TWI797266B - Hard mask composition - Google Patents

Abstract

Disclosed and claimed herein is a composition for forming a spin-on hard-mask, having a fullerene derivative substituted with an amine and a crosslinking agent. The formulation is drain compatible with other solvents used in the semiconductor industry.

Description

hard mask composition

This patent application is in the field of imaging for semiconductor manufacturing and more specifically in the field of etch masks using spin-on hard mask formulations.

The minimum feature size of semiconductor devices continues to shrink to increase device density. One way to achieve this high-density patterning is to use thin photoresist films to mitigate the problem of pattern collapse of high aspect ratio resist features upon development. One possible solution to this problem involves the use of fullerene resists with high resolution, high sensitivity and high etch durability. However, even though aspect ratios as high as 5:1 may be produced by this resist, the overall etch depth is significantly limited by the available resist thickness.

Multi-layer hard mask stacks enable further increases in the aspect ratio of etched images. These methods can use thick amorphous carbon, deposited in vacuum by chemical vapor deposition, and then coated with a thin silicon-rich layer. Then, a thin photoresist film is sufficient to pattern the Si-rich layer; thus avoiding pattern collapse. The silicon-rich layer in turn is used as a hard mask to pattern the carbon, thereby providing a high aspect ratio carbon pattern suitable for providing a mask for etching a silicon wafer. By alternating from silicon to carbon-rich materials and vice versa, optimization of the overall etch selectivity of various substrates can be achieved.

In recent years, methylene fullerene materials have been used in hard mask formulations. For example, Frommhold et al. in International Patent Application No. WO1013/117908 A1 describe a hard mask material comprising methylene fullerene and a crosslinking agent. However, there is still a need to not Hard mask formulations that form precipitates or residues containing solvents for other formulations such as photoresists, edge bead removers, strippers, organic developers, etc. This need is addressed by the materials described herein.

As used herein, unless the context indicates or requires otherwise, the conjunction "and" is intended to be inclusive and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, alternatively" is intended to be exclusive. When used in the context of alternative chemical substituents on a molecule, the conjunction "or" is intended to be exclusive. As used herein, the article "a" or "a" should be understood to mean one or more. As used herein, the term "exemplary" is used to indicate an example, and not necessarily to indicate a preference. As used herein, the term "external box ring" is understood as a ring structure fused to the outside of a fullerene on two adjacent carbon atoms. The number of members in the outer ring includes two carbon atoms in the fullerene. As used herein, diluent should be understood as weak solvent or non-solvent.

其中R₁、R₂、R₃、R₄、R₅、R₆、R₇和R₈包含至少一個胺基，且n為1-12。特別地，當在溶液中含有它們的製劑遇到其它製劑的溶劑時，這些化合物在動力學上保持穩定，並且可能是熱力學上的穩定溶液。因此，它們在半導體工業中被稱為「旋轉筒兼容(spin bowl compatible)」，因為當它們遇到來自其他製劑的不 同溶劑(例如：光阻劑、剝離劑、邊緣珠除去劑等)時，它們不會在旋轉筒或各種排水導管內形成沉澱物或殘留物。 We have discovered unexpected advantages in fullerene hard mask materials in which the fullerene derivatives contain substituents of [4+2] cycloaddition products or equivalents (I),

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ contain at least one amine group, and n is 1-12. In particular, these compounds remain kinetically stable and may be thermodynamically stable solutions when formulations containing them in solution encounter solvents of other formulations. Therefore, they are called "spin bowl compatible" in the semiconductor industry because when they encounter different solvents from other formulations (for example: photoresists, strippers, edge bead removers, etc.), They will not form deposits or residues in the spin bowl or in various drain conduits.

Disclosed herein is a hard mask composition comprising: a first solute comprising one or more fullerene derivatives having one or more outer rings, represented by general formula (II) means; a second solute comprising a crosslinking agent comprising two or more thermally or catalytically reactive groups; and a first solvent. Referring to (II), n is the number of outer rings and is an integer of 1 to 12, Q is a carbon atom having 60, 70, 76, 78, 80, 82, 84, 86, 90, 92, 94 or 96 carbon atoms Fullerene; and, for each outer ring, the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently a hydrogen atom, one having 1-20 Alkyl or an amine group of carbon atoms, provided that at least one and no more than three of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are amine groups, And wherein, if n is 2-12, the outer collars may be the same or different.

Further disclosed herein is a method of preparing a low particulate waste stream, wherein a hard mask composition described herein, or a concentrate thereof, is provided to the waste stream. A fluid is further provided to the same waste stream, the fluid comprising a second solvent or diluent such as: photoresist, resist stripper or remover, edge bead remover, organic developer, etc., wherein the solvent in the fluid Or the diluent may be the same or different than that in the hard mask composition. As an example, solvents or diluents in the fluid may include alcohols, amines, esters, lactones, ethers, ether alcohols, ether esters ester), ester alcohol, ketone, ketoester, aldehyde, lactone, lactam, imide, or sulfone . Other Additionally, the hard mask compositions and non-hard mask fluids can be used in any order, allowing for device flexibility. Solvents for hard mask materials are described below.

The one or more amine groups can be primary, secondary or tertiary amines with various substituents including, for example but not limited to: hydrogen atoms, straight or branched chain alkyl groups having 1-20 carbon atoms , an aromatic group having 1-20 carbon atoms or an aralkyl group having 1-20 carbon atoms. The aforementioned groups may contain, in place of carbon atoms, heteroatoms such as those found in groups III to VI in columns 1 to 3 of the periodic table. Primary amines have two hydrogen atoms bonded to the nitrogen atom, and secondary amines have one hydrogen atom.

In certain exemplary compositions, R ₁ , R ₂ , R ₃ or R ₄ comprise an alkyl group as described above. In certain other exemplary compositions, R ₁ , R ₂ , R ₃ or R ₄ comprise hydrogen atoms. In certain other exemplary compositions, R ₁ , R ₂ , R _{3 ,} or R ₄ comprise a hydrogen atom and an alkyl group as described above. In certain other exemplary compositions, R ₁ , R ₂ , R ₃ or R ₄ may comprise a primary, secondary or tertiary amine.

