KUDO TAKANORI (US)
US9201305B2 | 2015-12-01 | |||
US9274426B2 | 2016-03-01 | |||
US20120251956A1 | 2012-10-04 | |||
US4491628A | 1985-01-01 | |||
US5350660A | 1994-09-27 | |||
US5843624A | 1998-12-01 | |||
US6866984B2 | 2005-03-15 | |||
US6447980B1 | 2002-09-10 | |||
US6723488B2 | 2004-04-20 |
EUR. J. INORG. CHEM., 2006, pages 3283 - 3293
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS, vol. 97, 2012, pages 137 - 142
Claims What is claimed is: 1. A formulation comprising: (i) a crystalline S1 form of zirconium propionate (ZPPA) of formula the formula C72H128O64Zr12 x 4(C3H5O2) x 2(H2O) characterized by its powder X-ray diffractogram having peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees of 2θ; (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 2. A formulation consisting essentially of: (i) a crystalline S1 form of zirconium propionate (ZPPA) of formula the formula C72H128O64Zr12 x 4(C3H5O2) x 2(H2O) characterized by its powder X-ray diffractogram having peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees of 2θ; (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 3. A formulation consisting of: (i) a crystalline S1 form of zirconium propionate (ZPPA) of formula the formula C72H128O64Zr12 x 4(C3H5O2) x 2(H2O) characterized by its powder X-ray diffractogram having peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees of 2θ; (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 4. A formulation comprising: (i) zirconium propionate (ZPP); (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 5. A formulation consisting essentially of: (i) zirconium propionate (ZPP); (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 6. A formulation consisting of: (i) zirconium propionate (ZPP); (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 7. A formulation comprising: (i) a zirconium-contain material selected from: (a) a crystalline S1 form of zirconium propionate (ZPPA) of formula the formula C72H128O64Zr12 x 4(C3H5O2) x 2(H2O) characterized by its powder X-ray diffractogram having peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees of 2θ; (b) zirconium propionate (ZPP); and (c) combinations thereof, (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 8. A formulation consisting essentially of: (i) a zirconium-contain material selected from: (a) a crystalline S1 form of zirconium propionate (ZPPA) of formula the formula C72H128O64Zr12 x 4(C3H5O2) x 2(H2O) characterized by its powder X-ray diffractogram having peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees of 2θ; (b) zirconium propionate (ZPP); and (c) combinations thereof, (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 9. A formulation consisting of: (i) a zirconium-contain material selected from: (a) a crystalline S1 form of zirconium propionate (ZPPA) of formula the formula C72H128O64Zr12 x 4(C3H5O2) x 2(H2O) characterized by its powder X-ray diffractogram having peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees of 2θ; (b) zirconium propionate (ZPP); and (c) combinations thereof, (ii) one or more etch resistance modulator additive; (iii) one or more solvents, (iv) optionally one or more surfactant; and (v) optionally one or more water resistivity enhancer. 10. The formulation of any of claims 1-9, comprising (iv) the one or more surfactant. 11. The formulation of any of claims 1-9, comprising (v) the one or more water resistivity enhancer. 12. The formulation of any of claims 1-9, comprising (iv) the one or more surfactant and (v) the one or more water resistivity enhancer. 13. The formulation of any of claims 4-9, wherein the ZPP comprises ZPP assigned CAS No. 84057-80-7. 14. The formulation of any of claims 4-9, wherein the ZPP comprises Zr(CH3CH2COO)4-x(OH)x, where x = 1-3. 15. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species including, in any sequence, the repeat units: (A2)n (B2)m (C2)o (D2)p (A3)n1 (B3)m1 (C3)o1 (D3)p1 wherein each of n, n1, m, m1, o, o1, p and p1 = 0-10, a total of n, n1, m, m1, o, o1, p and p1 is between 2 and 10; and the repeat units are shown in the following table where “ ” represents an actual or potential direct valence bond from a protonated or unprotonated oxygen atom to another zirconium in an oligomer or polymeric zirconium complex, or alternatively a direct valence bond to H forming a Zr-OH moiety: 16. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.5 to about 1.1 as measured by proton NMR. 17. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.55 to about 1.05 as measured by proton NMR. 18. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.6 to about 0.9 as measured by proton NMR. 19. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.55 measured by proton NMR. 20. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.6 measured by proton NMR. 21. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.65 measured by proton NMR. 22. The formulation of any of claims 4-9, wherein the ZPP comprises an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.7 measured by proton NMR. 23. The formulation of any of claims 4-9, wherein the ZPP comprises about 0.5 wt % to about 6 wt % of water. 24. The formulation of any of claims 4-9, wherein the ZPP comprises about 1 wt % to about 5 wt % of water. 25. The formulation of any of claims 4-9, wherein the ZPP comprises about 0.5 wt % to about 6 wt % of propionic acid. 26. The formulation of any of claims 4-9, wherein the ZPP comprises about 5 wt % of propionic acid or less. 27. The formulation of any of claims 4-9, wherein the ZPP has an average diameter (nm) of about 7.0 nm to about 12.0 nm as measured by dynamic light scattering (DLS). 28. The formulation of any of claims 4-9, wherein the ZPP has an average diameter (nm) of about 8.5 nm to about 10.5 nm as measured by dynamic light scattering (DLS). 29. The formulation of any of claims 4-9, wherein the ZPP has an average diameter (nm) of about 7.5 nm as measured by dynamic light scattering (DLS). 30. The formulation of any of claims 4-9, wherein the ZPP has an average diameter (nm) of about 8.0 nm as measured by dynamic light scattering (DLS). 31. The formulation of any of claims 4-9, wherein the ZPP has an average diameter (nm) of about 8.5 nm as measured by dynamic light scattering (DLS). 32. The formulation of any of claims 4-9, wherein the ZPP has an average diameter (nm) of about 9.0 nm as measured by dynamic light scattering (DLS). 33. The formulation of any of claims 1-9, wherein the (ii) one or more etch resistance modulator additive comprises a compound of structure (1). wherein R11 is hydrogen or methyl; and L3 is a direct bond, substituted or unsubstituted C1-3 alkyl, or substituted or unsubstituted C7-16 aralkyl. 34. The formulation of claim 33, wherein L3 is a direct bond, C1 alkyl, or C15 aralkyl. 35. The formulation of claim 33, wherein L3 is a direct bond, C1 alkyl, or C15 aralkyl; and wherein the C1 alkyl or C15 aralkyl are substituted with hydrogen, methyl, C6-11 aryl, or a substituent of structure (1a): or structure (1b): 36. The formulation of any of claims 1-9, wherein the (ii) one or more etch resistance modulator additive comprises a compound shown in structures (2), (2A), (2B), (3), (3A), (3B), (3C), (3D) and (4) to (18): , wherein the linking groups Xp and Xpa are independently selected from a -O-, -CH2-, -C(CH3)2-, -SO2-; Rp1 is hydrogen or an alkyl moiety, Rp2, Rp3, Rp4, Rp5 are independently selected from hydrogen or an alkyl moiety. 37. The formulation of any of claims 1-9, wherein the (ii) one or more etch resistance modulator additive comprises 4,4’,4’’-trihydroxytriphenylmethane (THTPM): 38. The formulation of any of claims 1-9, wherein the (ii) one or more etch resistance modulator additive comprises 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP; 3D1): 39. The formulation of any of claims 1-9, wherein the (ii) one or more etch resistance modulator additive comprises 3D2: 40. The formulation of any of claims 1-9, wherein the (ii) one or more etch resistance modulator additive comprises 3D3: 41. The formulation of any of claims 1-9, wherein the (ii) one or more etch resistance modulator additive comprises two or more of: A. 4,4’,4’’-trihydroxytriphenylmethane (THTPM): B. 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP; 3D1): C. 3D2: D. 3D3: 42. The formulation of any of claims 1-9, wherein the formulation comprises approximately 0.1 wt% to approximately 1 wt% of the (ii) one or more etch resistance modulator additive. 43. The formulation of any of claims 1-9, wherein the formulation comprises approximately 0.5 wt% to approximately 1 wt% of the (ii) one or more etch resistance modulator additive. 44. The formulation of any of claims 1-9, wherein the formulation comprises approximately 0.5 wt% to approximately 0.75 wt% of the (ii) one or more etch resistance modulator additive. 45. The formulation of any of claims 1-9, wherein the formulation comprises about 0.5 wt% to about 0.75 wt % of 4,4’,4’’-trihydroxytriphenylmethane (THTPM): 46. The formulation of any of claims 1-9, wherein the formulation comprises about 0.6 wt% of 4,4’,4’’-trihydroxytriphenylmethane (THTPM): 47. The formulation of any of claims 1-9, wherein the formulation comprises about 0.5 wt% to about 0.75 wt % of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP): 48. The formulation of any of claims 1-9, wherein the formulation comprises about 0.6 wt% of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP): 49. The formulation of any of claims 1-9, wherein the formulation comprises about 0.5 wt% to about 0.75 wt % of NF0327: 50. The formulation of any of claims 1-9, wherein the formulation comprises about 0.6 wt% of NF0327: 51. The formulation of any of claims 1-9, wherein the formulation comprises about 0.5 wt% to about 0.75 wt % of NF0A28: . 52. The formulation of any of claims 1-9, wherein the formulation comprises about 0.6 wt% of NF0A28: 53. The formulation of any of claims 1-9, wherein the formulation comprises about 0.5 wt% to about 0.75 wt % of NF71A7: 54. The formulation of any of claims 1-9, wherein the formulation comprises about 0.6 wt% of NF71A7: 55. The formulation of any of claims 1-9, wherein the formulation comprises about 0.5 wt% to about 0.75 wt % of NF0127: 56. The formulation of any of claims 1-9, wherein the formulation comprises about 0.6 wt% of NF0127: 57. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises one or more of a glycol ether derivative, a glycol ether ester derivative a carboxylate, a carboxylate of a di- basic acid, a dicarboxylate of a glycol, a hydroxy carboxylate, a ketone ester, an alkyloxycarboxylic acid ester, a ketone derivative, a ketone ether derivative, a ketone alcohol derivative, an amide derivative and mixtures thereof. 58. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises a glycolic derivative. 59. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises a glycolic derivative one or more solvents selected from the group of ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dipropylene glycol monomethyl ether (DPGME) and mixtures thereof. 60. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises ethylene glycol. 61. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises propylene glycol. 62. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises, propylene glycol monomethyl ether acetate (PGMEA). 63. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises propyleneglycol monomethylether (PGME). 64. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises dipropylene glycol monomethyl ether (DPGME). 65. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propyleneglycol monomethylether (PGME). 66. The formulation of any of claims 1-9, wherein the (iii) one or more solvents comprises a mixture of approximately 70 wt% of propylene glycol monomethyl ether acetate (PGMEA) and 30 wt% of propyleneglycol monomethylether (PGME). 67. The formulation of any of claims 1-9, wherein the formulation comprises about 70 wt% to about 98 wt% of the one or more solvents. 68. The formulation of any of claims 1-9, wherein the formulation comprises about 90 wt% to about 98 wt% of the one or more solvents. 69. The formulation of any of claims 1-9, wherein the formulation comprises about 90 wt% of the one or more solvents. 