[go: up one dir, main page]

DE3822350A1 - Method for removing metal impurities on semiconductor crystal surfaces - Google Patents

Method for removing metal impurities on semiconductor crystal surfaces

Info

Publication number
DE3822350A1
DE3822350A1 DE3822350A DE3822350A DE3822350A1 DE 3822350 A1 DE3822350 A1 DE 3822350A1 DE 3822350 A DE3822350 A DE 3822350A DE 3822350 A DE3822350 A DE 3822350A DE 3822350 A1 DE3822350 A1 DE 3822350A1
Authority
DE
Germany
Prior art keywords
removing metal
crystal surfaces
cleaning media
hydrogen peroxide
metal impurities
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.)
Ceased
Application number
DE3822350A
Other languages
German (de)
Inventor
Helwig Dipl Chem Dr Schaefer
Alfred Dipl Chem Dr Lechner
Erich Dipl Chem Dr Pammer
Walter Dipl Chem Dr Rieger
Wolfgang Dipl Chem Dr Bensch
Volker Dipl Chem Dr Penka
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to DE3822350A priority Critical patent/DE3822350A1/en
Publication of DE3822350A1 publication Critical patent/DE3822350A1/en
Ceased legal-status Critical Current

Links

Classifications

    • H10P70/15—

Landscapes

  • Cleaning Or Drying Semiconductors (AREA)

Abstract

In a method for removing metal impurities on semiconductor crystal surfaces, the precleaned basic cleaning media are systematically admixed with complexing agents whose complex formation constants are large enough to preclude, in the pH range selected, the formation of hydroxides. The cleaning effect on silicon crystal wafers is improved, compared with the known processes, with the admixture of, for example, ethylenediamine tetraacetate to a hydrogen peroxide solution, by a factor of from 10 to 100 (decrease in the impurities by a factor of from 100 to 1,000). The method is used in the fabrication of very-large-scale-integrated (VLSI) semiconductor circuits.

Description

Die Erfindung betrifft ein Verfahren zum Entfernen von Metall- Verunreinigungen auf Halbleiterkristalloberflächen unter Ver­ wendung von vorgereinigten basischen Reinigungsmedien.The invention relates to a method for removing metal Contamination on semiconductor crystal surfaces under Ver use of pre-cleaned basic cleaning media.

Bei der Herstellung von hochintegrierten elektronischen Schal­ tungen muß der Reinheitsgrad des zum Beispiel bei Reinigungs­ und Ätzprozessen verwendeten Wasserstoffperoxids sehr hoch sein, um beispielsweise hochqualifizierte Isolationsschichten (Gateoxide) zu erhalten.In the manufacture of highly integrated electronic scarf the degree of purity, for example in cleaning and etching processes used hydrogen peroxide very high be, for example, highly qualified insulation layers (Gate oxides).

Bisher wurden Metall-Verunreinigungen durch Aufreinigungsver­ fahren der Reinigungsmedien, wie zum Beispiel des Wasserstoff­ peroxids, des Trimethylammoniumethanol (Cholin) oder des Was­ sers reduziert. Unter Aufreinigungsverfahren versteht man, daß die verwendeten Medien selbst vorgereinigt sind und möglichst wenig Metallkontamination selbst enthalten.So far, metal contamination by Aufreinigungsver drive the cleaning media, such as hydrogen peroxide, trimethylammonium ethanol (choline) or what sers reduced. Purification processes are understood to mean that the media used are pre-cleaned and if possible contains little metal contamination itself.