In certain exemplary compositions, _R5 , _R6 , _R7 or _R8 comprise an alkyl group as described above. In certain other exemplary compositions, _R5 , _R6 , _R7 or _R8 comprise a hydrogen atom. In certain other exemplary compositions, _R5 , _R6 , _R7, or _R8 comprise a hydrogen atom and an alkyl group as described above. In certain other exemplary compositions, _R5 , _R6 , _R7 , or _R8 may comprise a primary, secondary, or tertiary amine. In certain other exemplary compositions, _R5 or _R8 is an alternate site, wherein one alternate site comprises a primary, secondary, or tertiary amine, and the other alternate site comprises a hydrogen atom or an alkyl group. In certain other exemplary compositions, _R6 or _R7 is an alternate site, wherein one alternate site comprises a primary, secondary, or tertiary amine, and the other alternate site comprises a hydrogen atom or an alkyl group.

Chemical reactions leading to compounds as described herein may produce essentially disordered products. For example, as shown in (II), a fullerene with two externally inserted rings, each with a single amine group at an alternate position _R6 , can be attached to the fullerene such that positions _R6 and _R7 are in the same mode switching or orientation. Without wishing to be bound by theory, this disorder may be a contributing factor to the observed solvent compatibility.

The disclosed compositions and methods are contemplated to be advantageously used in any reasonable combination. For example, formulations with epoxy resins may also contain aminoplast crosslinkers such as methylol glycoluril resins or methylol melamine resins.

Additionally, a given formulation may contain substitutions and distributions of substitution patterns on the fullerenes without departing from the intended scope of the claims. Furthermore, a given formulation may contain a distribution of substitutions and substitution patterns on fullerenes having different numbers of carbon atoms without departing from the intended scope of the claims. For example, formulations may contain various fullerene allotropes, such as C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ , C 86 , C ₉₀ , C ₉₂ , _{C 94 ,} C ₉₆ , and C ₉₈ , each of which Can be substituted by 0-12 external insert rings. As another example, the formulation may contain multiple exo-substituted and unsubstituted fullerene allotropes, wherein the fullerenes before substitution are C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ , C ₈₆ , C ₉₀ , C ₉₂ , C ₉₄ and C ₉₆ , and at least some of the fullerene allotropes are substituted with 0 to 6 external ring-blocking substituents. As another example, formulations may contain multiple exosubstituted and unsubstituted fullerene allotropes, wherein the fullerenes before substitution are _C60 and _C70 , and at least some of the fullerene allotropes are replaced by 1-20 exoblock ring substituents are substituted, and some fullerene allotropes are unsubstituted.

The general formula (II) represents a substituted or unsubstituted fullerene derivative (as the case may be) having 1 to 12 substituents when substituted. Fullerenes can have different allotropes, including but not limited to C ₂₀ , C ₂₈ , C ₃₆ , C ₅₀ , C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₉₀ , C ₉₂ , C ₉₄ , C ₉₆ and C ₉₈ , some of which are shown in (III), which represent cage structures rather than bonds. In some cases, different allotropes may have the same number of carbon atoms. Euler's polyhedron formula V-E+F=2 applies to closed structures, where V, E, F are the number of vertices (carbon atoms), edges and faces. If there are 12 pentagons in a fullerene, then there will be V/2-10 hexagons. It is to be understood that fullerene derivatives include all fullerene allotropes having exo-substituents as described herein.

Cycloaddition reactions generally occur in the addition of one unsaturated entity to another to give cyclic products, where in most cases all atoms are conserved in the final product. two An entity (or more) may reside on a single molecule or on multiple molecules. Without being bound by theory, it is believed that addition reactions can occur by assuming electrons from the highest occupied molecular orbital (HOMO) of one entity to the lowest unoccupied molecular orbital (LUMO) of the other entity Density flows are explained.

In accordance with the subject matter disclosed herein, fullerenes can be substituted via a cycloaddition reaction through the double bond of a diene or similar group to form a ring structure utilizing two or more atoms on the fullerene. For example, in one embodiment, a diene or hetero-analogue thereof can be added via a cycloaddition reaction on a fullerene across the double bond to form a bridge spanning a pair of vertices where the two 6-membered rings meet, to form a so-called [6,6] bridge. In another embodiment, a [6,5] substitution in the apex between the 6-membered ring and the 5-membered ring of the diene group or diene precursor group can occur. The synthesis technique of this cycloaddition reaction can be found in Hirsch, et al., "Fullerenes: Chemistry and Reactions," WILEY-VCH Verlag GmbH and Co., Weinheim, Chapter 4, (2005), Diederich et al., Science, 271, 317, (1996), Filippone et al., “Exohedral Fullerenes,” Encyclopedia of Polymeric Nanomaterials, Springer- Verlag, Berlin, Heidelberg, pp.1-16, (2014) and Yang et al., J.Org. Found in Chem., 78, 1163, (2013).

In addition to single removal reactions, double or multiple removal reactions can be used to produce stable or transient dienes. For example, various 1,2-bis(halomethyl) compounds (1,2-bis(halomethyl)compounds) such as 1,2-bis(bromomethyl)benzene (1,2-bis(bromomethyl)benzene), Substituted 1,2-bis(bromomethyl)benzene, etc. can form dienes in situ by reacting with KI and phase transfer catalysts, and then perform single or multiple Diels Alder reactions with fullerenes, which are usually On the [6,6] side, but possibly also on the [6,5] edge. Fullerenes with different numbers of carbon atoms undergo similar reactions. Phase transfer catalysts such as crown ethers (for example: 1,4,7,10,13,16-hexaoxacyclooctadecane (18 crown-6) (1,4,7,10,13,16-hexaoxacyclooctadecane (18 Crown-6)) or quaternary ammonium salts (eg: (bu) ₄ NI) can be used to facilitate the reaction. These reactions are described in Taylor, "Lecture Notes On Fullerene Chemistry: A Handbook For Chemists," Imperial College Press, London, pp.177 ff., (1999) and described in Langa, et al., "Fullerenes: Principles and Applications," RSC Publishing, Cambridge, pp.21 ff., (2007). In addition to the substituted halogen, use one or more of the other A leaving group may be advantageous. Using these techniques, m,m+1-dihydro-m,m+1-dihydro-W aromatic and heteroaromatic compounds can be formed, where m represents methylene Examples of W include, but are not limited to, benzene, naphthalene, thiophene, pyrrole (1H and 2H), pyrazole, triazole, thiadiazole (thiadiazole), oxadiazole (oxadiazole), imidazole (imidazole), pyridine (pyridine), etc. Exemplary dienes that can be formed in this way include, but are not limited to, 2,3-diethylene-2,3-bis Hydrogen benzene (2,3-dimethylene-2,3-dihydrobenzene), 2,3-diethylene-2,3-dihydronaphthalene (2,3-dimethylene-2,3-dihydronaphthalene), 2,3- 2,3-dihydrophenanthrene (2,3-dimethylene-2,3-dihydrophenanthrene), 2,3-dimethylene-2,3-dihydropyridine (2,3-dimethylene-2 , 3-dihydropyridine) and so on.

