By a News Reporter-Staff News Editor at Life Science Weekly — From Washington, D.C., NewsRx journalists report that a patent application by the inventors Wang, Deyan (Hudson, MA); Bayes, Martin W. (Hopkinton, MA); Trefonas, Peter (Medway, MA); O’connell, Kathleen M. (Cumberland, RI), filed on March 6, 2013, was made available online on July 3, 2014 (see also Rohm and Haas Electronic Materials LLC).
The patent’s assignee is Rohm and Haas Electronic Materials LLC.
News editors obtained the following quote from the background information supplied by the inventors: “Formulations for Spin-On Mixed Metal Hardmask (SOMMH), based on organometal compounds, contain either polymeric organometal materials, or molecular organometal materials along with a proper polymer binder. For the latter, the polymer binder serves as a film forming agent, and upon curing, the molecular organometal compounds are linked into a cross-linked network. A curing bake can initiates cross-linking reactions by condensing an organic moiety (an alcohol in general) out of the coated film. Various amounts of organo material remains in the film after a curing bake. In the fabrication of electronic films, residuals of the SOMMH process need to be removed effectively. Compositions for the removal of films, for example, inorganic and/or polymeric films, are disclosed in the following references: WO 2012/009639, WO 2009/073596, WO 2008/098034, WO 2008/080097, WO 2007/120259, WO 2006/110645, WO 2006/054996, and WO 2003/091376. However, there is a need for new processes and compositions that can be used to remove cured organometal films.”
As a supplement to the background information on this patent application, NewsRx correspondents also obtained the inventors’ summary information for this patent application: “The invention provides a process for removing a film from a substrate, said process comprising applying a composition to the film, and
“wherein the composition comprises at least the following:
“a) water; and
“b) at least one compound selected from the following compounds (i-v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R.dbd.H, alkyl, substituted alkyl, ii) NR.sub.4F (Formula 2),
“wherein R.dbd.H, alkyl, substituted alkyl, iii) HF (hydrofluoric acid), iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid), or v) combinations thereof.
“The invention also provides a composition comprising at least the following:
“a) water; and
“b) at least one compound selected from the following compounds (i-v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R.dbd.H, alkyl, substituted alkyl, ii) NR.sub.4F (Formula 2),
“wherein R.dbd.H, alkyl, substituted alkyl, iii) HF (hydrofluoric acid), iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid), or v) combinations thereof.
DETAILED DESCRIPTION
“As discussed above, the invention provides a process for removing a film from a substrate, said process comprising applying a composition to the film, and wherein the composition comprises at least the following:
“a) water; and
“b) at least one compound selected from the following compounds (i-v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R.dbd.H, alkyl, substituted alkyl, ii) NR.sub.4F (Formula 2),
“wherein R.dbd.H, alkyl, substituted alkyl, iii) HF (hydrofluoric acid), iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid), or v) combinations thereof.
“In one embodiment, the film comprises one or more ‘metal-oxygen-carbon’ bonds.
“In one embodiment, the film is an organometal film. In a further embodiment, the organometal film comprises one or more ‘metal-oxygen-carbon’ bonds.
“In one embodiment, the substrate comprises a carbon.
“In one embodiment, the substrate comprises silicon, and further silicon oxide.
“In one embodiment, the substrate comprises an inorganic dielectric material (for example, silicon oxide and/or silicon nitride), an organic antireflective coating (for example, a BARC material), or a carbon underlayer.
“In one embodiment, the substrate is selected from an inorganic dielectric material (for example, silicon oxide and/or silicon nitride), an organic antireflective coating (for example, a BARC material), or a carbon underlayer.
“In one embodiment, the substrate comprises an inorganic dielectric material (for example, silicon oxide and/or silicon nitride), or an organic antireflective coating (for example, a BARC material).
“In one embodiment, the substrate is selected from an inorganic dielectric material (for example, silicon oxide and/or silicon nitride), or an organic antireflective coating (for example, a BARC material).
“In one embodiment, the substrate comprises an inorganic dielectric material (for example, silicon oxide and/or silicon nitride).
“In one embodiment, the substrate is selected from an inorganic dielectric material (for example, silicon oxide and/or silicon nitride).
“In one embodiment, the substrate comprises an organic antireflective coating (for example, a BARC material).
“In one embodiment, the substrate is selected from an organic antireflective coating (for example, a BARC material).
“In one embodiment, the substrate comprises a carbon underlayer.
“In one embodiment, the substrate is selected from a carbon underlayer.
