WO2004100244A1 - Verfahren zum texturieren von oberflächen von silizium-scheiben - Google Patents
Verfahren zum texturieren von oberflächen von silizium-scheiben Download PDFInfo
- Publication number
- WO2004100244A1 WO2004100244A1 PCT/DE2004/000835 DE2004000835W WO2004100244A1 WO 2004100244 A1 WO2004100244 A1 WO 2004100244A1 DE 2004000835 W DE2004000835 W DE 2004000835W WO 2004100244 A1 WO2004100244 A1 WO 2004100244A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- etching solution
- silicon wafers
- degrees celsius
- temperature
- concentrated
- Prior art date
Links
- 235000012431 wafers Nutrition 0.000 title claims abstract description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 63
- 239000010703 silicon Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005530 etching Methods 0.000 claims abstract description 74
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000004580 weight loss Effects 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus 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
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67075—Apparatus for fluid treatment for etching for wet etching
- H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the invention relates to a method for texturing surfaces of silicon wafers with the steps of immersing the silicon wafers in an etching solution of water, concentrated hydrofluoric acid and concentrated nitric acid and setting a temperature for the etching solution.
- the invention has for its object to provide a method of the type mentioned, which is particularly easy to perform, especially on an industrial scale and leads to silicon wafers with improved efficiency.
- This object is achieved according to the invention in a method of the type mentioned at the outset in that the etching solution consists in part of 20% to 55% water, 10% to 40% concentrated hydrofluoric acid and 20% to 60% concentrated nitric acid and that the temperature of the etching solution is between 0 Degrees Celsius and 15 degrees Celsius.
- the composition of the etching solution according to the invention consisting of 20% to 55% water, 10% to 40% concentrated hydrofluoric acid and 20% to 60% concentrated nitric acid and additionally the carrying out of the etching process at the relatively low etching bath temperature, which is clearly below room temperature, there is a noticeable improvement the efficiency achieved. Furthermore, the preparation of the etching solution is relatively uncritical and can be carried out in a relatively short time. On the other hand, the etching process can be checked relatively easily.
- the etching solution consists partly of 30% to 40% water, 15% to 30% concentrated hydrofluoric acid and 30% to 50% concentrated nitric acid.
- the temperature of the etching solution is between 7 degrees Celsius and 9 degrees Celsius.
- the silicon wafers expediently remain in the etching solution for between 3 minutes and 5 minutes.
- the etching solution consists in part of 31% water, 23% concentrated hydrofluoric acid and 46% concentrated nitric acid, the temperature of the etching solution being at at 8 degrees Celsius and the silicon wafers remain in the etching solution for between 1.5 minutes and 2 minutes.
- the silicon wafers are aligned essentially vertically and the etching solution has a flow component. As a result, both surfaces of the silicon wafers are textured in essentially the same manner.
- the silicon wafers are aligned essentially horizontally, the etching solution being at rest.
- the upward-facing surface is textured particularly well by gas bubbles bubbling away relatively quickly.
- the silicon wafers are moved by the etching solution. This results in particularly good textures on both surface sides of the silicon wafers.
- the silicon wafers are expediently multicrystalline in the method according to the invention.
- 1 is a schematic representation of the arrangement of silicon wafers in an etching solution according to the invention according to a first embodiment
- 2 shows a schematic illustration of the arrangement of silicon wafers in an etching solution according to the invention in accordance with a second exemplary embodiment
- FIG. 3 shows a schematic illustration of the arrangement of silicon wafers in an etching solution according to the invention in accordance with a third exemplary embodiment
- FIG. 6 shows a representation of a surface of a silicon wafer textured according to the invention obtained with an electron microscope.
- FIG. 1 shows a schematic representation of a number of multicrystalline silicon wafers 1 designed as so-called wafers, which are connected to a holder 2 in a manner known per se.
- the holder 2 is immersed in the representation according to FIG. 1 with the silicon wafers 1 in a horizontal orientation in a trough 3 which is filled with a resting etching solution 4 according to the invention.
- This horizontal arrangement leads to gas bubbles which arise during the etching process on the upward-facing surface of the silicon wafers 1 bubbling upward and thus on the upward-facing one Surface of the silicon wafers 1 is a very good texturing for reducing reflections.
- FIG. 2 shows a schematic illustration of the arrangement of silicon wafers 1 connected to a holder 2 corresponding to the exemplary embodiment according to FIG. 1 in an etching solution 4 according to the invention according to a second exemplary embodiment.