Other reaction schemes can be used to form useful dienes. For example, 1,4-dihydrophthalazine (1,4-dihydrophthalazine) can be used to form 2,3- _dimethylene -2,3-dihydrobenzene (2,3-dimethylene-2 ,3-dihydrobenzene). Other examples of diene precursors include, but are not limited to, 1,3-dihydro-2-benzothiophene 2,2-dioxide (1,3-dihydro-2-benzothiophene 2,2-dioxide), 1,4- Dihydro-2,3-benzoxepane 3-oxide (1,4-dihydro-2,3-benzoxathiine3-oxide). The latter two precursors form 2,3-dimethylene-2,3-dihydrobenzene by degassing SO ₂ as a gas or incipient gas. Exemplary dienes that can be formed in this manner include, but are not limited to, 2,3-dimethylene-2,3-dihydrobenzene (2,3-dimethylene-2,3-dihydrobenzene), 2,3-dihydrobenzene Methyl-2,3-dihydronaphthalene (2,3-dimethylene-2,3-dihydronaphthalene), 2,3-dihydronaphthalene-2,3-dihydrophenanthrene (2,3-dimethylene-2,3 -dihydrophenanthrene), 2,3-dimethylene-2,3-dihydropyridine (2,3-dimethylene-2,3-dihydropyridine), etc. These reactions are described in Chung, et al., J. Chem. Soc., Chem Commun., (1995), 2537. and Beer, et al., J. Mater. Chem., (1997), 7 , 1327. Using these techniques, m,m+1-dimethylene-m,m+1-dihydro-W aromatic and heteroaromatic compounds can be formed, where m indicates the position of the methylene group. Examples of W include, but are not limited to, benzene, naphthalene, thiophene, pyrrole (1H and 2H), pyrazole, triazole, thiadiazole, oxadiazole, imidazole, pyridine, and the like. Exemplary dienes that can be formed in this manner include, but are not limited to, 2,3-dihydrobenzene, 2,3-dihydronaphthalene, 2,3-dihydronaphthalene, 3-diylidene-2,3-dihydrophenanthrene, 2,3-diylidene-2,3-dihydropyridine, etc.

It should be noted that when n > 1, cycloaddition reactions can produce products with various substitutions on the fullerenes, with various values of n and various different substitution patterns for each value of n. Mixtures of these materials do not depart from the scope of the invention and may offer the advantages of enhanced solubility and reduced tendency to crystallize.

According to the subject matter disclosed herein, the crosslinking agent may be selected from epoxy phenolic novolak resin, epoxy cresylic novolak resin, epoxy bisphenol A resin , Epoxy bisphenol novolac resin (expoxy bisphenol novolak resin), alkylolmethyl melamine resin, alkylolmethyl glycoluril resin, alkylolmethyl guanamine resin, alkylolmethyl benzo- guanamine resin (alkylomethyl Benzo-Guanamine resin), glycosyl urea resin (glycosyl urea resin) or isocyanate (alkyd) resin (isocyanate (alkyd) resin).

Suitable amine-based crosslinkers include melamines such as CYMEL ^™ 300, 301, 303, 350, 370, 380, 1116 and 1130 manufactured by Cytec of West Paterson, NJ; benzoguanamine resins , such as CYMEL ^TM 1123 and 1125; glycoluril resins (glycoluril resins) CYMEL ^TM 1170, 1171 and 1172; and urea-based resins (urea-based resins), BEETLE ^TM 60, 65 and 80, also available from Cytec, West Paterson, NJ get. A number of similar amine or amidoplast compounds are commercially available from various suppliers. Epoxy phenolic and cresylic novolak resins are shown in (IV), wherein X can be H, CH ₃ and n can be 0-20. Epoxy bisphenol A resin (epoxy bisphenol A) is shown in the idealized structure (V), where n can be 0-20. Epoxy bisphenol Z resins are shown in idealized structure (VI), where n can be 0-20. A similar "epoxy bisphenol" crosslinker is considered. For example, based on 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane (1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane), 2,2-bis( 4-hydroxyphenyl) hexafluoropropane (2,2-bis(4-hydroxyphenyl)hexafluoropropane), 2,2-bis(4-hydroxyphenyl)butane (2,2-bis(4-hydroxyphenyl)butane) , bis-(4-hydroxyphenyl)diphenylmethane (bis-(4-hydroxyphenyl)diphenylmethane), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (2,2-bis( 3-methyl-4-hydroxyphenyl)propane), bis(4-hydroxyphenyl)-2,2-dichloroethylene (bis(4-hydroxyphenyl)-2,2-dichlorethylene), 1,1-bis(4- Hydroxyphenyl) ethane (1,1-bis(4-hydroxyphenyl)ethane), bis(4-hydroxydiphenyl)methane (bis(4-hydroxydiphenyl)methane), 2,2-bis(4-hydroxy- 3-isopropyl-phenyl)propane (2,2-bis(4-hydroxy-3-isopropyl-phenyl)propane), 1,3-bis(2-(4-hydroxyphenyl)-2-propyl ) Benzene (1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene), bis(4-hydroxyphenyl)sulfone (bis(4-hydroxyphenyl)sulfone), 1,4-bis(2 -(4-hydroxyphenyl)-2-propyl)benzene (1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene), 5,5'-(1-methylethyl) -bis[1,1'-(diphenyl)-2-ol]propane (5,5'-(1-methylethyliden)-bis[1,1'-(bisphenyl)-2-ol]propane), 1 ,1-bis(4-hydroyphenyl)-3,3,5-trimethyl-cyclohexane (1,1-Bis(4-hydroyphenyl)-3,3,5-trimethyl-cyclohexane), 4, Resins of diglycidyl ethers such as 4'-(9H-fluorene-9,9-diyl)dianiline (4,4'-(9H-fluorene-9,9-diyl)dianiline), and other Combinations with any of the above.