“The invention also provides a composition comprising at least the following:
“a) water; and
“b) at least one compound selected from the following compounds (i-v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R.dbd.H, alkyl, substituted alkyl, ii) NR.sub.4F (Formula 2),
“wherein R.dbd.H, alkyl, substituted alkyl, iii) HF (hydrofluoric acid), iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid), or v) combinations thereof.
“The following embodiments described herein apply to both an inventive process and an inventive composition, each as discussed above.
“An inventive process may comprise a combination of two or more embodiments as described herein.
“An inventive composition may comprise a combination of two or more embodiments as described herein.
“In one embodiment, the at least one compound of Component b) is present in an amount greater than, or equal to 0.3 weight percent, based on the weight of the composition.
“In one embodiment, the at least one compound of Component b) is present in an amount greater than, or equal to 0.5 weight percent, based on the weight of the composition.
“In one embodiment, the at least one compound of Component b) is present in an amount greater than, or equal to 1 weight percent, based on the weight of the composition.
“In one embodiment, the at least one compound of Component b) is present in an amount greater than, or equal to 3 weight percent, based on the weight of the composition.
“In one embodiment, the at least one compound of Component b) is present in an amount less than, or equal to 30 weight percent, based on the weight of the composition.
“In one embodiment, the at least one compound of Component b) is present in an amount less than, or equal to 20 weight percent, based on the weight of the composition.
“In one embodiment, the at least one compound of Component b) is present in an amount less than, or equal to 10 weight percent, based on the weight of the composition.
“In one embodiment, the at least one compound of Component b) is present in an amount less than, or equal to 5 weight percent, based on the weight of the composition.
“In one embodiment, the composition further comprises a polymer that comprises, in polymerized form, an alkylene oxide. In a further embodiment, the alkylene oxide is selected from ethylene oxide, propylene oxide, or a combination thereof.
“In one embodiment, the composition has a pH from 3 to 4; for example as determined using pH paper (for example, COLORPHAST, available from EMD Chemicals Inc.).
“An inventive process may comprise a combination of two or more embodiments as described herein.
“An inventive composition may comprise a combination of two or more embodiments as described herein.
“Component b
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i-v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R is H, a C1-C20 alkyl, or a C1-C20 substituted alkyl; ii) NR.sub.4F (Formula 2),
“wherein R is H, a C1-C20 alkyl, or a C1-C20 substituted alkyl; iii) HF (hydrofluoric acid); iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid); or v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i-v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R is H, a C1-C10 alkyl, or a C1-C10 substituted alkyl; ii) NR.sub.4F (Formula 2),
“wherein R is H, a C1-C10 alkyl, or a C1-C10 substituted alkyl; iii) HF (hydrofluoric acid); iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid); or v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i-v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R is H, a C1-C4 alkyl, or a C1-C4 substituted alkyl; ii) NR.sub.4F (Formula 2),
“wherein R is H, a C1-C4 alkyl, or a C1-C4 substituted alkyl; iii) HF (hydrofluoric acid); iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid); or v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i, ii or v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R.dbd.H, alkyl, substituted alkyl; ii) NR.sub.4F (Formula 2),
“wherein R.dbd.H, alkyl, substituted alkyl; or v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i, ii or v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R is H, a C1-C20 alkyl, or a C1-C20 substituted alkyl; ii) NR.sub.4F (Formula 2),
“wherein R is H, a C1-C20 alkyl, or a C1-C20 substituted alkyl; or v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i, ii or v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R is H, a C1-C10 alkyl, or a C1-C10 substituted alkyl; ii) NR.sub.4F (Formula 2),
“wherein R is H, a C1-C10 alkyl, or a C1-C10 substituted alkyl; or v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i, ii or v): i) NR.sub.4HF.sub.2 (Formula 1),
“wherein R is H, a C1-C4 alkyl, or a C1-C4 substituted alkyl; ii) NR.sub.4F (Formula 2),
“wherein R is H, a C1-C4 alkyl, or a C1-C4 substituted alkyl; v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i): i) NR.sub.4HF.sub.2 (Formula 1), wherein R.dbd.H, alkyl, substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i): i) NR.sub.4HF.sub.2 (Formula 1), wherein R is H, a C1-C20 alkyl, or a C1-C20 substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i): i) NR.sub.4HF.sub.2 (Formula 1), wherein R is H, a C1-C10 alkyl, or a C1-C10 substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (i): i) NR.sub.4HF.sub.2 (Formula 1), wherein R is H, a C1-C4 alkyl, or a C1-C4 substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (ii): ii) NR.sub.4F (Formula 2), wherein R.dbd.H, alkyl, substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (ii): ii) NR.sub.4F (Formula 2), wherein R is H, a C1-C20 alkyl, or a C1-C20 substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (ii): ii) NR.sub.4F (Formula 2), wherein R is H, a C1-C10 alkyl, or a C1-C10 substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (ii): ii) NR.sub.4F (Formula 2), wherein R is H, a C1-C4 alkyl, or a C1-C4 substituted alkyl.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (iii, iv, or v): iii) HF (hydrofluoric acid); iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid); or v) combinations thereof.
