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WO2010087930A1 - Gravure au fluor moléculaire de pellicules minces en silicium pour applications photovoltaïques et autres processus de dépôt chimique en phase vapeur à basse température - Google Patents

Gravure au fluor moléculaire de pellicules minces en silicium pour applications photovoltaïques et autres processus de dépôt chimique en phase vapeur à basse température Download PDF

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Publication number
WO2010087930A1
WO2010087930A1 PCT/US2009/069581 US2009069581W WO2010087930A1 WO 2010087930 A1 WO2010087930 A1 WO 2010087930A1 US 2009069581 W US2009069581 W US 2009069581W WO 2010087930 A1 WO2010087930 A1 WO 2010087930A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular fluorine
silicon thin
etching
mbara
thin film
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
PCT/US2009/069581
Other languages
English (en)
Inventor
Paul Alan Stockman
Richard Allen Hogle
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.)
Linde GmbH
Original Assignee
Linde GmbH
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 Linde GmbH filed Critical Linde GmbH
Priority to CN2009801559551A priority Critical patent/CN102292169A/zh
Publication of WO2010087930A1 publication Critical patent/WO2010087930A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • 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
    • H10F71/10—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
    • H10F71/103—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B11/00—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto
    • B08B11/04—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto specially adapted for plate glass, e.g. prior to manufacture of windshields
    • 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
    • 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
    • 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
    • Y02E10/547—Monocrystalline silicon PV cells
    • 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 new methods for the cleaning of amorphous and microcrystalline silicon thin films for photovoltaic applications and to devices formed thereby.
  • fluorine radicals are created by either in situ activation or external remote plasma source (RPS) activation of molecular fluorine or fluorine containing gases, e.g. NF 3 or SF 6 , to generate the fluorine radicals.
  • RPS remote plasma source
  • the rate at which the chamber cleaning can be accomplished is dependent upon the rate and efficiency of the activation of the fluorine containing gases. Therefore, the cleaning step can constitute a significant fraction of the overall fabrication cycle, resulting in reduced manufacturing capacity and the requirement for excessive tooling.
  • the equipment needed for activation of fluorine containing gases, especially RPS units can add significant expense to the fabrication process and are know to be troublesome points-of-failure, which reduce the effective uptime for the manufacturing process.
  • fluorine radicals produced by either in situ or RPS activation are very reactive and not very selective, thereby causing damage to seals, RF generators, and other important equipment inside or associated with the fabrication chamber.
  • RPS and in situ activation necessarily occurs at limited sources, with the distribution of fluorine radicals being highly anisotropic. This results in the requirement for so-called "overetch”, i.e. a time period of radical generation well in excess of the stoichiometric requirement for cleaning, in order to clean the harder to reach places in the reaction chamber.
  • Fluorine containing gases other than molecular fluorine such as NF 3 , SF 6 , and C x F y compounds, are not effective cleaning agents for silicon films at temperatures below 500 0 C, and for commercial applications, at temperatures below 900 0 C.
  • MEMS devices have also provided guidance for the thin film photovoltaic industry.
  • the aim of using molecular fluorine is to release devices fabricated from compounds like SiO 2 and Si 3 N 4 from a matrix of silicon.
  • the silicon film making up the matrix can be completely removed without any deleterious reactions of the molecular fluorine with the device components.
  • the present invention provides improved techniques and apparatus for the cleaning of amorphous and microcrystalline silicon thin films used in photovoltaic applications.
  • the present invention provides methods and apparatus for the use of molecular fluorine for cleaning of thin films that overcome the disadvantages noted above.
  • the present invention relates to the use of molecular fluorine for etching of silicon thin-films for photovoltaic applications.
  • the disadvantages noted above with respect to LCD and MEMS processes can be avoided.
  • the processes for production of thin-film photovoltaic devices are conducted at lower temperatures than the processes for thin-film transistor LCD devices.
  • photovoltaic processes are typically carried out between 50°Cand 300 0 C.
  • Molecular fluorine reacts well with silicon in this temperature range.
  • the use of molecular fluorine at the deposition temperature and at partial pressures between 1 mbara and 1000 mbara accelerates cleaning and thereby improves productivity. Pressures below those used for MEMS production can be employed effectively.
  • the fluorine is introduced to the chamber at an initial static partial pressure in stoichiometric excess of the silicon in the thin film to be cleaned.
  • the excess fluorine allows the cleaning to go to completion in a finite, and commercially desirable, time.
  • the fluorine is introduced to the chamber at an initial static partial pressure approximately equal to the stoichiometric amount required to fully clean the thin film.
  • the thin-film can be greatly reduced in thickness, which is often acceptable in order to allow for another deposition cycle.
  • the fluorine is introduced to the chamber at an initial partial pressure and additional fluorine is added at a steady or varying rate.
  • a vacuum pump may be used to keep the chamber at the constant or varying pressure.
  • the reaction rate can be varied in accordance with the user specified recipe, because the reaction rate will vary at a fixed temperature with changing partial pressure of available molecular fluorine.
  • this embodiment allows a relatively high and constant partial pressure to be maintained while the cleaning takes place, thereby accomplishing a constant cleaning rate.
  • the experiment comprised cleaning a 2 micron sample of silicon using molecular fluorine at 200 0 C.
  • the 2 micron silicon film was deposited on an aluminium under layer, which is not appreciably etched by molecular fluorine at 200 0 C below 1000 mbara.
  • a portion of the silicon thin film sample was covered by a sapphire disk, which is also not appreciably etched with molecular fluorine at 200 0 C below 1000 mbara.
  • the experiment consisted of exposing the silicon films to molecular fluorine at various partial pressures at 200 0 C, after which the silicon film samples were removed from the reaction chamber.
  • the sapphire disk was removed and the height difference of the etched and unetched surfaces were measured by profilometry in order to calculate the etch rate.
  • a / sec - mbara can be achieved, which means that a 2 ⁇ m film can be successfully cleaned in 60 seconds using molecular fluorine held at a constant partial pressure of 39 mbara and a temperature of 200 0 C.
  • the cleaning rate according to the present invention is therefore 5 to 20 times faster than currently available cleaning recipes relying on in situ or RPS activation.
  • the present invention provides many advantages over the prior art.
  • the rate of reaction of molecular fluorine with silicon films at any set temperature is dependent only upon the partial pressure of fluorine in the chamber, the partial pressure can be adjusted to achieve cleaning rates that are orders of magnitude faster than in situ or RPS cleaning with fluorine containing gases.
  • molecular fluorine is less reactive and more selective to the etching of silicon films than fluorine radicals and therefore causes less damage to seals, RF generators, and other important equipment associated with the fabrication chamber.
  • molecular fluorine is completely isotropic in its distribution within the chamber, and therefore can be reacted stoichiometrically.

