WO1998018570A1 - Procede de fabrication de revetement a base de parylene - Google Patents

Procede de fabrication de revetement a base de parylene Download PDF

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Publication number
WO1998018570A1
WO1998018570A1 PCT/US1997/019294 US9719294W WO9818570A1 WO 1998018570 A1 WO1998018570 A1 WO 1998018570A1 US 9719294 W US9719294 W US 9719294W WO 9818570 A1 WO9818570 A1 WO 9818570A1
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Prior art keywords
layer
level
parylene
parylene polymer
watts
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PCT/US1997/019294
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English (en)
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WO1998018570A9 (fr
Inventor
John Wary
Roger A. Olson
William F. Beach
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Specialty Coating Systems, Inc.
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Priority to AU50871/98A priority Critical patent/AU5087198A/en
Priority to EP97913758A priority patent/EP0934127B1/fr
Priority to DE69707005T priority patent/DE69707005T2/de
Priority to JP52062698A priority patent/JP2002505803A/ja
Publication of WO1998018570A1 publication Critical patent/WO1998018570A1/fr
Publication of WO1998018570A9 publication Critical patent/WO1998018570A9/fr

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    • 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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/145—After-treatment

Definitions

  • the present invention relates generally to improved parylene polymer layers, methods of making the same and methods of using the same.
  • Semiconductors are widely used in integrated circuits for electronic products systems such as computers and televisions. These integrated circuits typically combine many transistors on a single crystal silicon chip to perform complex functions and store data. Semiconductor and electronics manufacturers, as well as end users, desire integrated circuits which can accomplish more in less time in a smaller package while consuming less power. However, some of these desires may be in opposition to each other. For example, simply shrinking the feature sizes on a given circuit from 0.5 microns to 0.25 microns can increase power consumption by 30%. Likewise, doubling operational speed generally doubles power consumption. Miniaturization also generally results in increased capacitive coupling, or cross talk, between conductors which carry signals across the chip. This can limit achievable speed and degrade the noise margin used to insure proper device operation.
  • One way to diminish power consumption and cross talk effects is to decrease the dielectric constant of electrically insulating layers that separate layers of electrically conductive materials within the integrated circuit.
  • operational conditions may include high temperatures, it can be advantageous to use materials with relatively high thermal stability to form the insulating layers.
  • Silicon dioxide is one of the most common materials used in insulating layers for integrated circuits. However, silicon dioxide is non-ideal due to its comparatively high dielectric constant of about 3.9.
  • Parylene polymers are poly-p-xylylenes which may be prepared starting with a dimer having the structure:
  • parylene dimers wherein X is typically a hydrogen or a halogen.
  • X is typically a hydrogen or a halogen.
  • parylene dimers include the following:
  • Polymer films formed from these parylene dimers may have comparatively low dielectric constants and relatively high melting temperatures. However, these parylene polymer films have relatively high dielectric constants and inferior thermal stabilities, rendering them less attractive for use in integrated circuits.
  • a vapor deposition method is used to form parylene polymer layers from parylene dimers.
  • One such vapor deposition method is disclosed in Journal of Applied Polymer Science 13, 2325 (1969). According to this method, commonly referred to as the Gorham process, the parylene dimer is cracked at an elevated temperature to produce parylene monomer having the structure:
  • the parylene monomer is condensed onto a substrate at a temperature of from about room temperature to about -35°C. Under these conditions, the parylene monomer simultaneously polymerizes on the substrate to form a layer of the parylene polymer adhered to the substrate.
  • a vapor deposition process for forming poly-p-xylylene films from other than parylene dimer materials is disclosed in U.S. Patent No. 5,268,202 (You).
  • the method disclosed by this reference includes forming the monomer vapor inside the vacuum chamber in which deposition occurs, precluding the purification opportunities afforded by the parylene dimer process prior to deposition on the substrate. Therefore, the resulting poly-p-xylylene layers have relatively high impurity levels.
  • Journal of Vacuum Science and Technology Al 1C6). 3057 (1993) discloses that poly-p-xylylene films formed by the method of You have zinc impurity levels of about 3%.
  • Such a comparatively high level of zinc impurity results in problems with the poly-p- xylylene film relating to, for example, increased dielectric constant, decreased surface resistivity, ion movement within the layer, film surface charging effects and/or electron storm formation when the poly-p-xylylene film is used within a multi-level structure.
  • these poly-p- xylylene films cannot be used in integrated circuits.
  • Combining the use of a plasma with the deposition of a gaseous species has been used in many systems. For example, DUMIC Conference, February 1 1, 1997, ISMIC-222D/97/0098- 105 (hereinafter "DUMIC”) discloses the use of a pulsed plasma to manipulate the control of fluorocarbon thin films on silicon.
