EP1516360A1 - Dielectrique intercouches en fluoropolymeres forme au moyen d'un procede de depot chimique en phase vapeur - Google Patents

Dielectrique intercouches en fluoropolymeres forme au moyen d'un procede de depot chimique en phase vapeur

Info

Publication number
EP1516360A1
EP1516360A1 EP02737569A EP02737569A EP1516360A1 EP 1516360 A1 EP1516360 A1 EP 1516360A1 EP 02737569 A EP02737569 A EP 02737569A EP 02737569 A EP02737569 A EP 02737569A EP 1516360 A1 EP1516360 A1 EP 1516360A1
Authority
EP
European Patent Office
Prior art keywords
fluoromonomer
thin film
film device
gas phase
polymerization initiator
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
EP02737569A
Other languages
German (de)
English (en)
Inventor
Michael Mocella
Andrew E. Feiring
Theodore A. Treat
Eugene Lopata
Peter Rose
Yakov Brichko
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1516360A1 publication Critical patent/EP1516360A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/68—Organic materials, e.g. photoresists
    • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
    • H10P14/687—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC the materials being fluorocarbon compounds, e.g. (CHxFy) n or polytetrafluoroethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Definitions

  • a process for forming a fluoropolymer layer on a thin film device comprising: a.) delivering a gas phase fluoromonomer and a gas phase free radical polymerization initiator to said thin film device, b.) mixing said gas phase fluoromonomer and said gas phase free radical polymerization initiator to form a gas phase mixture of said fluoromonomer and said free radical polymerization initiator, c.) contacting said thin film device with said gas phase mixture of said fluoromonomer and said free radical polymerization initiator, and d.) initiating polymerization of said fluoromonomer with said free radical polymerization initiator, whereby said fluoromonomer polymerizes to form said fluoropolymer layer on said thin film device.
  • Fluoropolymers comprising the fluoropolymer layers formed by the present process are comprised of repeating units from fluoromonomers defined herein and may have a number averaged molecular weight of over 10,000. Fluoropolymer layers produced by the process of the present invention have a uniform thickness and are typically from about 500 angstroms to about 50,000 angstroms thick. Thin film devices on which fluoropolymer layers may be formed by the present process comprise devices known in the microelectronics industry as semiconductor wafers, integrated circuits, flat panel displays, micromechanical devices, microelectrical mechanical systems, and thin film optical and optoelectrical devices.
  • CF 2 CFOCH 2 CF 3
  • CF 2 CFOCH 2 C 2 F 5
  • CF 2 CFOCH 2 CF 2 CF 2 CF 3 .
  • Free radical polymerization initiators of the present process comprise initiators that can form free radicals which initiate polymerization of the fluoromonomer and result in formation of a fluoropolymer layer on the thin film , device. Initiators are preferably delivered to the thin film device in the gas phase, however it is contemplated that initiators may be present on, or integral with, the surface of the thin film device.
  • Free radical polymerization initiators of the present process include peroxides, saturated alkyl halides, haloalkenes, halogens and inorganic halides.
  • Peroxide initiators of the present invention contain at least one peroxide functional group (-OO-) and may be represented by R ⁇ OR 2 , wherein R 1 and R 2 are independently selected from saturated hydrocarbon radicals which may further comprise halogen, oxygen and nitrogen atoms.
  • Hydrocarbon peroxides such as di- t-butylperoxide may be used as initiator in the present process.
  • Saturated alkyl halide initiators of the present process may be represented by R-X wherein X is a halogen, preferably fluorine, and R is a hydrocarbon radical, and preferably branched (a secondary or tertiary radical). Preferably R is fluorinated and more preferably R is perfluorinated.
  • Saturated alkyl halide initiators include, for example, perfluorotetramethyl butane CF 3 (C(CF 3 ) 2 ) 2 CF3 as well as perfluorocarbon iodides such as F(C 2 F 4 ) X I, wherein x is from 1-4.
  • Haloalkene initiators of the present invention are represented by
  • Inorganic halide initiators of the present invention include nitrogen trifluoride and sulfur hexafluoride.
  • the present invention is a process for forming a fluoropolymer layer on a thin film device, and in part involves contacting said thin film device with a gas phase fluoromonomer.
  • the process involves mixing the gas phase fluoromonomer and gas phase free radical polymerization initiator to form a gas phase mixture of fluoromonomer and free radical polymerization initiator.
  • Mixing of the gases may occur by any process, but preferably occurs by diffusion following the direction of gaseous streams of the fluoromonomer and initiator into the same volume. Mixing may be controlled to occur prior to or during contacting of the gases with the thin film device.
  • gas phase fluoromonomer and gas phase free radical polymerization initiator may be delivered to the surface of the thin film device by chemical vapor deposition means.
  • the gases are distributed over the surface of the thin film device so that the fluoromonomer and radicals formed from the free radical polymerization initiator react and form a fluoropolymer layer on the surface of the device.
  • the function of the chemical vapor deposition means is to distribute the gases to the surface of the thin film device in a substantially controlled manner.
  • the chemical vapor deposition means preferably provides a substantially controlled flow profile of gases at a controlled flow rate to a particular surface area of the thin film device.
  • the present process may be carried out using chemical vapor deposition means having a linear injector as taught by DeDontney et al. in U.S. Patent No. 5,683,516, herein incorporated by reference.
  • the linear injector comprises an elongated member with end surfaces and at least one gas delivery surface extending along the length of the member and which includes a number of elongated passages formed therein. Also formed within the member are a number of thin distribution channels which extend between the elongated passages and the gas delivery surface.
  • a number of metering tubes may be inserted into each elongated passage and are spaced from the walls of said passages and extend between the ends.
  • the present process may be carried out using chemical vapor deposition means having an annular injector as taught by Young et al. in U.S. Patent No. 5,851 ,294, herein incorporated by reference.
  • the annular injector comprises a plenum body having at least one plenum formed therein and a plurality of nozzles for injecting fluoromonomer and initiator gases into a processing chamber.
  • the nozzles are spaced from the plenum and are positioned and configured to provide a uniform distribution of gases across the thin film device where they mix, react and form a uniform fluoropolymer layer on the thin film device.
  • the process of the present invention may be carried out in a contoured plate reactor as taught by Mahawill in U.S. Patent No. 4,834,022, herein incorporated by reference.
  • the contoured plate reactor is approximately cylindrical in shape.
  • the base of the reactor is inclined at an angle of approximately 3°-5° from the vertical and has a central platform with a recessed well.
  • the thin film device is placed in the well so that the surface of the device on which the fluoropolymer is deposited does not protrude above the platform surface.
  • the fluoromonomer and initiator gases are mixed in a region adjacent the cylindrical wall of the reactor and flow radially inward across the device surface where they mix, react and form a uniform fluoropolymer layer on the thin film device.
  • a Monoblok ® (Monoblok is a trade mark of ASML Thermal Division, Scotts Valley, CA, USA) linear injector as described in U.S. patent no. 5,683,516 was used to apply laminar reactant and initiator gas flows at a precisely metered rate to the wafer surface as it moved on a conveyor belt under the injector body through a heated, horizontal tunnel (muffle).
  • Trigonox-CTM as the initiator. This is a product of Akzo Nobel Polymer Chemicals LLC.
  • a Monoblok ® linear injector was used.
  • a gas being an equal weight mixture of tetrafluoroethylene (TFE) and CO 2 was flowed at a rate of 8 slm through the separator ports of the linear injector while a liquid bubbler system using N 2 gas as a carrier at 3 slm brought Trigonox-C through the center port of the injector.

