WO2000045435A1 - Polyimides utilises en tant que revetements microelectroniques - Google Patents

Polyimides utilises en tant que revetements microelectroniques Download PDF

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Publication number
WO2000045435A1
WO2000045435A1 PCT/US2000/002281 US0002281W WO0045435A1 WO 2000045435 A1 WO2000045435 A1 WO 2000045435A1 US 0002281 W US0002281 W US 0002281W WO 0045435 A1 WO0045435 A1 WO 0045435A1
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Prior art keywords
trifluoromethyl
phenyl
bis
integrated circuit
insulating layer
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PCT/US2000/002281
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English (en)
Inventor
Frank W. Harris
Stephen Z. D. Cheng
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The University Of Akron
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Priority to US09/890,378 priority Critical patent/US7074493B1/en
Priority to AU34759/00A priority patent/AU3475900A/en
Publication of WO2000045435A1 publication Critical patent/WO2000045435A1/fr

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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H01L21/0212—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC the material being fluoro carbon compounds, e.g.(CFx) n, (CHxFy) n or polytetrafluoroethylene
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/5329—Insulating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention is directed to polyimides having very low dielectric constants, low coefficients of thermal expansion, improved thermal stability and excellent solubility in conventional organic solvents. More particularly, the present invention is directed to a method of coating microelectronic aparatii, components, parts and elements with a polyimide film, the polyimide film comprising the polymerization product of a fixed aromatic diamine or fixed aromatic dianhydride having a fluorine-containing substituent and a 2,2'-disubstituted dianhydride and 2,2'-disubstituted diamine, respectively.
  • the polyimides of the present invention are easily processed in many conventional organic solvents and may be cast into thin films that are suited for coatings in the microelectronics industry.
  • Polyimides are useful as components that require excellent thermal, electrical and/or mechanical properties.
  • polyimide preparation characterization and applications, one can refer to Polyimides, Synthesis. Characterization and Applications , L. Mittal, ed Plenum, NY 1984.
  • Polyimides based on pyromellitic dianhydride and various organic diamines are disclosed in U.S. Pat. No. 4,485, 140 to Gannett et al.
  • Polyimides based on diamines such as 2,2'-di-(p-aminophenyloxy)-diphenyl and various dianhydrides are disclosed in U.S. Pat.
  • polyimides are insoluble in conventional solvents and processing is difficult.
  • the insolubility of polyimides originates from their high aromaticity, their rigid imide structure in the polymer backbone, as well as the formation of the inter and intramolecular charge transfer complexes and the ordered structures resulting form chain packing of the molecules.
  • polyimides derived from the above cited references lack consistency in satisfactory properties to be used as high clarity, low dielectric constant coating materials or as high compression strength fibers or fabrics. Therefore, is it desirable to develop polyimides that have lower dielectric constants, higher coefficients of thermal expansion, good thermal stability and that are soluble in conventional organic solvents, thus allowing processing in the imide form to avoid many problems associated with handling poly(amic) acid precursors.
  • the present invention therefore provides an integrated circuit comprising an integrated circuit and an insulating layer disposed on said integrated circuit, wherein said insulating layer is a polyimide film that is the polymerization product of an aromatic diamine having the general formula (I):
  • R is an organic substituent selected from the group consisting of CF3, o- trifluoromethyl phenyl, /72-trifluoromethyl phenyl, /7-trifluoromethyl phenyl and 3,5-bis[(w- trifluoromethyl) phenyl] ; or the polymerization product of an aromatic dianhydride having the general formula (III):
  • R is a substituent selected from the group consisting of trifluoromethyl, o- trifluoromethyl phenyl, /rc-trifluoromethyl phenyl, ⁇ -trifluoromethyl phenyl and 3,5'-bis[(r ⁇ - trifluoromethyl) phenyl] .
  • the present invention further provides an insulated electrically conductive component comprising an electrically conductive component; and an insulating layer that is the polymerization product of an aromatic diamine having the general formula (I):
  • R is an organic substituent selected from the group consisting of CF 3 , o- trifluoromethyl phenyl, / ⁇ -trifluoromethyl phenyl, 7-trifluoromethyl phenyl and 3,5-bis[(/w- trifluoromethyl) phenyl]; or the polymerization product of an aromatic dianhydride having the general formula (III):
  • R is a substituent selected from the group consisting of trifluoromethyl, o- trifluoromethyl phenyl, -trifluoromethyl phenyl, -trifluoromethyl phenyl and 3,5'-bis[(7J- trifluoromethyl) phenyl] .