  • the present invention relates to improved parylene polymer layer, methods of making these layers and methods of using these layers.
  • the improved parylene polymer layers have relatively low levels of impurities such as, for example, zinc.
  • the improved parylene polymer layers are formed by the use of a pulsed plasma treatment.
  • the improved.parylene polymers have other chemical species incorporated therein.
  • different combinations of the aforementioned aspects are combined to improved provide parylene polymer layers that have relatively low levels of impurities, that are formed using a pulsed plasma treatment and/or that have other chemical species incorporated therein.
  • the present invention provides a method of forming a parylene polymer layer.
  • the method comprises depositing monomers of parylene onto the surface of a substrate to form a layer, and treating the layer with a pulsed plasma treatment.
  • the present invention provides a multi-level structure.
  • the structure comprises a first layer, a parylene polymer layer and a layer of adhesion promotion material.
  • the parylene polymer layer is disposed along the first layer, and the layer of adhesion promotion material is disposed along the layer of adhesion promotion material.
  • the parylene polymer layer is formed form a material that has a structure:
  • m is an integer having a value of 0, 1, 2, 3 or 4, z is greater than 1
  • G is a halogen, an alkyl group, a cyclo hydrocarbon, an alkylene group or an alkylyne group having the general formula C n H y X w , wherein X is a halogen, n is an integer greater than zero and a sum of y and w is at most equal to a sum of 2n and 1, and wherein the parylene polymer layer has a zinc impurity level of at most about 66 parts per billion.
  • the present invention provides a method making a multi-level structure.
  • the method comprises depositing a monomer on the surface of a substrate to form a layer, and treating the layer with a pulsed plasma treatment to form a parylene polymer film on the surface of the first layer.
  • the parylene polymer has a structure:
  • m is an integer having a value of 0, 1 , 2, 3 or 4, z is greater than 1
  • G is a halogen, an alkyl group, a cyclo hydrocarbon, an alkylene group or an alkylyne group having the general formula C n H y X w , wherein X is a halogen, n is an integer greater than zero and a sum of y and w is at most equal to a sum of 2n and 1, and wherein the parylene polymer layer has a zinc impurity level of at most about 66 parts per billion.
  • the present invention provides a multi-level structure.
  • the structure comprises a first layer and a parylene polymer layer disposed along the surface of the first layer.
  • the parylene polymer layer is formed from a material having a structure:
  • the parylene polymer layer is formed by a process including the steps of: depositing monomers of parylene onto a surface of a substrate to form a layer; and treating the layer with a pulsed plasma treatment.
  • the present invention provides a multi-level structure.
  • the structure comprises a first layer and a parylene polymer layer disposed along the surface of the first layer.
  • the parylene polymer is formed by a process including the steps of: depositing monomers of parylene onto a surface of a substrate to form a layer; and treating the layer with a pulsed plasma treatment.
  • Fig. 1 is a cross-sectional view of one embodiment of a multi-level structure according to the present invention
  • Fig. 2 is a cross-sectional view of another embodiment of a multi-level structure according to the present invention
  • Fig. 3 is a block diagram of one embodiment of a vacuum deposition system which may be used to form parylene polymer layers according to the present invention
  • Fig. 4 is a cross-sectional view of a portion of one embodiment of an integrated circuit including a multi-level structure according to the present invention.
  • Fig. 5 is a block diagram of one embodiment of a vacuum chamber which may be used to form parylene polymer layers according to the present invention.
  • Fig. 1 depicts a multi-level structure 10 according to the present invention.
  • Structure 10 includes substrate layer 12 and parylene polymer layer 14.
  • parylene polymer it is herein meant to refer to a poly-p-xylylene.
  • a parylene polymer is formed from a parylene dimer.
  • Substrate layer 12 may be formed from any materials onto which parylene polymer layer 14 is capable of being deposited. These materials may include electrically conductive and electrically non-conductive materials. The particular material from which layer 12 is formed depends upon the application, and such materials are known to those skilled in the art.
  • substrate layer 12 may be formed from organic materials or inorganic materials including, but not limited to, aluminum, iron, steel, molybdenum, aluminum oxide, titanium oxide, lead oxide, copper oxide, iron oxide, beryllium oxide, manganese oxide, tungsten oxide, tantalum oxide, vanadium oxide, silicones, natural rubbers, plastics, plastic composites, cellulosic materials, epoxy-containing compounds, thermosetting compounds, thermoplastic compounds, oxides of silicon (e.g., fly ash, hydrated silica, silica, quartz, aerogels, xerogels and fumed silica) and the like.
