EP1181400B1 - Elektrochemische ätzanlage und verfahren zur ätzung eines ätzkörpers - Google Patents

Elektrochemische ätzanlage und verfahren zur ätzung eines ätzkörpers Download PDF

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Publication number
EP1181400B1
EP1181400B1 EP00922440A EP00922440A EP1181400B1 EP 1181400 B1 EP1181400 B1 EP 1181400B1 EP 00922440 A EP00922440 A EP 00922440A EP 00922440 A EP00922440 A EP 00922440A EP 1181400 B1 EP1181400 B1 EP 1181400B1
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EP
European Patent Office
Prior art keywords
electrode
chamber
etching
electrolyte
cell according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00922440A
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German (de)
English (en)
French (fr)
Other versions
EP1181400A1 (de
Inventor
Hans Artman
Wilhelm Frey
Franz Laermer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
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Robert Bosch GmbH
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Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP1181400A1 publication Critical patent/EP1181400A1/de
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Publication of EP1181400B1 publication Critical patent/EP1181400B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3063—Electrolytic etching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/12—Electrochemical machining

Definitions

  • the invention relates to an electrochemical etching system, in particular a CMOS-compatible etching system for etching silicon wafers, and their use according to the preamble of the independent claims.
  • An electrochemical etching system for etching an etching body is basically known to a person skilled in the art.
  • US Pat. No. 4,220,508 describes an electrochemical etching cell for etching aluminum or aluminum alloys, wherein a plate made of this material is immersed in an electrobath.
  • a cathode and an anode are further provided, which consist of aluminum, stainless steel or another metal.
  • an etching of an etching body which consists at least superficially of silicon, is not discussed in this document.
  • WO 94/21845 presents an electrochemical etching cell for etching a silicon wafer.
  • the anode and the cathode made of graphite plates.
  • Electrochemical etching systems for example for the production of porous silicon or for the surface porosification of silicon, usually consist of a 2-chamber system, between which a silicon wafer to be etched is clamped as a partition and wherein the two chambers are electrically coupled or connected only by the wafer , Furthermore, electrodes for supplying current are usually mounted in both chambers, which are usually made of platinum.
  • Such an etching system is for example described in detail and in its essential details already by Fujiyama et al. in US 5,458,755.
  • CMOS complementary metal-oxide semiconductor
  • JP-06275598 A the problem of contamination of the electrolyte and thus of the wafer material to be etched is treated by the material of the dissolving electrodes. It is proposed to attach a bar of silicon wafer directly in front of the dissolving electrode. Since this barrier is conductive and contacts the electrode directly, it acts as an electrode itself. In this document, this measure is not proposed for both electrodes.
  • the electrochemical etching system according to the invention for etching an etching body and its use with the characterizing features of the independent claims has the advantage over the prior art that it completely avoids contamination of the etching body, which at least superficially consists of silicon. This is especially true in the production of porous silicon from a silicon wafer. Thus, by this etching of the Etch body is not impaired in particular in its electrical or electronic or catalytic properties.
  • the advantage is achieved by having not only the surface of the positive metal electrode in contact with the electrolyte, but also the negative electrode in contact with the electrolyte made of a CMOS-compatible material, i. H.
  • the first electrode material and the second electrode material of the first and second electrodes is a CMOS-compatible material and in particular no element selected from the group of platinum, gold, iridium, rhodium, palladium, silver or copper.
  • the etching system according to the invention is particularly suitable for the production of porous silicon on a silicon wafer, wherein for example by the use of silicon electrodes contamination of the wafer with non-silicon substances such as platinum or palladium is prevented.
