DE102014114176B4 - Method of manufacturing a semiconductor device - Google Patents

Abstract

A method of manufacturing a semiconductor device (100), the method comprising:dispensing an anti-reflective material over a substrate (101) to form an anti-reflective coating layer (105), the anti-reflective material having a first concentration of a floatable component, the floatable component comprising a floatable crosslinking agent or a buoyant catalyst of a crosslinking reaction;forming a buoyant region (201) adjacent a top surface of the anti-reflective coating (105), the buoyant region (201) having a second concentration of the buoyant component that is greater than the first concentration; and applying a fluid (601) to the anti-reflective material to eliminate the anti-reflective material and the floating area (201).

Description

BACKGROUND ART

As consumer devices have become smaller and smaller in response to consumer demands, the dimensions of the individual components of these devices have inevitably been reduced. Semiconductor devices, which form a main part of these devices such as mobile phones, computer tablets and the like, have been compressed to become smaller and smaller, with a corresponding pressure on the individual components (e.g. transistors, resistors, capacitors, etc.) in the Semiconductor devices has been practiced to reduce their size as well.

A fundamental technology used in the manufacturing processes of semiconductor devices is the use of photolithographic materials. Such materials are applied to a surface and then subjected to energy that has itself been patterned. Such exposure changes the chemical and physical properties of the exposed areas of the photolithographic material. This change, together with the lack of change in areas of the photolithographic material that were not exposed, can be used to eliminate one area without removing the other.

However, as the size of individual devices has decreased, the process windows for photolithographic processing have become narrower. As such, advances in the field of photolithographic processing, such as the use of anti-reflection coatings to prevent unwanted reflections of incident light, have become necessary to further have the downsizing capability, and further improvements are needed to achieve the desired To meet development criteria in such a way that progress can continue towards smaller and smaller components.

U.S. 2012/0 070 782 A1 discloses a top antireflective layer, its composition, and photoresist formulations. In this case, in a spin-on process of an antireflection layer on a substrate, an upper layer is separated due to added polymers and the entire layer is removed from the substrate after a processing step.

U.S. 2012/0 157 367 A1 discloses a formulation and method for removing photoresist and a bottom anti-reflective coating on a semiconductor substrate in under a minute.

U.S. 2012/0 157 367 A1 a bottom anti-reflection layer which can be used in a positive exposure process. Two immiscible polymers are used here, with the first polymer separating from the second polymer during a coating process and forming an upper layer.

U.S. 2010/0 075 248 A1 discloses methods of providing ground anti-reflective coatings with improved cancellation performance. A combination of a short chain alcohol and tetraethylene glycol is used to improve removal performance over wet chemical removal solutions.

character list

• 1 ein anfängliches Verteilen einer Boden-Antireflexionsschicht auf einem Halbleitersubstrat gemäß einer Ausführungsform darstellt;
• 2 ein Ausbilden eines Aufschwimmbereichs gemäß einer Ausführungsform darstellt;
• 3 einen Ausheizvorgang gemäß einer Ausführungsform darstellt;
• die 4A-4B ein Aufbringen, Exponieren und Entwickeln eines Fotoresists gemäß einer Ausführungsform darstellen;
• 5 eine weitere Ausführungsform darstellt, in der die Antireflexionsbeschichtung in einem chemisch-mechanischen Poliervorgang gemäß einer Ausführungsform planarisiert wird;
• 6 stellt einen Schritt beim Beseitigen der Boden-Antireflexionsschicht und des Aufschwimmbereichs gemäß einer Ausführungsform dar;
• 7 stellt ein Beseitigen der Boden-Antireflexionsschicht und des Aufschwimmbereichs gemäß einer Ausführungsform dar;
• 8 stellt eine Mittelschicht dar, die in Verbindung mit der Boden-Antireflexionsschicht gemäß einer Ausführungsform verwendet wird; und
• 9 stellt einen Prozessablauf beim Verteilen der Boden-Antireflexionsschicht, Ausbilden des Aufschwimmbereichs und der Anwenden eines Fluids zum Beseitigen der Boden-Antireflexionsschicht gemäß einer Ausführungsform dar.

For a more thorough understanding of the present embodiments and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

• 1 Figure 13 illustrates an initial spreading of a bottom anti-reflection layer on a semiconductor substrate according to an embodiment;
• 2 Figure 12 illustrates forming a buoyancy zone according to an embodiment;
• 3 12 illustrates an annealing process according to one embodiment;
• the 4A-4B illustrate applying, exposing, and developing a photoresist according to one embodiment;
• 5 Figure 14 illustrates another embodiment in which the anti-reflective coating is planarized in a chemical mechanical polishing process according to one embodiment;
• 6 12 illustrates a step in eliminating the bottom anti-reflective coating and the flotation area, according to one embodiment;
• 7 Figure 12 illustrates eliminating the bottom anti-reflective layer and the flotation area according to one embodiment;
• 8th Figure 12 illustrates a middle layer used in conjunction with the bottom anti-reflective layer according to one embodiment; and
• 9 12 illustrates a process flow in spreading the bottom anti-reflective coating, forming the floating region, and applying a fluid to eliminate the bottom anti-reflective coating, according to one embodiment.

Corresponding numerals and symbols in the different figures generally refer to corresponding parts unless otherwise indicated. The figures are drawn in order to clearly illustrate the essential aspects of the embodiments and are not necessarily drawn to scale.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The solution according to the invention is provided by a method according to claims 1, 8 and 16. The manufacture and application of the present embodiments will be explained in detail below. However, it should be appreciated that the present disclosure provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts.

Embodiments are described with reference to a specific context, namely a bottom anti-reflective coating used in the manufacture of semiconductor devices. In the case of other coatings, however, other embodiments can also be used in different processes.

It will now open 1 Referring now to FIG. 1, a substrate 101 having fins 103 formed over the substrate 101 and a bottom anti-reflective coating (BARC) layer 105 applied over the fins 103 and the substrate 101 are illustrated. The substrate 101 may be substantially conductive or semiconductive with an electrical resistivity of less than 10 ³ ohm-meters and may comprise bulk silicon, doped or undoped, or a silicon-on-insulator (SOI) substrate active layer. In general, an SOI substrate includes a layer of semiconductor material such as silicon, germanium, silicon germanium, SOI, silicon germanium on insulator (SGOI), or combinations thereof. Other substrates that can be used include multilayer substrates, gradient substrates, or hybrid orientation substrates.

The fins 103 serve as a fin structure for the eventual formation of FinFET or multi-gate transistors (in 1 not shown separately). In one embodiment, the fins 103 may be formed from the material of the substrate 101 and as such may also comprise bulk silicon, doped or undoped, or they may be an active layer of a SOI substrate. Finns
103 may be formed by first depositing a mask material over the substrate 101, patterning the mask material, and then using the mask material as a mask to etch into the substrate 101, excavating the fins 103 from the substrate 101 material be formed.