  • layer 12 may comprise gallium arsenide or other binary semiconductors.
  • Substrate layer 12 may also be formed from a vacuum compatible liquid.
  • vacuum compatible it is herein meant to refer to a material that has a vapor pressure at the operating temperature of the vacuum chamber used such that the minimum pressure to which the vacuum chamber can be pumped is independent of the presence of the vacuum compatible material.
  • a vacuum compatible liquid is gamma-methacryloxypropyltrimethoxysilane.
  • substrate layer 12 may be a printed circuit board, a silicon backboard, a fiberglass backboard, a silicon wafer, paper, a key pad, a catheter, a pacemaker cover, a subcutaneous probe, a bird feather, a silicone O-ring, parts of a mechanical apparatus, such as an automobile, or the like.
  • Parylene polymer layer 14 is formed from a material having the structure:
  • G is a cyclo hydrocarbon, an alkylene or alkylyne group (i.e., G has at least one degree of unsaturation) then y + w is less than 2n+l by a factor of twice the degree of unsaturation.
  • Fig. 2 depicts another multi-level structure 20 according to the present invention.
  • Structure 20 includes parylene polymer layer 14 disposed between a first layer of material 16 and a second layer of material 18.
  • layers 16 and 18 may be formed from any of the materials listed above with reference to substrate layer 12.
  • layer 16 and/or layer 18 may take on any of the above-noted shapes of substrate layer 12.
  • Layer 16 and/or layer 18 may take on other shapes as well.
  • each of layers 16 and 18 may be formed from materials that are at least partially electrically conductive.
  • layers 16 and 18 may be formed from metals using standard photolithographic and etching techniques.
  • layers 16 and 18 may each correspond to a power plane, a ground plane or a metal interconnection trace layer.
  • Other processes for forming layers 16 and 18 are known to those skilled in the art and are intended to be within the scope of the present invention.
  • parylene polymer layer 14 may be relatively difficult to adhere to certain other materials. For these embodiments, it may be desirable to promote the adhesion of layer 14 to other surfaces. Accordingly, parylene polymer layer 14 may undergo certain surface treatments to increase its ability to adhere to other surfaces. Such treatments include, for example, continuous plasma treatment (i.e., substantially 100% duty cycle), corona treatment, charge treatment and/or other surface roughening treatments. These treatments are known to those skilled in the art and are intended to be within the scope of the present invention. For example, in a continuous plasma treatment, a radio frequency (RF) generator can be used in conjunction with a background pressure of one or more gases to produce a plasma.
  • RF radio frequency
  • a pulsed plasma treatment has been found to increase the adhesion of the parylene monomer.
  • pulsed plasma treatment it is herein meant to refer to a plasma treatment in which the duty cycle (i.e., the percentage of time that the plasma is on during the treatment) is less than about 100%.
  • the duty cycle of a pulsed plasma treatment is at most about 50%.
  • the duty cycle of a pulsed plasma treatment is from about 0.1% to about 50%o, more preferably from about 0.1%) to about 10% and most preferably about 0.2%.
  • Fig. 3 shows a block diagram of one embodiment of a vacuum system 80 having a pulsed plasma source appropriate for use in forming parylene polymer layers according to the present invention.
  • System 80 includes a parylene monomer source 82, a deposition chamber 84, a substrate 86, and a platen 88 (see discussion below).
  • system 80 includes a pulsed plasma source
  • Pulsed plasma source 90 connected to chamber 84 to allow a parylene polymer layer disposed on substrate 86 to undergo a pulsed plasma treatment.
  • Pulsed plasma source 90 includes an RF generator 92 (model 300-1 RF generator, available from Technics Company, located in Alexandria, VA).
  • a timing module 93 (model DMP10-.1-.4, available from Dynatronics, Inc., located in Amery, WI) interfaces pulsed plasma source 92 to a timing circuit 94 to control the duty cycle of the pulsed plasma treatment.
  • timing circuits 94 are known to those skilled in the art. Furthermore, while particular examples of an RF generator and a timing module are disclosed herein, other such devices are known to those skilled in the art and are intended to be within the scope of the present invention.
  • a background pressure of parylene monomer e.g., from about 10 to about 15 millitorr
  • a pulsed plasma treatment occurs such. For example, if the duty cycle of the pulsed plasma is about 0.2%>, the RF generator is on about 0.2%> of the time that the parylene monomer is being deposited on the surface of substrate 86.