  • CMOS-compatible material Under a CMOS-compatible material is understood in accordance with the general usage in semiconductor technology, a material that does not adversely affect the electrical properties of a circuit generated therewith.
  • a material which contaminates the etching body is understood to mean, in particular, a CMOS poison or a material which forms deep impurities in the etching body during its incorporation, ie impurities whose energy levels lie in the middle of the gap between conduction band and valence band of the material to be etched and thus providing a high transition matrix element for the recombination of Cause electrons and holes in the etch body ("recombination germ").
  • electrode materials for the first or second electrode are compounds from the group of at least weakly conductive compounds of the elements silicon, carbon, nitrogen, oxygen, titanium, aluminum, boron, antimony, tungsten, cobalt, tellurium, germanium, molybdenum, gallium, arsenic and selenium, in particular SiC, SiN, TiN, TiC, MoSi 2 or GaAs, in question, as well as pure electrode materials of the elements silicon, titanium, tungsten and molybdenum.
  • the concrete selection of the respective electrode material is advantageously carried out in each case taking into account the material of the etching body and the electrolyte used.
  • first electrode and / or the second electrode and / or the etching body are advantageously flat, in particular in the form of wafers, wherein the electrodes for use as sacrificial electrodes are very advantageously also substantially thicker than the actual etching body, so that they are optionally treated , can be freed from contamination and reused. This advantageously achieves an extension of the replacement cycles of the electrodes.
  • the electrochemical etching cell is advantageously constructed such that a first chamber and a second chamber are provided, each of which at least partially filled with an electrolyte and which are spatially separated from one another via a separating device. It stands each of the both chambers, each having an electrode in electrical connection via an electrolyte, wherein the etching body is at least partially the separation device and very advantageous at the same time also the only, at least weakly conductive electrical connection between the two chambers and connected as the cathode or anode electrodes.
  • a further very advantageous embodiment of the invention provides that the electrochemical etching cell in addition to the already mentioned two chambers has a further third chamber or a further third chamber and a further fourth chamber, each filled at least partially with an electrolyte and each have a further Separating device of the first chamber and second chamber are spatially separated.
  • the electrolyte in the third or fourth chamber is very advantageously in electrical connection only with the second or first electrode, which in turn at least partially serves as a separating device between the third and fourth chambers and respectively the first and second chambers.
  • the particular areal trained first and / or the second electrode in each case only with its surface facing the etching body with the contact with the etching body in contact electrolyte, so that a mixing of the electrolyte in the third or fourth chamber is avoided with the electrolyte in the first and second chamber.
  • the electrolyte of the first or second chamber facing away from the first and / or second electrode for easier electrical contacting of the electrodes at least partially be superficially provided with a metallization or a doping or, for example, in the case of the construction of the electrode of several layers, made of a metal.
  • an additional bath electrode immersed in an electrolyte located there in particular a platinum or palladium electrode, can be provided in the third and fourth chambers for easy electrical contacting of the first and second electrodes via the respective electrolyte.
  • the electrolytes in the individual chambers of the etching system according to the invention may advantageously also be different from each other, wherein the first and second chambers, in which the actual etching of the etchant takes place, advantageously with hydrofluoric acid or a mixture of hydrofluoric acid and ethanol, and the third and fourth Chamber are filled, for example, with dilute sulfuric acid as a contact electrolyte.
  • the individual chambers are also very advantageous separately filled with electrolyte and can be emptied separately, so that at any time a problem-free replacement of a contaminated electrolyte in each chamber is possible.
  • a simple replacement of a consumed or contaminated first or second electrode serving as a sacrificial electrode is thereby made possible without any problems at any time.