However, using substrate 101 material to form the fins 103 is only one illustrative method that can be used to form the fins 103 . Alternatively, the fins 103 may be formed by first depositing a semiconductor material such as silicon, silicon germanium, or the like over the substrate 101 and then masking and etching the semiconductor material to form the fins 103 over the substrate 101. In yet another alternative, the fins 103 may be formed by masking the substrate 101 and, for example, using an epitaxial growth process to grow the fins 103 on the substrate 101. FIG. These and any other suitable method may alternatively be used to form the fins 103, and all such methods are fully intended to be included within the scope of the embodiments.

The BARC layer 105 is applied over the fins 103 and fills in the areas between the fins 103 in preparation for an application of a photoresist 401 (in Fig 1 not shown, but below with reference to FIG 4 shown and described). As its name suggests, the BARC layer 105 acts to prevent the uncontrolled and undesired reflection of energy (eg, light), such as light, back into the overlying photoresist 401 during exposure of the photoresist 401, thereby preventing that the reflected light causes reactions in an undesired area of the photoresist 401. In addition, the BARC layer 105 can be used to provide a planar surface over the substrate 101 and fins 103, which helps to reduce the negative effects of energy impinging at an angle.

In one embodiment, the BARC layer 105 comprises a polymeric resin, a catalyst, and a crosslinking agent, all placed in a solvent. The polymeric resin may comprise a polymer having different monomers bonded together. In one embodiment, the polymer can have different monomers, such as a crosslinking monomer and a monomer containing chromophore units. In one embodiment, the monomer containing the chromophore moiety may include vinyl compounds (e.g., having conjugated double bonds) that are substituted and unsubstituted phenyl, substituted and unsubstituted anthracyl, substituted and unsubstituted phenanthryl, substituted and unsubstituted naphthyl, substituted and unsubstituted acridine, substituted and unsubstituted quinolinyl and ring-substituted quinolinyls (e.g., hydroxyquinolinyl), substituted and unsubstituted heterocyclic rings containing heteroatoms such as oxygen, nitrogen, sulfur, or combinations thereof, such as pyrrolidinyl, pyranyl, piperidinyl, acridinyl, quinolinyl. The substituents in these moieties can be any hydrocarbyl group and may also contain: heteroatoms such as oxygen, nitrogen, sulfur, or combinations thereof such as alkylenes, esters, ethers, combinations thereof, or the like, having a number of carbon atoms between 1 and 12 .

In specific embodiments, the monomers having chromophore units include styrene, hydroxystyrene, acetoxystyrene, vinyl benzoate, vinyl 4-tert-butyl benzoate, ethylene glycol phenyl ether acrylate, phenoxypropyl acrylate, N-methylmaleimide, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, 2-hydroxy- 3-phenoxypropyl acrylate, phenyl methacrylate, benzyl methacrylate, 9-anthracenyl methyl methacrylate, 9-vinyl anthracene, 2-vinyl naphthalene, N-vinyl phthalimide, N-(3-hydroxy)phenyl methacrylamide, N-(3-hydroxy-4-hydroxycarbonylphenylazo)phenyl methacrylamide, N- (3-Hydroxyl-4-ethoxycarbonylphenylazo)phenyl methacrylamide, N-(2,4-dinitrophenylaminophenyl)maleimide, 3-(4-acetoaminophenyl)azo-4-hydroxystyrene, 3-(4-ethoxycarbonylphenyl)azoacetoacetoxyethyl methacrylate, 3-(4 -hydroxyphenyl)azo-acetoacetoxyethyl methacrylate, tetrahydroammonium sulfate salt of 3-(4-sulfophenyl)azo-acetoacetoxyethyl methacrylate, combinations thereof, or the like. Alternatively, however, any suitable monomer containing chromophore units may be used to absorb the incident light and prevent the light from being reflected, and all such monomers are fully intended to be included within the scope of the embodiments.

The crosslinking monomer can be used to crosslink the monomer to other polymers in the polymeric resin to alter the solubility of the BARC layer 105, and can optionally have an acid labile group. In a specific embodiment, the crosslinking monomer can have a hydrocarbon chain that also includes, for example, a hydroxyl group, a carboxylic acid group, a carboxylic ester group, epoxy groups, urethane groups, amide groups, combinations thereof, and the like. Specific examples of crosslinking monomers that can be used include polyhydroxystyrene, poly(hydroxynaphthalene), poly(meth)acrylates, polyarylates, polyesters, polyurethanes, alkyd resins (aliphatic polyesters), poly(hydroxystyrene-methyl methacrylate), homopolymers and/or copolymers, obtained by polymerizing at least one of the following monomers: styrene, hydroxystyrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid, poly(hydroxystyrene-styrene). -methacrylate), poly(4-hydroxystyrene) and poly(pyromellitic dianhydride ethylene glycol propylene oxide).

wobei jedes R und R¹ ein Wasserstoff oder eine substituierte oder unsubstituierte Alkylgruppe sein kann, die von 1 bis zu 8 Kohlenstoffatomen aufweist; jedes R² kann ein substituiertes oder unsubstituiertes Alkyl sein, das von 1 bis zu 10 Kohlenstoffatomen aufweist, und jedes R³ kann ein substituiertes oder unsubstituiertes Alkyl, das von 1 bis 8 Kohlenstoffatomen aufweist, ein Alkoxy, das zwischen 1 bis 8 Kohlenstoffatomen aufweist, ein Alkenyl, das zwischen 2 bis 8 Kohlenstoffatomen aufweist, ein Alkinyl, das von 2 bis zu 8 Kohlenstoffatomen aufweist, Cyan, Nitro sein; m ist eine ganze Zahl von 0 bis 9; und x ist der Molenbruch in Prozent von Alkyleinheiten im Polymerharz und liegt zwischen circa 10% und circa 90%; und y ist der Molenbruch oder Prozentanteil von Anthraceneinheiten im Polymerharz und liegt zwischen circa 5% und circa 90%.The various monomers are polymerized together to form a polymer structure with a carbon chain backbone for the polymer resin. In one embodiment, the polymer structure may have a carbon chain backbone that is an acrylic, a polyester, an epoxy novolac, a polysaccharide, a polyether, a polyimide, a polyurethane, and mixtures thereof. An example of a specific polymer resin that can be used has the following structure:

wherein each R and R ¹ can be hydrogen or a substituted or unsubstituted alkyl group having from 1 up to 8 carbon atoms; each R ² can be substituted or unsubstituted alkyl having from 1 up to 10 carbon atoms, and each R ³ can be substituted or unsubstituted alkyl having from 1 to 8 carbon atoms, alkoxy having from 1 to 8 carbon atoms, an alkenyl having from 2 to 8 carbon atoms, an alkynyl having from 2 up to 8 carbon atoms, cyano, nitro; m is an integer from 0 to 9; and x is the mole fraction percent of alkyl moieties in the polymer resin and is between about 10% and about 90%; and y is the mole fraction or percentage of anthracene units in the polymer resin and is between about 5% and about 90%.