  • parylene monomer gas various ions, radicals and other species are formed from the parylene monomer gas. These species generally have high sticking coefficients and deposit on the surface of substrate 86 with high efficiency, resulting in a parylene polymer layer having enhanced properties as described herein.
  • the peak power of RF generator 92 during a pulsed plasma treatment can be varied depending upon the desired properties of the resulting parylene polymer layer. Generally, this peak power depends upon the volume of the deposition chamber, with the peak power increasing as the volume of the deposition chamber increases. If the peak power of generator 92 is too low, the pulsed plasma treatment may have minimal effect on improving the properties of a parylene polymer layer. However, if the peak power of generator 92 is too high, the resulting parylene polymer layer may be brittle, nontransparent or otherwise have undesirable properties.
  • the peak power of RF generator 92 during a pulsed plasma treatment relative to the volume of the deposition chambcr is preferably from about 0.05 Watts/inch 3 to about 100 Watts/inch 3 , more preferably from about 0.1 Watts/inch 3 to about 20 Watts/inch 3 and most preferably from about 0.1 Watts/inch 3 to about 10 Watts/inch 3 .
  • the increased adhesion associated with using a pulsed plasma treatment during parylene monomer deposition results in an increased thickness of the resulting parylene polymer film and an increased rate of deposition of the parylene monomer.
  • a parylene polymer layer formed using a pulsed plasma treatment is preferably at least about 1.5 times as thick, more preferably at least about 2 times as thick and most preferably at least about 3 times as thick.
  • the deposition rate of parylene monomer using a pulsed plasma treatment is preferably at least about 1.5 fast, more preferably at least 2 times as fast and most preferably at least 3 times as fast.
  • treating the surface of a parylene polymer layer using a pulsed plasma results in other advantages.
  • One such advantage relates to improved control over the surface onto which the parylene polymer layer is formed.
  • the in-plane dielectric constant (i.e., the dielectric constant parallel to a plane of the substrate) and out-of-plane dielectric constant (i.e., the dielectric constant in a plane perpendicular to the substrate) of the parylene polymer layer be approximately equal.
  • a parylene polymer layer formed using a pulsed plasma treatment can have a reduced dielectric constant and/or a dielectric constant that is more isotropic.
  • Pulsed plasma treatment or continuous plasma treatment of a parylene polymer layer can be performed during or after parylene monomer deposition.
  • a background pressure of a gas other than parylene monomer i.e., a background gas
  • the pressure of the background gas in the deposition chamber is from about 125 millitorr to about 375 millitorr, more preferably from about 200 millitorr to about 300 millitorr and most preferably from about 240 millitorr to about 260 millitorr.
  • a background gas is comprised of one or more noble gases. Examples of noble gases include helium, neon, argon and xenon.
  • a background gas can include one or more hydrocarbons. Such hydrocarbon background gases may be saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons, straight-chained hydrocarbons, branched hydrocarbons, cyclic hydrocarbons and the like.
  • a background gas can comprise one or more noble gases and one or more hydrocarbon gases. It has been found that the use of one or more hydrocarbon gases results in parylene polymer layers having improved properties (see discussion below).
  • parylene polymer layers may be performed on an entire parylene polymer layer or a portion of a parylene polymer layer.
  • certain treatments of parylene polymer layers have been disclosed herein, it is to be understood that other treatments of parylene polymer layers to enhance adhesion, or other properties, of these layers will be apparent to those skilled in the art and are intended to be within the scope of the present invention.
  • Parylene polymers are usually highly crystalline and linear materials, which can limit the strength or other physical properties of these layers.
  • additional chemical species e.g., monomers
  • parylene monomer may be added to the layer during synthesis of the layer.
  • these additional components should allow cross-linking to occur, increasing the strength and/or adhesion of the resulting layer.
  • An illustrative and nonlimiting list of such chemical species includes species having a molecular formula C x H y where each of x and y is an integer of at least one.
  • Incorporation of these chemical species into a parylene polymer layer can be accomplished by, for example, establishing a background pressure of these other components within the deposition chamber during parylene monomer deposition.
  • a pulsed plasma treatment or continuous plasma treatment can be used when a background pressure of one or more of these chemical species is present in the deposition chamber, but such pulsed plasma treatment or continuous plasma treatment is not required.
  • the parylene polymer in which a chemical species other than parylene monomer is incorporated into a parylene polymer, preferably should have an amount of the chemical species incorporated therein to improve the properties of the parylene polymer layer such that at least one of the advantages of the present invention as described herein is attained.
  • enhanced adhesion may be achieved by providing a layer of adhesion promoting material between layer 16 and layer 14 and/or between layer 18 and layer 14.