“In one embodiment, the at least one compound of Component b is selected from the following compounds (iii): iii) HF (hydrofluoric acid).
“In one embodiment, the at least one compound of Component b is selected from the following compounds (iv): iv) H.sub.2SiF.sub.6 (hexafluorosilicic acid).
“The compound of Component b may comprise a combination of two or more embodiments described herein.
“Component c
“In one embodiment, the composition further comprises Component c) a ‘water miscible’ solvent. Water miscible solvents include, but are not limited to, HBM (methyl-2-hydroxy isobutyrate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), DPGME (dipropylene glycol methyl ether, mixture of isomers), and combinations thereof.
“In one embodiment, the ‘water miscible’ solvent is present in an amount greater than, or equal to 50 weight percent, further greater than, or equal to, 60 weight percent, further greater than, or equal to, 70 weight percent, further greater than, or equal to, 80 weight percent, based on the weight of the composition.
“The ‘water miscible’ solvent of Component c may comprise a combination of two or more embodiments described herein.
“Composition A
“In one embodiment, the film is formed from a ‘composition A’ comprising at least one organometal compound.
“In one embodiment, the at least one organometal compound comprises at least one metal selected from Ti, Zr, Hf, Co, Mn, Zn, or combinations thereof.
“In one embodiment, the at least one organometal compound comprises at least one metal selected from Ti, Zr, Hf, Co, Mn, or Zn.
“In one embodiment, the organometal compound is chelated with at least two oxygen atoms.
“In one embodiment, the at least one organometal compound comprises at least one metal selected from Ti, Zr, Hf, or combinations thereof.
“In one embodiment, the at least one organometal compound comprises at least one metal selected from Ti, Zr, or Hf.
“In one embodiment, organometal compound comprises a metal selected from Ti, Zr, or combinations thereof.
“In one embodiment, the organometal compound comprises a metal selected from Ti or Zr.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00001##
“or combinations thereof, and
“wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from the following: i) hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone; and
“wherein R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are each independently selected from the following: i) a hydrogen atom, ii) a hydrocarbon group, iii) a substituted hydrocarbon group, iv) a hydrocarbon group containing at least one heteroatom in its backbone, or v) a substituted hydrocarbon group containing at least one heteroatom in its backbone.
“As used herein, R1=R.sub.1, R2=R.sub.2, R3=R.sub.3, and so forth.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00002##
“and
“wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each defined above, and
“wherein R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are each defined above.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00003##
“or combinations thereof; and
“wherein R5, R6, R7, R8, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone. In a further embodiment, R5, R6, R7, R8, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, or ii) a substituted hydrocarbon group. In a further embodiment, R5, R6, R7, R8, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00004##
“wherein R5, R6, R7, R8, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone. In a further embodiment, R5, R6, R7, R8, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, or ii) a substituted hydrocarbon group. In a further embodiment, R5, R6, R7, R8, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00005##
“or combinations thereof;
“wherein R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone. In a further embodiment, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, or ii) a substituted hydrocarbon group. In a further embodiment, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00006##
“wherein R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone. In a further embodiment, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, or ii) a substituted hydrocarbon group. In a further embodiment, R21, R22, R23 and R24 are each independently selected from the following: i) a hydrocarbon group.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00007##
“wherein R21 and R22 are each independently selected from the following: i) a hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone. In a further embodiment, R21 and R22 are each independently selected from the following: i) a hydrocarbon group, or ii) a substituted hydrocarbon group. In a further embodiment, R21 and R22 are each independently selected from the following: i) a hydrocarbon group.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00008##
“wherein R23 and R24 are each independently selected from the following: i) a hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone. In a further embodiment, R23 and R24 are each independently selected from the following: i) a hydrocarbon group, or ii) a substituted hydrocarbon group. In a further embodiment, R23 and R24 are each independently selected from the following: i) a hydrocarbon group.