In another embodiment, the polymeric resin may also include a surface energy modifying monomer (e.g., having a surface energy modifying group). The surface energy modification monomer is used to test and match the surface energy of the BARC layer 105 to the surface energy of the substrate 101 and fin (103) material (e.g., silicon). By adjusting the surface energies, capillary forces can be exploited to increase the BARC layer 105 gap filling performance.

wobei die R₁- und R₂-Gruppe gemeinsam die Oberflächenenergie-Modifikationsgruppe bilden und wobei R₁ eine Alkylgruppe mit Wasserstoff ist, die an die Kohlenwasserstoffe angehängt ist, und wobei R₁ eine gerade, verzweigte oder zyklische Struktur aufweisen kann. Die Alkylgruppe in R₁ kann auch Heteroatome umfassen, so z.B. Stickstoff- oder Sauerstoffatome, enthalten. R₂ kann mindestens eine von einer Hydroxyl-, Carboxyl-, Amin- oder Amidgruppe aufweisen.In one embodiment, the surface energy modification monomer can be used to increase the surface energy of the BARC layer 105 . In such an embodiment, the surface energy modifier group in the surface energy modifier monomer to increase the surface energy of the BARC layer 105 comprises one or more of a hydroxyl group, a carboxyl group, an amine group, or an amide group. In a specific embodiment, the surface energy modification monomer can have a structure such as the following:

wherein the R ₁ and R ₂ groups together form the surface energy modifier group and wherein R ₁ is an alkyl group having hydrogen attached to the hydrocarbons and wherein R ₁ can have a straight, branched or cyclic structure. The alkyl group in R ₁ can also contain heteroatoms, for example nitrogen or oxygen atoms. R ₂ may have at least one of a hydroxyl, carboxyl, amine, or amide group.

In specific embodiments, the surface energy modifier monomer may comprise an acrylic acid monomer, a methacrylic acid monomer, a hydrostyrene monomer, or a monomer derived from 2-hydroxyethyl acrylate. For example, in one embodiment where the surface energy modifying group is a hydrostyrene monomer, the surface energy modifying monomer may have the following structure:

In an embodiment where the surface energy modification monomer is an acrylic acid monomer, the surface energy modification monomer can have the following structure:

In an embodiment where the surface energy modifying group is a monomer derived from 2-hydroxyethyl acrylate, the surface energy modifying monomer can have the following structure:

However, as one skilled in the art will appreciate, the precise structures and examples described for raising the surface energy of the BARC layer 105 are intended to be illustrative and not limiting. Rather, any suitable functional group with any suitable monomer that would increase the surface energy of the BARC layer 105 may alternatively be employed. All of these are fully intended to be included within the scope of the embodiments.

Alternatively, the surface energy modification monomer can be used to reduce the surface energy of the BARC layer 105. In such an embodiment, the surface energy modifier group in the surface energy modifier monomer to reduce the surface energy of the BARC layer 105 comprises one or more of an alkyl group, a fluoro group, a chloro group, or a benzyl group. In specific embodiments, the surface energy modifying group can have a linear, branched, or cyclic alkyl or fluoro functional group.

wobei die R₃- und R₄-Gruppe gemeinsam die Oberflächenenergie-Modifikationsgruppe bilden und wobei R₃ eine Alkylgruppe mit Wasserstoff ist, die an die Kohlenwasserstoffe angehängt ist, und wobei R₃ eine gerade, verzweigte oder zyklische Struktur aufweisen kann. Die Alkylgruppe in R₃ kann auch Heteroatome umfassen, so z.B. Stickstoff- oder Sauerstoffatome, enthalten. In dieser Ausführungsform kann R₄ jedoch mindestens eine von einer Alkyl-, Fluor- oder Benzylgruppe enthalten und kann eine lineare, verzweigte oder zyklische Alkyl- oder Fluorgruppe aufweisen. Zum Beispiel kann das Polymerharz mit dem Oberflächenenergie-Modifikationsmonomer in einigen Ausführungsformen die folgenden Strukturen aufweisen:

In a specific embodiment, the surface energy modification monomer can have a structure such as the following:

wherein the R ₃ and R ₄ groups together form the surface energy modifier group and wherein R ₃ is an alkyl group having hydrogen attached to the hydrocarbons and wherein R ₃ can have a straight, branched or cyclic structure. The alkyl group in R ₃ can also contain heteroatoms, for example nitrogen or oxygen atoms. In this embodiment, however, R ₄ may contain at least one of an alkyl, fluoro, or benzyl group and may have a linear, branched, or cyclic alkyl or fluoro group. For example, in some embodiments, the polymer resin with the surface energy modification monomer can have the following structures:

By using the surface energy modification monomer, the surface energy of the polymeric resin and thus the BARC layer 105 can be modified to more closely match the surface energy of the substrate 101 and fins 103 . Instead of being repelled by the underlying material, the BARC layer 105 is drawn into even small openings between the structures by capillary forces through surface energy matching. This helps the BARC layer 105 fill such gaps without voids.

Also, as one skilled in the art will appreciate, the above description of the various monomers that can be polymerized to form the polymeric resin for the BARC layer 105 is intended for purposes of illustration and is not intended to limit the embodiments in any way way to restrict. Rather, any suitable monomer or combinations of monomers that perform the desired functions of the monomers described herein can also be employed. It is fully intended that all such monomers are included within the scope of the embodiments.

In another embodiment, one of the surface energy modifier monomer, the crosslinking monomer, or the monomer having the chromophore moiety may also have an inorganic component. In one embodiment, the inorganic component may contain a silicon atom and the surface energy modifying group may be bonded to the silicon atom in the surface energy modifying monomer. Alternatively, the chromophore group (in the monomer containing the chromophore moiety) can be attached to the inorganic moiety in the chromophore monomer, or the crosslinking group can be attached to the inorganic moiety in the crosslinking monomer. Any suitable combination of the inorganic component in any of the surface energy modification monomer, the chromophore monomer, or the crosslinking monomer can be employed.