  • the present invention further provides a method of coating an integrated circuit comprising the steps of preparing a polyimide comprising the polymerization product of an aromatic diamine having the general formula (I):
  • R is an organic substituent selected from the group consisting of CF 3 , o- trifluoromethyl phenyl, m-trifluoromefhyl phenyl, p-trifluoromethyl phenyl and 3,5-bis[(m- trifluoromethyl) phenyl] ; or the polymerization product of an aromatic dianhydride having the general formula (III):
  • R is a substituent selected from the group consisting of trifluoromethyl, o- trifluoromethyl phenyl, w-trifluoromethyl phenyl, / ⁇ -trifluoromethyl phenyl and 3,5'-bis[( w- trifluoromethyl) phenyl] ; applying the polyimide dispersed within the organic solvent to the surface of the integrated circuit forming a thin insulating layer or film on the surface of the circuit; and heating the integrated circuit with the insulating polyimide layer or film disposed thereon to a temperature sufficient to evaporate the organic solvent and to cure the polyimide.
  • the use of certain polyimides that are useful for insulating electronic and microelectronic components gives rise to unexpectantly superior properties.
  • the polyimides used in this invention have been found to exhibit superior dielectric constants, coefficients of thermal expansion, and thermal stability, even when compared to similar polyimide compounds.
  • the polyimides used in this invention are advantageously soluble in common organic solvents and, therefore, are easily processed and used for insulating electronic and microelectronic components.
  • the polyimides used in this invention are selected from the group of polyimides that are the polymerization product of polymerization product of an aromatic diamine having the general formula (I):
  • R is an organic substituent selected from the group consisting of CF3, o- trifluoromethyl phenyl, w-trifluoromethyl phenyl, 7-trifluoromethyl phenyl and 3,5-bis[(/?z- trifluoromethyl) phenyl].
  • polyimides used in this invention are selected from the group of polyimides that are the polymerization product of an aromatic dianhydride having the general formula (III):
  • R is a substituent selected from the group consisting of trifluoromethyl, o- trifluoromethyl phenyl, -trifluoromethyl phenyl, -trifluoromethyl phenyl and 3, 5 '-bis [(/72- trifluoromethyl) phenyl].
  • polyimides can be prepared in accordance with the techniques and teachings of U.S. Patent Nos. 5,395,918 and 5,071,997, and therefore both of these patents are incorporated herein by reference.
  • the polyimides used in this invention can be polymerized by using a one step polymerization method. This ability makes the polyimides employed in this invention extremely useful as coatings, layers or films for electronic or microelectronic applications.
  • the prior art coating methods involve a three step process including coating a microelectronic components, usually computer chips, with a poly(amic) acid precursor coating material, heating the poly(amic) acid precursor coating material to a temperature sufficient to burn off the excess organic solvent followed by a second heating step to cure the poly(amic) acid prescursor into a polyimide.
  • the coating method of the present invention is an improvement over the prior art in that the polyimide is highly soluble in most common organic solvents and, therefore, a solution containing the polyimide may be coated on the components in one step, without the steps further curing the poly(amic) acid precursors into polyimides.
  • the present invention is an improvement over the prior art methods of coating microelectronic components in that the polyimides disclosed exhibit excellent solubility in many common organic solvents without substantially decreasing the rigidity of the polyimide backbone structure. This is especially important for applications where the imidization condition of poly(amic) acid precursors can dramatically effect structure, morphology and final material properties. Maintaining the polyimide backbone structure minimizes reduction in thermal and mechanical properties.
  • the polyimides used in the present invention are soluble in most common organic solvents including, but not limited to, acetone, cyclopentanone, tetrahydrofuran (THF), N,N'-dimethylacetamide (DMAc), N,N'-dimethylformamide (DMF), N-methylpyrrolidone (NMP), -chlorophenol and /72- cresol.
  • the polyimide coatings of the present invention are soluble in many common non- toxic solvents and can be readily cast into flexible, tough films having low dielectric constants, high coefficients of thermal expansion and high thermal stability.
  • a one step polymerization method has been previously developed for organo-soluble aromatic polyimides.
  • the dianhydride and diamine are dissolved and stirred at 180-200°C in re fluxing high boiling m-cresol or -chlorophenol.
  • the water generated by the imidization is usually distilled off from the reaction mixture.
  • the formation of the polyimide is most likely to proceed via poly(amic) acid precursors, these precursors are only present as extremely short-lived intermediates. Imidization occurs simultaneously with the chain propagation reaction or shortly thereafter. Therefore, the one step imidization process of the present invention avoids the uncontrollable structure, morphology and properties associated with the two-step polymerization route.
  • polyimides of the present invention be used as coating or films for various microelectronic components and may be integrated with other electronic components acting as an inter layer dielectric in integrated circuits.
  • physical properties of polyimides namely the dielectric constant ( ⁇ ),the coefficient of thermal expansion (CTE), thermal stability, and solubility must be evaluated.
  • the polyimides used in this invention have been found to exhibit a dielectric constant that is less than 2.8, advantageously less than 2.7, and even more advantageously less than 2.5. Further, the polyimides used in this invention have been found to exhibit a coefficient of thermal expansion that is greater than about 23 x 10 "6 /°C, advantageously greater than about 42 x 10 "6 /°C, and most advantageously greater than about 54 x 10 "6 /°C.