70. The formulation of any of claims 1-9, wherein the formulation comprises about 91 wt% of the one or more solvents. 71. The formulation of any of claims 1-9, wherein the formulation comprises about 92 wt% of the one or more solvents. 72. The formulation of any of claims 1-9, wherein the formulation comprises about 93 wt% of the one or more solvents. 73. The formulation of any of claims 1-9, wherein the formulation comprises about 94 wt% of the one or more solvents. 74. The formulation of any of claims 1-9, wherein the formulation comprises about 95 wt% of the one or more solvents. 75. The formulation of any of claims 1-9, wherein the formulation comprises about 93 wt% of ArF Thinner. 76. The formulation of any of claims 1-9, wherein the formulation comprises about 94 wt% of ArF Thinner. 77. The formulation of any of claims 1-9, wherein the formulation comprises about 95 wt% of ArF Thinner. 78. The formulation of any of claims 1-9, wherein the formulation comprises about 93 wt% of PGMEA. 79. The formulation of any of claims 1-9, wherein the formulation comprises about 94 wt% of PGMEA. 80. The formulation of any of claims 1-9, wherein the formulation comprises about 95 wt% of PGMEA. 81. The formulation of any of claims 1-9 comprising the one or more surfactant, wherein the one or more surfactant is one or more of a polyoxyethylene alkyl ether, a polyoxyethylene alkylaryl ether, a polyoxyethylene-b-polyoxypropylene block copolymer, a sorbitane fatty acid esters, a nonionic surfactant of a polyoxyethylene sorbitane fatty acid esters, a fluorinated surfactant, an organosiloxane polymer, an acrylic acid polymer and a methacrylic acid polymer. 82. The formulation of any of claims 1-9 comprising the one or more surfactant, wherein the one or more surfactant comprises an organosiloxane polymer. 83. The formulation of any of claims 1-9 comprising the one or more surfactant, wherein the one or more surfactant comprises an organosiloxane polymer selected from the group of KF53, KF353A, KP-341, KP-351, X-22-4952, X-70-092, and X-70-093. 84. The formulation of any of claims 1-9 comprising the one or more surfactant, wherein the one or more surfactant comprises X-22-4952. 85. The formulation of any of claims 1-9, wherein the formulation comprises about 0.001 wt% to about 5 wt% of the one or more surfactant. 86. The formulation of any of claims 1-9, wherein the formulation comprises about 0.01 wt% to about 2.5 wt% of the one or more surfactant. 87. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 1 wt% of the one or more surfactant. 88. The formulation of any of claims 1-9, wherein the formulation comprises about 1 wt% of the one or more surfactant. 89. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.2 wt% of X-22-4952. 90. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.15 wt% of X-22-4952. 91. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% of X- 22-4952. 92. The formulation of any of claims 1-9, wherein the formulation comprises about 0.15 wt% of X-22-4952. 93. The formulation of any of claims 1-9, wherein the formulation comprises about 0.025 wt% to about 0.2 wt% of KF53. 94. The formulation of any of claims 1-9, wherein the formulation comprises about 0.025 wt% to about 0.1 wt% of KF53. 95. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% of KF53. 96. The formulation of any of claims 1-9, wherein the formulation comprises about 0.05 wt% of KF53. 97. The formulation of any of claims 1-9, wherein the formulation comprises about 0.025 wt% of KF53. 98. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.5 wt% of KF353A. 99. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% of KF353A. 100. The formulation of any of claims 1-9, wherein the formulation comprises about 0.13 wt% of KF353A. 101. The formulation of any of claims 1-9, wherein the formulation comprises about 0.2 wt% of KF353A. 102. The formulation of any of claims 1-9, wherein the formulation comprises about 0.3 wt% of KF353A. 103. The formulation of any of claims 1-9, wherein the formulation comprises about 0.001 wt% to about 0.1 wt% of KP341. 104. The formulation of any of claims 1-9, wherein the formulation comprises about 0.001 wt% of KP341. 105. The formulation of any of claims 1-9, wherein the formulation comprises about 0.05 wt% of KP341. 106. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% of KP341. 107. The formulation of any of claims 1-9 comprising the one or more water resistivity enhancer, wherein one or more water resistivity enhancer comprises one or more alkyl mono-carboxylic acids with 3 to 20 carbons, where the alkyl group may be a linear alkyl, a branched alkyl or a cyclic alkyl. 108. The formulation of any of claims 1-9 comprising the one or more water resistivity enhancer, wherein one or more water resistivity enhancer comprises one or more alkyl mono-carboxylic acids with 3 to 10 carbons, where the alkyl group may be a linear alkyl, a branched alkyl or a cyclic alkyl. 109. The formulation of any of claims 1-9 comprising the one or more water resistivity enhancer, wherein one or more water resistivity enhancer comprises one or more of propionic acid (PA), n- butyric acid, isobutyric acid (IBA), pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, tert-butylacetic acid, hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4- methylpentanoic acid, heptanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4- methylhexanoic acid, 5-methylhexanoic acid , 2,2-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 4,4-dimethylpentanoic acid, octanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2,2-dimethylhexanoic acid, 2,3-dimethylhexanoic acid, 2,4- dimethylhexanoic acid, 2,5-dimethylhexanoic acid, 3,3-dimethylhexanoic acid, 4.4-dimethylhexanoic acid, 5,5-dimethylhexanoic acid, 2-ethylhhexanoic acid, 3-ethylhhexanoic acid, 4-ethylhhexanoic acid, 2-propylpentanoic acid, nonanoic acid, 1-methyloctanoic acid, 2-methyloctanoic acid, 3- methyloctanoic acid, 4-methyloctanoic acid, 5-methyloctanoic acid, 6-methyloctanoic acid, 7- methyloctanoic acid, 2,2-dimethylheptanoic acid, 2,3-dimethylheptanoic acid, 2,4-dimethylheptanoic acid, 2,5-dimethylheptanoic acid, 3,3-dimethylheptanoic acid, 4,4-dimethylheptanoic acid, 5,5- dimethylheptanoic acid, 2-ethyl-2-methylhexanoic acid, 3-ethyl-3-methylhexanoic acid, 4-ethyl-4- methylhexanoic acid, 5,5-dimethylheptanoic acid, 2,2,5-trimethylhexanoic acid , 2,2,4- trimethylhexanoic acid , 2,2,3-trimethylhexanoic acid , 2,4,4-trimethylhexanoic acid, 2,5,5- trimethylhexanoic acid, 2-propylhexanoic acid, 3-propylhexanoic acid, 3-isopropylhexanoic acid, 2- isopropylhexanoic acid, 4-ethyl-5-methylhexanoic acid, 5,6-dimethylheptanoic acid, 2,3,4- trimethylhexanoic acid, 2,3,5-trimethylhexanoic acid, 3,4,5-trimethylhexanoic acid, 2-isopropyl-3,3- dimethylbutanoic acid, 2-(tert-butyl)pentanoic acid, 3-ethyl-4,4-dimethylpentanoic acid, 4,4,5- trimethylhexanoic acid, 3-ethyl-3,4-dimethylpentanoic acid, 2-isopropyl-2-methylpentanoic acid, decanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 4-methylnonanoic acid, 5- methylnonanoic acid, 6-methylnonanoic acid, 7-methylnonanoic acid, 8-methylnonanoic acid, 2,2- dimethyloctanoic acid, 3,3-dimethyloctanoic acid, 4,4-dimethyloctanoic acid, 5,5-dimethyloctanoic acid, 6,6-dimethyloctanoic acid, 7,7-dimethyloctanoic acid, 2,2,3-trimethylheptanoic acid ,2,2,4- trimethylheptanoic acid, 2,2,5-trimethylheptanoic acid, 2,2,6-trimethylheptanoic acid, 2,3,3- trimethylheptanoic acid, 2,4,4-trimethylheptanoic acid, 2,5,5-trimethylheptanoic acid, 2,6,6- trimethylheptanoic acid, 3,3,4-trimethylheptanoic acid, 3,3,5-trimethylheptanoic acid, 3,3,6- trimethylheptanoic acid, 4,5,5-trimethylheptanoic acid, 4,6,6-trimethylheptanoic acid, 5,6,6- trimethylheptanoic acid, 2,3,4,5-tetramethylhexanoic acid, 2-ethyl-3,4-dimethylhexanoic acid, 4- ethyl-2,3-dimethylhexanoic acid, 3-ethyl-2,4-dimethylhexanoic acid, 2,3,4-trimethylheptanoic acid, 2-isopropyl-3,3-dimethylpentanoic acid, 2-isopropyl-3,4-dimethylpentanoic acid, 2,3-diethyl-4- methylpentanoic acid, 2,2-diethyl-4-methylpentanoic acid, 3,3-diethyl-4-methylpentanoic acid, 2- ethyl-2-isopropylpentanoic acid, 2-ethyl-2-isopropyl-3-methylbutanoic acid, 3-isopropyl-3,4- dimethylpentanoic acid, 3-ethyl-3,4,4-trimethylpentanoic acid, 2,2-diethyl-3,3-dimethylbutanoic acid, 2-isopropyl-2,3,3-trimethylbutanoic acid, maleic acid, fumaric acid and combinations thereof. 110. The formulation of any of claims 1-9 comprising the one or more water resistivity enhancer, wherein the one or more water resistivity enhancer comprises one or more of propionic acid, n-butyric acid, isobutyric acid, t-butylacetic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, maleic acid, fumaric acid and combinations thereof. 111. The formulation of any of claims 1-9 comprising the one or more water resistivity enhancer, wherein the one or more water resistivity enhancer comprises propionic acid. 112. The formulation of any of claims 1-9 comprising the one or more water resistivity enhancer, wherein the one or more water resistivity enhancer comprises isobutyric acid. 113. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 2.0 wt % of the one or more water resistivity enhancer. 114. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 1.0 wt % of the one or more water resistivity enhancer. 115. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.5 wt % of the one or more water resistivity enhancer. 116. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.75 wt % of the one or more water resistivity enhancer. 117. The formulation of any of claims 1-9, wherein the formulation comprises about 1.0 wt% to about 2.0 wt % of the one or more water resistivity enhancer. 118. The formulation of any of claims 1-9, wherein the formulation comprises about 1.0 wt% to about 1.5 wt % of the one or more water resistivity enhancer. 119. The formulation of any of claims 1-9, wherein the formulation comprises about 1.5 wt% to about 2.0 wt % of the one or more water resistivity enhancer. 120. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% of the one or more water resistivity enhancer. 121. The formulation of any of claims 1-9, wherein the formulation comprises about 0.2 wt% of the one or more water resistivity enhancer. 122. The formulation of any of claims 1-9, wherein the formulation comprises about 0.3 wt% of the one or more water resistivity enhancer. 123. The formulation of any of claims 1-9, wherein the formulation comprises about 0.4 wt% of the one or more water resistivity enhancer. 124. The formulation of any of claims 1-9, wherein the formulation comprises about 0.5 wt% of the one or more water resistivity enhancer. 125. The formulation of any of claims 1-9, wherein the formulation comprises about 0.6 wt% of the one or more water resistivity enhancer. 126. The formulation of any of claims 1-9, wherein the formulation comprises about 0.7 wt% of the one or more water resistivity enhancer. 127. The formulation of any of claims 1-9, wherein the formulation comprises about 0.8 wt% of the one or more water resistivity enhancer. 128. The formulation of any of claims 1-9, wherein the formulation comprises about 0.9 wt% of the one or more water resistivity enhancer. 129. The formulation of any of claims 1-9, wherein the formulation comprises about 1.0 wt% of the one or more water resistivity enhancer 130. The formulation of any of claims 1-9, wherein the formulation comprises about 1.1 wt% of the one or more water resistivity enhancer. 131. The formulation of any of claims 1-9, wherein the formulation comprises about 1.2 wt% of the one or more water resistivity enhancer. 132. The formulation of any of claims 1-9, wherein the formulation comprises about 1.3 wt% of the one or more water resistivity enhancer. 133. The formulation of any of claims 1-9, wherein the formulation comprises about 1.4 wt% of the one or more water resistivity enhancer. 134. The formulation of any of claims 1-9, wherein the formulation comprises about 1.5 wt% of the one or more water resistivity enhancer. 135. The formulation of any of claims 1-9, wherein the formulation comprises about 1.6 wt% of the one or more water resistivity enhancer. 