- the silicon wafers 1 are arranged vertically, the etching solution 4 for example by moving the trough 3 back and forth or by using a stirring tool (not shown in FIG. 2) which is resistant to strong acids, the etching solution 4 along the silicon wafers 1 has a flow component indicated by dashed flow lines. It is thereby achieved that during the etching process, gas bubbles forming on both surfaces of the silicon wafers 1 detach prematurely and bead up, so that both surface sides of the silicon wafers 1 are textured uniformly.
- FIG. 3 shows a schematic representation of the arrangement of silicon wafers 1 in an etching solution 4 according to the invention in accordance with a third exemplary embodiment.
- a roller conveyor 5 with a number of mutually opposite, at least partially driven upper rollers 6 and lower rollers 7, with which the silicon wafers 1 to be textured are in a substantially horizontal path through the etching solution 4 according to the invention held in the tub 3 can be carried out.
- This exemplary embodiment is distinguished by the fact that it can be used particularly well for the continuous production of silicon wafers 1 with very good texturing of both surface sides.
- composition of an exemplary etching solution 4 according to the invention of water, concentrated hydrofluoric acid, that is to say with a concentration of at least about 50%, and concentrated nitric acid, that is to say with a concentration of at least about 65%, is as follows, with other concentrations of the hydrofluoric acid and the proportions of the nitric acid must be adjusted accordingly:
- the temperature of the etching solution 4 is kept according to the invention between approximately 0 degrees Celsius and approximately 15 degrees Celsius, preferably between approximately 7 degrees Celsius and approximately 9 degrees Celsius.
- HF hydrofluoric acid
- HN0 3 nitric acid
- the temperature of the etching solution 4 being kept at about 8 degrees Celsius.
- the process time in this particularly preferred embodiment is between 1.5 minutes and 2 minutes.
- the etching process is controlled by weighing textured silicon wafers 1 before and after the etching process, a specific target weight loss indicating the correct duration of the etching process depending on the size of the respective silicon wafer 1 and the desired etching removal. If the actual weight loss is below the target weight loss, the duration of the etching process is increased until the actual weight loss matches the target weight loss. If the actual weight loss is above the target weight loss, the duration of the etching process is shortened until the actual weight loss matches the target weight loss.
- the etching time is plotted on the abscissa 8.
- the average reflection, averaged over a wavelength range from 400 nanometers to 1100 nanometers, is plotted on the ordinate 9.
- the values approximated by a first approximation curve 10 originate from silicon wafers 1 textured using the method according to the invention.
- the measured values approximated by a second approximation curve 11 originate from silicon wafers textured using a comparison method.
- the comparison of the first approximation curve 10 for the method according to the invention with the second approximation curve for the comparison method shows that the mean reflection in silicon wafers 1 textured according to the invention is noticeably lower than in the silicon wafers textured with the comparison method.
- 5 shows in a graph the dependence of the reflection on the wavelength in the case of a silicon wafer textured in a conventional acidic etching solution and a silicon wafer 1 textured according to the invention.
- the wavelength in nanometers is plotted on the abscissa 12 and the reflection in percent on the ordinate 13.
- the open circles stand for measured values in the case of silicon wafers 1 textured with the method according to the invention with the exemplary etching solution 4 specified above, while the measured values represented with filled squares stand for a conventional method developed by IMEC (hereinafter referred to as “IMEC comparison method”) the article "Torwards Highly Efficient Industrial Cells and Modules from Multicrystalline Wafers” by F. Duerinckx, L. Frisson, PP Michiels et al., Published by 17th European Photovoltaic Solar Energy Conference, October 22-26, 2001, Kunststoff, Germany.
- the etching solution has HF, HN0 3 and some additives.
- the temperature of the etching solution is 21 degrees Celsius.
- the silicon wafers remain in the etching solution for 3 minutes.
- the diagram according to FIG. 5 shows that in silicon wafers 1 textured according to the invention with an average reflection of 23.8%), in particular from a wavelength of about 600 nanometers, the reflection values are up to about 2.5% lower than in accordance with FIG textured silicon wafers with an average reflection of 24.9%).
- Voc open terminal voltage and Eta: efficiency.