  • the present invention is directed toward an integrated circuit that includes at least one insulating layer that is formed from the polyimides defined hereinabove.
  • These polyimide layers of films have a thickness of between about 10 and about 1000 microns, preferably about 10 to about 500 microns and most preferably about
  • Microelectronic computer chips are well known in the art and the selection of any one specific electronic configuration should not limit the scope of the present invention.
  • design, manufacture and electrical, thermal and mechanical properties of microelectronic computer chips and related electronic or microelectronic circuits one can refer to Electronic Materials Handbook, Volume 1. ASM International, (1989), which is incorporated herein by reference.
  • the polyimides used are the polymerization product of a fixed fluorine substituent-containing dianhydride, namely 2,2'- bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and one of a series of 4,4'-diamino-2,2'-disubstituted biphenyls.
  • a fixed fluorine substituent-containing dianhydride namely 2,2'- bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and one of a series of 4,4'-diamino-2,2'-disubstituted biphenyls.
  • the 4,4'-diamino-2,2'-disubstituted biphenyls are selected from the group consisting of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (PFMB), 4,4'-diamino-2,2'-bis(/7-trifluorometheylphenyl)-biphenyl (P6FDPBZ), 4,4'- diamino-2 , 2 '-bis( ⁇ -trifluoromethy lphenyl)-bipheny 1 (O6FDPBZ) , 4,4' -diamino-2 ,2 '-bis(/ ⁇ z- trifluoromethylphenyl) biphenyl (M6FDPBZ) and 4,4'-diamino-2,2'bis[3,5- bis(trifluoromethyl)phenyl] biphenyl (M12FDPBZ).
  • PFMB 4,4'-diamino-2,
  • PFMB 4,4'-diamino-2,2'-bis(trifluoromethyl) biphenyl
  • PFMB 4,4'-diamino-2,2'-bis(trifluoromethyl) biphenyl
  • the 2,2'-disubstituted-4,4',5,5'-biphenyltetracarboxylic dianhydrides are selected from the group consisting of 2,2'-bis(trifluoromethyl)-4,4',5,5'- biphenyltetracarboxylic dianhydride (HFBPDA), 2,2'-bis[c-(trifluoromethyl)phenyl]- 4,4',5,5'-biphenyltetracarboxylic dianhydride (O6FDPBPDA), 2,2'-bis[/ ⁇ t-
  • the present invention is directed to an electrically conductive component including an insulating polyimide film or layer, the polyimide film or layer being prepared as discussed hereinabove.
  • the present invention also provides a method of coating an integrated circuit comprising preparing a polyimide film, the polyimide film being prepared as described hereinabove; applying the polyimide to the surface of the integrated circuit forming a thin insulating layer or film on the surface of the integrated circuit; and heating the integrated circuit having the polyimide film disposed thereon to a temperature sufficient to evaporated the excess organic solvent and to cure the polyimide.
  • Methods of applying the polyimide to the integrated circuit include, but are not limited to, spraying, dipping, spin-coating, brush-coating and flow-coating.
  • 6FDA-based, PFMB-based and DMB-based polyimides were synthesized according to the methods disclosed by Harris et al. , U.S. Patent Nos. 5,395,918 and 5,071 ,997, the entire disclosure of each patent incorporated herein by reference.
  • Acetone, chloroform, and tetrahydrofuran were purchased from Fisher Scientific Co.
  • the dielectric constants for 6FDA-based polyimide films was determined using
  • 6FDA-based polyimide films comprising the polymerization product of 6FDA and 4,4'-diamino-2,2'-dichlorobiphenyl (6FDA-DCB, comparative), 4,4'-diamino-2,2'-dibromobiphenyl (6FDA-DBB, comparative), 4,4'-diamino-2,2'-diiodobiphenyl (6FDA-DIB, comparative), 4,4'-diamino- 2,2'-dimethylbiphenyl (6FDA-DMB, comparative), 4,4'-diamino-2,2'-dicyanobiphenyl (6FDA-DCN, comparative), 4,4'-diamino-2,2'-bis(p-methylphenyl)biphenyl (6FDA- MPPBZ,
  • the dielectric constants for 6FDA-based polyimide films comprising the polymerization product of 6FDA and a 4,4'-diamino-2,2'-disubstituted biphenyl selected from one of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (PFMB), 4,4' -diamino-2 , 2 ' -bis(p-tr ifluoromethey lphenyl)-bipheny 1 (P6FDPBZ) , 4,4' -diamino-2 , 2 ' - bis(o-trifluoromethylphenyl)-biphenyl (O6FDPBZ), 4,4'-diamino-2,2'-bis(m- trifluoromethylphenyl) biphenyl (M6FDPBZ) and 4,4'-diamino-2,2'bis[3,5- bis(trifluoro
  • the thermal expansion and glass transition temperatures for 6FDA-based polyimide films was determined by using the Thermal Mechanical Analysis (TMA) and Differential
  • the glass transition temperatures (Tg) of the 6FDA-based polyimide films of the present invention were evaluated by Differential Scanning Calorimetry (DSC), using heating rate of 10°C/minute. Prior to any measurements, the polyimide film samples were heated to 390°C, held for 5 minutes, and subsequently cooled to room temperature at a rate of 10°C/minute in order to avoid hysteresis effects. Relatively large quantities of samples were used in the DSC sample pans in order to detect an observable Tg. The baseline of DSC was calibrated using a standard method known in the art and the temperature range was calibrated using Indium as the standard sample.