Schon geringe Mengen von Metall-Verunreinigungen in den Reini­ gungsmedien, zum Beispiel im Wasserstoffperoxid, können in der Halbleiterindustrie zu einer Verminderung der Isolatorwirkung von zum Beispiel des Gateoxids führen. Selbst bei Metallkonta­ minationen im ppb-Bereich kann mittels Oberflächenanalysen (vapor phase decomposition = VPD, surface photovoltation = SPV und Totalreflexions-Röntgenfluoreszenzanalyse = TRFA) Metall­ kontamination auf Siliziumkristallscheiben-Oberflächen durch die verwendete Wasserstoffperoxidlösung nachgewiesen werden.Even small amounts of metal contaminants in the cleaners media, for example in hydrogen peroxide, in the Semiconductor industry to reduce the insulator effect lead from, for example, the gate oxide. Even with metal contacts Minations in the ppb range can be done using surface analysis (vapor phase decomposition = VPD, surface photovoltation = SPV and total reflection X-ray fluorescence analysis = TRFA) metal contamination on silicon crystal wafer surfaces the hydrogen peroxide solution used can be detected.

Aufgabe der Erfindung ist es daher, die bekannten Reinigungslö­ sungen so zu verbessern, daß diese Metallkontamination auf den Kristallscheiben stark reduziert wird. Insbesondere sollen Me­ talle, wie zum Beispiel Eisen, Kupfer oder Aluminium sicher ent­ fernt werden.The object of the invention is therefore the known cleaning solutions to improve solutions so that this metal contamination on the Crystal slices is greatly reduced. In particular, Me metals such as iron, copper or aluminum  be removed.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß den Rei­ nigungsmedien zusätzlich Komplexbildner, deren Komplexbildungs­ konstanten groß genug sind, daß im gewählten pH-Bereich Hydro­ xidbildungen ausgeschlossen sind, zugegeben werden.This object is achieved in that the Rei cleaning media additionally complexing agents, their complexing constant large enough that in the selected pH range Hydro xid formations are excluded.

Es liegt im Rahmen der Erfindung, daß als Komplexbildner Ethy­ lendiamintetraacetat (EDTA) und als Reinigungsmedium bei Ver­ wendung von aus Silizium bestehenden Halbleiterkristallscheiben Wasserstoffperoxidlösungen verwendet werden.It is within the scope of the invention that as complexing agent Ethy lendiamine tetraacetate (EDTA) and as a cleaning medium for Ver use of silicon semiconductor wafers Hydrogen peroxide solutions can be used.

Das Verfahren nach der Lehre der Erfindung wurde am Beispiel von Eisen erprobt. Die Kontamination auf der Siliziumkristall­ scheibenoberfläche konnte durch Zusatz von Ethylendiamintetra­ acetat zu einer Wasserstoffperoxidlösung drastisch verringert werden. Der Reinigungseffekt ist in diesem Fall gegenüber be­ kannter Reinigungsverfahren um den Faktor 10 bis 100 verbes­ sert. Wird das erfindungsgemäße Verfahren vor der Gateoxidation angewandt, so steigt die Gateoxidqualität um den Faktor 5 bis 10.The method according to the teaching of the invention was based on the example tested by iron. Contamination on the silicon crystal disc surface could be added by adding ethylenediaminetetra acetate to a hydrogen peroxide solution drastically reduced will. In this case, the cleaning effect is compared to be known cleaning method by a factor of 10 to 100 sert. Will the inventive method before the gate oxidation applied, the gate oxide quality increases by a factor of 5 to 10th

Claims (3)