136. The formulation of any of claims 1-9, wherein the formulation comprises about 1.7 wt% of the one or more water resistivity enhancer. 137. The formulation of any of claims 1-9, wherein the formulation comprises about 1.8 wt% of the one or more water resistivity enhancer. 138. The formulation of any of claims 1-9, wherein the formulation comprises about 1.9 wt% of the one or more water resistivity enhancer. 139. The formulation of any of claims 1-9, wherein the formulation comprises about 2.0 wt% of the one or more water resistivity enhancer. 140. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 2.0 wt % of isobutyric acid. 141. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 1.0 wt % of isobutyric acid. 142. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.5 wt % of isobutyric acid. 143. The formulation of any of claims 1-9, wherein the formulation comprises about 0.2 wt% isobutyric acid. 144. The formulation of any of claims 1-9, wherein the formulation comprises about 0.3 wt% of isobutyric acid. 145. The formulation of any of claims 1-9, wherein the formulation comprises about 0.4 wt% of isobutyric acid. 146. The formulation of any of claims 1-9, wherein the formulation comprises about 1.6 wt% of isobutyric acid. 147. The formulation of any of claims 1-9, wherein the formulation comprises about 1.7 wt% of isobutyric acid. 148. The formulation of any of claims 1-9, wherein the formulation comprises about 1.8 wt% of isobutyric acid. 149. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 2.0 wt % of propionic acid. 150. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 1.0 wt % of propionic acid. 151. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.5 wt % of propionic acid. 152. The formulation of any of claims 1-9, wherein the formulation comprises about 0.2 wt% propionic acid. 153. The formulation of any of claims 1-9, wherein the formulation comprises about 0.3 wt% of propionic acid. 154. The formulation of any of claims 1-9, wherein the formulation comprises about 0.4 wt% of propionic acid. 155. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 2.0 wt % of 2-methylbutyric acid. 156. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 1.0 wt % of 2-methylbutyric acid. 157. The formulation of any of claims 1-9, wherein the formulation comprises about 0.1 wt% to about 0.5 wt % of 2-methylbutyric acid. 158. The formulation of any of claims 1-9, wherein the formulation comprises about 0.2 wt% 2- methylbutyric acid. 159. The formulation of any of claims 1-9, wherein the formulation comprises about 0.3 wt% of 2- methylbutyric acid. 160. The formulation of any of claims 1-9, wherein the formulation comprises about 0.4 wt% of 2- methylbutyric acid. 161. A crystalline S1 form of zirconium propionate (ZPPA) of formula the formula C72H128O64Zr12 x 4(C3H5O2) x 2(H2O) characterized by its powder X-ray diffractogram having peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees of 2θ. 162. The crystalline S1 form of zirconium propionate (ZPPA) of claim 161 characterized by a XRD pattern as depicted in FIG. 1. 163. A compound having the structure: wherein R1 and R2 are each independently H, -C(=O)C2H5, -C(=O)C3H7, or -C(=O)C4H9; and wherein R3 is independently -C(=O)C2H5, -C(=O)C3H7, or - C(=O)C4H9. 164. A compound (4,4’,4’’-tripropionyloxytriphenylmethane; THTPM-TP; 3D1) having the structure: 165. A compound (3D2) having the structure: 166. A compound (3D3) having the structure: 167. A formulation comprising one or more of 3D1 (4,4’,4’’-tripropionyloxytriphenylmethane; THTPM-TP), 3D2 and 3D3. 168. A compound having the structure: 169. A compound having the structure: 170. A compound having the structure: 171. A compound having the structure: 172. A compound having the structure: 173. A compound having the structure: 174. The use of a formulation according to any one of claims 1 to 160 or a crystalline S1 form of zirconium propionate (ZPPA) of claim 161 or 162 for forming a ZrOx film on a substrate. |
Table 2 [0067] In Table 2, “ ”represents an actual or potential direct valence bond from a protonated or unprotonated oxygen atom to another zirconium in an oligomer or polymeric zirconium complex, or alternatively a direct valence bond to H forming a Zr-OH moiety (i.e., that can also exist in equilibrium with free propionate groups or propionic acid molecules). Thus, the oligomer or polymeric species include linking/bridging moieties Zr-(OH) + -Zr and/or Zr-(O)-Zr and such oligomeric or polymeric species may also include, structurally, combinations of these linking moieties present along with some free ZrOH moieties. [0068] In one embodiment, the ZPP as used herein includes a monomer. In one embodiment, the ZPP as used herein includes an oligomer or polymeric species (or a mixture thereof) where the ZPP is about a 10-mer to about a 15-mer. In one embodiment, the ZPP as used herein includes an oligomer or polymeric species (or a mixture thereof) having an Mw of about a 10-mer to about a 15-mer of ZPP. In another embodiment, the ZPP has an average molecular weight of about 4,000 Da to about 10,000 Da. [0069] In one embodiment, the ZPP as used herein includes an oligomer or polymeric species (or a mixture thereof) including, in any sequence, the repeat units (where the monomer is defined by the structure in Table 2 corresponding to the letter of the respective row and the number of the respective column, e.g. A2 corresponds to structure in row A column 2): (A2) n (B2) m (C2) o (D2) p (A3) n1 (B3) m1 (C3) o1 (D3) p1 where each of n, n1, m, m1, o, o1, p and p1 = 0-10 and the total of n, n1, m, m1, o, o1, p and p1 is between 2 and 10. In a further aspect of this embodiment, the ZPP oligomeric and/or polymeric species constitute a mixture with one or more of ZPP monomer species A1, B1, C1 and D1. In a further aspect of this embodiment, n = 0. In a further aspect of this embodiment, m = 0. In a further aspect of this embodiment, o = 0. In a further aspect of this embodiment, m = 0. In a further aspect of this embodiment, p = 0. In a further aspect of this embodiment, n1 = 0. In a further aspect of this embodiment, m1 = 0. In a further aspect of this embodiment, o1 = 0. In a further aspect of this embodiment, m1 = 0. In a further aspect of this embodiment, p1 = 0. In a further aspect of this embodiment, the ZPP oligomeric and/or polymeric species will include one of A2 and A3 species in a terminal chain position(s). [0070] In one embodiment, the ZPP includes an oligomer or polymeric species that includes repeat units derived from free monomer species B1 and C1. In a further aspect of this embodiment, the repeat units derived from free monomer species B1 and C1 are in a wt % ratio of approximately 3:1. [0071] The hydroxyl group (which includes (i) bridging hydroxyl groups (i.e., protonated species) and (ii) any -OH groups from monomeric or polymeric species present) to propionate ligand ratio can be approximated by proton NMR. This can be accomplished by comparing the integration values of the -OH peaks and the -O(C=O)CH 2 -CH 3 peaks (attributable to the propionate ligands) in the proton NMR and then adjusting the ratio to account for the amount of water in a given ZPP sample (e.g., by a Karl-Fischer measurement) in view of an elemental analysis of the ZPP material being used. FIG.4 shows FTIR spectra of ZPP before (shown at bottom) and after (shown at top) thermal treatment (ca. > 100 ºC). After thermal treatment, there is a decrease in the -OH absorption band around 3400- 3600 cm -1 . This indicates that water, propionic acid and possibly ZrOH, are being removed by this thermal treatment. The water would be removed by evaporation while some ZrOH might be removed by formation of a Zr-O-Zr bridging group and free water. The water formed by any Zr-O-Zr bridging group formation would then also evaporate upon this thermal treatment. [0072] For example, a ZPP sample having an elemental analysis of C: 21.1, H:3.91, Zr:32 most closely aligns with an oligomer or polymeric material that predominantly includes ZPP monomer species B1 (where B1 may be present in free form and as part of the oligomeric or polymeric sample as B2 or B3). Based on this approximation, ZPP monomer species B1 has a calculated elemental analysis of C:26.56, H:4.46, Zr: 33.16 and a Mw of 271.38. If the ZPP sample has a water content of about 4.64 wt%, it would mean that ZPP sample includes at most about 95-96 wt% of the ZPP B1-B3 species. This equates to about 58 mole % of hydroxyl groups (i.e., bridging hydroxyl groups and any -OH groups from monomeric or polymeric species present) and about 42 mole % of water (due to the much larger effect of two -OH groups in the much higher Mw B1-B3 ZPP species compared to a lone -OH in a much lower Mw H 2 O molecule). This value then be used to adjust the integration values obtained from a proton NMR using a suitable proton NMR solvent (e.g., CDCl 3 , pyridine-d5 or THF- d8 with a small amount of D 2 O) where the solvent does not cutoff the spectrum the -OH peak. A preferred solvent is pyridine-d5 with a small amount of added D 2 O. [0073] For example, FIG.5 shows the proton NMR of ZPP in pyridine-d5 with a small amount of added D 2 O (with a blank control correcting for H 2 O impurity in the D 2 O ca.42.3 integration intensity) where the -OH peak is between about 5.5 and 6 ppm (integration = 156) and the propionate ligand (i.e., -CH 2 CH 3 ) peaks at about 0.5 to 2.5 ppm (integration = 539.5/5 protons = 107.9) are integrated (FIG. 6 compares the effect on the proton NMR based upon the addition of the D 2 O). The -OH peak is then adjusted to exclude H 2 O by multiplying by the estimated mole % of hydroxyl groups (i.e., 113.7 x 0.58 = 65.9). This leads to a ratio of -OH to propionate ligands of about 0.61 (i.e., 65.9 /107.9 = .61). As those skilled in the art will recognize, the -OH to propionate ligand ratio will have some variability due to the fact that the ZPP samples are oligomeric or polymeric and likely contain more than one of the ZPP species shown in Table 2. As such, this will affect estimating mole percent values for non- H 2 O hydroxyl groups and water in a given sample and the derived hydroxyl group to propionate ligand ratio. However, this value enables the ZPP being used in formulations thereof to be better characterized and is useful for adjusting the ZPP in a given formulation as needed in a specific application setting. [0074] Using the forgoing measurement methodology, in one embodiment, the ZPP includes an oligomer or polymeric species having hydroxyl group to propionate ligand ratio of about 0.5 to about 1.1 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.55 to about 1.05 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.6 to about 0.9 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.7 to about 0.8 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.5 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.55 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.6 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.65 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.7 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.75 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.8 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.85 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.9 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 0.55 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 1.0 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 1.05 as measured by proton NMR. In a further aspect of this embodiment, the hydroxyl group to propionate ligand ratio is about 1.1 as measured by proton NMR. [0075] In one embodiment, the ZPP includes zirconium propionate with CAS No.84057-80-7. [0076] In one embodiment, the ZPP includes between about 0.5 wt % to about 6 wt % of water. In one embodiment, the ZPP includes between about 1 wt % to about 5 wt% of water. In one embodiment, the ZPP includes between about 2 wt % to about 5 wt % of water. In one embodiment, the ZPP includes between about 3 wt % to about 5 wt% of water. In one embodiment, the ZPP includes between about 4 wt % to about 5 wt % of water. In one embodiment, the ZPP includes about 5 wt% of water or less. In one embodiment, the ZPP includes about 4 wt % of water or less. In one embodiment, the ZPP includes about 3 wt % of water or less. In one embodiment, the ZPP includes about 2 wt % of water or less. In one embodiment, the ZPP includes about 1 wt % of water or less. [0077] In one embodiment, the ZPP includes between about 0.5 wt % to about 6 wt %, preferably to about 5 wt % of propionic acid. In one embodiment, the ZPP includes between about 1 wt % to about 5 wt % of propionic acid. In one embodiment, the ZPP includes between about 2 wt% to about 5 wt % of propionic acid. In one embodiment, the ZPP includes between about 3 wt % to about 5 wt % of propionic acid. In one embodiment, the ZPP includes between about 4 wt % to about 5 wt % of propionic acid. In one embodiment, the ZPP includes about 5 wt % of propionic acid or less. In one embodiment, the ZPP includes about 4 wt % of propionic acid or less. In one embodiment, the ZPP includes about 3 wt % of propionic acid or less. In one embodiment, the ZPP includes about 2 wt % of propionic acid or less. In one embodiment, the ZPP includes about 1 wt % of propionic acid or less. [0078] As shown in FIG.7, the average (i.e., mean) diameter (nm) of ZPP can be measured by dynamic light scattering (DLS). In one embodiment, the ZPP has an average diameter (nm) of about 7.0 nm to about 12.