  • TMA Thermal Mechanical Analysis
  • Tg glass transition temperatures
  • CTEs coefficients of thermal expansion
  • the temperature of TMA was calibrated using standard Indium samples under the penetration mode according to the standard procedure known in the art.
  • the force and measurement length range were also calibrated by known methods in the art.
  • the polyimide films having thicknesses from about lO ⁇ m to about 30 ⁇ m and a 22 millimeter fixed width were heated to 300°C under nitrogen with a 1.0 MPa annealing stress (0.5 and 1.5 MPa were also used) and held at this temperature for 20 minutes.
  • the polyimide films were subjected to different stresses with a heating rate of 10°C/minute.
  • the Tg was taken as the temperature at the point of change in slope of dimensional change versus temperature.
  • the Tgs obtained at each stress level were then extrapolated to zero stress.
  • the CTE value was taken as the mean of the dimensional change between 50°C and 150°C. The CTEs obtained at each stress level were then extrapolated to zero stress.
  • the coefficients of thermal expansion (CTEs) for the 6FDA-based polyimide films comprising the polymerization product of 6FDA and 4,4'- diamino-2,2'-disubstituted biphenyl selected from one of 4,4'-diamino-2,2'- bis(trifluoromethyl)biphenyl (PFMB), 4,4'-diamino-2,2'-bis(p-trifluorometheylphenyl)- biphenyl (P6FDPBZ), 4,4'-diamino-2,2'-bis(o-trifluoromethylphenyl)-biphenyl
  • PFMB 4,4'-diamino-2,2'-bis(p-trifluorometheylphenyl)- biphenyl
  • P6FDPBZ 4,4'-diamino-2,2'-bis(o-trifluoromethylphenyl)-biphenyl
  • the 6FDA-based polyimide films comprising the polymerization product of 6FDA and a 4,4'-diamino-2,2'-disubstituted biphenyl having one of the 2'2-disubstituted groups trifluoromethyl and trifluoromethyl substituted phenyl at papa-, meta- and ortho- positions, exhibit improved CTEs and lower Tgs in comparison to those 6FDA-based polyimide films comprising the polymerization product of 6FDA and a 4,4'-diamino-2,2'-disubstituted biphenyls without a fluorine-containing substituent at the 2,2' positions of the diamine, which are from about 35.5 x 10-6/°C to about 39.0 x 10- 6/°C.
  • Tgs glass transition temperatures
  • PFMB 4,4'-diamino-2,2'-disubstituted biphenyl selected from one of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (PFMB), 4,4'-diamino-2,2'-bis(p-trifluorometheylphenyl)-biphenyl (P6FDPBZ), 4,4'-diamino-2,2'- bis(o-trifluoromethylphenyl)-biphenyl (O6FDPBZ), 4,4'-diamino-2,2'-bis(m- trifluoromethylphenyl) biphenyl (M6FDPBZ) and 4,4'-diamino-2,2'bis[3,5- bis(trifluoromethyl)phenyl] biphenyl (M12FDPBZ)
  • PFMB 4,4'-diamino-2,2'-disub
  • the glass transition temperatures (Tgs) for the 6FDA-based polyimide films comprising the polymerization product of 6FDA and a 4,4'- diamino-2,2'-disubstituted biphenyl selected from one of 4,4'-diamino-2,2'- bis(trifluoromethyl)biphenyl (PFMB), 4,4'-diamino-2,2'-bis(p-trifluoromefheylphenyl)- biphenyl (P6FDPBZ), 4,4'-diamino-2,2'-bis(o-trifluoromethylphenyl)-biphenyl
  • PFMB 4,4'-diamino-2,2'-bis(p-trifluoromefheylphenyl)- biphenyl
  • P6FDPBZ 4,4'-diamino-2,2'-bis(o-trifluoromethylphenyl)-biphenyl
  • the glass transition temperatures (Tgs) for the 6FDA-based polyimide films comprising the polymerization product of a 4,4'-diamino-2,2'- disubstituted biphenyl without a fluorine-containing substituent at the 2,2'- positions of the diamine, as determined by TMA, is in the range of about 319°C to about 336°C, and as determined by DSC, is in the range of about 350°C to about 362°C.
