicon and metal impurities, can be eliminated by the alkaline post-cleaning and the acid subsequent cleaning, other impurities remain.
  • cleaning of the surface of the textured silicon substrate to remove organic compounds is performed.
  • the organic ones Compounds are located on the surface of the textured silicon substrate and may be, for example, residues of the etching process and / or the contact of the semiconductor substrate with other substances and / or persons.
  • cleaning is understood to be cleaning by removal of substances to be removed.
  • Examples provide a method of treating a surface of a textured silicon substrate.
  • the method includes cleaning the surface of the textured silicon substrate to effect removal of organic compounds that are on the surface of the textured silicon substrate.
  • the method includes removing porous silicon at the surface of the textured silicon substrate.
  • the method further includes performing a metal cleaning of the surface of the textured silicon substrate.
  • Such apparatus includes process media supply means for providing media for cleaning, alkaline post-cleaning, and acid post-cleaning of the surface, and includes substrate handling means for positioning the silicon substrate to treat the surface.
  • FIG. 1a is a schematic flowchart of a method according to an embodiment
  • FIG. 1 b is a schematic flow diagram of a method according to an embodiment, in which a cleaning of a surface of a textured silicon substrate takes place;
  • FIG. 2 is a schematic flow diagram of a method according to an embodiment, which comprises an optional etching step, optional rinsing steps and an optional drying step;
  • FIG. 1 b is a schematic flow diagram of a method according to an embodiment, in which a cleaning of a surface of a textured silicon substrate takes place;
  • FIG. 2 is a schematic flow diagram of a method according to an embodiment, which comprises an optional etching step, optional rinsing steps and an optional drying step;
  • FIG. 1 b is a schematic flow diagram of a method according to an embodiment, in which a cleaning of a surface of a textured silicon substrate takes place;
  • FIG. 2 is a schematic flow diagram of a method according to an embodiment, which comprises an optional etching step, optional rinsing steps and an optional drying step;
  • FIG. 1 b
  • FIG. 3 is a schematic flowchart of a method according to an embodiment, which includes removal of porous silicon and / or metal;
  • FIG. 4 is a schematic flow diagram of a method according to an embodiment comprising an alkaline post-purification
  • FIG. 5 is a flowchart of a prior art RCA cleaning
  • Fig. 6 is a schematic flow diagram of a prior art process used to remove the porous silicon and perform metal cleaning
  • FIG. 7 is a schematic flowchart of a method according to an embodiment having an ozone-based treatment
  • FIG. 8 is a schematic illustration of one for performing a method according to the present disclosure.
  • Fig. 9 is a schematic representation of an alternative example of a device for
  • a substrate handling device is implemented as a horizontal transport system with rollers
  • Fig. 10 is a schematic representation of an alternative example of a device for
  • a process media provider comprises a process media pool
  • FIG. 11 is a schematic flow diagram of a method 1000 according to the prior art.
  • FIG. 1 a shows a schematic flow diagram of a method 100 according to an exemplary embodiment.
  • the method 100 includes a step 110.
  • the step 110 includes cleaning the surface of the textured silicon substrate to effect removal of organic compounds that are on the surface of the textured silicon substrate.
  • the step 110 further includes removing porous silicon at the surface of the textured silicon substrate and performing metal cleaning of the surface of the textured silicon substrate.
  • the cleaning, the removal of porous silicon and the execution of the metal cleaning can also take place in at least partially separate steps, while otherwise stated, at least two of the three purification steps can be carried out in a common step, or As shown in FIG. 1 a, all three cleaning steps can be carried out in a common step 110.
  • One embodiment of the cleaning steps of removal of porous silicon, metal cleaning and removal of organic compounds in one step can be understood to mean that a corresponding purification step, in particular an isolated and specially arranged cleaning step, for example in a separate process media pool or a separate Section of a system, during the process is not carried out again, in particular not subsequently, at least as long as no further processing of the substrate takes place, which leads to new impurities, which may require a re-cleaning.
  • FIG. 1 b shows a schematic flow diagram of a method 150 according to an exemplary embodiment, in which, in a step 160, the cleaning of the surface of the textured silicon substrate to effect removal of organic compounds present on the surface of the textured silicon substrate.
  • a step 170 of the method 150 the removal of porous silicon takes place on the surface of the textured silicon substrate.