  • layer 16 and/or layer 18 may be formed from an adhesion promotion material.
  • Adhesion promotion materials appropriate for use in the present invention include, but arc not limited to, organosilane compounds, metals, metal oxides and semiconductor oxides. Examples of such organosilane compounds include A- 150 (available from Union Carbide Technologies), A- 174 (available from Union Carbide Technologies) and VM 651 (available from DuPont Chemicals).
  • layer 14 may or may not undergo any of the above-noted surface treatments.
  • layer 16 and/or layer 18 may be formed from materials that reduce or eliminate the diffusion of materials through parylene polymer layer 14.
  • Materials appropriate for use in these applications are disclosed in, for example, U.S. Patent No. 5,470,802. Other such materials are known to those skilled in the art and are intended to be within the scope of the present invention.
  • layer 14 may be difficult to planarize.
  • layer 16 and/or layer 18 may be formed from a material that is more readily planarized. Typically, such a material is a dielectric material, but, in some instances, it may be an electrical conductor.
  • FIG. 4 shows a portion 30 of a multi-level electronic circuit according to the present invention.
  • Portion 30 includes silicon wafer substrate 22, electrically insulating layer 24, electrically conductive layer 26, electrically conductive layer 28 and parylene polymer layer 14 disposed between layers 26 and 28.
  • Silicon wafer substrate 22 may be formed from any of the standard substrate materials used in the electronics industry, such as, for example, a silicon backboard or a fiberglass backboard. Other appropriate structures for wafer substrate 22 are known to those skilled in the art and are intended to be within the scope of the present invention.
  • Electrically insulating layer 24 typically functions to protect wafer substrate 22 from electrically conductive layers 26 and 28. Layer 24 is usually formed from silicon dioxide, although other appropriate materials may be used. Electrically insulating layer 24 may be formed according to any of the standard techniques known to those skilled in the art. Electrically conductive layers 26 and 28 may be formed from metals or other materials appropriate for use in electronic circuits. Layers 26 and 28 may comprise metal conductor lines which are formed according to standard photolithographic and etching techniques.
  • layers 26 and 28 may each correspond to a power plane, a ground plane or an interconnection trace layer. Electrically conductive layers 26 and 28 may be interconnected through parylene polymer layer 14 by use of vias, or through holes (not shown), which are formed in parylene polymer layer 14 by conventional processes known to those skilled in the art.
  • parylene polymer layer 14 is formed using a vapor deposition process.
  • the vapor deposition process allows the monomer to be formed outside the deposition portion of the vacuum chamber such that the monomers can undergo a purification process prior to being deposited onto the substrate.
  • parylene polymer layer 14 is formed using a vacuum chamber 40 as depicted in Fig. 5.
  • Vacuum chamber 40 includes vaporization zone 42, a pyrolysis zone 44, a post-pyrolysis zone 46 and a deposition zone 48. Examples of such vacuum chamber are disclosed in, for example, commonly assigned U.S. Patent No. 5,546,473, which is herein incorporated by reference.
  • vaporization zone 42 is placed within vaporization zone 42 at about room temperature and subsequently heated to a temperature of from about 70°C to about 150°C to vaporize the dimer.
  • the vaporized dimer passes into pyrolysis zone 44 which is maintained at a temperature of from about 600°C to about 720°C to pyrolize the dimer (i.e., cleave certain chemical bonds) and form a monomer having the following structure:
  • post-pyrolysis zone 46 which is maintained at a temperature of at most about room temperature. At this temperature, residual vaporized dimer can adhere to the walls of post-pyrolysis zone 46 while the monomer generally passes through post-pyrolysis zone 46 without adhering to the walls of zone 46. Thus, post-pyrolysis zone 46 reduces the amount of vaporized dimer that ultimately enter deposition chamber 48. In certain embodiments, this feature can be advantageous because the vaporized dimer can constitute an impurity in parylene polymer layer 14, which may have an undesirable local effect on the dielectric constant or other properties of layer 14. After passing through post-pyrolysis zone 46, the monomer enters deposition chamber 48 which includes substrate 50.
  • Substrate 50 is placed on a platen 52 that includes a standard temperature controlling device 54 that controls the temperature by the platen by heating and/or cooling platen 54.
  • a standard temperature controlling device 54 controls the temperature by the platen by heating and/or cooling platen 54.
  • the temperature of substrate 50 and platen 52 is typically held at a temperature of from about room temperature to about -25 °C during deposition of the monomer onto substrate 50.
  • reducing the temperature of substrate 50 and platen 52 during monomer deposition can provide several advantages, including more control of the overall process of making parylene polymer layer 14 by allowing for increased manipulation of the monomer.