  • the first and / or second electrode is advantageously contacted electrically via the electrolyte filled in the third or fourth chamber with a bath electrode located there, and thus with an external electrode Power supply connected, which impresses the etching system during operation, a current.
  • the first and / or the second electrode also makes it possible, in a very advantageous manner, to examine in a simple manner the suitability of different electrode materials, such as graphite, for etching an etching body and to optimize the electrode materials for the respective material of the etching body.
  • a tunnel made of nonconductive material, in particular polypropylene, can furthermore advantageously be provided in a manner known per se.
  • FIG. 1 shows a first electrochemical etching system
  • FIG. 2 shows an alternative embodiment of the etching system
  • FIG. 3 shows a third embodiment of the etching system.
  • FIG. 1 shows as the first exemplary embodiment an electrochemical etching cell 1 according to the invention with four chambers, a first chamber 19, a second chamber 19 ', a third chamber 17 and a fourth chamber 18, which are each filled at least partially with an electrolyte.
  • the first and second chambers 19, 19 ' is for the actual etching of an etching body 15, for example, with a mixture of hydrofluoric acid and ethanol, while the third and fourth chambers 17, 18 are filled, for example, with dilute sulfuric acid as a contact electrolyte.
  • the four chambers 17, 18, 19, 19 'thus define four electrolyte regions associated with the chambers 17, 18, 19, 19', a first electrolyte region 29, a second electro-lyte region 29 ', a third electrolyte region 27 and a fourth electrolyte region 28, one another spatially separated by separating devices, but at the same time allow an electrical connection of the chambers 17, 18, 19, 19 '.
  • the first chamber 19 is spatially separated from the second chamber 19 'via a first separator 31, the first chamber 19 from the third chamber 17 via a second separator 32 and the second chamber 19' from the fourth chamber 18 via a third separator 33 spatially separated, so that no exchange of electrolyte between the chambers 17, 18, 19, 19 'occurs.
  • the first separator 31 is formed in a conventional manner by a ⁇ tzSystemhalterung 11 made of Teflon or polypropylene, in the partially fitted or used the ⁇ tzSystem 15, so that this superficially on the one hand with the electrolyte in the first chamber 19 and the other with the electrolyte in the second chamber 19 'is in contact.
  • the etching body 15 is in the illustrated example a known per se, planar silicon wafer.
  • the second separation device 32 and the third separation device 33 are each formed by an electrode holder 10 made of Teflon, in each of which a second electrode 13 'and a first electrode 13 is inserted, so that these surface at least partially on the one hand with the Electrolytes of the third and first chamber 17, 19 'and on the other hand with the electrolyte of the second and fourth chamber 19', 18 are in contact.
  • a metallic contact electrode for contacting the first and second electrodes 13, 13 'is in the third and fourth chamber 17, 18 each have a platinum electrode or a palladium electrode as a bath electrode 34, 34' is provided, each immersed in the electrolytes located there.
  • the bath electrodes 34, 34 ' are further connected to a voltage source, not shown, which impresses an electric current in a manner known per se to the etching cell 1.
  • the first electrode 13 or its side facing the etching body 15 is connected as an anode and the second electrode 13 'or its side facing the etching body 15 is connected as a cathode.
  • the first electrode 13 and the second electrode 13 'in the illustrated example consist of a planar silicon wafer or a silicon wafer, which is preferably substantially thicker than the silicon wafer used as the etching body 15.
  • the electrodes 13, 13 'with respect to the electrode material used in each case are preferably selected such that they consist of silicon at least superficially as the surfaces of the etching body 15. This ensures that the material of the first electrode 13 and the material of the second electrode 13 ', the etching body 15 is not contaminated during operation of the etching cell 1 and thus impaired after the etching in its electrical or catalytic properties.
  • the etching cell 1 now flows an external Tootician fondter current through the Badelektroden 34, 34 ', the Electrolytes, the first and second electrodes 13, 13 'and the etching body 15, wherein this is etched at least superficially in a Wegank Society 14'.