  • a metal cleaning of the surface of the textured silicon substrate is carried out.
  • An order of steps 160, 170 and 180 is arbitrary. Prior to and / or after any one of steps 160, 170, and / or 180, rinsing of the silicon substrate may be accomplished, for example, by performing step 1020. Collectively, steps 160, 170, and 180 provide step 110 of method 100.
  • the cleaning in the step 1 10 and / or 160 for removing the organic compounds may be wholly or partly by contacting the silicon substrate with an oxidative component.
  • oxidative components are, for example, hydrogen peroxide (H2O2) or ozone (O3).
  • the silicon substrate may also be associated with an alkaline component, for example potassium hydroxide (KOH).
  • KOH potassium hydroxide
  • a RCA (Radio Cooperation of America) cleaning can be carried out, which includes a wet chemical cleaning process.
  • RCA cleaning may include cleaning the semiconductor substrate in two baths.
  • a first bath may include an aqueous solution of ammonium hydroxide and hydrogen peroxide.
  • a second bath into which the semiconductor substrate is subsequently added may include an aqueous solution of hydrochloric acid and hydrogen peroxide.
  • the cleaning can be carried out at room temperature, but can also be carried out in other temperature ranges. By using a slightly higher temperature range, for example, in a range between 40 ° C and 70 ° C, a high purification efficiency can be obtained. This means that the cleaning can take place in a bath, for example in a so-called batch process.
  • the method may also include a plurality of baths into which the respective semiconductor substrate is successively brought. Alternatively, at least one bath can be replaced by wetting with the liquid to be applied, for example by using spray nozzles.
  • Removal 170 of porous silicon at the surface of the textured silicon substrate or the corresponding substep in step 1 10 may be accomplished by alkaline post-cleaning and / or by treatment with ozone.
  • the performing 180 of the metal cleaning of the surface of the textured silicon substrate or the corresponding sub-step in the step 1 10 may be carried out by an acid post-cleaning and / or by the treatment with ozone.
  • the metal cleaning 180 and / or the corresponding partial step in the step 1 10 can also be obtained by contacting the semiconductor substrate to be cleaned with an aqueous solution comprising water and at least one of hydrogen chloride (HCl) and hydrofluoric acid (HF). Alternatively or additionally, a solution comprising hydrofluoric acid, hydrogen chloride and ozone can also be used.
  • an order of alkaline and acid purification is arbitrary. That is, unlike in FIG. 1 b, step 180 may be executed first and then step 170 may be executed. An order is also arbitrary with regard to step 160, that is, step 160 may be executed before or after step 170 and / or before or after step 180.
  • the alkaline post-purification can be obtained, for example, by carrying out the step 1030.
  • the acid post-purification can be carried out, for example, by carrying out step 1040.
  • ozone can also be used.
  • steps 160 or 170 and / or 180 it becomes possible to combine steps 160 or 170 and / or 180 together to perform at least two of steps 160, 170 and 180 in a common step. According to an exemplary embodiment, this can also be carried out such that the steps 160, 170 and 180 are performed together in the step 110. That is, the cleaning in step 160 and / or 110 may also effect removal of porous silicon (step 170) and / or texture additives, and / or metals (step 180).
  • ozone concentration for such a step may range from 1 ppm to 150 ppm, from 5 to 150 ppm, or from at least 10 to 150 ppm. Exemplary embodiments also apply without restriction to lower limits of more than 30 ppm, about 31 ppm or more, 35 ppm or more, 40 ppm or more or even 100 ppm or more with simultaneous use of the said upper limits. Referring to both method 150 of FIG. 1 b and method 100 of FIG. 1 a, preferred embodiments of methods 100 and 150 will be discussed.
  • a combination of ozone with hydrofluoric acid (HF) and / or HCl may be used in addition to oxidative removal of organic materials by ozone, ie, ozone the organic compounds can be removed by a removing mechanism simultaneously organic residues can be removed by the impurities or residues are removed by the substrate or the substrate is etched.
  • HF hydrofluoric acid
  • embodiments provide for using a concentration of at most 1% HF and / or HCl. For example. removes the HF silicon oxide and by removing the oxide layer also adhering to the surface organic impurities or their degradation products are replaced.
  • the combination HF / HCl and ozone can be additionally removed metal impurities.