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 7.5 nm to about 11.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.0 nm to about 11.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.5 nm to about 10.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 9.0 nm to about 10.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 7.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 7.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 9.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 9.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 10.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 10.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 11.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 11.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 12.0 nm. [0079] ZPP and ZPPA Formulations [0080] In another aspect, the disclosed and claimed subject matter relates to formulations and the preparation thereof that include ZPP and/or ZPPA. [0081] In one embodiment, the formulations include (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In a further aspect, the formulations consist essentially of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In a further aspect, the formulations consist of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). [0082] In another embodiment, the formulations above further include one or both of (iv) one or more surfactant and (v) one or more water resistivity enhancer. [0083] Thus, in another embodiment, the formulations include (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In a further aspect, the formulations consist essentially of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In a further aspect, the formulations consist of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’- trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred surfactant is an organosiloxane polymer, and in particular an organosiloxane polymer sold under the tradename X- 22-4952 (manufactured by Shin-Etsu Chemical Co., Ltd.; see https://www.shinetsusilicone- global.com/products/type/oil/detail/search/deg25.shtml). [0084] In another embodiment, the formulations include (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist essentially of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’- trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred water resistivity enhancer is isobutyric acid. [0085] In yet another embodiment, the formulations include (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents, (iv) one or more surfactant and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist essentially of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents, (iv) one or more surfactant and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist of (i) a zirconium-contain material selected from the group of (a) ZPPA, (b) ZPP) and (c) combinations thereof, (ii) one or more etch resistance modulator additive and (iii) one or more solvents, (iv) one or more surfactant and (v) one or more water resistivity enhancer. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred surfactant is X-22-4952. In each of these embodiments, a preferred water resistivity enhancer is isobutyric acid. [0086] In one embodiment, the formulations include (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In a further aspect, the formulations consist essentially of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In a further aspect, the formulations consist of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). [0087] In another embodiment, the formulations above further include one or both of (iv) one or more surfactant and (v) one or more water resistivity enhancer. [0088] Thus, in another embodiment, the formulations include (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In a further aspect, the formulations consist essentially of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In a further aspect, the formulations consist of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’- trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred surfactant is an organosiloxane polymer, and in particular an organosiloxane polymer sold under the tradename X- 22-4952 (manufactured by Shin-Etsu Chemical Co., Ltd.; see https://www.shinetsusilicone- global.com/products/type/oil/detail/search/deg25.shtml). [0089] In another embodiment, the formulations include (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist essentially of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’- trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred water resistivity enhancer is isobutyric acid. [0090] In yet another embodiment, the formulations include (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents, (iv) one or more surfactant and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist essentially of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents, (iv) one or more surfactant and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist of (i) ZPPA, (ii) one or more etch resistance modulator additive and (iii) one or more solvents, (iv) one or more surfactant and (v) one or more water resistivity enhancer. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred surfactant is X-22-4952. In each of these embodiments, a preferred water resistivity enhancer is isobutyric acid. [0091] In one embodiment, the formulations include (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In a further aspect, the formulations consist essentially of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In a further aspect, the formulations consist of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). [0092] In another embodiment, the formulations above further include one or both of (iv) one or more surfactant and (v) one or more water resistivity enhancer. [0093] Thus, in another embodiment, the formulations include (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In a further aspect, the formulations consist essentially of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In a further aspect, the formulations consist of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (iv) one or more surfactant. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred surfactant is X-22-4952. [0094] In another embodiment, the formulations include (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist essentially of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents and (v) one or more water resistivity enhancer. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’- trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred water resistivity enhancer is isobutyric acid. [0095] In yet another embodiment, the formulations include (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents, (iv) one or more surfactant and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist essentially of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents , (iv) one or more surfactant and (v) one or more water resistivity enhancer. In a further aspect, the formulations consist of (i) ZPP, (ii) one or more etch resistance modulator additive and (iii) one or more solvents , (iv) one or more surfactant and (v) one or more water resistivity enhancer. In each of these embodiments, a preferred etch resistance modulator additive is 4,4’,4’’-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is AZ ® ArF Thinner (i.e., a mixture of PGMEA and PGME). In each of these embodiments, a preferred surfactant is X-22-4952. In each of these embodiments, a preferred water resistivity enhancer is isobutyric acid. [0096] (ii) Etch Resistance Modulating Additive [0097] One or more etch resistance modulating additives are added for the purpose of improving the coating formation property of the coating to be formed, preventing intermixing with an upper layer (such as a silicon-containing interlayer and a resist), and/or preventing diffusion of a low- molecular-weight component into the upper layer. [0098] Exemplified embodiments of the etch resistance modulating additives include: melamine, guanamine, glycoluril, and urea compounds substituted by at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group; epoxy compounds; thioepoxy compounds; isocyanate compounds; azide compounds; and compounds having a double bond- containing group such as an alkenyl ether group. These may be used as an additive or may alternatively be introduced as a pendant group into a polymer side chain. Preferably, compounds containing a hydroxy group or multiple hydroxy groups can be used as the etch resistance modulating additives. [0099] Examples of the epoxy compounds include tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of the melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, and any mixture of any of such compounds. Examples of the guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, and any mixture of any of such compounds. Examples of the glycoluril compounds include tetramethylolglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, and any mixture of any of such compounds. Examples of the urea compounds include tetramethylolurea, and tetramethoxymethylurea. [0100] Examples of the compounds containing an alkenyl ether group include ethylene glycol divinyl ether, and triethylene glycol divinyl ether. [0101] Examples of the etch resistance modulating additives containing a hydroxy group or multiple hydroxy groups include those represented by structure (1). [0102] In structure (1), R11 is hydrogen or methyl and L 3 is a direct bond, substituted or unsubstituted C 1-3 alkyl, or substituted or unsubstituted C 7-16 aralkyl. L 3 is preferably a direct bond, C 1 alkyl, or C 15 aralkyl. The substituent of the alkyl or aralkyl is preferably hydrogen, methyl, C 6-11 aryl, or a substituent of structure (1a): or structure (1b): In a preferred aspect, L 3 is unsubstituted C 1-3 alkyl or unsubstituted C 1-3 aralkyl. [0103] The following are exemplified embodiments of the etch resistance modulating additives represented by structure (1). The disclosed and claimed subject matter is not limited to these examples.
Table 3 [0104] Other examples of the etch resistance modulating additives containing a hydroxy group or multiple hydroxy groups include those having monomeric, dimeric (two) or more such as trimeric phenolic compound, tetramer phenol moieties, or higher (e.g., 10 phenolic moieties) where the phenolic moieties in these compounds are linked together through a linking group such as an alkylene moiety, an oxy moiety, a -SO 2 - moiety and the like. Non-limiting examples of such compounds are shown in structures (2), (2A), (2B), (3), (3A), (3B), (3C), (3D) and (4) to (18), wherein the linking groups Xp and Xpa are independently selected from a -O-, -CH 2 -, -C(CH 3 ) 2 -, -SO 2 -; Rp1 is hydrogen or an alkyl moiety, Rp2, Rp3, Rp4, Rp5 are independently selected from hydrogen or an alkyl moiety.