  • cooling substrate 50 and platen 52 allows for the walls of deposition chamber 48 to be heated during monomer deposition.
  • reducing the temperature of substrate 50 and platen 52 during monomer deposition results in a more efficient deposition process and a more efficient use of the parylene dimer starting material.
  • device 54 may be used to increase the temperature of substrate 50 and platen 52 to a temperature of from about 100°C to about 400 °C to anneal the parylene polymer layer.
  • a temperature of from about 100°C to about 400 °C to anneal the parylene polymer layer.
  • polymerization of the parylene monomer occurs spontaneously at the temperatures of substrate 50 noted above.
  • the dimer Prior to placing the dimer within vaporization zone 46, the dimer is first purified. Since the dimer of the present invention has a high degree of symmetry, it is readily purified by crystallization. Typically, these solvents are relatively unsymmetric in order to have a high temperature coefficient of solubility. However, if the solvent is too symmetric, separation of the solvent from the dimer may be difficult. Without wishing to be bound by any theories, it is believed that this increased difficulty in solvent dimer separation results from the accidental accommodation of the solvent within the dimer lattice.
  • Solvents appropriate for use in dimer crystallization according to the present invention include, but are not limited to, chloroform, tetrahydrofuran, methylene chloride, and linear hydrocarbons such as n-hexane and n-heptane.
  • the solvent is n-hexane.
  • this solution is typically passed through a chromato graphic bed including a polar material such as, for example, alumina.
  • the polar nature of the chromatographic bed removes many of the polar or ionic impurities present within the solution.
  • the chromatographic bed can remove fine impurities within the solution by filtration.
  • parylene polymer layers in accordance with the present invention may have zinc impurity levels of 66 parts per billion or less.
  • This feature of the present invention is desirable because impurities within parylene polymers can result in several different negative effects, including, but not limited to, an increase in the dielectric constant of the parylene polymer layer, a decrease in the surface resistivity of the parylene polymer layer and/or electron storm formation within the multi-level structure.
  • parylene polymer layer 14 While particular apparatuses and methods of making parylene polymer layer 14 have been described herein, one skilled in the art would understand that at least certain aspects of these apparatuses and methods may be varied or modified, and such variations and modifications are intended to be within the scope of the present invention.
  • the parylene dimer may be cleaved by use of a plasma.
  • Such methods are disclosed in, for example, Russian Patent Nos. RU
  • parylene polymer layer 14 When used in integrated circuits or for other electronics applications, parylene polymer layer 14 should have a minimal dielectric constant to enhance circuit operating speed and decrease power consumption. Accordingly, these parylene polymer layers preferably have a dielectric constant of at most about 2.6, more preferably at most about 2.4 and most preferably at most about 2.2.
  • parylene polymer layers in accordance with the present invention preferably have a dissipation factor of less than about 0.001.
  • parylene polymer layers with a thickness of about one micrometer preferably have a breakdown voltage of at least about 750 volts.
  • Parylene polymer layer 14 preferably has a Young's modulus of about 5 gigapascals.
  • the elongation to break of parylene polymer layers according to the present invention is preferably at least about 20%.
  • Parylene polymer layer 14 preferably has an ultimate tensile strength of at least about 122 megapascals.
  • parylene polymer layers have water absorption values of at most about 0.5%> by weight, more preferably at most about 0.2% by weight and most preferably at most about 0.1 % by weight.
  • Parylene polymer layers in accordance with the present invention preferably have a thermal stability such that these layers demonstrate less than 1% weight loss per 2 hours at a temperature of at least about 450 °C.
  • Parylene polymer layer 14 preferably has a crystalline melting point of above about 500°C.
  • the surface resistivity of parylene polymer layers in accordance with the present invention is preferably about 1.3xl0 14 ohms.
  • the volume resistivity of parylene polymer layer 14 is preferably about 5.3xl0' 6 ohms.
  • Parylene polymer layers in accordance with the present invention preferably have a density of about 1.58.
  • the thermal expansion at 25 °C of parylene polymer layer 14 is preferably at most about 35 parts per million.
  • parylene polymer layers have a coefficient of friction of about 0.2.
  • Example 1 The following are illustrative examples of embodiments of the present invention. They are not to be construed as limiting. Example 1
  • the following process was performed in a jacketed Soxhlet extractor (available as catalog number LG-6950, from Lab Glass, located in Vineland, NJ or as catalog number CG-1328, available from Chem Glass, located in Vineland, NJ).
  • An amount of the crude dimer used as the starting material in the synthesis of the parylene polymer layers of the present invention was placed within a glass extraction thimble with a fritted glass disk at its bottom.