  • the HF concentration is kept within the scope of the described embodiments at most 1, 5% or at most 1%, preferably between 0.05% and 0.5%.
  • the HCI concentration is maintained in the described embodiments at most 1, 5% or at most 1%, preferably between 0.05% and 0.5%.
  • short treatment times which may be shorter than 5 minutes, preferably between 0.5 minutes and 3.5 minutes, are sufficient.
  • the solution may preferably have a pH in a range of at least 0 and at most 7 and be used at a process temperature of at least 5 ° C and at most 80 ° C. Preference is given to temperatures of at least 20 ° C and at most 65 ° C or at least 50 ° C and at most 65 ° C.
  • the solution is preferably heated to temperatures above room temperature, namely taking into account the upper limit of 80 ° C, 65 ° C or 50 ° C to temperatures of at least 30 ° C, at least 35 ° C or at least 40 ° C, since with increasing temperature, the solubility of organic compounds / residues is improved and thus small or shortêtstre- bridges for the introduction of ozone in the solution and / or high ozone concentrations are allowed.
  • a high ozone concentration up to about 150 ppm may be used or even exceed it.
  • embodiments provide for reducing the temperature from the described 23 ° C to obtain good ozone solubility in the medium.
  • FIG. 2 shows a schematic flow diagram of a method 200 according to an exemplary embodiment.
  • the method 200 includes a plurality of optional steps, including an optional step 210, in which etching of the semiconductor substrate occurs, such as to obtain texturing of at least one surface of the semiconductor substrate.
  • etching organic contaminants may form.
  • texture additives may contain organic compounds and may remain on the surface during or after the etching step.
  • One or more targets of the etch 210 and / or a major focus thereof may be on an acidic isotropic texture provided with an additive to treat multicrystalline diamond wire sawn silicon substrates.
  • the additive may be organic or inorganic.
  • An additive used may comprise as a component a polymer.
  • the etching 210 may be performed in various ways. One type is, for example, a metal-assisted chemical etching using metal particles. This can also be described by the English technical term "Metai Assisted Chemical Etching (MACE)". It can also be an acid isotropic texture, d. h., Mixture be used.
  • MACE Metal Assisted Chemical Etching
  • Such an acid isotropic texture with organic and / or inorganic additives may be, for example, a combination of hydrofluoric acid, nitric acid (HNO3) and at least one additive.
  • water can also be added so that the acid isotropic texture with additive can also be a combination of hydrofluoric acid, nitric acid, water and the additive.
  • an additive from the group consisting of alcohol, surfactant, glycol can be contained.
  • additives may adhere to the surface and alter the wetting behavior for further steps and / or inhibit the attack of further etchants, ie inhibit.
  • the additive may have one or more components and thus also be understood as an additive or a combination of several additives.
  • the use of several additives may be such that the combination of the additives only work together in a solution or in the bath used, which means that, when the additives are combined in themselves, no interaction takes place yet.
  • the detachment of impurities on the wafer, such as metals and / or metal ions can also be inhibited.
  • an electrochemical etching can also be carried out.
  • Further examples for use during the etching process include, for example, a chemical edge isolation, a smoothing of the surface, i. h., performing a polish, selective emitter removal, removal of sawing damage, especially in diamond-sawn silicon substrates, single-side treatment (single-sided treatment), or treatment of both major sides (double-sided treatment). That is, the use of an acidic isotropic texture can optionally be done using an additive, which additive may be organic or inorganic. In one example, the etch may be done without additive.
  • the etch 210 may result in residues on at least one of the surfaces of the semiconductor substrate. These residues may be porous silicon, may alternatively or additionally include metal contaminants, but may alternatively or additionally include organic contaminants.
  • an optional step 220 may be carried out, in which a rinsing of the semiconductor substrate takes place.
  • the purging 220 or the removal of the additive components can take place in at least one step and / or one pass. This means that it can also be flushed more often.
  • the purging 220 may include contacting the semiconductor substrate with water, that is, a medium of the purging operation 220 may be water. Alternatively or additionally, ozone, hydrofluoric acid, hydrogen chloride and / or other agents may also be used.
  • the rinsing process 220 can take place in a temperature range of, for example, at least 5 ° C. and at most 90 ° C., for example in order to avoid the boiling of water.
  • a rinsing process which can be referred to by the technical term "Quick Dump Rinse" can be used.