- FIG. 6 shows an enlarged photographic representation of a surface of a silicon wafer 1 textured according to the invention with a scaling indication. It can be seen from FIG. 6 that the texturing according to the method according to the invention sometimes leads to relatively elongated band-like depressions, in a pronounced reflection-reducing structuring of the surface. It goes without saying that the method according to the invention can also be used with monocrystalline silicon wafers or silicon wafers drawn directly from the melt, so-called film silicon.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/555,141 US7192885B2 (en) | 2003-05-07 | 2004-04-22 | Method for texturing surfaces of silicon wafers |
ES04728758.6T ES2314393T5 (es) | 2003-05-07 | 2004-04-22 | Método de texturización de las superficies de obleas de silicio |
EP04728758.6A EP1620881B2 (de) | 2003-05-07 | 2004-04-22 | Verfahren zum texturieren von oberflächen von silizium-scheiben |
DE502004008209T DE502004008209D1 (de) | 2003-05-07 | 2004-04-22 | Verfahren zum texturieren von oberflächen von silizium-scheiben |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10320212A DE10320212A1 (de) | 2003-05-07 | 2003-05-07 | Verfahren zum Texturieren von Oberflächen von Silizium-Scheiben |
DE10320212.9 | 2003-05-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004100244A1 true WO2004100244A1 (de) | 2004-11-18 |
Family
ID=33394195
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2004/000835 WO2004100244A1 (de) | 2003-05-07 | 2004-04-22 | Verfahren zum texturieren von oberflächen von silizium-scheiben |
Country Status (6)
Country | Link |
---|---|
US (1) | US7192885B2 (de) |
EP (2) | EP1620881B2 (de) |
AT (1) | ATE410784T1 (de) |
DE (3) | DE20321702U1 (de) |
ES (1) | ES2314393T5 (de) |
WO (1) | WO2004100244A1 (de) |
Cited By (11)
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US7276724B2 (en) | 2005-01-20 | 2007-10-02 | Nanosolar, Inc. | Series interconnected optoelectronic device module assembly |
US7649141B2 (en) | 2003-06-30 | 2010-01-19 | Advent Solar, Inc. | Emitter wrap-through back contact solar cells on thin silicon wafers |
WO2010025125A1 (en) * | 2008-08-29 | 2010-03-04 | Evergreen Solar, Inc. | Single-sided textured sheet wafer and manufactoring method therefore |
US7732229B2 (en) | 2004-09-18 | 2010-06-08 | Nanosolar, Inc. | Formation of solar cells with conductive barrier layers and foil substrates |
US7838868B2 (en) | 2005-01-20 | 2010-11-23 | Nanosolar, Inc. | Optoelectronic architecture having compound conducting substrate |
US7863084B2 (en) | 2004-02-05 | 2011-01-04 | Applied Materials, Inc | Contact fabrication of emitter wrap-through back contact silicon solar cells |
WO2011032880A1 (en) | 2009-09-21 | 2011-03-24 | Basf Se | Aqueous acidic etching solution and method for texturing the surface of single crystal and polycrystal silicon substrates |
WO2012020274A1 (en) | 2010-08-10 | 2012-02-16 | Rena Gmbh | Process and apparatus for texturizing a flat semiconductor substrate |
US8247243B2 (en) | 2009-05-22 | 2012-08-21 | Nanosolar, Inc. | Solar cell interconnection |
DE102012214428A1 (de) | 2012-08-14 | 2014-02-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur sauren Texturierung von siliziumhaltigen Substraten |
DE102014206675A1 (de) | 2014-04-07 | 2015-10-08 | Gebr. Schmid Gmbh | Verfahren und Lösung zur Herstellung und Nachbehandlung von Wafern |
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GB2449309A (en) * | 2007-05-18 | 2008-11-19 | Renewable Energy Corp Asa | A method for exposing a solar cell wafer to a liquid |
KR101088280B1 (ko) * | 2007-10-24 | 2011-11-30 | 미쓰비시덴키 가부시키가이샤 | 태양전지의 제조 방법 |
DE102007063202A1 (de) | 2007-12-19 | 2009-06-25 | Gebr. Schmid Gmbh & Co. | Verfahren und Vorrichtung zur Behandlung von Silizium-Wafern |
TW201001524A (en) * | 2008-04-01 | 2010-01-01 | Stichting Energie | Arrangement and method for etching silicon wafer |
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TWI445199B (zh) * | 2011-04-12 | 2014-07-11 | Topcell Solar Internat Co Ltd | 減少太陽能電池表面的蝕刻痕的設備 |
DE102011115532A1 (de) | 2011-04-18 | 2012-10-18 | Sovello Gmbh | Verfahren zur Herstellung eines texturierten Siliziumsubstrats |