1. Verfahren zum Entfernen von Metall-Verunreinigungen auf Halb­ leiterkristalloberflächen durch Verwendung von vorgereinigten basischen Reinigungsmedien, dadurch gekenn­ zeichnet, daß den Reinigungsmedien zusätzlich Komplex­ bildner, deren Komplexbildungskonstanten groß genug sind, daß im gewählten pH-Bereich Hydroxidbildungen ausgeschlossen sind, zugegeben werden.1. A method for removing metal contaminants on semi-conductor crystal surfaces by using pre-cleaned basic cleaning media, characterized in that the cleaning media are additionally complexing agents, the complexing constants of which are large enough that hydroxide formation is excluded in the selected pH range. 2. Verfahren nach Anspruch 1, dadurch gekenn­ zeichnet, daß als Komplexbildner Ethylendiamintetra­ acetat (EDTA) zugegeben wird.2. The method according to claim 1, characterized records that as a complexing agent ethylenediaminetetra acetate (EDTA) is added. 3. Verfahren nach Anspruch 1 oder 2, dadurch ge­ kennzeichnet, daß als Reinigungsmedien bei Ver­ wendung von aus Silizium bestehenden Halbleiterkristallscheiben Lösungen, die Wasserstoffperoxid enthalten, verwendet werden.3. The method according to claim 1 or 2, characterized ge indicates that the cleaning media at Ver use of silicon semiconductor wafers Solutions containing hydrogen peroxide can be used.
DE3822350A 1988-07-01 1988-07-01 Method for removing metal impurities on semiconductor crystal surfaces Ceased DE3822350A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE3822350A DE3822350A1 (en) 1988-07-01 1988-07-01 Method for removing metal impurities on semiconductor crystal surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE3822350A DE3822350A1 (en) 1988-07-01 1988-07-01 Method for removing metal impurities on semiconductor crystal surfaces

Publications (1)

Publication Number Publication Date
DE3822350A1 true DE3822350A1 (en) 1990-01-04

Family

ID=6357781

Family Applications (1)

Application Number Title Priority Date Filing Date
DE3822350A Ceased DE3822350A1 (en) 1988-07-01 1988-07-01 Method for removing metal impurities on semiconductor crystal surfaces

Country Status (1)

Country Link
DE (1) DE3822350A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5081068A (en) * 1989-07-17 1992-01-14 Mitsubishi Denki Kabushiki Kaisha Method of treating surface of substrate with ice particles and hydrogen peroxide
EP0528053A4 (en) * 1991-02-28 1993-06-30 Mitsubishi Gas Chemical Company, Inc. Cleaning liquid for semiconductor substrate
EP0560324A1 (en) 1992-03-11 1993-09-15 Mitsubishi Gas Chemical Company, Inc. Cleaning fluid for semiconductor substrate
EP0702399A1 (en) * 1994-09-14 1996-03-20 Siemens Aktiengesellschaft Process for wet chemical removal of contaminants from semiconductor crystal surfaces
EP0690482A3 (en) * 1994-06-27 1996-04-17 Siemens Ag Method for reducing metallic contamination of silicon substrates in the manufacture of semiconductors
WO1996024158A1 (en) * 1995-02-03 1996-08-08 Aktsionernoe Obschestvo 'nauchno-Proizvodstvennoe Predpriyatie 'sapfir' Compound for cleaning solid surfaces
US5962384A (en) * 1997-10-28 1999-10-05 International Business Machines Corporation Method for cleaning semiconductor devices
US6066609A (en) * 1997-07-31 2000-05-23 Siemens Aktiengesellschaft Aqueous solution for cleaning a semiconductor substrate
EP0789071A4 (en) * 1995-07-27 2004-07-28 Mitsubishi Chem Corp METHOD FOR TREATING A SUBSTRATE SURFACE AND TREATMENT THEREFOR
US7938982B2 (en) 2004-06-16 2011-05-10 Memc Electronic Materials, Inc. Silicon wafer etching compositions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Beyer, K.D.: Silicon Surface Cleaning. In: IBM TDB, Bd. 20, Nr. 5, Okt. 1977, 1746-1747 *
JP-Abstract 62-115833 *
Tolliver, D.L.: Contamination Control: New Dimensions in VLST Manufacturing. In: Solid State Technology, März 1984, S. 129-137 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5081068A (en) * 1989-07-17 1992-01-14 Mitsubishi Denki Kabushiki Kaisha Method of treating surface of substrate with ice particles and hydrogen peroxide
EP0528053A4 (en) * 1991-02-28 1993-06-30 Mitsubishi Gas Chemical Company, Inc. Cleaning liquid for semiconductor substrate
US5302311A (en) * 1991-02-28 1994-04-12 Mitsubishi Gas Chemical Company, Inc. Cleaning solution of semiconductor substrate
US5705089A (en) * 1992-03-11 1998-01-06 Mitsubishi Gas Chemical Company, Inc. Cleaning fluid for semiconductor substrate
EP0560324A1 (en) 1992-03-11 1993-09-15 Mitsubishi Gas Chemical Company, Inc. Cleaning fluid for semiconductor substrate
EP0690482A3 (en) * 1994-06-27 1996-04-17 Siemens Ag Method for reducing metallic contamination of silicon substrates in the manufacture of semiconductors
EP0702399A1 (en) * 1994-09-14 1996-03-20 Siemens Aktiengesellschaft Process for wet chemical removal of contaminants from semiconductor crystal surfaces
WO1996024158A1 (en) * 1995-02-03 1996-08-08 Aktsionernoe Obschestvo 'nauchno-Proizvodstvennoe Predpriyatie 'sapfir' Compound for cleaning solid surfaces
EP0789071A4 (en) * 1995-07-27 2004-07-28 Mitsubishi Chem Corp METHOD FOR TREATING A SUBSTRATE SURFACE AND TREATMENT THEREFOR
US6066609A (en) * 1997-07-31 2000-05-23 Siemens Aktiengesellschaft Aqueous solution for cleaning a semiconductor substrate
US5962384A (en) * 1997-10-28 1999-10-05 International Business Machines Corporation Method for cleaning semiconductor devices
US6191085B1 (en) 1997-10-28 2001-02-20 International Business Machines Corporation Method for cleaning semiconductor devices
US7938982B2 (en) 2004-06-16 2011-05-10 Memc Electronic Materials, Inc. Silicon wafer etching compositions