By using an inorganic material in the monomers, the surface energy of the BARC layer 105 can be changed. If it is also modified so that the surface energy of BARC layer 105 is similar to the surface energy of the underlying material (i.e., substrate 101 and fins 103), then capillary forces can be used to force BARC layer 105 into small voids between structures such as fins 103. This will then help fill in the gaps and avoid defects that may occur as a result of non-uniform filling of the BARC layer 105.

wobei R₆ und R₇ gemeinsam die Oberflächenenergie-Modifikationsgruppe bilden und wobei R₆ eine Alkylgruppe mit Wasserstoff ist, die an die Kohlenwasserstoffe angehängt ist, und wobei R₆ eine gerade, verzweigte oder zyklische Struktur aufweisen kann. Die Alkylgruppe in R₆ kann auch Heteroatome umfassen, so z.B. Stickstoff- oder Sauerstoffatome enthalten. R₇ kann mindestens eine von einer Hydroxyl-, Carboxyl-, Amin- oder Amidgruppe enthalten.In one embodiment, the surface energy modification monomer with the energy modification group can be used to increase the surface energy of the BARC layer 105 . In such an embodiment, the surface energy modifying group to increase the surface energy of the BARC layer 105 comprises one or more of a hydroxyl group, a carboxyl group, an amine group, or an amide group. In a specific embodiment, the surface energy modification monomer can have a structure such as the following:

where R ₆ and R ₇ together form the surface energy modifier group and where R ₆ is an alkyl group having hydrogen attached to the hydrocarbons and where R ₆ can have a straight, branched or cyclic structure. The alkyl group in R ₆ can also contain heteroatoms, for example nitrogen or oxygen atoms. R ₇ may contain at least one of a hydroxyl, carboxyl, amine, or amide group.

In specific embodiments, the surface energy modifier monomer can be an acrylic acid group, a methacrylic acid group, or a hydrostyrene group. In an embodiment where the surface energy modifying monomer comprises silicon and the surface energy modifying group is hydrostyrene, the surface energy modifying monomer can have the following structure:

In an embodiment where the surface energy modifying monomer comprises silicon and the surface energy modifying group is a hydroxyl group, the surface energy modifying monomer may have the following structure:

In another embodiment, the surface energy modifying monomer comprises silicon and the surface energy modifying group is a methacrylic acid group. In another embodiment, the surface energy modifying monomer comprises silicon and the surface energy modifying group is an acrylic acid monomer.

However, as one skilled in the art will appreciate, the precise structures and examples described for raising the surface energy of the BARC layer 105 are intended to be illustrative and not limiting. Instead, any suitable functional group that would increase the surface energy of the BARC layer 105 can alternatively be used. All of these are fully intended to be included within the scope of the embodiments.

Alternatively, the surface energy modifier monomer can be used with an inorganic component to reduce the surface energy of the BARC layer 105. In such an embodiment, the surface energy modifier group in the surface energy modifier monomer to reduce the surface energy of the BARC layer 105 comprises one or more of an alkyl group, fluoro group, or benzyl group. In specific embodiments, the surface energy modification monomer can have a linear, branched, or cyclic alkyl or fluoro functional group.

wobei R₈ und R₉ gemeinsam die Oberflächenenergie-Modifikationsgruppe bilden und wobei R₈ eine Alkylgruppe mit Wasserstoff ist, die an die Kohlenwasserstoffe angehängt ist, und wobei R₈ eine gerade, verzweigte oder zyklische Struktur aufweisen kann. Die Alkylgruppe in R₈ kann auch Heteroatome umfassen, so z.B. Stickstoff- oder Sauerstoffatome, enthalten. In dieser Ausführungsform kann R₉ jedoch mindestens eine von einer Alkyl-, Fluor-, Benzylgruppe enthalten und kann eine lineare, verzweigte oder zyklische Alkyl- oder Fluorgruppe aufweisen. Zum Beispiel kann das Oberflächenenergie-Modifikationsmonomer in einigen Ausführungsformen eine der folgenden Strukturen aufweisen:

wobei R10 ein Alkyl mit einer Anzahl von einem bis zu sechs Kohlenstoffatomen ist.In a specific embodiment, the surface energy modification monomer can have a structure such as the following

where R ₈ and R ₉ together form the surface energy modifier group and where R ₈ is an alkyl group having hydrogen attached to the hydrocarbons and where R ₈ can have a straight, branched or cyclic structure. The alkyl group in R ₈ can also contain heteroatoms, for example nitrogen or oxygen atoms. In this embodiment, however, R ₉ may contain at least one of an alkyl, fluoro, benzyl group, and may have a linear, branched, or cyclic alkyl or fluoro group. For example, in some embodiments, the surface energy modification monomer can have one of the following structures:

where R10 is an alkyl of one to six carbon atoms.

In addition, in this embodiment, the inorganic element (e.g., silicon) is not limited to being present only on the polymer backbone. Instead, the inorganic element can be arranged in the polymer resin. As an example, the crosslinking polymer may be formed with an inorganic functional group such as silicon ethoxyl or silicon methoxyl, although any other suitable crosslinking material may be employed.

The catalyst can be a compound used to initiate a crosslinking reaction between the polymers in the polymer resin and can be, for example, a thermal acid generator, a photoacid generator, a photobase generator, suitable combinations thereof, or the like. In an embodiment where the catalyst is a thermal acid generator, the catalyst generates an acid when sufficient heat is applied to the BARC layer 105 . Specific examples of the thermal acid generator include butanesulfonic acid, triflic acid, nanofluorobutanesulfonic acid, nitrobenzyl tosylates such as 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-nitrobenzyl tosylate; 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl-4-chlorobenzenesulfonate, 2-trifluoromethyl-6-nitrobenzyl-4-nitrobenzenesulfonate; phenolsulfonate esters such as phenyl, 4-methoxybenzenesulfonate; alkylammonium salts of organic acids such as triethylammonium salt of 10-camphorsulfonic acid, combinations thereof, or the like.

In an embodiment in which the catalyst is a photoacid generator, the catalyst may comprise: halogenated triazines, onium salts, diazonium salts, aromatic diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide floating catalyst sulfonate, oxime sulfonate, diazodisulfone, disulfone, o-nitrobenzyl sulfonate, sulfonated esters, halogenated sulfonyloxydicarboximides, diazodisulfones, α-cyanoxyamine sulfonates, imide sulfonates, ketodiazosulfones, sulfonyldiazoesters, 1,2-di(arylsulfonyl)hydrazines, nitrobenzyl esters, and the s-triazine derivatives, suitable combinations thereof, and the like.

Specific examples of photoacid generators that can be used include: α-(trifluoromethylsulfonyloxy)bicyclo[2.2.i]hept-5-ene-2,3-dicarboximide (MDT), N-hydroxynaphthalimide (DDSN), Ben zoin tosylate, t-butylphenyl-α-(p-toluenesulfonyloxy)-acetate and t-butyl-α-(p-toluenesulfonyloxy)-acetate, triarylsulfonium and diaryliodonium hexafluoroantimonates, hexafluoroarsenates, trifluoromethanesulfonates, iodonium perfluorooctanesulfonate, N-camphorsulfonyloxynaphthalimide, N-pentafluorophenylsulfonyloxynaphthalimide , ionic iodonium sulfonates such as diaryliodonium (alkyl or aryl) sulfonate and bis (di-t-butylphenyl) iodonium camphoryl sulfonate, perfluoroalkane sulfonates such as perfluoropentane sulfonate, perfluorooctane sulfonate, perfluoromethane sulfonate, aryl (eg phenyl or benzyl) triflates such as eg triphenylsulfonium triflate or bis-(t-butylphenyl)iodonium triflate, pyrogallol derivatives (eg trimesylate of pyrogallol), trifluoromethanesulfonate esters of hydroxyimides, α,α'-bis-sulfonyl-diazomethanes, sulfonate esters of nitro-substituted benzyl alcohols, naphthoquinone-4-diazides, alkyldisulfones and the like.