In accordance with the subject matter disclosed herein, suitable thermal acid generators may include alkyl esters of organic sulfonic acids, alicyclic esters of organic sulfonic acids, organic sulfonic acids amine salts of organic sulfonic acids, 2-nitrobenzyl esters of organic sulfonic acids, 4-nitrobenzyl esters of organic sulfonic acids of organic sulfonic acids), organic sulfonic acids Benzoin esters of organic sulfonic acids, β-hydroxyalkyl esters of organic sulfonic acids, β-hydroxycycloalkyl esters of organic sulfonic acids hydroxycycloalkyl esters of organic sulfonic acids), triaryl sulfonium salts of organic sulfonic acids, alkyl diaryl sulfonium salts of organic sulfonic acids, organic sulfonic acids Dialkyl aryl sulfonium salts of organic sulfonic acids, trialkyl aryl sulfonium salts of organic sulfonic acids, diaryl iodonium salts of organic sulfonic acids iodonium salts of organic sulfonic acids), alkyl aryl sulfonium salts of organic sulfonic acids, or ammonium salts of tris(organosulfonyl) methides methides).

Onium salts contain cations and anions. Exemplary cations of onium salts include triaryl sulfonium, alkyl diaryl sulfonium, dialkyl aryl sulfonium, trialkyl sulfonium, diaryl sulfonium, Diaryl iodonium, alkyl aryl iodonium, dialkyl iodonium, triaryl selenium, alkyl diaryl selenonium, Dialkyl aryl selenonium (dialkyl aryl selenonium), trialkyl selenium (trialkyl selenonium). Specific examples of cations in onium salts include triphenylsulfonium, tri(p-tolyl)sulfonium, 1,4-phenylene bis(diphenylsulfonium) ( 1,4-phenylenebis(diphenylsulfonium)) (with a charge of +2), diphenyliodonium and bis(4-tert-butylphenyl)iodonium (bis(4-tert-butylphenyl)iodonium), but not limited thereto .

In addition, exemplary anions in the onium salt include halides, PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ and BF ₄ ⁻ , but are not limited thereto. In addition, anions based on oxoacids may be used. These include C ₁ -C ₁₀ perfluoroalkane sulfonates (C ₁ -C ₁₀ perfluoroalkane sulfonates), such as trifluoromethane sulfonate, perfluoro butane sulfonate and perfluorobutane sulfonate Perfluoro octane sulfonate, C ₁ -C ₁₈ linear, branched and alicyclic alkane sulfonates (C ₁ -C ₁₈ linear, branched and alicyclic alkane sulfonates), such as dodecane Sulfonate (dodecane sulfonate), methane sulfonate (methane sulfonate) and camphor sulfonate (camphor sulfonate), C ₁ -C ₁₈ aromatic and substituted aromatic sulfonate (C ₁ -C ₁₈ aromatic and substituted aromatic sulfonates), such as toluene sulfonate and dodecylbenzene sulfonate, C ₁ -C ₁₈ fluorinated aryl sulfonates (C ₁ -C ₁₈ fluorinated aryl sulfonates), Such as trifluoromethyl benzene sulfonates, pentafluoro benzene sulfonate, etc., C ₁ -C ₁₈ carboxylates and halogenated carboxylates (carboxylates and halogenated carboxylates), such as Benzoate, acetate, chloroacetate, dichloroacetate, trichloroacetate, trifluoroacetate, perfluorovalerate (perfluoropentanoate), pentafluoropropanoate (pentafluoropropanoate), perfluorooctanoate (perfluorooctanoate), perfluorobenzoate (perfluorobenzoate), etc., but not limited thereto. Furthermore, suitable anions include C ₁ -C ₂₀ tris(alkylsulfonyl)methanides (C ₁ -C ₂₀ tris(alkane sulfonyl)methanides), tris(fluoroalkane sulfonyl)methanides (tris(fluoroalkane sulfonyl)methanides )methanides), (R ₃ C ^- ), bis(alkane sulfonyl)imides and bis(fluoroalkane sulfonyl)imides ), (R ₂ N ^- ), such as tris(trifluoromethylsulfonyl)methane (tris(trifluoromethylsulfonyl)methanide), bis(trifluoromethylsulfonyl)imide (bis(trifluoromethylsulfonyl)imide), etc. , but not limited to this. In addition, oxo-acid anions can be bound to polymers, thus limiting acid diffusion in hard mask materials, but not limited thereto. These include polymeric acids such as poly(vinyl sulfonate), poly(styrene-4-sulfonate), poly( Tetrafluoroethylene-co-1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethyleneoxy)ethanesulfonate) (poly(tetrafluoroethylene-co-1,1,2, 2-tetrafluoro-2-(1,2,2-trifluorovinyloxy)ethanesulfonate)), poly((meth)acrylic acid) (poly((meth)acrylic acid)), etc. In addition, sulfonated and fluorosulfonated (meth) acrylic monomers can be incorporated into various polymers. It is understood that oxoacid anions may contain other elements such as Se, P, As, Sb to form selenates, phosphonates, arsenonates, stibonates wait. Ester thermal acid generators may include, for example, any of the aforementioned oxoacid anions to form carboxylate, sulfonate, selenonate, phosphonate, arsenate Salt (arsenonate) and capric acid ester (stibononate esters).