  • a short chromatographic bed of particulate alumina was placed at the bottom of the thimble.
  • the thimble was purchased with a diameter of 41 mm and a height of 130 mm. The height of the thimble was increased to 180 mm to accommodate larger samples (i.e., up to about 70 grams) of the crude dimer.
  • a flask of boiling n-hexane was placed below the thimble, and gaseous n-hexane was condensed in a condenser mounted above the thimble.
  • the condensed n-hexane dripped onto the crude dimer to form a leachant solution of the condensed n-hexane, purified dimer and impurities, including dirt, dust, and/or polymers or oligomers of the monomer formed by the dimer.
  • the leachant solution passed through the chromatographic bed and fritted glass at the bottom of the thimble.
  • the chromatographic bed removed many polar or ionic impurities present within the leachant solution due to the polar nature of alumina.
  • the chromatographic bed removed fine impurities by filtration.
  • a siphoning mechanism was used to periodically empty the leachant solution from the Soxhlet extractor holding the thimble. This process returned the n-hexane from the leachant solution to the flask of boiling n-hexane. After a period of from about 10 to about 20 hours, the crude dimer ended up in the flask of boiling n-hexane.
  • the extraction was conducted at the boiling n-hexane to speed up the dimer dissolution process.
  • a conduit jacket surrounded the extraction volume, so the extraction volume was heated by vapors of n-hexane as these vapors traveled from the boiling flask to the condenser. While this hot filtration process is advantageous because impurities are removed while the solution is hot, it is to be noted that, in conventional crystallization equipment, such a hot filtration can be difficult and/or dangerous when flammable solvents are used. Furthermore, for practical reasons, such a filtration may be performed at temperatures below the solvent boiling temperature, resulting in increased solvent use and decreased dimer solubility. However, using a Soxhlet apparatus, the boiling solvent vapors are held within the apparatus by the jacket, allowing for increased efficiency in the purification process.
  • the resulting purified dimer of the present invention was tested by inductively coupled plasma-mass spectrometry of the vaporized dimer.
  • the sample is ashed to remove carbon containing components, leaving nonvolatile oxides of the trace elements to be determined.
  • This ash is taken up in an aqueous buffer solution.
  • the aqueous buffer solution of the sample ash is fed to an energized plasma.
  • the high temperature of the plasma atomizes the trace elements.
  • the atomized plasma is fed to the source of a mass spectrometer for quantification of each specific impurity elements.
  • n-hexane n-hexane
  • a 1 liter flask having an initial volume of about 0.7 1 of n-hexane is utilized.
  • a parylene polymer layer was formed was formed without a pulsed plasma treatment as follows.
  • the deposition apparatus was as described in U.S. Patent No. 5,546,473.
  • 0.5 grams of parylene dimer were placed into a crucible within the vaporization zone.
  • the parylene dimer had the molecular structure:
  • the crucible was heated to 105°C for thirty minutes, and the dimer was vaporized.
  • the vaporized dimer passed into the pyrolysis zone which was held at 640°C.
  • the dimer was pyrolized to form parylene monomer in the pyrolysis zone, and the parylene monomer was passed through the post- pyrolysis zone which was held at -100° C.
  • Parylene monomer deposited on the surface of a six inch silicon wafer which was attached to a platen held at - 15 °C.
  • the resulting parylene polymer layer had a thickness of 1 micrometer, and the deposition rate was 70 ⁇ per minute.
  • Example 3 A parylene polymer layer was formed using the method described in Example 2, but a pulsed plasma treatment was used during the parylene monomer deposition. The resulting parylene polymer layer had a thickness of 3 micrometers, and the deposition rate was 2100A per minute.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention, qui a trait à des structures multi-niveaux comportant une première couche sur laquelle a été déposée une couche de polymère parylène, concerne également des procédés de fabrication de ces couches. Ces couches de polymère parylène, qui font preuve de qualités améliorées d'adhérence et/ou de résistance, renferment une concentration relativement faible d'impuretés. Dans certaines réalisations, ces couches sont produites grâce à l'intervention d'un traitement au plasma pulsé.