In another embodiment, the catalyst can be a photobase generator. In such an embodiment, the photobase generator may include quaternary ammonium dithiocarbamates, α-aminoketones, oximurethane-containing molecules such as dibenzophenone oxime hexamethylenediurethane, ammonium tetraorganylborate salts, and cyclic N-(2-nitrobenzyloxycarbonyl)amines, suitable combinations thereof, or the like.

In one embodiment, the buoyant crosslinking agent is also included with the polymer resin and the catalyst. The floating crosslinking agent reacts with the polymers in the polymer resin and forms linear or branched structures of polymers having larger molecular weight molecules, thereby improving the crosslink density. In one embodiment, the buoyant crosslinking agent can be an aliphatic polyether, such as a polyether polyol, a polyglycidyl ether, a vinyl ether, a glycoluril, a triazine, combinations thereof, or the like.

wobei n eine ganze Zahl von 1 bis 300 darstellt; m eine ganze Zahl von 2 bis 6 darstellt; R₁ ein Wasserstoffatom oder eine Alkylgruppe darstellt, die 1 bis 10 Kohlenstoffatome aufweist; und R₂ eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, eine Alkenylgruppe mit 2 bis 6 Kohlenstoffatomen, eine Alkinylgruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkylcarbonylgruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkylcarbonylaminogruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkyloxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkylaminogruppe mit 1 bis 10 Kohlenstoffatomen, eine Alkyldiaminogruppe mit 1 bis 10 Kohlenstoffatomen oder eine Kombination derselben darstellt und eine organische Gruppe ist, die in der Lage ist, eine Valenzzahl von 2 bis 6 entsprechend der Anzahl m der Polyoxyalkylengruppen aufzuweisen. Spezifische Beispiele für Alkylgruppen, die für R₁ verwendet werden können, schließen eine Methylgruppe, Ethylgruppe, Propylgruppe, Isopropylgruppe, n-Butylgruppe und n-Pentylgruppe ein.In one embodiment where the buoyant crosslinking agent is a polyether polyol, the buoyant crosslinking agent has the following structure:

wherein n represents an integer from 1 to 300; m represents an integer from 2 to 6; R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and R ₂ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkylcarbonylamino group having 2 to 10 carbon atoms, an alkyloxyalkyl group having 2 to 10 carbon atoms , an alkylamino group having 1 to 10 carbon atoms, an alkyldiamino group having 1 to 10 carbon atoms or a combination thereof and is an organic group capable of having a valence number of 2 to 6 corresponding to the number m of the polyoxyalkylene groups. Specific examples of alkyl groups that can be used for R ₁ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and n-pentyl group.

Specific examples of an alkyl group that can be used for R ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, cyclobutyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl- n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl cyclobutyl group, 2-methyl cyclobutyl group, 3-methyl cyclobutyl group, 1,2-dimethyl cyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4- methyl n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3- dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2- Trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1,4-dimethyl-cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl- cyclopentyl group, 3-methyl cyclopentyl group, 1-ethyl cyclobutyl group, 2-ethyl cyclobutyl group, 3-ethyl cyclobutyl group, 1,2-dimethyl cyclobutyl group, 1,3-dimethyl cyclobutyl group, 2,2-dimethyl cyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethyl cyclobutyl group, 3,3-dimethyl cyclobutyl group, 1-n-propyl cyclopropyl group, 2-n-propyl cyclopropyl group, 1-isopropyl cyclopropyl group, 2-isopropyl cyclopropyl group, 1,2,2-trimethyl cyclopropyl group, 1, 2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group and 2- ethyl-3-methyl-cyclopropyl group.

Specific examples of the alkenyl group that can be used for R ₂ include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl- 1-propenyl group, 2-methyl-2-propenyl group, 1-ethyl-ethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propyl-ethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2- methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1- isopropyl ethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4- hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butyl-ethenyl group, 2-methyl- 1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-i-pentenyl group, 3-methyl- 2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3- pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butyl-ethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-isobutyl-ethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3- dimethyl-3-butenyl group, 2-isopropyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1- n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl 2-propenyl group, 1-tert-butyl-ethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1- isopropyl-1-propenyl group, 1-isopropyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl- 3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylenecyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group and 3-cyclohexenyl group.

Specific examples of the alkynyl group that can be used for R ₂ include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 3-methyl-1-butynyl group, 1,1-dimethyl- 2-propynyl group, 2-ethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 1-methyl-2-pentynyl group, 1-methyl-3-pentynyl group, 1- Methyl-4-Pentynyl Group, 2-Methyl-3-Pentynyl Group, 2-Methyl-4-Pentynyl Group, 3-Methyl-1-Pentynyl Group, 3-Methyl-4-Pentynyl Group, 4-Methyl-1-Pentynyl Group, 4-Methyl- 2-pentynyl group, 1,1-dimethyl-2-butynyl group, 1,1-dimethyl-3-butynyl group, 1,2-dimethyl-3-butynyl group, 2,2-dimethyl-3-butynyl group, 3,3-dimethyl- 1-butynyl group, 1-ethyl-2-butynyl group, 1-ethyl-3-butynyl group, 1-n-propyl-2-propynyl group, 2-ethyl-3-butynyl group, 1-methyl-1-ethyl-2-propynyl group and 1-isopropyl-2-propynyl group.