In addition, ester-type and onium type thermal acid generators can be used as photoacid generators at the wavelengths at which they absorb electromagnetic radiation, which can be used as other photoacid generators from hard mask compositions. Electron acceptors for components, but not limited thereto. In addition, triazine-type photoacid generators may be used. Suitable halogenated triazines include halomethyl-s-triazines. Suitable halotriazines include for example 2-[1-(3,4-benzodioxol)]-4,6-bis(trichloromethyl)-1,2,5-triazine (2-[1-(3,4-benzodioxolyl)]-4,6-bis(trichloromethyl)-1,2,5-triazine), 2-[1-(2,3-benzodioxolyl) Alkenyl))]-4,6-bis(trichloromethyl)-1,3,5-triazine (2-[1-(2,3-benzodioxolyl)]-4,6-bis(trichloromethyl)- 1,3,5-triazine), 2-[1-(3,4-benzodioxolyl)]-4,6-bis(tribromomethyl)-1,3,5-tri Azine (2-[1-(3,4-benzodioxolyl)]-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-[1-(2,3-benzodioxolyl) Pentenyl)]-4,6-bis(tribromomethyl)-1,3,5-triazine (2-[1-(2,3-benzodioxolyl)]-4,6-bis(tribromomethyl)- 1,3,5-triazine), 2-(2-furylethylene)-4,6-bis(trichloromethyl))1,3,5-triazine (2-(2-furfylethylidene)-4, 6-bis(trichloromethyl)1,3,5-triazine), 2-[2-(5-methylfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3,5 -Triazine (2-[2-(5-methylfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-[2-(4-methylfuryl)ethylene Base]-4,6-bis(trichloromethyl)-1,3,5-triazine (2-[2-(4-methylfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3, 5-triazine), 2-[2-(3-methylfuryl)ethylene]-4,6-bis-(trichloromethane base)-1,3,5-triazine (2-[2-(3methylfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-[2-(4,5 -Dimethylfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3,5-triazine (2-[2-(4,5-dimethylfuryl)ethylene]-4, 6-bis(trichloromethyl)-1,3,5-triazine), 2-[2-(5-methoxyfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3 ,5-triazine (2-[2-(5-methoxyfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-[2-(4-methoxyfuryl) ) Ethylene]-4,6-bis(trichloromethyl)-1,3,5-triazine (2-[2-(4-methoxyfuryl)ethylene]-4,6-bis(trichloromethyl)-1 ,3,5-triazine), 2-[2-(3-methoxyfuryl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine (2- [2-(3-methoxyfuryl)ethylene]-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-[2-(4,5-Dimethoxy-furyl)ethylene ]-4,6-bis(trichloromethyl)-1,3,5-triazine (2-[2-(4,5-dimethoxy-furyl)ethylene]-4,6-bis(trichloromethyl)-1 ,3,5-triazine), 2-(2-(2-furylethylene)-4,6-bis(tribromomethyl)-1,3,5-triazine (2-(2-( 2-furfylethylidene)-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-[2-(5-methylfuryl)ethylene]-4,6-bis(tribromomethyl) base)-1,3,5-triazine (2-[2-(5-methylfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-[2-(4 -Methylfuryl)-ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine (2-[2-(4-methylfuryl)-ethylene]-4,6 -bis(tribromomethyl)-1,3,5-triazine), 2-[2-(3-methylfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5 -Triazine (2-[2-(3-methylfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-[2-(4,5-dimethoxyfuran Base) ethylene] -4,6-bis(tribromomethyl)-1,3,5-triazine (2-[2-(4,5-dimethoxyfuryl)ethylene]-4,6-bis(tribromomethyl )-1,3,5-triazine), 2-[2-(5-methoxyfuryl]ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine (2-[2-(5-methoxyfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-[2-(4-methoxyfuryl)ethylidene] -4,6-bis(tribromomethyl)-1,3,5-triazine (2-[2-(4-methoxyfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5- triazine), 2-[2-(3-methoxyfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine (2-[2-(3 -methoxyfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-[2-(4,5-dimethoxyfuryl)ethylidene]-4,6- Bis(tribromomethyl)-1,3,5-triazine (2-[2-(4,5-dimethoxyfuryl)ethylene]-4,6-bis(tribromomethyl)-1,3,5-triazine), 2,4,6-bis-(trichloromethyl)-1 ,3,5-triazine (2,4,6-tris-(trichloromethyl)-1,3,5-triazine), 2,4,6-ginseng-(trichloromethyl)-1,3,5- Triazine (2,4,6-tris-(tribromomethyl)-1,3,5-triazine), 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine ( 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-phenyl-4,6-bis(tribromomethyl)-1,3,5-triazine (2- phenyl-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5- Triazine (2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) base)-1,3,5-triazine (2-(4-methoxyphenyl)-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-(2-(1-naphthyl)- 4,6-bis(trichloromethyl)1,3,5-triazine (2-(2-(1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), 2 -(1-naphthyl)-4,6-bis(tribromomethyl)-1,3,5-triazine(2-(1-naphthyl)-4,6-bis(tribromomethyl)-1,3, 5-triazine), 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (2-(4-methoxy-1- naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1, 3,5-triazine (2-(4-methoxy-1-naphthyl)-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-(4-chlorophenyl)-4,6 -Bis(tribromomethyl)-1,3,5-triazine (2-(4-chlorophenyl)-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-styryl- 4,6-bis(trichloromethyl)-1,3,5-triazine (2-styryl-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-styryl-4 ,6-bis(tribromomethyl)-1,3,5-triazine (2-styryl-4,6-bis(tribromomethyl)-1,3,5-triazine), 2-(4-methoxy Styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine (2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine ), 2-(4-methoxystyryl)-4,6-bis(tribromomethyl)-1,3,5-triazine (2-(4-methoxystyryl)-4,6-bis( tribromomethyl)-1,3,5-triazine), 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine ( 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine), 2(3,4,5-trimethoxystyryl)-4,6- Bis(trichloromethyl)-1,3,5-triazine (2(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine), 2-(3 -Chloro-1-phenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (2-(3-chloro-1-phenyl)-4,6- bis(trichloromethyl)-1,3,5-triazine), 2-(3-chlorophenyl)-4,6-bis(tribromomethyl)-1,3,5-triazine (2-(3- chlorophenyl)-4,6-bis(tribromomethyl)-1,3,5-triazine), etc. Other triazine photoacid generators useful in the present invention are disclosed in US Patent No. 5,366,846, incorporated herein by reference.

s-triazine compounds are condensation reaction products of certain methyl-halomethyl-s-triazines and certain aldehydes or aldehyde derivatives. Such s-triazine compounds can be prepared according to US Pat. No. 3,954,475 and Wakabayashi et al., Bulletin of the Chemical Society of Japan , 42, 2924-30 (1969).

According to the subject matter disclosed herein, the first solvent may include propylene glycol methyl ether acetate, ethyl lactate, anisole, cyclohexanone, toluene ), chloroform (chloroform), chlorobenzene (chlorobenzene), o-dichlorobenzene (o-dichlorobenzene), m-dichlorobenzene (m-dichlorobenzene), p-dichlorobenzene (p-dichlorobenzene), o-xylene ( o-xylene), m-xylene, p-xylene, carbon disulfide, 1-chloronaphthalene, 1-methylnaphthalene, 1,2,4-trimethylbenzene, tetrahydronaphthalene, 1,2,3-tribromopropane, bromoform ), cumene, benzene, carbontetrachloride, chloroform, n-hexane, cyclohexane, tetrahydrofuran, acetonitrile ), methanol (methanol), water (water), pentane (pentane), heptane (heptanes), octane (octane), isooctane (isooctane), decane (decane), dodecane (dodecane), tetradecane, acetone, isopropanol, dioxane, mesitylene, dichloromethane, or a mixture comprising any of the foregoing.