  • Overflow rinse and / or cascade rinse aid can be used.
  • a purging process may involve a fixed consumption of purging medium, advantageously, the purging process may be dynamically adjusted to the degree of contamination of the wafer and / or the purging medium.
  • Step 220 may be performed, in particular, if the method includes step 210.
  • a pre-etched semiconductor substrate may also be provided for cleaning and / or removing porous silicon and / or metal.
  • a cleaning of organic compounds from the semiconductor substrate takes place. This can be done, for example, in the context of step 110 and / or step 160. At the same time this can lead to metal contamination.
  • the method 200 further comprises an optional step 240, in which a rinsing of the semiconductor substrate can take place, in particular if the cleaning 230 and the removal of the porous silicon and / or the execution of the metal cleaning takes place in at least two steps.
  • the method 200 includes a step 250 in which the removal of porous silicon and / or metal is accomplished by an ozone-based treatment.
  • the metal impurities occurring in step 230 can be removed.
  • steps 170 and 180 are combined, using the ozone-based treatment for the combination.
  • steps 230 and 250 may also be performed in common, i. H. at the same time, so that the step 240 can be omitted without restriction, since the cleaning of the organic compounds, the removal of the porous silicon and / or the metal cleaning takes place at the same time.
  • the mutual generation of new impurities by carrying out the purification steps 210 and 230 offers the potential for improvement in the fact that these newly generated impurities are immediately removed or prevented in the same step.
  • This allows a small dimension of the corresponding plant to be obtained, for example if a common pool, bath or common treatment area is used for all three purification steps.
  • the method may be adapted based on different adjustment parameters and / or materials used such that the ozone-based treatment is configured to effect one or more of the alkaline post-cleaning, the removal of porous silicon, the metal cleaning, and the removal of organic compounds. For example.
  • adding components, constituents or additives to the cleaning medium can cause different settings.
  • all three cleaning steps can be obtained in a common pool under at least approximately constant conditions. Purification of organic contaminants can be carried out particularly effectively at higher temperatures and higher ozone concentrations and, taken alone, can also be carried out only with ozone and water. An additional removal of porous silicon can be obtained by adding hydrofluoric acid. It is known to perform a metal cleaning only with HF / HCl. Use of a combination of hydrofluoric acid, hydrogen chloride and ozone and / or a combination of hydrofluoric acid and ozone allows all three steps to be carried out simultaneously, removal of organic compounds, metal residues and porous silicon.
  • the method 200 comprises a step 270, in which a drying of the semiconductor substrate takes place.
  • Step 270 may be after cleaning.
  • the drying can be carried out in a temperature range of at least 0 ° C, d. h., A state in which water is liquid, to allow evaporation of the raw material water.
  • a temperature range of at least 25 ° C and at most 100 ° C is preferred.
  • the temperature may be constant or variable over a course of step 270. For example, a variable temperature profile with increasing temperature can help to minimize material stress in the semiconductor substrate.
  • IFA isopropyl alcohol
  • Step 260 may be after ozone-based treatment and prior to drying in step 270, or before one end of the process.
  • the end of the Method may include depositing the semiconductor substrate, which may also be understood as a drying, for example in ambient air.
  • Step 260 may include wetting the semiconductor substrate with a medium comprising at least one of water, ozone, hydrofluoric acid, and / or hydrogen chloride.
  • a possible ozone concentration is in the range of 1 ppm to 5 ppm or less.
  • the time that the semiconductor substrate contacts ozone in step 260 and / or the concentration thereof is configured to clean off any residue from step 270, while in step 750, the substrate itself may be treated with ozone.
  • rinsing may be performed in step 260 in a temperature range of 5 ° C to 90 ° C.
  • Step 350 is performed in place of step 250 and includes removal of the porous silicon and / or the metal. While this is obtained in the method 200 by the ozone-based treatment, optionally combinatorial, another step of removing the porous silicon and / or the metal may be performed in step 350, for example, by performing an alkaline post-purification and / or by using an acidic After cleaning is carried out. It is understood that in step 350 also several partial steps are executable. According to embodiments, a method may also include steps 250 and 350.
  • the method 400 differs from these embodiments in that the method comprises a step 451 in which an alkaline post-purification is performed. This step may be after the optional step 240. In a step 452, which can be carried out after step 451, the semiconductor substrate is rinsed. The step 452 may be the same or similar to the step 220. After the step 452, an acid post-cleaning may be performed in a step 453, in which, for example, the metal cleaning is performed.