  • the polyimide films for the thermal stability were prepared as follows: solutions of 6FDA-based polyimides in cyclopentanone, DMAc (12%w/w), and/or m-cresol (5%) were filtered through 5um Whatman Teflon syringe filters. The solutions were subsequently cast onto clear glass substrates. The thickness of the polyimide films was controlled using a doctor knife. The wet films were placed in an oven at 60°C in order to slowly evaporate the solvent. After 24 hours, the samples were placed in a vacuum oven and dried at 180°C for 48 hours. The film thicknesses could be control from 20 to lOO ⁇ m by this method. The resulting 6FDA-based polyimide films were used for Thermogravimetric Analysis (TGA).
  • TGA Thermogravimetric Analysis
  • the 6FDA-based polyimide films prepared for TGA measurements were heated to 300°C and held for 20 minutes, followed by subsequent cooling to 30°C prior to measurements.
  • the polyimide films were then heated in nitrogen and air, using a heating rate of 10°C/minute and heated to 650°C. 2% and 5 % weight loss temperature were used to evaluate the thermal and thermo-oxidative stability of the 6FDA-based polyimide films.
  • the results of the thermal and thermo-oxidative experiments, as evaluated by TGA, are shown in Table III, below.
  • polyimides comprising the reaction product of 6FDA and one of 4,4'- diamino-2 , 2 '-bis(trifluoromethyl)biphenyl (PFMB) , 4 ,4 '-diamino-2 ,2 ' -bis(p- trifluorometheylphenyl)-biphenyl (P6FDPBZ), 4,4'-diamino-2,2'-bis(o- trifluoromethylphenyl)-biphenyl (O6FDPBZ), 4,4'-diamino-2,2'-bis(m- trifluoromethylphenyl) biphenyl (M6FDPBZ) and 4,4'-diamino-2,2'bis[3,5- bis(trifluoromethyl)phenyl] biphenyl (M12FDPBZ) exhibit a 5% weight loss in air at 471°C to 518°C, and a 5 % weight loss in nitrogen at 480°
  • the 6FDA-based aromatic polyimides are soluble in many conventional organic solvents, such as acetone, cyclopentanone, tetrahyofuran, dimethlacetamide (DMAc), N,N'-dimethyl formamide (DMF) and N-methylpyrrolidone (NMP).
  • organic solvents such as acetone, cyclopentanone, tetrahyofuran, dimethlacetamide (DMAc), N,N'-dimethyl formamide (DMF) and N-methylpyrrolidone (NMP).
  • 6FDA-based polyimides may be attributed partially to the incorporation of the twisted- biphenyl diamines.
  • the non-coplanar diamine disrupt the chain packing, eliminate crystallinity and interrupt conjugations along the chain backbones.
  • the resulting loose packing generates more free volume, which permit solvent molecules to penetrate into the polymer systems.
  • the dielectric constants for PFMB-based polyimide films was determined using ASTM-150 method at 1MHz on polyimide films having a thickness of 10 to 40 microns.
  • the results of the dielectric experiments for PFMB-based polyimides are shown in Table V, below.
  • the dielectric constants for PFMB-based polyimide films was determined using ASTM-150 method at 1MHz on PFMB-based polyimide films having a thickness of 10 to 40 microns.
  • the dielectric constants for PFMB-based polyimide films comprising the polymerization product of PFMB and one of 2,2'-bis(trifluoromethyl)-4,4',5,5'- biphenyltetracarboxylic dianhydride (PFMB-HFBPDA), 2,2'-bis[ ⁇ -
  • O6FDPBPDA 2,2'-bis[/72-(trifluoromethyl)phenyl]-4,4',5,5'-biphenyltetracarboxylic dianhydride
  • PFMB-M6FDPBPDA 2,2'-bis[p-(trifluoromethyl)phenyl]-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • PFMB-P6FDPBPDA 2,2'-bis[3,5- bis(trifluoromethyl)phenyl]-4,4',5,5'-biphenyltetracarboxylic dianhydride
  • PFMB- M12FDPBPDA 2,2'-bis[3,5- bis(trifluoromethyl)phenyl]-4,4',5,5'-biphenyltetracarboxylic dianhydride
  • PFMB-DPBPDA 2,2'-diphenyl- 4,4',5,5'-biphenyltetracarboxylic dianhydride
  • PFMB-BPDA 4,4', 5,5'- biphenyltetracarboxylic dianhydride
  • PFMB-DBBPDA 2,2'-dibromo-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • PFMB-DBBPDA 2,2'-dibromo-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • the thermal expansion and glass transition temperatures for PFMB-based polyimide films was determined by using the Thermal Mechanical Analysis (TMA) and Differential Scanning Calorimetry (DSC) methods.