Table 4 [0105] In one embodiment, the etch resistance modulating additive has structure (3), as described above. In a further aspect of this embodiment, the etch resistance modulating additives has structure (3C) as described above (i.e., 4,4’,4’’-trihydroxytriphenylmethane; THTPM). [0106] In a further aspect of this embodiment, the etch resistance modulating additives has structure (3D) as described above. In one aspect of this embodiment, each of R 1 and R 2 is a propionyl group (i.e., 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP; 3D 1 )): In another aspect of this embodiment, one of R 1 and R 2 is a propionyl group and the other of R 1 and R 2 is hydrogen (i.e., 3D 2 ):
In another aspect of this embodiment, each of R 1 and R 2 is hydrogen (i.e., 3D 3 ). . [0107] In a further embodiment, the etch resistance modulating additive is a mixture of more than one etch resistance modulating additive. In one aspect of this embodiment, the mixture includes the etch resistance modulating additives having structure (3C) (i.e., 4,4’,4’’- trihydroxytriphenylmethane; THTPM). In one aspect of this embodiment, the mixture includes the etch resistance modulating additive having structure (3D 1 ) (i.e., 4,4’,4’’- tripropionyloxytriphenylmethane (THTPM-TP)). In one aspect of this embodiment, the mixture includes the etch resistance modulating additive having structure (3C) (i.e., 4,4’,4’’- trihydroxytriphenylmethane; THTPM) and (3D 1 ) (i.e., 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP)). In another aspect of this embodiment, the mixture includes the etch resistance modulating additives having structure (3C) (i.e., 4,4’,4’’-trihydroxytriphenylmethane; THTPM) and one or more of the etch resistance modulating additives 3D 1 (THTPM-TP), 3D 2 and 3D 3 . [0108] Other polyphenol compounds or polymers can be used as well. Examples of suitable Polyphenol compounds or polymers include those disclosed in U.S. Patent No. 9,274,426 and/or U.S. Patent Application Publication No.2012/0251956. Phenolic OH groups can be protected by acid labile groups, such as ester groups, acetal group, also heterocyclic structure can be included in the structures. [0109] Other etch resistance modulating additives are also contemplated. In some embodiments, etch resistance modulating additives (19) or (20) can be included. These crosslinking agents are available, for example, from Sanwa Chemical Co., Ltd., Honshu Chemical Industry Co., Ltd., Asahi Yukizai Corporation, and Nippon Carbide Industries Co., Inc. Table 5 [0110] In one embodiment of the disclosed and claimed subject matter, the amount of the etch resistance modulating additives is preferably approximately 0.1 wt % to approximately 30 wt % of total solid components in composition. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 1 wt% to approximately 20 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 2 wt % to approximately 15 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 5 wt % to approximately 12 wt %. In one embodiment of the disclosed and claimed subject matter, the amount of the etch resistance modulating additives is preferably approximately 0.1 wt % to approximately 1 wt % of total solid components in composition. In one embodiment of the disclosed and claimed subject matter, the amount of the etch resistance modulating additives is preferably approximately 0.5 wt % to approximately 1 wt % of total solid components in composition. In one embodiment of the disclosed and claimed subject matter, the amount of the etch resistance modulating additives is preferably approximately 0.5 wt % to approximately 0.75 wt % of total solid components in composition. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 0.5 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 0.6 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 0.7 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 0.8 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 0.9 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 1 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 2 wt%. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 3 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 4 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 5 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 6 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 7 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 8 wt%. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 9 wt %. In a further aspect of this embodiment, the amount of the etch resistance modulating additives is approximately 10 wt %. [0111] In one embodiment, the formulation includes about 0.5 wt% to about 5 wt % of 4,4’,4’’- trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 2 wt% to about 5 wt % of 4,4’,4’’-trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 0.5 wt% to about 0.75 wt % of 4,4’,4’’- trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 0.5 wt% to about 1 wt % of 4,4’,4’’-trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 1 wt% to about 2 wt % of 4,4’,4’’- trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 3 wt% to about 4 wt % of 4,4’,4’’-trihydroxytriphenylmethane (THTPM). [0112] In a further aspect of this embodiment, the formulation includes about 0.5 wt% of 4,4’,4’’-trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 0.6 wt% of 4,4’,4’’-trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 0.7 wt% of 4,4’,4’’- trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 0.8 wt% of 4,4’,4’’-trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 0.9 wt% of 4,4’,4’’-trihydroxytriphenylmethane (THTPM). In a further aspect of this embodiment, the formulation includes about 1 wt% of 4,4’,4’’- trihydroxytriphenylmethane (THTPM). [0113] In one embodiment, the formulation includes about 0.5 wt% to about 5 wt % of 4,4’,4’’- tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 2 wt% to about 5 wt % of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.5 wt% to about 0.75 wt % of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.5 wt% to about 1 wt % of 4,4’,4’’- tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.5 wt% to about 1 wt % of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 1 wt% to about 2 wt % of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 3 wt% to about 4 wt % of 4,4’,4’’- tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.5 wt% of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.6 wt% of 4,4’,4’’- tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.7 wt% of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.8 wt% of 4,4’,4’’- tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 0.9 wt% of 4,4’,4’’-tripropionyloxytriphenylmethane (THTPM-TP). In a further aspect of this embodiment, the formulation includes about 1 wt% of 4,4’,4’’- tripropionyloxytriphenylmethane (THTPM-TP). [0114] In one embodiment, the formulation includes about 0.5 wt % to about 0.75 wt% of either of NF0327, NF0A28, NF71A7 or NF0127, as shown in table 4 above. In a further aspect of this embodiment, the formulation includes about 0.6 wt% of either of NF0327, NF0A28, NF71A7 or NF0127, as shown in table 4 above. [0115] In some embodiment, the formulations include more than one etch resistance modulating additive. [0116] (iii) Solvent(s) [0117] As noted above, the ZPP and/or ZPPA formulations include one or more solvents suitable for use in spin casting. In this regard, the one or more solvents can include a glycol ether derivative, a glycol ether ester derivative a carboxylate, a carboxylate of a di-basic acid, a dicarboxylate of a glycol, a hydroxy carboxylate, a ketone ester, an alkyloxy carboxylic acid ester, a ketone derivative, a ketone ether derivative, a ketone alcohol derivative, an amide derivative and mixtures thereof. [0118] In some embodiments, the one or more solvents is a glycolic solvents chosen from alkylene diols, oligo(alkylenoxy) alkylene ) diols [HO-(alkylene-O-alkylene-O)n-H] (n= 1 to 4), monoalkyl dialkyl ethers, and alkyl carboxylates /alkyl ethers derivatives of alkylene diol monoalkyl and also to mixtures of at least two of these solvents. In a more specific embodiment, the one or more solvent includes an alkylene diol . In another more specific embodiment, the one or more solvent includes an oligo(alkylenoxy) alkylene) diol [HO-(alkylene-O-alkylene-O)n-H] (n= 1 to 4). In another more specific embodiment, the one or more solvent includes a monoalkyl carboxylates of an alkylene diol. In yet another more specific embodiment, the one or more solvent includes a monoalkyl carboxylate of oligo(alkylenoxy) alkylene) diol [HO-(alkylene-O-alkylene-O)n-H] (n= 1 to 4). In a more specific embodiment of this aspect, the alkylene moieties in these glycolic derivatives may be a C- 2 to C-6 linear alkylene, or a C-3 to C-7 branched alkylene or in the case of the oligo oligo(alkylenoxy) alkylene) a mixture of these. In a more specific embodiment, the alkyl moieties in the monoalkyl ethers, dialkyl ether these are individually selected from methyl, ethyl, propyl, isopropyl, butyl, tertbutyl, isobutyl. In a more specific embodiment, these glycolic solvents containing alkyl carboxylate these alkyl carboxylates are selected from acetate, propionate, isobutyrate, and butyrate. In a more specific embodiment, the glycolic derivative solvent is selected from ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate (PGMEA), propyleneglycol monomethyl ether (PGME), and di(propylene glycol) methyl ether (DPGME) or a mixture of at least two of these solvents. In a more specific embodiment, the glycolic derivative solvent is selected from propylene glycol, propylene glycol monomethyl ether acetate (PGMEA), propyleneglycol monomethyl ether (PGME) and di(propylene glycol) methyl ether (DPGME) or a mixture of at least two of these solvents. [0119] The term “dipropylene glycol” also designated by dipropylene glycol dimethyl ether or with the abbreviation DPGDME is a mixture with the general formula CH 3 OC 3 H 6 OC 3 H 6 OCH 3 . This mixture also has the synonymous name bis(methoxypropyl) ether, DMFG, Proglyde™, DMM and Proglyme™. [0120] In some embodiments, the formulations preferably include one or both of PGMEA (propylene glycol monomethyl ether acetate) and PGME (propyleneglycol monomethyl ether). One preferred solvent is AZ ® ArF thinner. AZ ® ArF thinner is a trivial name for a mixture of 70 wt% of PGMEA and 30 wt% of PGME. Another preferred solvent is AZ ® EBR7030 which is a mixture of 30 wt% of PGMEA and 70 wt% of PGME. Other weight ratio mixtures of PGMEA and PGME can also be used such as a mixture of 60 wt% of PGMEA and 40 wt% of PGME etc., or 100% PGMEA. [0121] In one embodiment, the formulations include from about 70 wt% to about 98 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include from about 70 wt% to about 80 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include from about 80 wt% to about 90 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include from about 90 wt% to about 95 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include from about 90 wt% to about 98 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 90 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 91 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 92 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 93 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 94 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 95 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 96 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 97 wt% of the one or more solvents. In a further aspect of this embodiment, the formulations include about 98 wt% of the one or more solvents. [0122] In one embodiment, the formulation includes about 93 wt% of AZ ® ArF Thinner. [0123] In one embodiment, the formulation includes about 94 wt% of AZ ® ArF Thinner. [0124] In one embodiment, the formulation includes about 95 wt% of AZ ® ArF Thinner. [0125] In one embodiment, the formulation includes about 93 wt% of PGMEA. [0126] In one embodiment, the formulation includes about 94 wt% of PGMEA. [0127] In one embodiment, the formulation