  • the first and second electrodes 13, 13' at least superficially etched in an etching region 14, ie they serve as sacrificial electrodes in the etching process of the etching body 15. Due to their significantly greater thickness However, they are not etched through the etching body 15, but merely attacked on the surface, etched off or removed or, for example, porosified. In the case of wear, for example after the etching of a plurality of etching bodies 15, they can therefore be exchanged, reprocessed or, if necessary, regularly cleaned of adhering contaminations.
  • porous silicon is formed, while at the same time on the anodic side of the first electrode 13 facing the etching body also an at least slight etching in a corresponding Elektrodensley Society 14 occurs, ie in the concrete example, a superficial formation of porous silicon.
  • this also applies to the side of the second electrode 13 'facing away from the etching body 15, which assumes the role of the anode in the third chamber 17.
  • the metallic bath electrode 34 anodically connected in the fourth chamber 18 also dissolves slightly, but only the side of the first electrode 13 facing away from the etching body 15 is contaminated with platinum, for example. Due to the spatial separation of the individual chambers 17, 18, 19, 19 'between which only an electrical connection via However, the electrodes 13, 13 'and the etching body 15 is between which but no electrolyte exchange is possible, however, this contamination remains away from the etching body 15. It can thus be removed in a preparation of the electrodes 13, 13 'from the corresponding side again.
  • Dissolution of silicon from one of the electrodes 13, 13 'in the electrolyte in the first or second chamber 19, 19' occurring during the etching, for example, is not critical for the etching body 15, since it consists of the same material and thus is not contaminated.
  • the electrodes 13, 13 ' are preferably connected via seals with the electrode holders 10 and screwed via closable window 16 in side walls of the etching system 1 with this.
  • a per se known quick release is provided for a simple replacement of the etching body 15.
  • FIG. 2 illustrates a second exemplary embodiment of an etching cell according to the invention.
  • This etching cell is essentially analogous to the etching cell 1 according to FIG. 1 in essential points, but has another embodiment of the contacting of the electrodes 13, 13 '.
  • the third chamber 17 and the fourth chamber 18, the bath electrodes 34, 34 'and the electrolytes located in these chambers 17, 18 can be dispensed with.
  • the first electrode 13 and the second electrode 13 ' are each provided with a metallization 20 known per se on the side facing away from the etching body 15.
  • the electrodes 13, 13 ' may also be provided on this side with a very high doping, so that a good electrical conductivity is ensured.
  • the electrodes 13, 13 ' can also consist of a layered body which has a metal layer on its side remote from the etching body 15 or consists of a metal.
  • Further embodiments of the electrical contacting of the electrodes 13, 13 ' provide that they are provided in a conventional manner on the side facing away from the etching body 15 with pin, network or surface contacts or, depending on the electrode material, particularly simple that the electrodes 13, 13 'in the first and second chambers 19, 19' partially immersed directly in the electrolyte and are electrically contacted directly at a non-immersed location. They thus serve as sacrificial electrodes instead of the known from the prior art platinum electrodes.
  • FIG. 3 a third exemplary embodiment of the etching system according to the invention explained with the aid of FIG. 3, in which, in contrast to FIG. 1, additionally only a tunnel 30 of a non-conductive material, such as polypropylene, known per se is provided.
  • This tunnel 30 is connected on both sides with the ⁇ tzSystemung 11 and surrounds an example circular wafer as the etching body 15 concentric.
  • the tunnel 30 causes a homogenization of the flow lines in the etching system 1 and thus an excellent thickness homogeneity of the etching of Etching body 15, in particular in the etching of silicon to porous silicon.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
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EP00922440A 1999-04-01 2000-03-17 Elektrochemische ätzanlage und verfahren zur ätzung eines ätzkörpers Expired - Lifetime EP1181400B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19914905 1999-04-01
DE19914905A DE19914905A1 (de) 1999-04-01 1999-04-01 Elektrochemische Ätzanlage und Verfahren zur Ätzung eines Ätzkörpers
PCT/DE2000/000857 WO2000060143A1 (de) 1999-04-01 2000-03-17 Elektrochemische ätzanlage und verfahren zur ätzung eines ätzkörpers