  • TMA Thermal Mechanical Analysis
  • DSC Differential Scanning Calorimetry
  • DMB non-fluorine substituent-containing diamine
  • CTE coefficient of thermal expansion
  • Tgs glass transition temperatures
  • Tg glass transition temperatures of the PFMB-based and DMB-based polyimide films of the present invention comprising the polymerization product of PFMB or DMB and one of 2,2'-bis(trifluoromethyl)-4,4',5,5'-biphenyltetracarboxylic dianhydride (HFBPD A) , 2 , 2 ' -bis [o-(trifluoromethy l)pheny 1] -4 ,4 ' , 5 , 5 ' -biphenyltetracarboxylic dianhydride (O6FDPBPDA), 2,2'-bis[ -(trifluoromethyl)phenyl]-4,4',5,5'- biphenyltetracarboxylic dianhydride (M6FDPBPDA), 2,2'-bis[p-(trifluoromethyl)phenyl]- 4,4',5,5'-biphenyltetracarboxylic dianhydride (P6
  • Tgs glass transition temperatures
  • DPBPDA 2,2'-diphenyl-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • BPDA 4,4', 5,5'- biphenyltetracarboxylic dianhydride
  • DBBPDA 2,2'-dibromo-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • TMA Thermal Mechanical Analysis
  • CTEs coefficients of thermal expansion
  • the temperature of TMA was calibrated using standard Indium samples under the penetration mode according to the standard procedure known in the art.
  • the force and measurement length range were also calibrated by known methods in the art.
  • the polyimide films having thicknesses from about lO ⁇ m to about 30 ⁇ m and a 22 millimeter fixed width were heated to 300°C under nitrogen with a 1.0 MPa annealing stress (0.5 and 1.5 MPa were also used) and held at this temperature for 20 minutes.
  • the polyimide films were subjected to different stresses with a heating rate of 10°C/minute.
  • the Tg was taken as the temperature at the point of change in slope of dimensional change versus temperature.
  • the Tgs obtained at each stress level were then extrapolated to zero stress.
  • the CTE value was taken as the mean of the dimensional change between 50°C and 150°C.
  • the CTEs obtained at each stress level were then extrapolated to zero stress.
  • the thermal expansion and glass transition temperatures for PFMB-based and DMB- based polyimide films was determined by using the TMA method.
  • the coefficients of thermal expansion (CTEs) and glass transition temperatures (Tgs) for the PFMB-based and DMB-based polyimide films are shown in Table VI, below.
  • CTE coefficient of thermal expansion
  • PFMB-based polyimide films comprising the polymerization product of PFMB and one of 2,2'-bis(trifluoromethyl)-4,4',5,5'-biphenyltetracarboxylic dianhydride (HFBPDA), 2,2'- bis[ ⁇ -(trifluoromethyl)phenyl]-4,4',5,5'-biphenyltetracarboxylic dianhydride (O6FDPBPDA), 2,2'-bis[ ⁇ n-(trifluoromethyl)phenyl]-4,4' ,5, 5 '-biphenyltetracarboxylic dianhydride (M6FDPBPDA), 2,2'-bis[p-(trifluoromethyl)phenyl]-4,4',5,5'- biphenyltetracarboxylic dianhydride (P6FDPBPDA) and 2,2'-bis[3,5- bis(trifluoromethyl)phenyl]-4
  • CTE coefficient of thermal expansion
  • DMB-based polyimide films comprising the polymerization product of DMB and one of 2,2'-bis(trifluoromethyl)- 4,4',5,5'-biphenyltetracarboxylic dianhydride (HFBPDA), 2,2'-bis[o- (trifluoromethyl)phenyl]-4,4' ,5,5'-biphenyltetracarboxylic dianhydride (O6FDPBPDA), 2 ,2 ' -bis [ ⁇ 72-(trifluoromethy l)pheny l]-4 , 4 ' , 5 , 5 ' -biphenyltetracarboxylic dianhydride
  • M6FDPBPDA 2,2'-bis
  • P6FDPBPDA 2,2'-bis[3,5-bis(trifluoromethyl)phenyl]-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • CTE coefficient of thermal expansion
  • the glass transition temperature (Tg) PFMB-based polyimide films comprising the polymerization product of PFMB and one of 2,2'-bis(trifluoromethyl)-4,4',5,5'- biphenyltetracarboxylic dianhydride (HFBPDA), 2,2'-bis[o-(trifluoromethyl)phenyl]- 4,4',5,5'-biphenyltetracarboxylic dianhydride (O6FDPBPDA), 2,2'-bis[rn- (trifluoromethyl)phenyl]-4,4',5,5'-biphenyltetracarboxylic dianhydride (M6FDPBPDA), 2 , 2 ' -bis [p-(t ⁇ ifluoromethy l)pheny 1] -4 ,4 ' , 5 , 5 '-biphenyltetracarboxylic dianhydride
  • P6FDPBPDA and 2,2'-bis[3,5-bis(trifluoromethyl)phenyl]-4,4',5,5'- biphenyltetracarboxylic dianhydride are in the range of about 332°C to about 372°C, while the glass transition temperature (Tg) for the PFMB-based polyimide films comprising the polymerization product of PFMB and one of 2,2'-diphenyl-4,4',5,5'- biphenyltetracarboxylic dianhydride (DPBPDA, comparative), 4, 4', 5,5'- biphenyltetracarboxylic dianhydride (BPDA, comparative), 2,2'-dibromo-4,4',5,5'- biphenyltetracarboxylic dianhydride (DBBPDA), are in the range of about 304°C to about 346°C.