PCT/US1997/019294 1996-10-25 1997-10-24 Procede de fabrication de revetement a base de parylene WO1998018570A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU50871/98A AU5087198A (en) 1996-10-25 1997-10-24 Process for making a parylene coating
EP97913758A EP0934127B1 (fr) 1996-10-25 1997-10-24 Procede de fabrication de revetement a base de parylene
DE69707005T DE69707005T2 (de) 1996-10-25 1997-10-24 Verfahren zur herstellung einer parylenbeschichtung
JP52062698A JP2002505803A (ja) 1996-10-25 1997-10-24 パリレンコーティングの製造方法

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US73831996A 1996-10-25 1996-10-25
US08/738,319 1996-10-25
US92893197A 1997-09-12 1997-09-12
US08/928,931 1997-09-12

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WO1998018570A1 true WO1998018570A1 (fr) 1998-05-07
WO1998018570A9 WO1998018570A9 (fr) 1998-08-20

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FR2787812A1 (fr) * 1998-12-23 2000-06-30 Leybold Systems Gmbh Procede pour revetir des substrats en matiere synthetique
US6534616B2 (en) 1997-10-24 2003-03-18 Quester Technology, Inc. Precursors for making low dielectric constant materials with improved thermal stability
US7066877B2 (en) 2000-03-15 2006-06-27 Ams Research Corporation Parylene-coated components for inflatable penile prosthesis
US7077304B2 (en) 2001-01-30 2006-07-18 Kulicke & Soffa Investments, Inc. Bonding tool with polymer coating
WO2007003502A2 (fr) * 2005-07-01 2007-01-11 Siemens Aktiengesellschaft Revetement de parylene et procede pour produire un revetement de parylene
WO2007025868A1 (fr) * 2005-08-27 2007-03-08 Oerlikon Leybold Vacuum Gmbh Objets munis d'un revetement
EP1965970A2 (fr) * 2005-12-27 2008-09-10 Specialty Coating Systems, Inc. Impression thermique recto-verso en polychromie
CN102140666A (zh) * 2011-01-14 2011-08-03 成都图南电子有限公司 一种粘接钕铁硼磁体涂覆方法及其制备得到的多层结构
GB2479154A (en) * 2010-03-30 2011-10-05 Camvac Ltd Electron flux coated substrate
WO2017099586A1 (fr) * 2015-12-10 2017-06-15 Veco B.V. Filtre pour la préparation de boissons

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KR20040051097A (ko) * 2002-12-11 2004-06-18 패럴린코리아(주) 패럴린(parylene) 고분자 코팅의 접착력을 증진시키는전처리 방법 및 이를 응용한 장치
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534616B2 (en) 1997-10-24 2003-03-18 Quester Technology, Inc. Precursors for making low dielectric constant materials with improved thermal stability
FR2787812A1 (fr) * 1998-12-23 2000-06-30 Leybold Systems Gmbh Procede pour revetir des substrats en matiere synthetique
US7066877B2 (en) 2000-03-15 2006-06-27 Ams Research Corporation Parylene-coated components for inflatable penile prosthesis
US7077304B2 (en) 2001-01-30 2006-07-18 Kulicke & Soffa Investments, Inc. Bonding tool with polymer coating
WO2007003502A3 (fr) * 2005-07-01 2007-08-16 Siemens Ag Revetement de parylene et procede pour produire un revetement de parylene
WO2007003502A2 (fr) * 2005-07-01 2007-01-11 Siemens Aktiengesellschaft Revetement de parylene et procede pour produire un revetement de parylene
WO2007025868A1 (fr) * 2005-08-27 2007-03-08 Oerlikon Leybold Vacuum Gmbh Objets munis d'un revetement
US8119243B2 (en) 2005-08-27 2012-02-21 Oerlikon Leybold Vacuum Gmbh Coated articles
EP1965970A2 (fr) * 2005-12-27 2008-09-10 Specialty Coating Systems, Inc. Impression thermique recto-verso en polychromie
EP1965970A4 (fr) * 2005-12-27 2010-05-26 Specialty Coating Systems Inc Revêtements fluorés
GB2479154A (en) * 2010-03-30 2011-10-05 Camvac Ltd Electron flux coated substrate
CN102140666A (zh) * 2011-01-14 2011-08-03 成都图南电子有限公司 一种粘接钕铁硼磁体涂覆方法及其制备得到的多层结构
WO2017099586A1 (fr) * 2015-12-10 2017-06-15 Veco B.V. Filtre pour la préparation de boissons
NL2015934A (en) * 2015-12-10 2017-06-22 Veco B V Filter for brewing beverages.

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DE69707005D1 (de) 2001-10-31
CN1089281C (zh) 2002-08-21
JP2002505803A (ja) 2002-02-19
DE69707005T2 (de) 2002-07-04
KR20000052803A (ko) 2000-08-25
EP0934127B1 (fr) 2001-09-26
AU5087198A (en) 1998-05-22
KR100517008B1 (ko) 2005-09-27
EP0934127A1 (fr) 1999-08-11

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