Specific examples of the alkylcarbonyl group which can be used for R ₂ include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, cyclopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, tert-butylcarbonyl group, cyclobutylcarbonyl group, 1-methylcyclopropylcarbonyl group, 2-methylcyclopropylcarbonyl group, n-pentylcarbonyl group, 1-methyl-n-butylcarbonyl group, 2-methyl-n-butylcarbonyl group, 3-methyl-n-butylcarbonyl group, 1,1-dimethyl-n-propylcarbonyl group, 1,2-dimethyl- n-propylcarbonyl group, 2,2-dimethyl-n-propylcarbonyl group, 1-ethyl-n-propylcarbonyl group, cyclopentylcarbonyl group, 1-methyl-cyclobutylcarbonyl group, 2-methyl-cyclobutylcarbonyl group, 3-methyl-cyclobutylcarbonyl group, 1,2-dimethyl-cyclopropylcarbonyl group, 2,3-dimethylcyclopropylcarbonyl group, 1-ethylcyclopropylcarbonyl group, 2-ethylcyclopropylcarbonyl group, n-hexylcarbonyl group, 1-methyl-n-pentylcarbonyl group, 2-methyl-n-pentylcarbonyl group, 3-methyl-n-pentylcarbonyl group, 4- methyl-n-pentylcarbonyl group, 1,1- dimethyl-n-butylcarbonyl group, 1,2-dimethyl-n-butylcarbonyl group, 1,3-dimethyl-n-butylcarbonyl group, 2,2-dimethyl-n-butylcarbonyl group, 2,3-dimethyl-n-butylcarbonyl group, 3,3- dimethyl-n-butylcarbonyl group, 1-ethyl-n-butylcarbonyl group, 2-ethyl-n-butylcarbonyl group, 1,1,2-trimethyl-n-propylcarbonyl group, 1,2,2-trimethyl-n-propylcarbonyl group, 1-ethyl- 1-methyl-n-propylcarbonyl group, 1-ethyl-2-methyl-n-propylcarbonyl group, cyclohexylcarbonyl group, 1-methyl-cyclopentylcarbonyl group, 2-methyl-cyclopentylcarbonyl group, 3-methyl-cyclopentylcarbonyl group, 1-ethyl-cyclobutylcarbonyl group, 2-ethyl- cyclobutylcarbonyl group, 3-ethylcyclobutylcarbonyl group, 1,2-dimethylcyclobutylcarbonyl group, 1,3-dimethylcyclobutylcarbonyl group, 2,2-dimethylcyclobutylcarbonyl group, 2,3-dimethylcyclobutylcarbonyl group, 2,4-dimethylcyclobutylcarbonyl group, 3, 3-dimethylcyclobutylcarbonyl group, 1-n-propylcyclopropylcarbonyl group, 2-n-propylcyclopropylcarbonyl group, 1-isopropylcyclopropylcarbonyl group, 2-isopropylcyclopropylcarbonyl group, 1,2,2-trimethylcyclopropylcarbonyl group, 1,2,3- Trimethylcyclopropylcarbonyl group, 2,2,3-trimethylcyclopropylcarbonyl group, 1-ethyl-2-methylcyclopropylcarbonyl group, 2-ethyl-1-methylcyclopropylcarbonyl group, 2-ethyl-2-methylcyclopropylcarbonyl group and 2-ethyl-3- methylcyclopropylcarbonyl group.

Specific examples of the alkylcarbonylamino group which can be used for R ₂ include methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, isopropylcarbonylamino group, cyclopropylcarbonylamino group, n-butylcarbonylamino group, isobutylcarbonylamino group, s-butylcarbonylamino group, tert-butylcarbonylamino group, cyclobutylcarbonylamino group, 1-methylcyclopropylcarbonylamino group, 2-methylcyclopropylcarbonylamino group, n-pentylcarbonylamino group, 1-methyl-n-butylcarbonylamino group, 2-methyl-n-butylcarbonylamino group, 3-methyl-n-butylcarbonylamino group, 1,1-dimethyl-n-propylcarbonylamino group, 1,2-dimethyl- n-propylcarbonylamino group, 2,2-dimethyl-n-propylcarbonylamino group, 1-ethyl-n-propylcarbonylamino group, cyclopentylcarbonylamino group, 1-methyl-cyclobutylcarbonylamino group, 2-methyl-cyclobutylcarbonylamino group, 3-methyl-cyclobutylcarbonylamino group, 1,2-dimethyl-cyclopropylcarbonylamino group, 2,3-dimethylcyclopropylcarbonylamino group, 1-ethylcyclopropylcarbonylamino group, 2-ethylcyclopropylcarbonylamino group, n-hexylcarbonylamino group, 1-methyl-n-pentylcarbonylamino group, 2-methyl-n-pentylcarbonylamino group, 3-methyl-n-pentylcarbonylamino group, 4- methyl-n-pentylcarbonylamino group, 1,1-dimethyl-n-butylcarbonylamino group, 1,2-dimethyl-n-butylcarbonylamino group, 1,3-dimethyl-n-butylcarbonylamino group, 2,2-dimethyl-n-butylcarbonylamino group, 2,3- dimethyl-n-butylcarbonylamino group, 3,3-dimethyl-n-butylcarbonylamino group, 1-ethyl-n-butylcarbonylamino group, 2-ethyl-n-butylcarbonylamino group, 1,1,2-trimethyl-n-propylcarbonylamino group, 1,2,2- Trimethyl-n-propylcarbonylamino group, 1-ethyl-1-methyl-n-propylcarbonylamino group, 1-ethyl-2-methyl-n-propylcarbonylamino group, cyclohexylcarbonylamino group, 1-methyl-cyclopentylcarbonylamino group, 2-methyl-cyclopentylcarbonylamino group, 3-methyl-cyclopentylcarbonylamino group, 1-ethylcyclobutylcarbonylamino group, 2-ethylcyclobutylcarbonylamino group, 3-ethylcyclobutylcarbonylamino group, 1,2-dimethylcyclobutylcarbonylamino group, 1,3-dimethylcyclobutylcarbonylamino group, 2,2-dimethylcyclobutylcarbonylamino group, 2,3-dimethylcyclobutylcarbonylamino group, 2,4-dimethylcyclobutylcarbonylamino group, 3,3-dimethylcyclobutylcarbonylamino group, 1-n-propylcyclopropylcarbonylamino group, 2-n-propylcyclopropylcarbonylamino group, 1-isopropylcyclopropylcarbonylamino group, 2-isopropylcyclopropylcarbonylamino group, 1,2,2- trimethylcyclopropylcarbonylamino group, 1,2,3-trimethylcyclopropylcarbonylamino group, 2,2,3-trimethylcyclopropylcarbonylamino group, 1-ethyl-2-methylcyclopropylcarbonylamino group, 2-ethyl-1-methylcyclopropylcarbonylamino group, 2-ethyl-2- methyl-cyclopropylcarbonylamino group and 2-ethyl-3-methyl-cyclopropylcarbonylamino group.

Specific examples of the alkyloxyalkyl group that can be used for R ₂ include methyloxymethyl group, ethyloxyethyl group, ethyloxymethyl group, propyloxypropyl group, propyloxymethyl group, tert-butyloxy-tert-butyl group and methyl-tert-butyl group.

Specific examples of the alkylamino group which can be used for R ₂ include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, cyclopropylamino group, n-butylamino group, isobutylamino group, s-butylamino group, tert-butylamino group, cyclobutylamino group, 1-methylcyclopropylamino group, 2-methylcyclopropylamino group, n-pentylamino group, 1-methyl-n-butylamino group, 2-methyl-n-butylamino group, 3-methyl-n-butylamino group and 1,1-dimethyl-n-propylamino group.