Similar Documents

Publication Publication Date Title
JP3075290B2 (en) Cleaning liquid for semiconductor substrates
DE69816219T2 (en) CLEANING TREATMENT
DE69206944T2 (en) Process for cleaning integrated circuits during manufacture
DE69519955T2 (en) PH-regulated alkaline cleaner with non-ionic surfactant for cleaning microelectronic substrates
DE69219547T2 (en) Process for using halocarboxylic acids as cleaning agents in the manufacture of integrated circuits
EP0982765B1 (en) Cleaning method of semiconductor substrate
JP4516176B2 (en) Substrate cleaning solution for electronic materials
DE3822350A1 (en) Method for removing metal impurities on semiconductor crystal surfaces
EP0698917B1 (en) Process for cleaning semiconductor wafers
DE4340589A1 (en) Process for cleaning semiconductor components
EP0702399A1 (en) Process for wet chemical removal of contaminants from semiconductor crystal surfaces
US6375752B1 (en) Method of wet-cleaning sintered silicon carbide
JP2599021B2 (en) Silicon wafer etching method and cleaning method
DE60003703T2 (en) COMPOSITIONS AND METHODS FOR REDUCING / ELIMINATING SCRATCHES AND DEFECTS IN THE SILICON DIOXIDE CMP METHOD
DE4209865C2 (en) Process for improving the effectiveness of aqueous cleaning agents for removing metal-containing residues on semiconductor surfaces
JPH0817776A (en) Silicon wafer cleaning method
DE19531031A1 (en) Process for drying silicon
CN113186541A (en) Application of post-chemical mechanical polishing cleaning solution
JPH07161672A (en) Substrate surface cleaning method and surface cleaning agent
JP3040067B2 (en) Method for cleaning substrate having semiconductor layer
JPH05109683A (en) Method for removing metallic impurities from semiconductor silicon wafer cleaning liquid
JP2688293B2 (en) Wafer surface cleaning method
JP3198878B2 (en) Surface treatment composition and substrate surface treatment method using the same
JP3329902B2 (en) Surface treatment method and surface treatment device
Nagamura et al. High-performance photomask cleaning process using electrolyzed water

Legal Events

Date Code Title Description
OP8 Request for examination as to paragraph 44 patent law
8131 Rejection