includes about 95 wt% of PGMEA. [0128] (iv) Surfactant(s) [0129] As noted above, in some embodiments of ZPP and/or ZPPA formulations can optionally include one or more surfactants. In some embodiments, the amount of the surfactant is from about 0.001 wt% to about 5 wt % of the composition, preferably from about 0.01 wt% to about 2.5 wt% and, more preferably, from about 0.1 wt% to about 1.0 wt% of the composition. In some embodiments, the ZPP and/or ZPPA formulations can include about 1.0 wt% or less of a surfactant. [0130] There is no particular restriction with regard to the surfactant, and the examples of it include a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether; a polyoxyethylene alkylaryl ether such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; a polyoxyethylene polyoxypropylene block copolymer; a sorbitane fatty acid ester such as sorbitane monolaurate, sorbitane monovalmitate, and sorbitane monostearate; a nonionic surfactant of a polyoxyethylene sorbitane fatty acid ester such as polyoxyethylene sorbitane monolaurate, polyoxyethylene sorbitane monopalmitate, polyoxyethylene sorbitane monostearate, polyethylene sorbitane trioleate, and polyoxyethylene sorbitane tristearate; a fluorinated surfactant such as Brij 30, Brij 32 (Croda, USA), Triton X-100 (Trion Chemical, USA), F-Top EF301, EF303, and EF352 (Jemco Inc. Japan), Megaface F171, F172, F173, R08, R30, R90, and R94 (DIC Corp, Japan), Florad FC-430, FC-431, FC-4430, and FC-4432 (3M, USA), Asahi Guard AG710, Surflon S-381, S-382, S-386, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30, and KH-40 (Asahi Glass Co., Ltd. Japan); an organosiloxane polymer or a silicone-containing surfactant such as KF53, KP-341, KP-351, X22-4952, X70-092, and X70-093 (ShinEtsu Silicone Co. Ltd., Japan); and an acrylic acid or a methacrylic acid polymer such as Polyflow No.75 and No.95 (Kyoeisha Yushikagaku Kogyo K. K. Japan). [0131] In some embodiments, the ZPP and/or ZPPA formulations include one or more silicon containing surfactants. In one aspect of these embodiments, a preferred surfactant is an organosiloxane polymer, and in particular an organosiloxane polymer sold under the tradename X-22-4952. [0132] In one embodiment, the formulation includes about 0.1 wt% to about 0.2 wt% of X-22-4952. [0133] In one embodiment, the formulation includes about 0.1 wt% to about 0.15 wt% of X- 22-4952. [0134] In one embodiment, the formulation includes about 0.1 wt% of X-22-4952. [0135] In one embodiment, the formulation includes about 0.15 wt% of X-22-4952. [0136] In one embodiment, the formulation includes about 0.025 wt% to about 0.2 wt% of KF53. [0137] In one embodiment, the formulation includes about 0.025 wt% to about 0.1 wt% of KF53. [0138] In one embodiment, the formulation includes about 0.1 wt% of KF53. [0139] In one embodiment, the formulation includes about 0.05 wt% of KF53. [0140] In one embodiment, the formulation includes about 0.025 wt% of KF53. [0141] In one embodiment, the formulation includes about 0.1 wt% to about 0.5 wt% of KF353A. [0142] In one embodiment, the formulation includes about 0.1 wt% of KF353A. [0143] In one embodiment, the formulation includes about 0.13 wt% of KF353A. [0144] In one embodiment, the formulation includes about 0.2 wt% of KF353A. [0145] In one embodiment, the formulation includes about 0.3 wt% of KF353A. [0146] In one embodiment, the formulation includes about 0.001 wt% to about 0.1 wt% of KP341. [0147] In one embodiment, the formulation includes about 0.001 wt% of KP341. [0148] In one embodiment, the formulation includes about 0.05 wt% of KP341. [0149] In one embodiment, the formulation includes about 0.1 wt% of KP341. [0150] In some embodiments, the compositions of the disclosed and claimed subject matter will be free of or substantially free of surfactants. [0151] (v) Water Resistivity Enhancer [0152] As noted above, the ZPP and/or ZPPA formulations optionally include one or more water resistivity enhancers to affect or improve resistance to moisture. [0153] In one embodiment, the one or more water resistivity enhancers includes one or more alkyl mono-carboxylic acids with 3 to 20 carbons, where the alkyl group may be a linear alkyl, a branched alkyl or a cyclic alkyl. In a further aspect of this embodiment the one or more alkyl mono- carboxylic acid has from 3 to 10 carbon atoms. [0154] In another embodiment, the one or more water resistivity enhancers includes one or more of carboxylic acids, such as propionic acid (PA), n-butyric acid, isobutyric acid (IBA), pentanoic acid, 2- methylbutanoic acid, 3-methylbutanoic acid, tert-butylacetic acid, hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, heptanoic acid, 2-methylhexanoic acid, 3- methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid , 2,2-dimethylpentanoic acid, 2,3- dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 4,4-dimethylpentanoic acid, octanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5- methylheptanoic acid, 6-methylheptanoic acid, 2,2-dimethylhexanoic acid, 2,3-dimethylhexanoic acid, 2,4- dimethylhexanoic acid, 2,5-dimethylhexanoic acid, 3,3-dimethylhexanoic acid, 4.4-dimethylhexanoic acid, 5,5-dimethylhexanoic acid, 2-ethylhhexanoic acid, 3-ethylhhexanoic acid, 4-ethylhhexanoic acid, 2- propylpentanoic acid, nonanoic acid, 1-methyloctanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 4-methyloctanoic acid, 5-methyloctanoic acid, 6-methyloctanoic acid, 7-methyloctanoic acid, 2,2- dimethylheptanoic acid, 2,3-dimethylheptanoic acid, 2,4-dimethylheptanoic acid, 2,5-dimethylheptanoic acid, 3,3-dimethylheptanoic acid, 4,4-dimethylheptanoic acid, 5,5-dimethylheptanoic acid, 2-ethyl-2- methylhexanoic acid, 3-ethyl-3-methylhexanoic acid, 4-ethyl-4-methylhexanoic acid, 5,5- dimethylheptanoic acid, 2,2,5-trimethylhexanoic acid , 2,2,4-trimethylhexanoic acid , 2,2,3- trimethylhexanoic acid , 2,4,4-trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, 2-propylhexanoic acid, 3-propylhexanoic acid, 3-isopropylhexanoic acid, 2-isopropylhexanoic acid, 4-ethyl-5- methylhexanoic acid, 5,6-dimethylheptanoic acid, 2,3,4-trimethylhexanoic acid, 2,3,5-trimethylhexanoic acid, 3,4,5-trimethylhexanoic acid, 2-isopropyl-3,3-dimethylbutanoic acid, 2-(tert-butyl)pentanoic acid, 3- ethyl-4,4-dimethylpentanoic acid, 4,4,5-trimethylhexanoic acid, 3-ethyl-3,4-dimethylpentanoic acid, 2- isopropyl-2-methylpentanoic acid, decanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 4- methylnonanoic acid, 5-methylnonanoic acid, 6-methylnonanoic acid, 7-methylnonanoic acid, 8- methylnonanoic acid, 2,2-dimethyloctanoic acid, 3,3-dimethyloctanoic acid, 4,4-dimethyloctanoic acid, 5,5-dimethyloctanoic acid, 6,6-dimethyloctanoic acid, 7,7-dimethyloctanoic acid, 2,2,3-trimethylheptanoic acid ,2,2,4-trimethylheptanoic acid, 2,2,5-trimethylheptanoic acid, 2,2,6-trimethylheptanoic acid, 2,3,3- trimethylheptanoic acid, 2,4,4-trimethylheptanoic acid, 2,5,5-trimethylheptanoic acid, 2,6,6- trimethylheptanoic acid, 3,3,4-trimethylheptanoic acid, 3,3,5-trimethylheptanoic acid, 3,3,6- trimethylheptanoic acid, 4,5,5-trimethylheptanoic acid, 4,6,6-trimethylheptanoic acid, 5,6,6- trimethylheptanoic acid, 2,3,4,5-tetramethylhexanoic acid, 2-ethyl-3,4-dimethylhexanoic acid, 4-ethyl-2,3- dimethylhexanoic acid, 3-ethyl-2,4-dimethylhexanoic acid, 2,3,4-trimethylheptanoic acid, 2-isopropyl-3,3- dimethylpentanoic acid, 2-isopropyl-3,4-dimethylpentanoic acid, 2,3-diethyl-4-methylpentanoic acid, 2,2- diethyl-4-methylpentanoic acid, 3,3-diethyl-4-methylpentanoic acid, 2-ethyl-2-isopropylpentanoic acid, 2- ethyl-2-isopropyl-3-methylbutanoic acid, 3-isopropyl-3,4-dimethylpentanoic acid, 3-ethyl-3,4,4- trimethylpentanoic acid, 2,2-diethyl-3,3-dimethylbutanoic acid, 2-isopropyl-2,3,3-trimethylbutanoic acid, maleic acid, fumaric acid and combinations thereof. In one aspect of this embodiment, the one or more water resistivity enhancers includes one or more of propionic acid, n-butyric acid, isobutyric acid, t- butylacetic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, maleic acid, fumaric acid and combinations thereof. In one aspect of this embodiment, the one or more water resistivity enhancers includes pentanoic acid. In another aspect of this embodiment, the one or more water resistivity enhancers includes isobutyric acid. In another aspect of this embodiment, the one or more water resistivity enhancers includes 2-methylbutyric acid. In another aspect of this embodiment, the one or more water resistivity enhancers includes propionic acid. [0155] In one embodiment, the amount of the water resistivity enhancer is from about 1 wt% to about 15 wt% of the formulation. In a further aspect of this embodiment, the amount of the water resistivity enhancer is from about 2 wt% to about 10 wt% of the formulation. In a further aspect of this embodiment, the amount of the water resistivity enhancer is from about 3 wt% to about 8 wt% of the formulation. In a further aspect of this embodiment, the amount of the water resistivity enhancer is from about 4 wt% to about 6 wt% of the formulation. In a further aspect of this embodiment, the amount of the water resistivity enhancer is from about 5 wt% to about 6 wt% of the formulation. In a further aspect of this embodiment, the amount of the water resistivity enhancer is about 5 wt% of the formulation. In a further aspect of this embodiment, the amount of the water resistivity enhancer is about 5.6 wt% of the formulation. In a further aspect of this embodiment, the amount of the water resistivity enhancer is about 6 wt% of the formulation. [0156] In one embodiment, the formulation includes about 0.1 wt% to about 2.0 wt % of the one or more water resistivity enhancer. [0157] In one embodiment, the formulation includes about 0.1 wt% to about 1.0 wt % of the one or more water resistivity enhancer. [0158] In one embodiment, the formulation includes about 0.1 wt% to about 0.5 wt % of the one or more water resistivity enhancer. [0159] In one embodiment, the formulation includes about 0.1 wt% to about 0.75 wt % of the one or more water resistivity enhancer. [0160] In one embodiment, the formulation includes about 1.0 wt% to about 2.0 wt % of the one or more water resistivity enhancer. [0161] In one embodiment, the formulation includes about 1.0 wt% to about 1.5 wt % of the one or more water resistivity enhancer. [0162] In one embodiment, the formulation includes about 1.5 wt% to about 2.0 wt % of the one or more water resistivity enhancer. [0163] In one embodiment, the formulation includes about 0.1 wt% of the one or more water resistivity enhancer. [0164] In one embodiment, the formulation includes about 0.2 wt% of the one or more water resistivity enhancer. [0165] In one embodiment, the formulation includes about 0.3 wt% of the one or more water resistivity enhancer. [0166] In one embodiment, the formulation includes about 0.4 wt% of the one or more water resistivity enhancer. [0167] In one embodiment, the formulation includes about 0.5 wt% of the one or more water resistivity enhancer. [0168] In one embodiment, the formulation includes about 0.6 wt% of the one or more water resistivity enhancer. [0169] In one embodiment, the formulation includes about 0.7 wt% of the one or more water resistivity enhancer. [0170] In one embodiment, the formulation includes comprises about 0.8 wt% of the one or more water resistivity enhancer. [0171] In one embodiment, the formulation includes comprises about 0.9 wt% of the one or more water resistivity enhancer. [0172] In one embodiment, the formulation includes about 1.0 wt% of the one or more water resistivity enhancer. [0173] In one embodiment, the formulation includes about 1.1 wt% of the one or more water resistivity enhancer. [0174] In one embodiment, the formulation includes about 1.2 wt% of the one or more water resistivity enhancer. [0175] In one embodiment, the formulation includes about 1.3 wt% of the one or more water resistivity enhancer. [0176] In one embodiment, the formulation includes about 1.4 wt% of the one or more water resistivity enhancer. [0177] In one embodiment, the formulation includes comprises about 1.5 wt% of