  • Tg glass transition temperature
  • Tg glass transition temperature for the DMB-based polyimide films comprising the polymerization product of DMB and one of 2, 2' -bis (tr ifluoromethy 1)- 4,4',5,5'-biphenyltetracarboxylic dianhydride (HFBPDA), 2,2'-bis[ ⁇ -
  • M6FDPBPDA 2,2'-bis[/7-(trifluoromethyl)phenyl]-4,4',5,5'-biphenyltetracarboxylic dianhydride
  • P6FDPBPDA 2,2'-bis[3,5-bis(trifluoromethyl)phenyl]-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • M12FDPBPDA glass transition temperature for the DMB-based polyimide films comprising the polymerization product of DMB and one of 2,2'-diphenyl-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • BPDA 2,2'-dibromo-4,4',5,5'- biphenyl
  • PFMB-HFBPDA 2,2'-bis(trifluoromethyl)- 4,4',5,5'-biphenyltetracarboxylic dianhydride
  • PFMB-O6FDPBPDA 2,2'-bis[ -(trifluoromethyl)phenyl]-4,4',5,5'-biphenyltetracarboxylic dianhydride
  • PFMB-M6FDPBPDA 2,2'-bis[p-(trifluoromethyl)phenyl]-4,4',5,5'- biphenyltetracarboxylic dianhydride
  • the PFMB-based aromatic polyimides are soluble in many conventional organic solvents, such as acetone, cyclopentanone, tetrahyofuran, N- methylpyrrolidone (NMP),m-cresol and p-chlorophenol.
  • DMB-based aromatic polyimides were prepared by the 2,2'-disubsitution of pendant groups on 4,4',5,5'-biphenyltetracarboxylic dianhydrides in polyimide backbones. The polyimides were considered to be soluble if a solution of 5 % (wt/wt) concentration could be prepared.
  • Table IX The results of the solubility experiments are shown in Table IX, below.
  • the DMB-based aromatic polyimide BPDA-DMB is only soluble in p-chlorophenol.
  • the DMB-based polyimide M12FDPBPDA-DMB is soluble in soluble in many conventional organic solvents, such as acetone, cyclopentanone, tetrahyofuran, N-methylpyrrolidone (NMP), -cresol and/7-chlorophenol.
  • the DMB-based polyimides DBBPDA-DMB, HFBPDA-DMB, DPBPDA-DMB, O6FDPBPDA-DMB, M6FDPBPDA-DMB and P6FDPBPDA are not soluble in acetone, but are soluble in cyclopentanone, tetrahyofuran, N-methylpyrrolidone (NMP), ⁇ n-cresol and -chlorophenol
  • Table IX demonstrate, with the exception of BPDA- DMB which contains the 4,4' ,5 ,5 '-bipohenyltetracarboxylic dianhydride (BPDA) without disubstituted groups at the 2,2'-positions, that the solubility of the resulting polyimides can be improved through the use of 2,2'-disubstituted-4,4',5,5'-biphenyltetracarboxylic dianhydrides in polyimide.
  • BPDA 4,4' ,
  • the polyimide coatings of this invention have excellent dielectric constants, coefficients of thermal expansion, and thermal stability. Additionally, the polyimides used in this invention are advantageously soluble in common organic solvents and, therefore, are easily processed and used for insulating electronic and microelectronic components.

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Abstract

La présente invention concerne un circuit intégré comportant une couche isolante comprenant le produit de polymérisation du dianhydride aromatique 2,2'-bis(3,4-dicarboxphenyle)hexafluoropropane dianhydride (6FDA) ou la diamine aromatique 4,4'-diamino-2,2'-bis(trifluoromethyle)biphenyle (PFMB) avec du fluor 4,4'-diamino-2,2'-disubstitués biphenyles renfermant des substituants et 2,2'-disubstitués-4,4'5,5'-biphenyletetracarboxyliques dianhydrides respectivement. L'invention concerne également un procédé de revêtement d'un circuit intégré comportant la préparation d'un polyimide dans un solvant organique, l'application du polyimide dispersé au sein du solvant à la surface d'un circuit intégré formant une mince couche ou un film isolant(e) disposé dessus à une température suffisante permettant l'évaporation du solvant et la cuisson du polyimide. Les films polyimide à base de 6FDA et de PFMB selon l'invention possèdent de faibles constantes diélectriques, des coefficients élevés de dilatation thermique, une excellente stabilité thermique et une excellente solubilité dans les solvants traditionnels.