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un procédé de formation d'une couche de fluoropolymères sur un composant à couches minces. Ce procédé comprend les étapes consistant à : mettre ce composant à couches minces en contact avec un fluoromonomère en phase gazeuse ; et à induire la polymérisation de ce fluoromonomère au moyen d'un initiateur de polymérisation radicalaire, la polymérisation dudit fluoromonomère entraînant la formation d'une couche de fluoropolymères sur le composant à couches minces.
EP02737569A 2002-06-21 2002-06-21 Dielectrique intercouches en fluoropolymeres forme au moyen d'un procede de depot chimique en phase vapeur Ceased EP1516360A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2002/019702 WO2004001832A1 (fr) 2002-06-21 2002-06-21 Dielectrique intercouches en fluoropolymeres forme au moyen d'un procede de depot chimique en phase vapeur

Publications (1)

Publication Number Publication Date
EP1516360A1 true EP1516360A1 (fr) 2005-03-23

Family

ID=29998721

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02737569A Ceased EP1516360A1 (fr) 2002-06-21 2002-06-21 Dielectrique intercouches en fluoropolymeres forme au moyen d'un procede de depot chimique en phase vapeur

Country Status (6)

Country Link
EP (1) EP1516360A1 (fr)
CN (1) CN100336184C (fr)
AU (1) AU2002310491A1 (fr)
CA (1) CA2487486A1 (fr)
RU (1) RU2304323C2 (fr)
WO (1) WO2004001832A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013102011A2 (fr) * 2011-12-30 2013-07-04 Gvd Corporation Revêtements pour dispositifs électrofluidiques et d'électromouillage
JP6356702B2 (ja) 2013-02-15 2018-07-11 マサチューセッツ インスティテュート オブ テクノロジー 滴状凝縮のためのグラフトポリマー表面、ならびに関連使用および製造方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3400688A1 (de) * 1984-01-11 1985-07-18 Chemische Werke Hüls AG, 4370 Marl Ausschleusung von schwermetallasche durch zentrifugalbehandlung oder druckfiltration
US4834022A (en) * 1985-11-08 1989-05-30 Focus Semiconductor Systems, Inc. CVD reactor and gas injection system
CA2072384A1 (fr) * 1991-08-29 1993-03-01 Clifford L. Spiro Compositions a base de fluorure de carbone
RU2046678C1 (ru) * 1992-11-17 1995-10-27 Институт микроэлектроники РАН Способ плазменной полимеризации
US6022414A (en) * 1994-07-18 2000-02-08 Semiconductor Equipment Group, Llc Single body injector and method for delivering gases to a surface
TW359943B (en) * 1994-07-18 1999-06-01 Silicon Valley Group Thermal Single body injector and method for delivering gases to a surface
TW356554B (en) * 1995-10-23 1999-04-21 Watkins Johnson Co Gas injection system for semiconductor processing
US5888591A (en) * 1996-05-06 1999-03-30 Massachusetts Institute Of Technology Chemical vapor deposition of fluorocarbon polymer thin films
JPH10209148A (ja) * 1997-01-27 1998-08-07 Sony Corp 低誘電率絶縁体膜の形成方法およびこれを用いた半導体装置
EP1119034A4 (fr) * 1998-09-28 2002-12-04 Tokyo Electron Ltd Depot de film assiste par plasma
US6458718B1 (en) * 2000-04-28 2002-10-01 Asm Japan K.K. Fluorine-containing materials and processes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2004001832A1 *

Also Published As

Publication number Publication date
RU2304323C2 (ru) 2007-08-10
AU2002310491A1 (en) 2004-01-06
WO2004001832A1 (fr) 2003-12-31
CN1628376A (zh) 2005-06-15
CN100336184C (zh) 2007-09-05
RU2005101341A (ru) 2005-06-27
CA2487486A1 (fr) 2003-12-31
HK1076921A1 (zh) 2006-01-27

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