Alternatively, according to the subject matter disclosed herein, the first solvent may include anisole, toluene, chloroform, chlorobenzene, o-dichlorobenzene benzene), m-dichlorobenzene, p-dichlorobenzene, o-xylene, m-xylene, p-xylene ), carbon disulfide (carbon disulfide), 1-chloronaphthalene (1-chloronaphthalene), 1-methylnaphthalene (1-methylnaphthalene), 1,2,4-trimethylbenzene (1,2,4-trimethylbenzene), four Tetrahydronaphthalene, 1,2,3-tribromopropane, bromoform, cumene, benzene, carbontetrachloride , chloroform, n-hexane, cyclohexane, tetrahydrofuran, acetonitrile, methanol, water, pentane, heptane ( heptanes), octane, isooctane, decane, dodecane, tetradecane, mesitylene, dichloromethane, or a mixture comprising any of the foregoing.

According to the subject matter disclosed herein, the second solvent or diluent may comprise alcohol (alcohol), amine (amine), ester (ester), lactone (lactone), ether (ether), ether alcohol (ether alcohol), ether ester ( ether ester, ester alcohol, ketone, ketoester, aldehyde, lactone, lactam, imide, or sulfone ). The second solvent or diluent may further contain an aromatic solvent or a solvent containing a halogen atom.

In particular, the second solvent or diluent may include ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers ), propylene glycol dialkyl ethers, alkyl phenyl ethers, such as anisole, acetate esters, hydroxyacetate esters, Lactate esters such as ethyl lactate, methyl lactate, propyl lactate, butyl lactate, ethylene glycol monoalkyl ether acetate Ethylene glycol monoalkylether acetates, propylene glycol monoalkylether acetates, alkoxyacetate esters, (non-)cyclic ketones, acetylene Acetate (acetoacetate esters), pyruvate esters (pyruvate esters) and propionate esters (propionate esters). Specific examples of these solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (ethylene glycol monobutyl ether), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dipropyl ether Diethylene glycol dibutyl ether, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyletheracetate ), propylene glycol monoethyletheracetate, propylene glycol monopropyletheracetate, isopropenyl acetate, isopropenyl propionate, methyl ethyl ketone ), cyclohexanone (cyclohexanone), 2-heptanone (2-heptanone), 3-heptanone (3-heptanone), 4-heptanone (4-heptanone), 2-hydroxypropionate ethyl ester (2-hydroxypropionate ethyl), 2-hydroxy-2-methylpropionate ethyl, ethoxy acetate ethyl, hydroxyacetate ethyl, 2-hydroxy -3-methyl butyrate (2-hydroxy-3-methyl methylbutyrate), 3-methoxybutyrate (3-methoxybutylacetate), 3-methyl-3-methoxybutyrate ( 3-methyl-3-methoxybutylacetate), 3-methyl-3-methoxybutyl propionate (3-methyl-3-methoxybutyl propionate), 3-methyl-3-methoxybutyl butyrate (3-methyl-3-methoxybutyl butylate), ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate (ethyl acetoacetate), 3-methoxy propionate methyl ester (methyl 3-methoxypropionate), 3-methoxy propionate ethyl ester (ethyl 3-methoxy propionate), 3-ethoxy propionate methyl ester (3- ethoxy propionate methyl) and 3-ethoxy propionate ethyl (3-ethoxy propionate ethyl). Above-mentioned solvent can be used alone, also can Mix two or more. In addition, at least one high boiling point solvent such as benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ether), acetonylacetone, isoholon, caproic acid, capric acid, 1-octanol, 1-nonanol , benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma-butyrolactone (γ-butyrolactone), ethylene carbonate, propylene carbonate and phenylcellosolve acetate were added to the above solvent.

According to the subject matter disclosed herein, the claimed composition may suitably comprise from 1 g/l to 800 g/l total solids. According to the subject matter disclosed herein, the claimed composition may further suitably comprise from 2.5 g/l to 500 g/l total solids. According to the subject matter disclosed herein, the claimed composition may further suitably comprise from 5 g/l to 100 g/l total solids.

Depending on the subject matter disclosed herein, the fullerene loading may suitably range from 10% to 90% of the total solids in the composition. According to the subject matter disclosed herein, the loading of crosslinker may suitably be 90% to 10% of the total solids in the composition. According to the subject matter disclosed herein, the loading of thermal acid generator may suitably range from 0% to 40% of the total solids in the composition. According to the subject matter disclosed herein, the photoacid generator may suitably comprise from 0% to 40% of the total solids in the composition. All solid composition percentages are by weight.

Other materials may be present in the composition to enhance film forming properties. These include surfactants, wetting agents, rheology modifiers, defoamers, and more.

In accordance with the subject matter disclosed herein, a film formed from any of the compositions may be heated at a temperature sufficient to cause crosslinking of the coating film. The presence of a thermal acid generator lowers the temperature at which crosslinking occurs. An exemplary temperature range may be 80°C to 350°C. Another exemplary temperature range may be 100°C to 250°C. Another exemplary temperature range may be 120°C to 160°C.

In accordance with the subject matter disclosed herein, films formed with any of the compositions may be exposed to electromagnetic radiation during heating, prior to heating, or at ambient temperature at an exposure dose sufficient to cause crosslinking of the coating film. The presence of a photoacid generator lowers the temperature at which crosslinking occurs. Exemplary exposure wavelengths may be 190 nm to 520 nm, depending on the sensitivity of the photoacid generator. Other exemplary exposure wavelengths may be 225 nm to 400 nm, depending on the sensitivity of the photoacid generator. Exemplary exposure doses may range from 0.1 mJ/cm ² to 1000 mJ/cm ² . Another exemplary exposure dose range may be 1 mJ/cm ² to 500 mJ/cm ² . Yet another exemplary exposure dose range may be 10 mJ/cm ² to 100 mJ/cm ² .

Coating may suitably be done by spraying, knife coating, spin coating or a combination thereof, but is not limited thereto. Regarding spin coating, for example, the rotation speed may suitably be in the range of 100 rpm to 8000 rpm. As another example, the rotational speed may suitably be in the range of 200 rpm to 5000 rpm. As yet another example, the rotational speed may be in the range of 800 rpm to 2000 rpm. The rotation time may suitably be 10 seconds to 150 seconds. Substrates coated by any of the above methods may suitably be soft baked prior to crosslinking. A suitable soft bake temperature may be in the range of 50°C to 150°C.