PCT/US2000/002281 1999-01-29 2000-01-28 Polyimides utilises en tant que revetements microelectroniques WO2000045435A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009041593A1 (fr) * 2007-09-28 2009-04-02 Toyo Boseki Kabushiki Kaisha Composition de résine polyimide photosensible de type positif
US9120789B2 (en) 2010-02-01 2015-09-01 Cancer Research Technology Limited 1-(5-tert-butyl-2-phenyl-2H-pyrazol-3-yl)-3-[2-fluoro-4-(1-methyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-7-yloxy)-phenyl]-urea and related compounds and their use in therapy
US9155737B2 (en) 2007-12-19 2015-10-13 Institute Of Cancer Research: Royal Cancer Hospital (The) Pyrido[2,3-B]pyrazin-8-substituted compounds and their use
US9708317B2 (en) 2013-11-25 2017-07-18 Cancer Research Technology Limited Process for the preparation of 8-(4-aminophenoxy)-4H-pyrido[2,3-B]pyrazin-3-one derivatives
US9725447B2 (en) 2013-11-25 2017-08-08 Cancer Research Technology Limited 1-(5-tert-butyl-2-aryl-pyrazol-3-yl)-3-[2-fluoro-4-[(3-oxo-4H-pyrido[2,3-b]pyrazin-8-yl)oxy]phenyl]urea derivatives as RAF inhibitors for the treatment of cancer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4499149A (en) * 1980-12-15 1985-02-12 M&T Chemicals Inc. Siloxane-containing polymers
US5677041A (en) * 1993-03-25 1997-10-14 Texas Instruments Incorporated Integrated circuits formed in radiation sensitive material and method of forming same
US5766740A (en) * 1995-05-26 1998-06-16 Sheldahl, Inc. Adherent film with low thermal impedance and high electrical impedance used in an electronic assembly with a heat sink
US5814894A (en) * 1995-04-07 1998-09-29 Nitto Denko Corporation Semiconductor device, production method thereof, and tape carrier for semiconductor device used for producing the semiconductor device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4499149A (en) * 1980-12-15 1985-02-12 M&T Chemicals Inc. Siloxane-containing polymers
US5677041A (en) * 1993-03-25 1997-10-14 Texas Instruments Incorporated Integrated circuits formed in radiation sensitive material and method of forming same
US5814894A (en) * 1995-04-07 1998-09-29 Nitto Denko Corporation Semiconductor device, production method thereof, and tape carrier for semiconductor device used for producing the semiconductor device
US5766740A (en) * 1995-05-26 1998-06-16 Sheldahl, Inc. Adherent film with low thermal impedance and high electrical impedance used in an electronic assembly with a heat sink

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009041593A1 (fr) * 2007-09-28 2009-04-02 Toyo Boseki Kabushiki Kaisha Composition de résine polyimide photosensible de type positif
US9155737B2 (en) 2007-12-19 2015-10-13 Institute Of Cancer Research: Royal Cancer Hospital (The) Pyrido[2,3-B]pyrazin-8-substituted compounds and their use
US9540372B2 (en) 2007-12-19 2017-01-10 Institute Of Cancer Research: Royal Cancer Hospital (The) Pyrido[2,3-b]pyrazin-8-substituted compounds and their use
US9120789B2 (en) 2010-02-01 2015-09-01 Cancer Research Technology Limited 1-(5-tert-butyl-2-phenyl-2H-pyrazol-3-yl)-3-[2-fluoro-4-(1-methyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-7-yloxy)-phenyl]-urea and related compounds and their use in therapy
US9439893B2 (en) 2010-02-01 2016-09-13 Cancer Research Technology Limited 1-(5-tert-butyl-2-phenyl-2H-pyrazol-3-yl)-3-[2-fluoro-4-(1-methyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-B]pyridin-7-yloxy)-phenyl]-urea and related compounds and their use in therapy
US9820976B2 (en) 2010-02-01 2017-11-21 Cancer Research Technology Limited 1-(5-tert-butyl-2-phenyl-2H-pyrazol-3-yl)-3-[2-fluoro-4-(1-methyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-7-yloxy)-phenyl]-urea and related compounds and their use in therapy
US9708317B2 (en) 2013-11-25 2017-07-18 Cancer Research Technology Limited Process for the preparation of 8-(4-aminophenoxy)-4H-pyrido[2,3-B]pyrazin-3-one derivatives
US9725447B2 (en) 2013-11-25 2017-08-08 Cancer Research Technology Limited 1-(5-tert-butyl-2-aryl-pyrazol-3-yl)-3-[2-fluoro-4-[(3-oxo-4H-pyrido[2,3-b]pyrazin-8-yl)oxy]phenyl]urea derivatives as RAF inhibitors for the treatment of cancer
US10100053B2 (en) 2013-11-25 2018-10-16 Cancer Research Technology Limited Process for the preparation of 8-(4-aminophenoxy)-4H-pyrido[2,3-b]pyrazin-3-one derivatives
US10167282B2 (en) 2013-11-25 2019-01-01 Cancer Research Technology Limited 1-(5-tert-butyl-2-aryl-pyrazol-3-yl)-3-[2-fluoro-4-[(3-oxo-4H-pyrido [2, 3-B]pyrazin- 8-yl)oxy]phenyl]urea derivatives as RAF inhibitors for the treatment of cancer

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