US20130130508A1 (en) * | 2011-09-02 | 2013-05-23 | Air Products And Chemicals, Inc. | Compositions and Methods for Texturing of Silicon Wafers |
DE102011054359A1 (de) * | 2011-10-10 | 2013-04-11 | Q-Cells Se | Verfahren zur Behandlung eines Halbleiterwafers |
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DE102014013591A1 (de) | 2014-09-13 | 2016-03-17 | Jörg Acker | Verfahren zur Herstellung von Siliciumoberflächen mit niedriger Reflektivität |
CN104701423A (zh) * | 2015-03-23 | 2015-06-10 | 中建材浚鑫科技股份有限公司 | 一种新型单晶硅槽式碱制绒的方法 |
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CN107034518A (zh) * | 2017-06-26 | 2017-08-11 | 张兆民 | 一种单晶硅制绒添加剂 |
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DE102017212442A1 (de) | 2017-07-20 | 2019-01-24 | Singulus Technologies Ag | Verfahren und Vorrichtung zum Texturieren einer Oberfläche eines multikristallinen Diamantdraht-gesägten Siliziumsubstrats unter Verwendung von ozonhaltigem Medium |
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-
2003
- 2003-05-07 DE DE20321702U patent/DE20321702U1/de not_active Expired - Lifetime
- 2003-05-07 DE DE10320212A patent/DE10320212A1/de not_active Withdrawn
-
2004
- 2004-04-22 DE DE502004008209T patent/DE502004008209D1/de not_active Expired - Lifetime
- 2004-04-22 US US10/555,141 patent/US7192885B2/en not_active Expired - Lifetime
- 2004-04-22 WO PCT/DE2004/000835 patent/WO2004100244A1/de active Search and Examination
- 2004-04-22 AT AT04728758T patent/ATE410784T1/de active
- 2004-04-22 EP EP04728758.6A patent/EP1620881B2/de not_active Expired - Lifetime
- 2004-04-22 EP EP08016611A patent/EP2019420A1/de not_active Withdrawn
- 2004-04-22 ES ES04728758.6T patent/ES2314393T5/es not_active Expired - Lifetime
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Cited By (17)
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---|---|---|---|---|
US7649141B2 (en) | 2003-06-30 | 2010-01-19 | Advent Solar, Inc. | Emitter wrap-through back contact solar cells on thin silicon wafers |
US7863084B2 (en) | 2004-02-05 | 2011-01-04 | Applied Materials, Inc | Contact fabrication of emitter wrap-through back contact silicon solar cells |
US8525152B2 (en) | 2004-09-18 | 2013-09-03 | Nanosolar, Inc. | Formation of solar cells with conductive barrier layers and foil substrates |
US7732229B2 (en) | 2004-09-18 | 2010-06-08 | Nanosolar, Inc. | Formation of solar cells with conductive barrier layers and foil substrates |
US7968869B2 (en) | 2005-01-20 | 2011-06-28 | Nanosolar, Inc. | Optoelectronic architecture having compound conducting substrate |
US7838868B2 (en) | 2005-01-20 | 2010-11-23 | Nanosolar, Inc. | Optoelectronic architecture having compound conducting substrate |
US7919337B2 (en) | 2005-01-20 | 2011-04-05 | Nanosolar, Inc. | Optoelectronic architecture having compound conducting substrate |
US7276724B2 (en) | 2005-01-20 | 2007-10-02 | Nanosolar, Inc. | Series interconnected optoelectronic device module assembly |
US8309949B2 (en) | 2005-01-20 | 2012-11-13 | Nanosolar, Inc. | Optoelectronic architecture having compound conducting substrate |
US8198117B2 (en) | 2005-08-16 | 2012-06-12 | Nanosolar, Inc. | Photovoltaic devices with conductive barrier layers and foil substrates |
WO2010025125A1 (en) * | 2008-08-29 | 2010-03-04 | Evergreen Solar, Inc. | Single-sided textured sheet wafer and manufactoring method therefore |
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DE102012214428A1 (de) | 2012-08-14 | 2014-02-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur sauren Texturierung von siliziumhaltigen Substraten |
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Also Published As
Publication number | Publication date |
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ATE410784T1 (de) | 2008-10-15 |
DE10320212A1 (de) | 2004-12-02 |
DE502004008209D1 (de) | 2008-11-20 |
US7192885B2 (en) | 2007-03-20 |
EP1620881A1 (de) | 2006-02-01 |
ES2314393T5 (es) | 2018-10-29 |
US20060068597A1 (en) | 2006-03-30 |
ES2314393T3 (es) | 2009-03-16 |
DE20321702U1 (de) | 2008-12-24 |
EP2019420A1 (de) | 2009-01-28 |
EP1620881B1 (de) | 2008-10-08 |
EP1620881B2 (de) | 2018-06-20 |
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