  • the ozone-based treatment can be used to remove the porous silicon and / or the Perform metal cleaning, which means removing the metal residues.
  • ozone for rinsing
  • Steps 32 and 36 described there relate to the two RCA cleaning baths, with a quick dump rinse purging comprising ozone (O3) after each bath.
  • ozone O3
  • DE 10 2010 054 370 A1 a use of ozone for cleaning is described.
  • the alkaline etch process is combined with an additional purification step using hydrofluoric acid and ozone to provide a polished and clean surface that is used for Si0 2 / SiN x stack passivation.
  • only a removal of detergent residues occurs.
  • the use of the ozone-based treatment in step 250 offers the possibility of reducing the number of chemical process steps, since at the same time the porous silicon materials as well as the metals and optionally also the organic compounds can be cleaned off.
  • a reduction in the number of rinsing steps can be obtained.
  • This allows the reduction of the process time and thus an increase in throughput based on existing plants and / or processes.
  • a reduction of the chemical consumption is made possible and a smaller dimension of the sequentially operating plants, that is, shorter plants.
  • Further advantages obtained therefrom in particular if the low consumption of chemicals consists in avoiding hydrogen chloride, potassium hydroxide and / or hydrogen peroxide, lies in the low costs for operating the plant.
  • the smaller number of purification steps makes it possible to obtain lower costs. Indirectly, disposal costs can also be saved since fewer (different) wastewater types are obtained.
  • ozone can be made to remove porous silicon and / or perform metal cleaning and / or cleaning of the organic compounds by treating the surface of the textured silicon substrate with the ozone-based treatment.
  • the method 600 comprises a step 630 which, for example, can be implemented as step 1030 of the method 1000 and is used to remove the porous silicon. Furthermore, the method 600 includes a step 640 that for metal cleaning, such as performing step 1040 of method 1000.
  • FIG. 7 shows a schematic flowchart of a method 700 according to an embodiment comprising a step 750 of ozone-based treatment.
  • step 750 not only steps 630 and 640 of method 600 may be performed, but also step 160 of cleaning the surface of the textured silicon substrate from the organic compounds.
  • the ozone-based treatment may thus include the etching of porous silicon, i. h., the removal thereof, and combine the metal cleaning in one step. Alternatively or additionally, the ozone treatment may also be used to remove organic residues.
  • the ozone treatment 750 can be carried out, for example, in at least one step, which means that it can also be carried out repeatedly or iteratively.
  • Ozone concentrations of ozone contained, for example, in a liquid, such as aqueous solution in a bath in which the semiconductor substrate is dipped or which is sprayed over the semiconductor substrate may be in a range of at least 1 to at most 150 ppm. Preference is given to concentrations of at least 5 or at least 10 ppm.
  • a solution may comprise water, an acid, hydrofluoric acid and / or hydrogen chloride.
  • the solution may preferably have a pH in a range of at least 0 and at most 7 and be used at a process temperature of at least 5 ° C and at most 80 ° C. Preference is given to temperatures of at least 20 ° C and at most 65 ° C or at least 50 ° C and at most 65 ° C.
  • the ozone in the ozone-based treatment, may be dissolved in or part of an aqueous solution, so that wetting the semiconductor substrate with the aqueous solution causes the aqueous solution to react with the semiconductor substrate (s) thereon.
  • the ozone can occur in addition to the form in the dissolved state, even in the form of elementary gas bubbles. This is the combination of dissolved ozone and gaseous ozone.
  • the ozone gas bubbles can in one example positively affect the flow to the wafer and remove residues more effectively from the surface.
  • the wetting can take place by means of a bath, into which the semiconductor substrate is introduced, and / or by means of spraying. The described methods can be carried out in devices designed for this purpose.
  • both applications as a batch method (devices with multiple wells) or in-line methods (devices for spraying the semiconductor substrate) are provided.
  • the wafer is immersed in the process solution while being treated during in-line transport.
  • the ozone-based treatment is particularly advantageous combined with the cleansing of the organic matter.
  • Such a method may thus also be referred to as a method for treating etched surfaces of a semiconductor substrate using ozone-containing medium.