Specific examples of the alkyldiamino group which can be used for R ₂ include methyldiamino group, ethyldiamino group, n-propyldiamino group, isopropyldiamino group, cyclopropyldiamino group, n-butyldiamino group, isobutyldiamino group, s-butyldiamino group, tert-butyldiamino group, cyclobutyldiamino group, 1-methylcyclopropyldiamino group, 2-methylcyclopropyldiamino group, n-pentyldiamino group, 1-methyl-n-butyldiamino group, 2-methyl-n-butyldiamino group, 3-methyl-n-butyldiamino group and 1,1-dimethyl-n-propyldiamino group.

wobei m eine ganze Zahl von 2 bis 6 darstellt und R₂ (ähnlich zu den oben mit Bezug auf Polyether-Polyol beschriebenen Gruppen) eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, eine Alkenylgruppe mit 2 bis 6 Kohlenstoffatomen, eine Alkinylgruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkylcarbonylgruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkylcarbonylaminogruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkyloxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen, eine Alkylaminogruppe mit 1 bis 10 Kohlenstoffatomen, eine Alkyldiaminogruppe mit 1 bis 10 Kohlenstoffatomen oder Kombinationen derselben darstellt, eine gerade, verzweigte oder zyklische Struktur aufweist und eine organische Gruppe ist, die eine Valenzzahl von 2 bis 6 entsprechend der Anzahl von m Glycidylethergruppen aufweist.In one embodiment where the buoyant crosslinking agent is a polyglycidyl ether, the buoyant crosslinking agent has the following structure:

where m is an integer from 2 to 6 and R ₂ is (similar to the groups described above with respect to polyether polyol) an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 10 carbon atoms , an alkylcarbonyl group having 2 to 10 carbon atoms, an alkylcarbonylamino group having 2 to 10 carbon atoms, an alkyloxyalkyl group having 2 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkyldiamino group having 1 to 10 carbon atoms, or combinations thereof, a straight, branched or has cyclic structure and is an organic group having a valence number of 2 to 6 corresponding to the number of m glycidyl ether groups.

wobei n von eins bis sechs geht, R eine Arylgruppe oder eine Alkylgruppe ist und X ein Alkyl, Alkoxys, Carboxys oder Kombinationen derselben ist.In one embodiment where the buoyant crosslinking agent is a vinyl ether, the buoyant crosslinking agent has the following structure:

where n is from one to six, R is an aryl group or an alkyl group, and X is alkyl, alkoxy, carboxy, or combinations thereof.

In specific embodiments where the buoyant crosslinking agent is a vinyl ether, the buoyant crosslinking agent has one of the following structures:

In an embodiment where the buoyant crosslinking agent is a glycoluril, the buoyant crosslinking agent can be a methylated glycoluril such as methoxymethylated glycoluril. In a specific embodiment where the buoyant crosslinking agent is a methoxymethylated glycoluril, the buoyant crosslinking agent has the following structure:

In an embodiment where the buoyant crosslinker is a triazene, the buoyant crosslinker can be a triazene such as 3,3-dimethyl-1-phenylene triazene, a 3,3-dimethyl-1-phylene triazene containing aryl group, or bis(triazene). In a specific embodiment, the floating crosslinking agent is a triazene having the following structure:

In one embodiment, the buoyant crosslinking agent also has a substituted fluorine atom that has been incorporated into the structure of the buoyant crosslinking agent. In a specific embodiment, the fluorine atom can be incorporated into the crosslinking structure as one or more fluorine atoms substituted, for example, for a hydrogen atom in an alkyl group located in the structure of the buoyant crosslinking agent.

Alternatively, the fluorine atom may be part of an alkyl fluoride group substituted into the structure of the buoyant crosslinking agent. As specific examples, the fluorine atom can be incorporated into an alkyl fluoride group having one of the following structures:

However, any suitable number of carbon and fluorine atoms may alternatively be employed.

As one skilled in the art will also appreciate, it is intended that the specific examples given above regarding the structures and groups that can be used in a buoyant crosslinking agent are for illustration only and are not intended to represent every possible structure or group that may be used to form of the floating crosslinking agent can be used. Any suitable alternative structure and any suitable alternative Groups can be used to form the floating crosslinking agent. All such structures and groups are fully intended to be included within the scope of the embodiments.

The individual components of the BARC layer 105 can be incorporated into the BARC solvent to aid in the mixing and placement of the BARC layer 105. To aid in the mixing and placement of the BARC layer 105, the solvent is selected based at least in part on the materials and monomers selected for the polymeric resin of the BARC layer 105 as well as the catalyst. In particular, the BARC solvent is selected such that the polymer resin, catalysts, and floating crosslinking agent can be evenly dissolved in the BARC solvent and distributed over the substrate 101 and the fins 103 .

In one embodiment, the BARC solvent can be an organic solvent and can be any suitable solvent such as ketones, alcohols, polyalcohols, ethers, glycol ethers, cyclic ethers, aromatic hydrocarbons, esters, propionates, lactates, lactic esters, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxy propionates, cyclic lactones, ring-containing monoketone compounds, alkylene carbonates, alkylene alkoxy acetate, alkyl pyrovates, lactate esters, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol alkyl ether acetates, alkylene glycol alkyl ether esters, alkylene glycol monoalkyl esters, or the like.

Specific examples of materials that can be used as the BARC solvent include acetone, methanol, ethanol, toluene, xylene, 4-hydroxy-4-methyl-2-pentanone, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, Ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoetheryl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethyl 2-hydroxypropion at, methyl-2-hydroxy -2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl-3 -ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate, propylene glycol, propylene glycol monoacetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl methyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl lactate, ethyl lactate , propyl lactate and butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate, β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β -Methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanolactone, α-hydroxy-γ-butyrolactone, 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 4-methyl-2 -pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3 -Hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2 -octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2 -Methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2 ,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone, pylene carbonate, vinylene carbonate, ethylene carbonate and butylene carbonate, acetate-2-methoxyethyl, acetate-2-ethoxyethyl, acetate-2-(2-ethoxyethoxy)ethyl, acetate-3- methoxy-3-methylbutyl, acetate-1-methoxy-2-propyl, dipropylene glycol, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, dipropylene glycol monoacetate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl puruvate, ethyl puruvate, propyl puruvate, methyl methoxypropionate, ethyl ethoxypropionate, n-methylpyrrolidone (NMP), 2-methoxymethyl ether (diglyme), ethylene glycol monomethyl ether, propylene glycol monomethyl ether; Ethyl Lactate or Methyl Lactate, Methyl Propionate, Ethyl Propionate and Ethyl Ethoxypropionate, Methyl Ethyl Ketone, Cyclohexanone, 2-Heptanone, Carbon Dioxide, Cyclopentanone, Cyclohexanone, Ethyl 3-Ethoxypropionate, Ethyl Lactate, Propylene Glycol Methyl Ether Acetate (PGMEA), Methylene Cellosolve, Butyl Acetate and 2-Ethoxyethanol, N-Methylformamide , N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate , ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate or the like.