the one or more water resistivity enhancer. [0178] In one embodiment, the formulation includes about 1.6 wt% of the one or more water resistivity enhancer. [0179] In one embodiment, the formulation includes about 1.7 wt% of the one or more water resistivity enhancer. [0180] In one embodiment, the formulation includes about 1.8 wt% of the one or more water resistivity enhancer. [0181] In one embodiment, the formulation includes about 1.9 wt% of the one or more water resistivity enhancer. [0182] In one embodiment, the formulation includes about 2.0 wt% of the one or more water resistivity enhancer. [0183] In one embodiment, the formulation includes about 0.1 wt% to about 2.0 wt % of isobutyric acid. [0184] In one embodiment, the formulation includes about 0.1 wt% to about 1.0 wt % of isobutyric acid. [0185] In one embodiment, the formulation includes about 0.1 wt% to about 0.5 wt % of isobutyric acid. [0186] In one embodiment, the formulation includes about 0.2 wt% isobutyric acid. [0187] In one embodiment, the formulation includes about 0.3 wt% of isobutyric acid. [0188] In one embodiment, the formulation includes about 0.4 wt% of isobutyric acid. [0189] In one embodiment, the formulation includes about 1.6 wt% of isobutyric acid. [0190] In one embodiment, the formulation includes about 1.7 wt% of isobutyric acid. [0191] In one embodiment, the formulation includes about 1.8 wt% of isobutyric acid. [0192] In one embodiment, the formulation includes about 0.1 wt% to about 2.0 wt % of propionic acid. [0193] In one embodiment, the formulation includes about 0.1 wt% to about 1.0 wt % of propionic acid. [0194] In one embodiment, the formulation includes about 0.1 wt% to about 0.5 wt % of propionic acid. [0195] In one embodiment, the formulation includes about 0.2 wt% propionic acid. [0196] In one embodiment, the formulation includes about 0.3 wt% of propionic acid. [0197] In one embodiment, the formulation includes about 0.4 wt% of propionic acid. [0198] In one embodiment, the formulation includes about 0.1 wt% to about 2.0 wt % of 2- methylbutyric acid. [0199] In one embodiment, the formulation includes about 0.1 wt% to about 1.0 wt % of 2- methylbutyric acid. [0200] In one embodiment, the formulation includes about 0.1 wt% to about 0.5 wt % of 2- methylbutyric acid. [0201] In one embodiment, the formulation includes about 0.2 wt% 2-methylbutyric acid. [0202] In one embodiment, the formulation includes about 0.3 wt% of 2-methylbutyric acid. [0203] In one embodiment, the formulation includes about 0.4 wt% of 2-methylbutyric acid. [0204] III. Method of Preparing ZPPA-Based Films [0205] Another aspect of the disclosed and claimed subject matter relates to the use of ZPPA and formulations thereof to form ZrOx films. [0206] Solutions including ZPPA can be coated on a substrate using techniques well known to those skilled in the art, such as dipping, spin coating or spraying. Preferably the solutions are spin coated. The film thickness of the underlayer coating ranges from about 5 nm to about 400 nm, preferably about 10 nm to about 120 nm. The coating is further heated on a hot plate or convection oven for a sufficient length of time to remove any residual solvent and induce curing, and thus insolubilizing the antireflective coating to prevent intermixing between the antireflective coating and the layer to be coated above it. The preferred temperatures are generally below about 450 °C, and can range, for example, from about 90 °C to about 300 °C, or about 160 °C to about 250 °C. The coating may be coated over other layer or layers of antireflective coating(s), such as a high carbon (greater than about 80% or about 85% or about 90%) content antireflective coating. [0207] The substrates over which the underlayer coating is formed can be any of those typically used in the semiconductor industry. Suitable substrates include, without limitation, low dielectric constant materials, silicon, silicon substrate coated with a metal surface, copper coated silicon wafer, copper, aluminum, polymeric resins, silicon dioxide, metals, doped silicon dioxide, silicon nitride, tantalum, polysilicon, ceramics, aluminum/copper mixtures; gallium arsenide and other such Group III/V compounds. The substrate may also be other antireflective coatings or underlayers, such as high carbon underlayers coated over the above-mentioned substrates. The substrate may comprise any number of layers made from the materials described above. [0208] A film of photoresist can be coated on top of the underlayer coating and baked to substantially remove the photoresist solvent. An edge bead remover may be applied after the coating steps to clean the edges of the substrate using processes well known in the art. Photoresists can be any of the types used in the semiconductor industry, provided the photoactive compound in the photoresist and the antireflective coating substantially absorb at the exposure wavelength used for the imaging process. Photoresists useful for immersion lithography are preferred. Typically, photoresists suitable for imaging with immersion lithography may be used, where such photoresists have a refractive index higher than 1.85 and also are hydrophobic having water contact angle in the range of about 75° to about 95°. [0209] There are several major deep ultraviolet (uv) exposure technologies that have provided significant advancement in miniaturization, and these radiation of 248 nm, 193 nm and 13.5 nm. Chemically amplified photoresists are often used. Photoresists for 248 nm have typically been based on substituted polyhydroxystyrene and its copolymers/onium salts, such as those described in U.S. Patent Numbers 4,491,628 and US 5,350,660. On the other hand, photoresists for exposure at 193 nm and 157 nm require non-aromatic polymers since aromatics are opaque at this wavelength. U.S. Patent Numbers 5,843,624 and 6,866,984 disclose photoresists useful for 193 nm exposure. Generally, polymers containing alicyclic hydrocarbons are used for photoresists for exposure below 200 nm. Alicyclic hydrocarbons are incorporated into the polymer for many reasons, primarily since they have relatively high carbon to hydrogen ratios which improve etch resistance, they also provide transparency at low wavelengths and they have relatively high glass transition temperatures. U.S. Patent Number 5,843,624 discloses polymers for photoresist that are obtained by free radical polymerization of maleic anhydride and unsaturated cyclic monomers. Any of the known types of 193 nm photoresists may be used, such as those described in U.S. Patent Numbers 6,447,980 and 6,723,488 which are hereby incorporated herein by reference. Photoresists that absorb extreme ultraviolet radiation (EUV) of 13.5nm are also useful and are known in the art. Thus, photoresists absorbing in the range of about 12 nm to about 250 nm are useful. The novel coatings can also be used in process with nanoimprinting and e-beam resists. [0210] After the coating process, the photoresist can be image wise exposed. The exposure may be done using typical exposure equipment. The exposed photoresist is then developed in an aqueous developer to remove the treated photoresist. The developer is preferably an aqueous alkaline solution including, for example, tetramethylammonium hydroxide (TMAH), typically 2.38 wt% TMAH. The developer may further include surfactant(s). An optional heating step can be incorporated into the process prior to development and after exposure. [0211] The process of coating and imaging photoresists is well known to those skilled in the art and is optimized for the specific type of photoresist used. The photoresist patterned substrate can then be dry etched with an etching gas or mixture of gases, in a suitable etch chamber to remove the exposed portions of the underlayers and optional other antireflective coatings. Various etching gases are known in the art for etching underlayer coatings, such as those comprising O 2 , CF 4 , CHF 3 , Cl 2 , HBr, SO 2 , CO, etc. In one embodiment, the article comprises a semiconductor substrate with a high carbon antireflective film, over which the novel zirconium underlayer is coated. A photoresist layer is coated above this. The photoresist is imaged as disclosed above and the underlayer is dry etched using gases comprising fluorocarbons. After the underlayer is etched, the high carbon film can be dry etched using oxygen or oxygen mixtures. [0212] In one embodiment, ZPPA and ZPP formulation thereof may be applied to a substrate with the following steps: a. ZPPA or ZPP formulation is poured on a silicon substrate and spin coated with the spin speed is adjusted to give desired thickness; and b. the coated silicon wafer is baked on a hotplate at different temperature and for different periods of time vary depending on desired properties. [0213] In one embodiment, the baking temperature is approximately 200 C to 600C and baking time 30sec to 1hr are selected. Typically baking temperature is 250 °C to approximately 500 °C and the baking time is approximately 60 sec. to approximately 300 sec. [0214] In another embodiment, the baking may be single step bake or multiple step bake (e.g. baking at approximately 250 °C/approximately 60 sec, then approximately 450 °C/approximately 120 sec). [0215] EXAMPLES [0216] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. The examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way. [0217] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter, including the descriptions provided by the following examples, covers the modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents. [0218] Materials and Methods: [0219] The reactions were conducted under air/moisture free environment. Propionic acid (Millipore Sigma), propionic anhydride (Millipore Sigma) and 1-methoxy-2-propanol (PGME; EMD Performance Materials) were kept over molecular sieves (3 Å) and were then distilled under an inert atmosphere and atmospheric pressure. [0220] A SuperNova (Oxford Diffraction) Diffractometer with Atlas CCD Detector was used to determine X-Ray crystallography structure. Radiation: Cu Ka (1.5418 Å); monochromator: X-ray mirrors; measuring software: CrysAlisPro 39.46; evaluation software: OLEX 2 1.2.8. [0221] The simultaneous thermal analysis (STA) was carried out on an STA 449 F3 Jupiter from Netzsch Gerätebau GmbH with a heating rate of 10 oC/min from 30 oC to 1000 oC under inert and air conditions. [0222] Dynamic light scattering (DLS) measurements used to measure ZPP and ZPPA sizes were performed at 25 °C using a Malvern Zetasizer Nano-S - Model No. ZEN1600. [0223] A Tokyo Electron Ltd Clean Track ACT 8, ACT 12 or Mark 8 was used for Coating and baking of ZPPA or ZPP formulations. C, H and Zr content (wt%) were determined by Elemental Analysis by Intertek of Whitehouse, NJ. [0224] The refractive index (n) and the extinction coefficient (k) were measured on a J.A. Woollam VUV-VASE VU-302 Spectroscopic Ellipsometer. Samples were coated on Si wafer at target film thickness and baked at 250 °C/60 sec + 450 °C/90 sec and measured the optical parameters. [0225] Bulk etch rates were measured using TRION DUAL CHAMBER MINILOCK III as follows. ZPPA or ZPP formulation was spin coated on a silicon wafer, baked at 250 °C/60 sec + 450 °C/90 sec. Spin speed was adjusted to desired film thickness. The coated coupon wafers were loaded into the Trion etcher and etched setting Ar 80sccm, CF420sccm, Pressure 50mT, Top RF 1000W, Bot RF 400W, Etch time 120sec. The film thickness of the coupons was measured before and after the etching and bulk etch rate was obtained. [0226] XPS measurements were performed on Thermo Fisher Scientific – K-Alpha X-ray Photoelectron Spectrometer (XPS), KA1191 using the following testing protocol: The wafers were coated with the MHM at target film thickness and baked at 250 °C/60 sec + 450 °C/90sec. The wafers were then submitted for XPS analysis. Depending on the film thickness of each wafer, after XPS measurement completed, Ar Sputtering rate and atomic % is be reported. [0227] Moisture sensitivity was evaluated using Humidity control chamber (Ets Electro-tech