The following examples are illustrative and are not intended to limit the scope of the appended claims. For example, various substrates, substrate preparation methods, etching chemistries and conditions, or resist types and exposure conditions may be used as appropriate.

Example

Substrate preparation: A silicon (100) substrate (Si-Mat silicon material, n-type) was used for all experimental procedures. Wafers were used as supplied without additional cleaning or surface treatment.

Example 1. The following is a synthetic method suitable for the preparation of 3,4-bis(bromomethyl)aniline (3,4-bis(bromomethyl)aniline)

The temperature of the oil bath was raised to 80 °C. Add a stir bar and 3.03g (17.0mmol, 177.98g/mol, 2.1 equivalents) of N-bromosuccinimide (N-bromosuccinimide, NBS) into a clean 250mL round-bottomed flask, and use a dropper to 0.984g (8.12mmol, 121.18g/mol, 1 equivalent) of 3,4-dimethylaniline (3,4-dimethylaniline) in carbon tetrachloride, and 12.6mg of benzoyl peroxide ( benzoyl peroxide). The flask was fitted with a condenser, capped, then pumped and purged three times with nitrogen and vacuum. Anhydrous carbon tetrachloride (50 mL) was added via syringe and reacted carefully in an oil bath at 80 °C and stirred overnight at reflux. Succinimide was observed floating to the top of the reaction mixture, indicating completion of the reaction. Carbon tetrachloride was removed by rotary evaporation. Hexane was added, the resulting mixture was sonicated, and the succinimide was removed by filtration. The hexane was then removed by rotary evaporation to give the desired product, 3,4-bis(bromomethyl)aniline, as an oil, possibly a mixture of isomers. This material was used directly in the next reaction without further purification or other manipulations.

Example 2. The preparation of monosubstituted fullerene adducts (VIII) is described below.

The temperature of the oil bath was raised to 130°C. In a clean 500mL three-necked round bottom flask containing a stirring bar, add 1.334g (1.85mmol, 2 equivalents, 720.64g/mol) of C60 fullerene, 0.6635g (3.997mmol, 4.32 equivalents, 166.00g/mol) of Potassium iodide and 3.977 g (15.05 mmol, 16.26 equiv, 264.3220 g/mol) of [18]crown [6]. The round bottom flask was equipped with a condenser, sealed, pumped and purged three times with nitrogen and vacuum. Anhydrous toluene (-330 mL) was added through the tube and the mixture was brought to reflux. Then 374 mg (0.925 mmol, 1 equiv, 404.22 g/mol, 1.312 g/mL) of dibromide was added via syringe in anhydrous toluene, and the reaction was refluxed and stirred overnight in the dark. After cooling, the reaction mixture was washed with 5% sodium hydroxide solution and water (350 mL), dried over magnesium sulfate, filtered, and the toluene was removed by rotary evaporation. The material was purified using silica gel chromatography using decalin as eluent, followed by Cosmosil Buckyprep material as stationary phase (from NacalaiTesque; pyrenylpropyl group bonded silica) and toluene as mobile phase. Phase column for preparative intermediate pressure liquid chromatography (preparative intermediate pressure liquid chromatography). Fractions containing pure product were combined and the solvent was removed using rotary evaporation. The samples were placed in an oven overnight at 70°C under reduced pressure to remove residual solvent. The product was isolated as a brown crystalline solid. Purity was determined by HPLC on a column with Cosmosil Buckyprep material as stationary phase (from Nacalai Tesque; pyrenylpropyl bonded silica) and toluene as mobile phase. By scaling up the reaction in Example 2, multiple substitution products can be prepared.

Example 3. The following is the preparation of mixed fullerene (IX) polysubstituted amines.

Add 2.0 g (2.78 mmol, 1 equivalent, 720.64 g/mol) of C60 fullerene, 200 mL of 1-2 dichlorobenzene (1-2 dichlorobenzene ,ODCB) and 6.11g (33.4mmol, 12 equivalents, 183.23g/mol) of 5-amino-1,3-dihydrobenzo[c]thiophene-2,2-dioxide (5-amino-1 ,3-dihydrobenzo[c]thiophene-2,2-dioxide). The round bottom flask was equipped with a condenser, sealed, pumped and purged three times with nitrogen and vacuum. The mixture was refluxed and stirred for 24 hours in the dark. After cooling, the reaction mixture was purified on a bed of silica gel, and the resulting solution of the desired product was crystallized and dried in a vacuum oven. The resulting powder is a mixture of substituted fullerenes with a typical degree of substitution of n = 1 to 8, as shown by MALDI

Example 4. The following is the preparation method of mixed fullerene (IX) polysubstituted amines.

Similar to Example 3, except that a mixture comprising C ₆₀ and C ₇₀ dullerenes with the same weight ratio was used. The resulting powder is a mixture of mixed substituted mixed fullerenes (X). Typical degrees of substitution are n=1 to 8, as indicated by MALDI.

Example 5. The formulation and testing of mixing fullerene 10 with a crosslinker is described below.

Formulations of (X) and epoxy novolak resin CL1201 (purchased from Huntsman Chemical (1:1 w/w ratio)) were prepared in anisole solvent at a solids concentration of 100 g/l. Before use, the formulation was filtered using a 200 nm size filter. When spinning at 1500 RPM, a good quality, uniform film was produced. After baking on a hot plate in air at 300 °C for 3 minutes, the film thickness was 199-202 nm as measured using a dektak surface profiler. An elution test was performed with casting solvent (anisole) for 1 minute and the film thickness was remeasured to be 201 nm. Film quality before and after elution was good with no major defects.

Example 6. The following example shows the temperature testing of the formulation of Example 5.

Same as Example 5, except that the film was baked on a hot plate at 160° C. for 3 minutes. Elution in the casting solvent as previously described showed no significant change in film thickness.

Example 8. The following shows the solubility of the formulation of Example 5 when challenged with a solvent or diluent.

To the formulation of Example 5 (100 µl) was added 900 µl of propylene glycol methyl ether acetate, and the solution was mixed in a vial. The resulting solution was a dark brown, non-turbid mixture with no evidence of a solid precipitate in the vial either immediately or after 24 hours.

comparative example. The following shows the solubility of similar mixed fullerenes without amine substitution in hard mask formulations.