Landscapes

  • Engineering & Computer Science (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)
  • Drying Of Semiconductors (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne des techniques améliorées pour le nettoyage de pellicules minces de silicium amorphes et microcristallines utilisées dans les applications photovoltaïques. Plus en détail, l'invention concerne des procédés pour l'utilisation de fluor moléculaire pour le nettoyage de pellicules minces utilisées dans les applications photovoltaïques et les dispositifs ainsi formés.
PCT/US2009/069581 2009-01-27 2009-12-28 Gravure au fluor moléculaire de pellicules minces en silicium pour applications photovoltaïques et autres processus de dépôt chimique en phase vapeur à basse température Ceased WO2010087930A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009801559551A CN102292169A (zh) 2009-01-27 2009-12-28 用于光伏和其它低温化学气相沉积工艺的硅薄膜的分子氟蚀刻

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14750009P 2009-01-27 2009-01-27
US61/147,500 2009-01-27

Publications (1)

Publication Number Publication Date
WO2010087930A1 true WO2010087930A1 (fr) 2010-08-05

Family

ID=42395933

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/069581 Ceased WO2010087930A1 (fr) 2009-01-27 2009-12-28 Gravure au fluor moléculaire de pellicules minces en silicium pour applications photovoltaïques et autres processus de dépôt chimique en phase vapeur à basse température

Country Status (4)

Country Link
KR (1) KR20110139201A (fr)
CN (1) CN102292169A (fr)
TW (1) TW201034232A (fr)
WO (1) WO2010087930A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011051251A1 (fr) * 2009-10-26 2011-05-05 Solvay Fluor Gmbh Processus de gravure pour la production d'une matrice tft
EP2608900A4 (fr) * 2010-08-25 2016-04-20 Linde Ag Nettoyage de chambre de dépôt chimique en phase vapeur avec fluor moléculaire
CN105981192A (zh) * 2013-12-13 2016-09-28 E.I.内穆尔杜邦公司 形成电活性层的体系

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124211A (en) * 1994-06-14 2000-09-26 Fsi International, Inc. Cleaning method
US6544345B1 (en) * 1999-07-12 2003-04-08 Asml Us, Inc. Method and system for in-situ cleaning of semiconductor manufacturing equipment using combination chemistries
US6620256B1 (en) * 1998-04-28 2003-09-16 Advanced Technology Materials, Inc. Non-plasma in-situ cleaning of processing chambers using static flow methods
WO2007116033A1 (fr) * 2006-04-10 2007-10-18 Solvay Fluor Gmbh Procédé de gravure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124211A (en) * 1994-06-14 2000-09-26 Fsi International, Inc. Cleaning method
US6620256B1 (en) * 1998-04-28 2003-09-16 Advanced Technology Materials, Inc. Non-plasma in-situ cleaning of processing chambers using static flow methods
US6544345B1 (en) * 1999-07-12 2003-04-08 Asml Us, Inc. Method and system for in-situ cleaning of semiconductor manufacturing equipment using combination chemistries
WO2007116033A1 (fr) * 2006-04-10 2007-10-18 Solvay Fluor Gmbh Procédé de gravure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
REICHE ET AL.: "Modification of Si(100Surfaces by SF6 Plasma Etching -Application to Wafer Direct Bonding.", CRYSTAL RESEARCH TECHNOLOGY, vol. 35, no. 6-7, 2000, pages 807 - 821 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011051251A1 (fr) * 2009-10-26 2011-05-05 Solvay Fluor Gmbh Processus de gravure pour la production d'une matrice tft
EP2608900A4 (fr) * 2010-08-25 2016-04-20 Linde Ag Nettoyage de chambre de dépôt chimique en phase vapeur avec fluor moléculaire
CN105981192A (zh) * 2013-12-13 2016-09-28 E.I.内穆尔杜邦公司 形成电活性层的体系

Also Published As

Publication number Publication date
TW201034232A (en) 2010-09-16
KR20110139201A (ko) 2011-12-28
CN102292169A (zh) 2011-12-21

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