  • the embodiments described herein and in this context relate to a method and apparatus for treating a textured silicon substrate, and more particularly to a method of cleaning using an ozone-containing medium. It is compared to the prior art, not focused on the rinse, but on a separate step using the ozone-containing medium, in which the corresponding and to be removed substances are removed by the ozone. This means that the ozone interacts with the semiconductor substrate or the residues.
  • step 210 for etching the semiconductor substrate is also optional. If the method 700 is configured to include step 210, it may be performed prior to ozone-based processing 750 and performed to obtain the textured silicon substrate. As already explained above, the ozone-based treatment with hydrofluoric acid and / or hydrogen chloride can be carried out.
  • etching may include at least one of metal assisted chemical etching, electrochemical etching, acidic isotropic texture etching, and acid isotropic texture etching with organic and / or inorganic additives.
  • the etching may alternatively or additionally comprise chemical edge isolation and / or surface smoothing and / or selective emitter removal and / or saw damage removal, and / or one-sided treatment or two-sided treatment.
  • FIG. 8 schematically illustrates an example of an apparatus 80 for performing a method according to the present disclosure.
  • the device 80 comprises a process media supply device for providing media for cleaning, alkaline post-cleaning and acid surface refinishing.
  • the device 80 further includes a substrate handling device configured to position the substrate 82.
  • the substrate 82 may be a wafer.
  • the process media delivery device may be configured to include rollers 86 that permit transport and wetting of the substrate 82 with an acidic or alkaline and / or ozone containing medium.
  • at least one of the rollers 86 may have a cavity for receiving the medium and may be formed so that the medium can reach the substrate through a lateral surface, for example over a porous surface of the roller.
  • the process media supply device may comprise a media pool in which the acidic or alkaline and / or ozone-containing medium is located.
  • the apparatus 80 may include a plurality of rollers and / or media basins for communicating the substrate 82 with different media. Alternatively, the roller and / or the basin between individual steps can be emptied, optionally cleaned and refilled.
  • the substrate handling device has rollers 86, over which the substrate 82 is transported.
  • the rollers 86 may represent a horizontal transport system, which means that there may be functional integration between the process media supply device and the substrate handling device.
  • the rollers 86 may function to transport the media to the underside of the substrate 82.
  • the rollers 86 may be at least partially arranged in the medium and have a porous or sponge-like surface or provide the medium from an inner hollow body. Thereby, the underside of the substrate 82 can be wetted with the medium and thus treated.
  • FIG. 9 shows an alternative example of an apparatus 90 for carrying out a method according to the present disclosure, in which the substrate handling device is in turn implemented as a horizontal transport system with rollers 86 over which the substrate 82 is transported.
  • the device 90 may be similar to the device described in DE 10 2009 060 931 A1 or WO 201 1/076920 A1, so that, for example, the device 90 for treating silicon wafers 82 is shown as silicon substrates, in the direction of passage of these silicon wafers.
  • Wafer 82 lie along a horizontal Transport path, which is formed by transport rollers 86 on transport shafts 87.
  • Several silicon wafers can be driven side by side through the system 90 and many behind each other at a small distance.
  • the process media supply device may comprise a still pipe 94 provided as a wetting device, which has a distance of a few centimeters to the top of the substrates 82, such as silicon wafers and extends over the entire width of the transport path ,
  • the surge pipe 94 or more still pipes 94 in a row cover the transport path in length.
  • the distance of the surge pipes 94 may be, for example, about 15 cm, but possibly also slightly more or less or even change in the course of the transport path.
  • a subsequent metering 98 for replenishing additive as a separate connection can be provided on the stilling pipe 94.
  • an additive mentioned above or several of them can be added or added to the etching solution 85. This can be done so shortly before the application of the etching solution 85 from the stilling tube 94, that evaporation of the aforementioned volatile additives is kept very low or can be completely avoided.
  • the surge pipe 94 has on its underside a plurality of surge nozzles 96, which may be formed as simple holes, openings or slots. Through them, the medium or the etching solution 85 can emerge and come on the top of the silicon wafer 82 and distribute there, as shown.
  • the alkaline etching solution described in DE 10 2009 060 931 A1 it is possible to use another, for example, acidic etching solution, as described, for example, in DE 10 2007 063 202 A1, in which case the cleaning is additionally carried out.