systems Inc). Samples in glass vials were put inside the humidity chamber box at 45% RH, opened inside the chamber and observed changes for 24 hr. [0228] Contact angles in water were measured using Data Physics Contact Angle measurement system, OCA 20L. [0229] I. Zirconium Propionate Polymorph S1 (ZPPA) and Related Compounds [0230] A. Synthesis 1 of Zirconium Propionate Polymorph S1 (ZPPA) [0231] The reaction was conducted under air/moisture free environment. Propionic acid (Millipore Sigma), propionic anhydride (Millipore Sigma) and 1-methoxy-2-propanol (PGME; EMD Performance Materials) were kept over molecular sieves (3 Å) and were then distilled under an inert atmosphere and atmospheric pressure. The propionic acid (19.48 g; 0.263 mol) was added to propionic anhydride (103.08 g, 0.792 mol) all at once and the mixture was stirred continuously for 2 minutes. Thereafter, 100.93 g (0.263 mol) zirconium (IV) (tert-butoxide) 4 (Millipore Sigma) was added dropwise over 45 minutes. During this addition, the temperature was controlled to bring it to approximately to 60 ºC. The mixture was then stirred at 62-65 ºC for 18 hours. Thereafter, 118.50 g (1.315 mol) of 1-methoxy-2-propanol was added by portion into the solution, and the crude ZPPA was stirred for an additional 5 hours at 62 ºC. The mixture was transferred to a dry round bottom flask filled with nitrogen. The flask was placed onto a vacuum rotary evaporator with a heating bath to distill out the volatile components. Removal of volatiles gave 81.9 g of the solid with residual PGME (~20% by 1H NMR). The PGME was removed by drying in a vacuum oven at 90 ºC for 3 days. [0232] The ZPPA characteristics are described above. [0233] B. Synthesis 2 of Zirconium Propionate Polymorph S2 [0234] Zirconium (IV) (tert-butoxide) 4 (32.65 g; 0.085 mol) was added to 2-methylpropanoic acid (7.50g; 0.085 mol) and propionic anhydride (33.22 g; 0.255 mol) over 34 min then stirred for 20 hours, followed with the addition of 1-methoxy-2-propanol (22.9 g; 0.254 mol) as described in Example 1. 27.43 g of zirconium (IV) isobutyrato-propionate solid solvate I with residual volatiles of 6.92 % wt. was obtained. [0235] C. Synthesis 3 of Zirconium Propionate Polymorph S3 [0236] Zirconium (IV) (tert-butoxide) 4 (27.48 g; 0.0716 mol) was added to 2-methylpropanoic acid (12.94 g; 0.146 mol), and propionic anhydride (27.85 g; 0.214 mol) over 25 min then stirred for 20 hours, followed with the addition of 1-methoxy-2-propanol (12.96 g; 0.144 mol) as described in Example 1. 22.92 g of zirconium (IV) isobutyrato-propionate solid solvate II with residual volatiles of 11.33 % wt. was obtained. [0237] D. Synthesis 4 of Zirconium Propionate Polymorph S4 [0238] Zirconium (IV) (tert-butoxide) 4 (19.77 g; 0.0515 mol) was added to methacrylic acid (4.43 g; 0.0515 mol), and propionic anhydride (19.97 g; 0.153 mol) over 41 min then stirred for 20 hours, followed with the addition of 1-methoxy-2-propanol (13.96 g; 0.155 mol) as described in Example 1. 17.28 g of Zirconium (IV) methacrylato-propionate solid solvate with residual volatiles of 21.7 % wt. was obtained. [0239] E. Synthesis 5 of Zirconium Propionate Polymorph S5 [0240] Zirconium (IV) (tert-butoxide) 4 (28.43 g; 0.074 mol) was added to 2-(2- methoxyethoxy)acetic acid (9.94 g; 0.074 mol) and propionic anhydride (28.93 g; 0.222 mol) over 52 min then stirred for 18 hours as described in Example 1. 30.7 g of zirconium (IV) 2-(2-methoxyethoxy)acetato- propionate as glass like solvate with residual volatiles of 17.24 % wt. was obtained. [0241] F. Synthesis 6 of Zirconium Propionate Polymorph S6 [0242] Zirconium (IV) (tert-butoxide) 4 (24.24 g; 0.0618 mol) was added to 2-[2-(2- methoxyethoxy)ethoxy]acetic acid (11.26 g; 0.063 mol) and propionic anhydride (24.67 g; 0.190 mol) over 35 min then stirred for 22 hours as described in Example 1. 30.7g of zirconium (IV) 2-[2-(2- methoxyethoxy)ethoxy]acetato-propionate as low temperature melting solvate with residual volatiles of 28.58 % wt. was obtained. [0243] G. Synthesis 7 of Zirconium Propionate Polymorph S7 [0244] Zirconium (IV) (tert-butoxide) 4 (30.11 g; 0.0785 mol) was added to benzoic acid (9.77g; 0.08 mol), and propionic anhydride (30.79 g; 0.236 mol) over 29 min then stirred for 19.7 hours, followed with the addition of 1-methoxy-2-propanol (21.36 g; 0.237 mol ) as described in Example 1. 29.08 g of zirconium (IV) benzoato-propionate solvate with residual volatiles of 19.8 % wt. was obtained. [0245] H. Synthesis 8 of Zirconium Propionate Polymorph S8 [0246] Zirconium (IV) (tert-butoxide) 4 (31.43 g ; 0.082 mol) was added to 4-methoxybenzoic acid (8.97 g; 0.059 mol) and propionic anhydride (31.24 g; 0.240 mol) over 53 min then stirred for 21 hours as described in Example 1. 35.15 g of zirconium (IV) 4-methoxybenzoato-propionate as glassy solvate with residual volatiles of 16.71 % wt. was obtained. [0247] I. Synthesis 9 of Zirconium Propionate Polymorph S9 [0248] Zirconium (IV) (tert-butoxide) 4 (24.37 g; 0.0635 mol) was added to phenylacetic acid (8.69g; 0.0638 mol) and propionic anhydride (24.73 g; 0.19 mol) over 50 min then stirred for 19 hours, followed with the addition of 1-methoxy-2-propanol (17.17 g; 0.0.191 mol) as described in Example 1. 23.95 g of zirconium (IV) phenylacetato-propionate as glass like solvate with residual volatiles of 5.6 % wt. was obtained. [0249] J. Synthesis 10 of Zirconium Propionate Polymorph S10 [0250] Zirconium (IV) (tert-butoxide) 4 (19.44 g; 0.0507 mol) was added to propionic anhydride (19.78 g; 0.152 mol) over 44 min then stirred for 15.5 hours, followed with the addition of DI water (1.11 g; 0.062 mol) then stirred as in Example 1. 12.71 g of zirconium (IV) hydroxo- propionate solid solvate with residual volatiles of 13.1 % wt. was obtained. [0251] II. Synthesis of THTPM Tris-Propionate (THTPM-TP) [0252] A. Reaction in Solvent Synthesis [0253] 4,4’,4’’-Trihydroxytriphenylmethane (THTPM, 5.04 g, 17.24 mmol) and propionic anhydride (13.46 g, 103.44 mmol) were refluxed in toluene (50 ml) for 6.5 hours that 1 H NMR (DMS—d6) showed the reaction was completed. After cooling to room temperature, volatiles were removed from the crude by distilling using a rotary evaporator. Removal of volatiles gave 7.9 g of solid which was then crystallized from 25.8 g of isopropanol. After drying in the vacuum oven at 95 ºC, 7.39g (93.1% yield) of the tri-ester as the greenish crystalline powder was obtained. [0254] B. Solvent Free Synthesis [0255] 4,4’,4’’-Trihydroxytriphenylmethane (THTPM, 3.03 g, 10.36 mmol) and propionic anhydride (7.19 g, 55.25 mmol) were stirred at 120 ºC for 6.5 hours. After cooling to room temperature, the crude was poured into 400 mL of DI water and the resulting crystalline material was recovered by filtration the next day. After drying in the vacuum oven at 95 ºC, 4.53 g (94.9% yield) with purity of 95.6 % by 1 H NMR (DMS—d6) was obtained. [0256] Characterization: MP 100.7 ºC; 1H NMR (400 Mz,CDCl3) δ 7.08 (d, J=8.54 Hz, 6H, Ar-H), 6.99 (d, J=8.54 Hz, 6H, Ar-H), 5.51 ( s, 1H, C-H), 2.56 (q, J=7.48 Hz, 6H, C-H 2 ), 1.24 (t, J=7.48 Hz, 9H, C-H3) ppm; 13 C NMR (400 Mz, CDCl3) δ 172.9, 149.4, 140.9, 130.3, 121.5, 55.1, 27.8, 9.1 ppm; FTIR (KBr) 3044, 2982, 2944, 2882, 1756, 1604, 1593, 1505, 1462, 1417, 1357, 1269 cm -1 . Analysis Calculated for C 28 H 28 O 6 : C 73.03, H 6.13; Found: C 72.86, H 6.06. [0257] III. Exemplified Formulations [0258] ZPPA Formulations [0259] A. Formulation 1 [0260] A formulation including ZPPA was prepared by mixing (i) 246.8 g of a 15.4% ZPPA solution in ArF Thinner, (ii) 2 g of isobutyric acid (Millipore Sigma), (iii) 4 g of 4,4’,4’’- trihydroxytriphenylmethane (Asahi Yukizai), (iv) 8.25 g of 10% X22-4952 (ShinEtsu) solution in AZ ® ArF Thinner and (v) 289 g of AZ ® ArF Thinner. The components were mixed overnight and then filtered through a 0.2 µm filter. [0261] Performance: Film uniformity (3 sigma%) 3.8; Etch rate (A/sec) 1.37; and Moisture resistance (h) 15. Refractive index (n) and the extinction coefficient (k): n 2.44, k 0.54 at 193 nm, n 2.11, k 0.03 at 248 nm. [0262] B. Formulation 2 [0263] A formulation including ZPPA was prepared by mixing (i) 388.6 g of a 15.4% ZPPA solution in ArF Thinner, (ii) 1.43 g of isobutyric acid (Millipore Sigma), (iii) 28.64 g of a 10% 4,4’,4’’- trihydroxytriphenylmethane (Asahi Yukizai) solution in ArF Thinner, (iv) 6.75 g of a 10% X22-4952 (ShinEtsu) solution in AZ ® ArF Thinner, (v) 12.56 g of gamma-valerolactone and (vi) 12 g of AZ ® ArF Thinner. The components were mixed overnight and then filtered through a 0.2 µm filter. [0264] Performance: Film uniformity (3 sigma%) 3.5; Etch rate (A/sec) 1.38; and Moisture resistance (h) 13. Refractive index (n) and the extinction coefficient (k): n 2.49, k 0.60 at 193 nm, n 2.15, k 0.03 at 248 nm. [0265] ZPP Formulations [0266] The ZPP used in these formulations has an average molecular weight of about 4,000 Da to about 10,000 Da. [0267] C. Formulation 3 [0268] 32.39 g of ZPP, 2 g of isobutyric acid (Millipore Sigma), 3.409 g of 4,4’,4’’- trihydroxytriphenyl-methane (Asahi Yukizai) and 7.5g of 10% X22-4952 (ShinEtsu) were combined with 455 g of AZ ® ArF Thinner. The solution was mixed overnight and then filtered through a 0.2 µm filter. [0269] Performance: Film uniformity (3 sigma%) 3.6; Etch rate (A/sec) 1.34; and Moisture resistance (h) 12. Refractive index (n) and the extinction coefficient (k): n 2.55, k 0.63 at 193 nm, n 2.20, k 0.04 at 248 nm. [0270] D. Formulation 4 [0271] 431.8 g of ZPP , 17.05 g of isobutyric acid (Millipore Sigma), 454.55 g of 10% 4,4’,4’’- trihydroxytriphenylmethane (Asahi Yukizai), 80 g of 10% X22-4952 (ShinEtsu) and 285 g of gamma- valerolactone were combined with 8.656 kg of AZ ® ArF Thinner. The solution was mixed overnight and then filtered through a 0.2 µm filter. [0272] Performance: Film uniformity (3 sigma%) 3.7; Etch rate (A/sec) 1.36; and Moisture resistance (h) 12. Refractive index (n) and the extinction coefficient (k): n 2.53, k 0.62 at 193 nm, n 2.19, k 0.03 at 248 nm. [0273] E. Formulations 5-45 [0274] Additional exemplary formulations are described in Tables 6-9. In these examples, the Zr material, etch resistance modulator additive, one or more solvents, surfactant and water resistivity enhancers are mixed overnight and then filtered through a 0.2 µm filter.
Table 6
Table 7
Table 8
Ingredient (wt%) Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 37 38 39 40 41 42 43 44 45 ZPPA S2 5.46 -- -- -- -- -- -- -- -- ZPPA S3 -- 5.46 -- -- -- -- -- -- -- ZPPA S4 -- -- 5.46 -- -- -- -- -- -- ZPPA S5 -- -- -- 5.46 -- -- -- -- -- Zr Material ZPPA S6 -- -- -- -- 5.46 -- -- -- -- Z PPA S7 -- -- -- -- -- 5.46 -- -- -- Z PPA S8 -- -- -- -- -- -- 5.46 -- -- ZPPA S9 -- -- -- -- -- -- -- 5.46 -- ZPPA S10 -- -- -- -- -- -- -- -- 5.46 Etch Resistance THPTM 0.57 0.57 0.57 0.57 0.57 0.57 0.57 0.57 0.57 Modulator Additive Solvent(s) ArF Thinner 93.53 93.53 93.53 93.53 93.53 93.53 93.53 93.53 93.53 Surfactant X22-4952 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Water Resistivity IBA 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 Enhancer Film Uniformity 3.8 3.9 4.1 4.2 4.4 3.9 4.5 3.9 3.8 (3 sigma%) Performance Etch Rate (A/sec) 1.25 1.32 1.28 1.34 1.36 1.32 1.2 1.15 1.23 Moisture Resistance (h) 14 16 17 14 13 14 14 15 14 Table 9 [0275] V. Preparation and Performance of Films [0276] As shown in examples 1-4 and 5-45, this invention provides spin on metal-organic formulations. All formulations in examples 1-45 are spin coatable and forms excellent etching resistance and Ar sputtering etch rate. Besides these formulations have good stability in moist environment. [0277] All the formulations have good film thickness uniformity and 3 sigma % is < 10% and 3.2- 6.5%. Bulk etch rate is low 0.6 ~ 0.8A/sec and good resistance under the condition. Ar sputtering rate is 1.2-~1.6A/sec. Ar sputtering rate and bulk etch rate ration is generally high, > 1.5 and good etching selectivity. The formulations are stable to moisture and did not show change > 8 hours in moisture chamber. [0278] Although the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter.