WO2001057921A1 - Solution décapante et procédé - Google Patents

Solution décapante et procédé Download PDF

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Publication number
WO2001057921A1
WO2001057921A1 PCT/US2001/002569 US0102569W WO0157921A1 WO 2001057921 A1 WO2001057921 A1 WO 2001057921A1 US 0102569 W US0102569 W US 0102569W WO 0157921 A1 WO0157921 A1 WO 0157921A1
Authority
WO
WIPO (PCT)
Prior art keywords
etching solution
water
carboxylic acid
etching
solution
Prior art date
Application number
PCT/US2001/002569
Other languages
English (en)
Inventor
George Matamis
Heidi L. Denton
Michael J. Davison
Jeffrey A. Smith
Original Assignee
Motorola Inc.
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 Motorola Inc. filed Critical Motorola Inc.
Priority to JP2001557084A priority Critical patent/JP2003536242A/ja
Priority to AU2001233002A priority patent/AU2001233002A1/en
Priority to EP01905084A priority patent/EP1256126A1/fr
Priority to KR1020027010076A priority patent/KR20020075907A/ko
Publication of WO2001057921A1 publication Critical patent/WO2001057921A1/fr

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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
    • H01L21/02—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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • 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

Definitions

  • the present invention generally provides an etching solution that is a mixture of anhydrous HF, a carboxylic acid and water.
  • the solution is useful for the etching of oxides used in the fabrication of MEMS devices such as, for example, micro-sensors and micro- machines.
  • An important advantage of the etching solution of the present invention is that it has a high etch selectivity for silicon oxide relative to other materials including metals, nitrides and polysilicon that form the structural components of MEMS and electronic devices.
  • the etching solution of the present invention can remove sacrificial oxides with only relatively minor etching of these other non-oxide materials.
  • the etching solution of the present invention improves the fabrication process of MEMS and electronic devices.
  • the etching solution is described further below in one embodiment of the present invention with an example of its use PhosphoSilicate Glass (PSG) created by chemical vapor deposition.
  • PSG PhosphoSilicate Glass
  • Thermally grown Si0 2 and PSG are two examples of oxide films used as a sacrificial oxide layer in the formation of a micro-machined structure.
  • the sacrificial oxide layer is in contact with portions of the micro-structure prior to sacrificial oxide etching.
  • the etching solution is also generally applicable to the removal of other types of oxides that may be used in MEMS and electronic devices where metals, nitrides and/or polysilicon materials that form the micro- structure or electronic components could be exposed to the etching solution during oxide removal.
  • the carboxylic acid used can be selected generally as any acid having one or more carboxyl groups and more specifically including, for example, oxalic acid, formic acid, lactic acid, tartaric acid, malic acid, succinic acid, citric acid and acetic acid. It has been found that acetic acid, combined with the above identified ingredients, is particularly useful for selectively etching thermally grown Si0 2 and PSG.
  • the mixing ratio of anhydrous HF to carboxylic acid is not considered to be critical, but it has been found that a preferred range is approximately 0.1% anhydrous HF, up to the solubility limit of the particular carboxylic acid.
  • One preferred mixture, which has shown superior experimental results is approximately 10% anhydrous HF relative to the carboxylic acid. Dilution of the solution with respect to the amount of HF, will result in slower etch rates. It should be understood that the mixing ratio of anhydrous HF to carboxylic acid is not a limitation of the present invention.
  • the preferred range of water introduced to one embodiment of the present etching solution is in the range of approximately 0.5% to 5.0% by weight.
  • use of an anhydrous carboxylic acid, e.g., glacial acetic acid, is preferred in order to more precisely control the amount of water in the etching solution.
  • the etching solution is created by injecting anhydrous HF into an aqueous solution of a carboxylic acid, such as glacial acetic acid, having a precisely controlled minimal amount of water.
  • a carboxylic acid such as glacial acetic acid
  • the temperature required for use of the etching solution according to the present invention is not considered to be critical. In general, during etching it is preferred to use a cooler temperature of below approximately 30 degrees Celsius (°C), e.g., in the range of approximately 15°C-30°C. An advantage of such a cooler temperature is a reduction in the evaporative loss of the etching solution. Also, it is preferable that the etching solution is in the liquid phase during etching.
  • the etching was performed at 18 °C. and the sample etch rates measured as follows:
  • Etch selectivities of sacrificial oxides relative to metals, polysilicons, and nitrides are derived from the associated etch rates.
  • an etching solution of HF, carboxylic acid, and a minimal controlled amount of water approximately in the ratio of 10:89:1
  • the etch selectivity for thermally grown SiO? relative to aluminum or copper is in the range of approximately 9 to 80; whereas, the etch selectivity for thermally grown Si0 2 relative to polysilicon is in the range of approximately 65 to 320.
  • the etch selectivity for thermally grown Si0 2 relative to silicon nitride is in the range of approximately 9-40.
  • the etch selectivity for PSG relative to aluminum or copper is in the range of approximately 666 to 50,000.
  • the etch selectivity for PSG relative to polysilicon is in the range of approximately 5,000 to 200,000.
  • the etch selectivity for PSG relative to silicon nitride is in the range of approximately 714 to 25,000.
  • the wide range of etch selectivities for PSG is dependent on certain process parameters which include, but are not limited to whether the PSG film is annealed, the phosphorous doping level and the deposition temperature .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)
  • Micromachines (AREA)
  • Pressure Sensors (AREA)