Publications (2)

Publication Number Publication Date
EP1181400A1 EP1181400A1 (de) 2002-02-27
EP1181400B1 true EP1181400B1 (de) 2007-02-28

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EP00922440A Expired - Lifetime EP1181400B1 (de) 1999-04-01 2000-03-17 Elektrochemische ätzanlage und verfahren zur ätzung eines ätzkörpers

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Country Link
US (1) US6726815B1 (ko)
EP (1) EP1181400B1 (ko)
JP (1) JP4511741B2 (ko)
KR (1) KR100698798B1 (ko)
DE (2) DE19914905A1 (ko)
ES (1) ES2282103T3 (ko)
WO (1) WO2000060143A1 (ko)

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KR100451132B1 (ko) * 2001-11-08 2004-10-02 홍석인 다공성 실리콘을 이용한 효소고정화 전극 제작 방법
US7998335B2 (en) * 2005-06-13 2011-08-16 Cabot Microelectronics Corporation Controlled electrochemical polishing method
US7909967B2 (en) * 2006-07-13 2011-03-22 Semitool, Inc. Electro-chemical processor
US7927469B2 (en) * 2006-08-25 2011-04-19 Semitool, Inc. Electro-chemical processor
US7935230B2 (en) * 2006-06-29 2011-05-03 Semitool, Inc. Electro-chemical processor
DE102007024199B4 (de) 2007-05-24 2015-06-25 Robert Bosch Gmbh Herstellungsverfahren eines mikromechanischen Bauelements mit porösifizierter Membran
KR101374932B1 (ko) * 2007-09-28 2014-03-17 재단법인서울대학교산학협력재단 확산 제한 식각과정에 의한 수평 변환 다공성 실리콘 광학필터의 제조방법 및 그에 의한 필터구조
US8906218B2 (en) 2010-05-05 2014-12-09 Solexel, Inc. Apparatus and methods for uniformly forming porous semiconductor on a substrate
US9076642B2 (en) 2009-01-15 2015-07-07 Solexel, Inc. High-Throughput batch porous silicon manufacturing equipment design and processing methods
JP5333582B2 (ja) * 2009-05-12 2013-11-06 日本軽金属株式会社 電解コンデンサ用アルミニウム電極板の製造方法
JP2011026638A (ja) * 2009-07-22 2011-02-10 Shin Etsu Handotai Co Ltd 陽極酸化装置
CN102844883B (zh) 2010-02-12 2016-01-20 速力斯公司 用于制造光电池和微电子器件的半导体衬底的双面可重复使用的模板
EP2619790B1 (en) 2010-09-24 2018-03-28 Solexel, Inc. High-throughput batch porous silicon manufacturing equipment design and processing methods
KR20140061287A (ko) * 2010-11-03 2014-05-21 솔렉셀, 인크. 기판 상에 다공성 반도체를 균일하게 형성하기 위한 장치 및 방법
JP6009268B2 (ja) * 2012-08-09 2016-10-19 芝浦メカトロニクス株式会社 洗浄液生成装置、洗浄液生成方法、基板洗浄装置及び基板洗浄方法
RU2537488C2 (ru) * 2012-08-22 2015-01-10 Закрытое акционерное общество "Инструменты нанотехнологии" Устройство травления поверхности для металлографического анализа
US9217206B2 (en) * 2013-09-27 2015-12-22 Sunpower Corporation Enhanced porosification
CN112820828B (zh) * 2019-11-15 2023-08-04 夏泰鑫半导体(青岛)有限公司 半导体装置及其制造方法

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Also Published As

Publication number Publication date
EP1181400A1 (de) 2002-02-27
WO2000060143A1 (de) 2000-10-12
DE50014121D1 (de) 2007-04-12
DE19914905A1 (de) 2000-10-05
JP4511741B2 (ja) 2010-07-28
US6726815B1 (en) 2004-04-27
KR100698798B1 (ko) 2007-03-26
ES2282103T3 (es) 2007-10-16
KR20010112373A (ko) 2001-12-20
JP2002541324A (ja) 2002-12-03

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