  • a method described there can be carried out in two steps. Both steps can use acid etching solutions. In the first step, focusing on the texture of the top, and in the second step on a polish from the bottom. Between the steps a rinsing with water can take place.
  • the process media delivery device may include lower spray nozzles and upper spray nozzles to provide the media from both sides relative to the substrate 82 to treat both major surfaces of the wafer 82.
  • spray nozzles may be provided only on one side.
  • five surge nozzles 96 are shown on FIG. can another number, z. B. only one nozzle or a higher number, such as two, three, four, six, ten or more, may be provided.
  • FIG. 10 shows an alternative example of an apparatus 120 for performing a method in accordance with the present disclosure in which the process media provider includes a process media bath 122 in which the media 84, such as an acidic media, is located.
  • the process media provider includes a process media bath 122 in which the media 84, such as an acidic media, is located.
  • a substrate handling device 124 which is only very schematically shown in FIG. 10, is designed to place the substrate 82 in, for example, a horizontal orientation (left-hand part of FIG. 10) or in a vertical orientation (right-hand part of FIG. 10) Dip medium 84.
  • the substrate handling device 124 may for this purpose include suitable holders or grippers for simultaneously gripping and dipping substrates into the medium 84, one or more substrates at a time.
  • the substrate handling device may include transport rollers or transport chains described in more detail, which are configured to float one or more substrates over the surface of the media 84, or formed to one or more substrates Substrate substrates in the medium 84.
  • the medium 84 may each be at least one medium of the respective process step described in connection with the methods of the disclosure set forth herein.

Landscapes

  • Weting (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

L'invention concerne un procédé comprenant les étapes consistant à nettoyer la surface d'un substrat de silicium texturé et à éliminer les composés organiques qui se trouvent sur la surface du substrat de silicium texturé, puis à éliminer le silicium poreux à la surface du substrat de silicium texturé et à réaliser un nettoyage de la surface du substrat de silicium texturé de manière à la purifier des impuretés métalliques.
PCT/EP2019/051875 2018-01-26 2019-01-25 Procédé et dispositif pour nettoyer des surfaces gravées d'un substrat semi-conducteur Ceased WO2019145486A1 (fr)

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DE102018201239.3 2018-01-26
DE102018201239 2018-01-26
DE102018206980.8 2018-05-04
DE102018206980.8A DE102018206980A1 (de) 2018-01-26 2018-05-04 Verfahren und Vorrichtung zur Reinigung von geätzten Oberflächen eines Halbleitersubstrats

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CN112701187B (zh) * 2020-12-28 2022-11-22 天合光能股份有限公司 一种切片电池边缘钝化方法及设备
CN114975686B (zh) * 2022-05-26 2024-12-24 正泰新能科技股份有限公司 一种单晶硅片及其制绒方法

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US6503333B2 (en) 2000-11-30 2003-01-07 Taiwan Semiconductor Manufacturing Company, Ltd Method for cleaning semiconductor wafers with ozone-containing solvent
DE102007026082A1 (de) * 2007-05-25 2008-11-27 Gebr. Schmid Gmbh & Co. Verfahren zur Behandlung von flachen Substraten sowie Verwendung des Verfahrens
DE102007063202A1 (de) 2007-12-19 2009-06-25 Gebr. Schmid Gmbh & Co. Verfahren und Vorrichtung zur Behandlung von Silizium-Wafern
JP2011515872A (ja) * 2008-03-25 2011-05-19 アプライド マテリアルズ インコーポレイテッド 結晶太陽電池の表面クリーニング及び凹凸形成プロセス
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DE102009060931A1 (de) 2009-12-23 2011-06-30 Gebr. Schmid GmbH & Co., 72250 Verfahren und Vorrichtung zur Behandlung von Siliziumsubstraten
DE102010054370A1 (de) 2010-12-13 2012-06-14 Centrotherm Photovoltaics Ag Verfahren zur Herstellung von Siliziumsolarzellen mit vorderseitiger Textur und glatter Rückseitenoberfläche
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WO2016080348A1 (fr) * 2014-11-21 2016-05-26 三菱電機株式会社 Procédé de fabrication de cellule solaire, et cellule solaire
DE102016210883A1 (de) 2016-06-17 2017-12-21 Singulus Technologies Ag Vorrichtung und Verfahren zur Behandlung von Substraten unter Verwendung einer Auflagerolle mit porösem Material

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