The formulation of Example 5 was prepared except that the fullerene derivative used did not have any amine substitution. The formulation was tested as in Example 7. A cloudy light brown mixture formed immediately after the addition of PGMEA and the mixture remained unchanged after 24 hours.

Although the present invention has been shown and described with reference to specific embodiments, various changes and modifications apparent to those skilled in the art to which this invention pertains are considered to be within the spirit of the subject matter described in the appended claims. within scope and concept.

Claims (16)

A hard mask composition comprising: a. a first solute, said first solute comprising one or more fullerene derivatives with one or more outer rings, represented by the following general formula:

b. a second solute comprising a crosslinking agent; said crosslinking agent comprising two or more thermally or catalytically reactive groups; c. a solvent selected from the group consisting of: propylene glycol Methyl ether acetate, ethyl lactate, anisole, cyclohexanone, toluene, chloroform, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-xylene, m-xylene, p-dichlorobenzene Toluene, carbon disulfide, 1-chloronaphthalene, 1-methylnaphthalene, 1,2,4-trimethylbenzene, tetralin, 1,2,3-tribromopropane, bromoform, cumene, benzene, tetralin Chlorocarbon, chloroform, n-hexane, cyclohexane, tetrahydrofuran, acetonitrile, methanol, water, pentane, heptane, octane, isooctane, decane, dodecane, tetradecane, acetone, isopropanol , dioxane, mesitylene, dichloromethane, and mixtures comprising any of the foregoing; wherein n is the number of outer rings and is an integer from 1 to 12, and Q is an integer having 60, 70, 76, 78, 80, A fullerene of 82, 84, 86, 90, 92, 94 or 96 carbon atoms; for each outer ring, the substituents R ₁ , R ₂ , R _{3 , R 4} , R ₅ , R ₆ , _{R 7} and R ₈ are independently a hydrogen atom, an alkyl group having 1-12 carbon atoms or an amine group, provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R At least one and no more than three of ₈ are amine groups, and wherein, if n is 2-12, the outer rings may be the same or different. The hard mask composition according to claim 1, wherein the amine groups are primary amine groups. The hard mask composition of claim 1, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen atoms or amine groups, provided that R ₁ At least one and not more than three of , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are amino groups. The hard mask composition according to claim 3, wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, and R ₅ , R ₆ , R ₇ and R ₈ independently contain at least one hydrogen atom and at least an amine group. The hard mask composition as claimed in claim 4, wherein _R6 and _R7 contain hydrogen atoms, and _R5 and _R8 are substitution sites such that one substitution site contains a hydrogen atom and the other substitution site contains a primary amine. The hard mask composition of claim 4, wherein R _{and R} contain hydrogen atoms, and R and _R are substitution sites _such that one substitution site contains a hydrogen atom and the other substitution site contains primary amine. The hard mask composition of claim 6, wherein the one or more fullerene derivatives comprise a mixture comprising substances wherein Q=60 and Q=70, n=2-8. The hard mask composition of claim 1, comprising a mixture of fullerene derivatives, characterized by at least one of the following: Q distribution, n distribution, or different outer ring closures. The hard mask composition as claimed in item 1, wherein the crosslinking agent is selected from 4,4'-(9H-fluorene-9,9-diyl)diphenylamine, epoxy novolac resin, epoxy cresol Novolak resin, epoxy bisphenol A resin, epoxy bisphenol A novolak resin, epoxy bisphenol C resin, poly[(o-cresyl glycidyl ether)- Co-formaldehyde, alkanolmethyl melamine resins, alkanolmethyl glycoluril resins, alkanolmethyl guanamine resins, alkanolmethyl benzoguanamine resins, glycosidyl urea resins or alkyd resins. The hard mask composition as claimed in claim 1, further comprising one or more thermal acid generators, wherein the one or more thermal acid generators are selected from the group consisting of alkyl esters of organic sulfonic acids, alicyclic esters of organic sulfonic acids Esters, amine salts of organic sulfonic acids, 2-nitrobenzyl esters of organic sulfonic acids, 4-nitrobenzyl esters of organic sulfonic acids, benzoin esters of organic sulfonic acids, β-hydroxyalkanes of organic sulfonic acids β-hydroxycycloalkyl esters of organic sulfonic acids, triaryl permeic acid salts of organic sulfonic acids, alkyldiaryl permetic salts of organic sulfonic acids, dialkylaryl permeic salts of organic sulfonic acids, organic sulfonic acids trialkylperiumium salts of organic sulfonic acids, diaryliodonium salts of organic sulfonic acids, alkylaryl periumium salts of organic sulfonic acids or ammonium salts of tris(organosulfonyl)methides. The hard mask composition as claimed in item 1, wherein the first solvent comprises: anisole, toluene, chloroform, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-xylene, m-xylene, p-xylene, carbon disulfide, 1-chloronaphthalene, 1-methylnaphthalene, 1,2,4-trimethylbenzene, tetralin, 1,2,3-tribromopropane, bromoform, iso Propylbenzene, benzene, carbon tetrachloride, chloroform, n-hexane, cyclohexane, pentane, heptane isomers, octane, isooctane, decane, dodecane, tetradecane, mesitylene, Dichloromethane or mixtures containing any of the foregoing. A method of producing a low particulate waste stream, comprising: a. providing the waste stream with the hard mask composition or concentrate thereof as claimed in claim 1; b. providing the waste stream with a second solvent or a A fluid of diluent; wherein the second solvent or the diluent comprises alcohol, amine, ester, lactone, ether, ether alcohol, ether ester, ester alcohol, ketone, ketone ester, aldehyde, lactone, lactam, imide or sulfide. The method of claim 12, wherein the second solvent or the diluent is non-aromatic and non-halogen-containing. The method of claim 12, wherein the fluid further includes a solute. A method of producing a low particulate waste stream, comprising: a. providing the waste stream with the hard mask composition or concentrate thereof as claimed in claim 6; b. providing the waste stream with a second solvent or a A fluid of diluent; wherein the second solvent or the diluent comprises alcohol, amine, ester, lactone, ether, ether alcohol, ether ester, ester alcohol, ketone, ketone ester, aldehyde, lactone, lactam, imide or sulfide. The method of claim 15, wherein the second solvent or the diluent is non-aromatic and non-halogen-containing.