“In one embodiment, the organometal compound is selected from the following compounds:
“##STR00009##
“wherein R5, R6, R7 and R8 are each independently selected from the following: i) a hydrocarbon group, ii) a substituted hydrocarbon group, iii) a hydrocarbon group containing at least one heteroatom in its backbone, or iv) a substituted hydrocarbon group containing at least one heteroatom in its backbone. In a further embodiment, R5, R6, R7 and R8 are each independently selected from the following: i) a hydrocarbon group, or ii) a substituted hydrocarbon group. In a further embodiment, R5, R6, R7 and R8 are each independently selected from the following: i) a hydrocarbon group.
“The organometal compound may comprise a combination of two or more embodiments described herein.
“In one embodiment, the ‘composition A’ further comprises a polymer comprising, in polymerized from, at least one ‘monomer that comprises at least one hydroxyl group.’
“In one embodiment, the polymer comprises less than 1 weight percent silicon, based on the weight of the polymer.
“In one embodiment, the polymer comprises less than 0.5 weight percent silicon, based on the weight of the polymer.
“In one embodiment, the polymer comprises less than 0.1 weight percent silicon, based on the weight of the polymer.
“In one embodiment, the polymer comprises a ‘monomer that comprises at least one hydroxyl group’ based on the weight of the polymer. In a further embodiment, the polymer comprises from 5 to 100 weight percent of the ‘monomer that comprises at least one hydroxyl group’ based on the weight of the polymer.
“In one embodiment, the ‘monomer that comprises at least one hydroxyl group’ is selected from HEMA, OH-styrene, or combinations thereof.
“In one embodiment, the ‘monomer that comprises at least one hydroxyl group’ is selected from a hydroxy acrylate monomer or a hydroxy alkyl acrylate monomer.
“In one embodiment, the ‘monomer that comprises at least one hydroxyl group’ is selected from OH-acrylate, OH-methacrylate, or OH-ethacrylate.
“In one embodiment, the polymer further comprises an acrylate monomer or an alkyl acrylate monomer.
“In one embodiment, the polymer further comprises an acrylate, a methacrylate, or an ethacrylate.
“In one embodiment, the polymer has a molecular weight distribution (Mw/Mn) less than, or equal to, 4.0, or less than, or equal to, 3.5, or less than, or equal to, 3.0, or less than, or equal to, 2.5.
“In one embodiment, the polymer has a molecular weight distribution (Mw/Mn) greater than, or equal to, 1.1, or greater than, or equal to, 1.5, or greater than, or equal to, 1.7.
“In one embodiment, the polymer has a number average molecular weight (Mn) less than, or equal to, 15000 g/mole, or less than, or equal to, 12000 g/mole, or less than, or equal to, 10000 g/mole.
“In one embodiment, the polymer has a number average molecular weight (Mn) greater than, or equal to, 4000 g/mole, or greater than, or equal to, 5000 g/mole, or greater than, or equal to, 6000 g/mole.
“In one embodiment, the polymer has a weight average molecular weight (Mw) less than, or equal to, 35000 g/mole, or less than, or equal to, 30000 g/mole, or less than, or equal to, 25000 g/mole.
“In one embodiment, the polymer has a weight average molecular weight (Mw) greater than, or equal to, 7000 g/mole, or greater than, or equal to, 7500 g/mole, or greater than, or equal to, 8000 g/mole.
“In one embodiment, the organometal compound is present in an amount greater than 10 weight percent, based on the weight of the polymer and the organometal compound.
“In one embodiment, the organometal compound is present in an amount greater than 20 weight percent, based on the weight of the polymer and the organometal compound.
“In one embodiment, the organometal compound is present in an amount greater than 50 weight percent, based on the weight of the polymer and the organometal compound.
“In one embodiment, the organometal compound is present in an amount greater than 75 weight percent, based on the weight of the polymer and the organometal compound.
“The polymer may comprise a combination of two or more embodiments described herein.
“The organometal compound may comprise a combination of two or more embodiments described herein.
“Composition A may comprise a combination of two or more embodiments described herein.”
For additional information on this patent application, see: Wang, Deyan; Bayes, Martin W.; Trefonas, Peter; O’connell, Kathleen M. Methods and Compositions for Removal of Metal Hardmasks. Filed March 6, 2013 and posted July 3, 2014. Patent URL: http://appft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&u=%2Fnetahtml%2FPTO%2Fsearch-adv.html&r=2456&p=50&f=G&l=50&d=PG01&S1=20140626.PD.&OS=PD/20140626&RS=PD/20140626
Keywords for this news article include: Silicon, Acrylates, Hydrocarbons, Acyclic Acids, Hydrofluoric Acid, Organic Chemicals, Fluorine Compounds, Noncarboxylic Acids, Rohm and Haas Electronic Materials LLC.
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