Abstract

L'invention concerne une solution décapante de fluorure d'hydrogène (HF), d'acide carboxylique et d'eau possédant une forte sélectivité de décapage pour l'oxyde de silicium par rapport au métal, au polysilicium et au nitrure. La solution décapante se forme en injectant du HF anhydre dans un acide carboxylique ayant un quantité minimale d'eau calculée avec précision. La solution décapante est utile dans la fabrication de dispositifs à systèmes mécaniques microélectriques (MEMS), ainsi que dans la fabrication de dispositifs MEMS associés à des composants électroniques intégrés sur la même puce.
PCT/US2001/002569 2000-02-04 2001-01-26 Solution décapante et procédé WO2001057921A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2001557084A JP2003536242A (ja) 2000-02-04 2001-01-26 エッチ液およびエッチング方法
AU2001233002A AU2001233002A1 (en) 2000-02-04 2001-01-26 Etching solution and method
EP01905084A EP1256126A1 (fr) 2000-02-04 2001-01-26 Solution decapante et procede
KR1020027010076A KR20020075907A (ko) 2000-02-04 2001-01-26 에칭 용액 및 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US49786400A 2000-02-04 2000-02-04
US09/497,864 2000-02-04

Publications (1)

Publication Number Publication Date
WO2001057921A1 true WO2001057921A1 (fr) 2001-08-09

Family

ID=23978615

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/002569 WO2001057921A1 (fr) 2000-02-04 2001-01-26 Solution décapante et procédé

Country Status (5)

Country Link
EP (1) EP1256126A1 (fr)
JP (1) JP2003536242A (fr)
KR (1) KR20020075907A (fr)
AU (1) AU2001233002A1 (fr)
WO (1) WO2001057921A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1538664A1 (fr) * 2002-09-13 2005-06-08 Daikin Industries, Ltd. Agent d'attaque et procede d'attaque
WO2007140193A1 (fr) * 2006-05-25 2007-12-06 Honeywell International Inc. Agents d'attaque chimique sélectifs du carbure de tantale, procédés de production et utilisations de ceux-ci
US8092698B2 (en) 2004-08-03 2012-01-10 Samsung Electronics Co., Ltd. Methods of forming semiconductor devices formed by processes including the use of specific etchant solutions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4828451B2 (ja) * 2006-03-27 2011-11-30 東京エレクトロン株式会社 基板処理方法、半導体装置の製造方法および基板処理装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395304A (en) * 1982-05-11 1983-07-26 Rca Corporation Selective etching of phosphosilicate glass
US5824601A (en) * 1997-06-30 1998-10-20 Motorola, Inc. Carboxylic acid etching solution and method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395304A (en) * 1982-05-11 1983-07-26 Rca Corporation Selective etching of phosphosilicate glass
US5824601A (en) * 1997-06-30 1998-10-20 Motorola, Inc. Carboxylic acid etching solution and method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1538664A1 (fr) * 2002-09-13 2005-06-08 Daikin Industries, Ltd. Agent d'attaque et procede d'attaque
EP1538664A4 (fr) * 2002-09-13 2007-04-04 Daikin Ind Ltd Agent d'attaque et procede d'attaque
US8092698B2 (en) 2004-08-03 2012-01-10 Samsung Electronics Co., Ltd. Methods of forming semiconductor devices formed by processes including the use of specific etchant solutions
WO2007140193A1 (fr) * 2006-05-25 2007-12-06 Honeywell International Inc. Agents d'attaque chimique sélectifs du carbure de tantale, procédés de production et utilisations de ceux-ci

Also Published As

Publication number Publication date
EP1256126A1 (fr) 2002-11-13
JP2003536242A (ja) 2003-12-02
KR20020075907A (ko) 2002-10-07
AU2001233002A1 (en) 2001-08-14

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