However, as one skilled in the art will appreciate, the materials listed and described above as examples of materials that may be employed for the solvent component of the BARC layer 105 are for purposes of illustration only and are not intended to limit the embodiments. Rather, any suitable material capable of dissolving the polymeric resin, catalyst, and floating crosslinking layer may alternatively be employed to aid in the mixing and application of the BARC layer 105 . All such materials are fully intended to be included within the scope of the embodiments.

In addition, other ingredients may also be added to the BARC layer 105 material if desired. For example, in one embodiment, the monomeric dyes, surface-leveling agents, adhesion-promoting agents, anti-foaming agents, and the like may alternatively be employed. Any suitable additive may be added to the material for the BARC layer 105, and all such additives are fully intended to be included within the scope of the embodiments.

In one embodiment, the polymer resin, catalysts, and floating crosslinking agent are added to the BARC solvent along with any desired additives or other agents to form the BARC layer 105 material. Once added, the mixture is then mixed to achieve an even and constant composition throughout the material for the BARC layer 105 to ensure that there are no defects caused by uneven mixing or non-constant composition of the material for the BARC layer 105 are caused. Once mixed together, the BARC layer 105 material can either be stored prior to use or used immediately.

In its original mixed form, the material for the BARC layer 105 can have a constant component composition, with the polymer resin having a concentration between about 0.1% and about 60%, the catalyst having a concentration between about 0.01% and about 10%, and the buoyant crosslinking agent has a concentration of between about 0.01% and about 30%. However, although these concentrations are illustrative, any suitable combination of the various constituents of the material for the BARC layer 105 may be used, and all such combinations are fully intended to be included within the scope of the embodiments.

Once the BARC layer 105 material has been prepared, the BARC layer 105 material can be deployed by applying the BARC layer 105 material to the substrate 101 and the fins 103 . The BARC layer 105 material may be applied to the substrate 101 and the fins 103 such that the BARC layer 105 material covers an upper exposed surface of the substrate 101 and the fins 103, and may be applied using a process such as a spin coating process, dip coating process, air knife coating process, curtain coating process, wire bar coating process, gravure coating process, lamination process, extrusion coating process, combinations thereof, or the like. In one embodiment, the material for the BARC layer 105 may first be deposited such that it has a constant concentration and a thickness across a top of the fins 103 between about 10 nm and about 1000 nm, such as about 100 nm.

2 12 shows the floating crosslinker forming a floating region 201 along a top surface of the BARC layer 105. FIG. In one embodiment, the floating crosslinker moves toward the top of the BARC layer 105 when the BARC layer 105 is applied, for example, in the spin-on process. This movement is initiated because the addition of fluorine atoms causes the floating crosslinker to have a high surface energy. This high surface energy, together with the weak interaction between the fluorine atoms and the other atoms in the BARC layer 105, triggers the movement of the floating crosslinker toward the top surface of the BARC layer 105.

In an embodiment with the formation of the floating region 201, the floating region 201 has a higher concentration of the floating crosslinker than a remainder of the BARC layer 105, eg having a concentration between about 0.01% and about 10%, such as about 2%. , while the remainder of the BARC layer 105 (outside the floating region 201) will have a concentration of the floating crosslinker no greater than about 5%. Additionally, the floating region 201 has a thickness T ₁ less than about 50% of the total thickness of the BARC layer 105, such as between about 1 nm and about 100 nm, such as about 10 nm However, figures may vary and are for illustration only, and any benefits can be derived from suitable concentrations other than those listed herein.

3 shows a preheating of the BARC layer 105 (in 3 represented by the wavy lines labeled 301) which includes both the anneal itself and its consequent effects. In one embodiment, once the BARC layer 105 is deposited on the substrate 101 and the fins 103 , the preheating 301 of the BARC layer 105 is performed to cure and dry the BARC layer 105 prior to application of the photoresist 401 . The curing and drying of the BARC layer 105 removes some of the BARC solvent components but leaves behind the polymer resin, catalysts, crosslinking agent, and other additives. In one embodiment, the preheating 301 may be performed at a temperature suitable to vaporize the BARC solvent, such as between about 40°C and 400°C (such as between about 100°C and 150°C), although the exact temperature depends on the materials chosen for the BARC layer 105. The preheating is performed for a time sufficient to cure and dry the BARC layer 105, such as from about 10 seconds to about 5 minutes, such as about 90 seconds. In addition, the preheating causes the floating crosslinking agent to react with the polymeric resin and begin bonding and crosslinking of the individual polymers of the polymeric resin into larger molecular polymers.

However, as will be apparent to one skilled in the art, the curing process described above (in which a thermal anneal is performed to cure the BARC layer 105) is merely an illustrative process that can be used to cure the BARC layer 105 and the to initiate crosslinking reactions and is not intended to limit the embodiments. Rather, any suitable curing process may alternatively be employed, such as exposing the BARC layer 105 to an energy source (e.g., photolithographic exposure at a wavelength between about 10 nm to about 1000 nm), irradiating the BARC layer 105 to cure the BARC -cure layer 105, or even electro-cure the BARC layer 105, or the like. All such curing operations are fully intended to be included within the scope of the embodiments.

If all components of the BARC layer 105 material have a constant concentration throughout the BARC layer 105, then during preheat 301, where the solvent evaporates and crosslinking occurs, a number of problems can occur in filling the gap between the fins 103 occur. In particular, because of the evaporation of the solvent at the surface of the BARC layer 105, the concentrations of the remaining components can increase, which causes the crosslinking reactions to proceed faster than in the rest of the BARC layer 105, such as between the fins 103 voids within BARC layer 105 occur because of this non-uniform reaction between the top of BARC layer 105 and the rest of BARC layer 105 .

In addition, the crosslinking reaction itself can cause void formation. In particular, the crosslinking reaction will produce a number of reaction by-products as the polymers of the polymeric resin bond to one another. These reaction byproducts can vaporize and outgas during preheat 301 , causing voids to form between the crosslinked polymers across BARC layer 105 .

The crosslinking of the polymers, once fully developed, also causes shrinkage to occur. In particular, the crosslink density of the BARC layer 105 will increase as the polymers crosslink with each other, resulting in a lower overall BARC layer 105 volume. This reduced volume will create stresses along the surfaces on which the BARC layer 105 is coated (i.e., the substrate 101 and the fins 103). These stresses can tear the BARC layer 105 away from the surface structures and cause voids to form adjacent to the surfaces such as the fins 103 .

In addition, the crosslinking reaction will also change the polymer resins, which will become more hydrophobic. This change will also decrease the adhesion between the BARC layer 105 and the substrate 101. Such a decrease in adhesion, if the decrease is large enough, can result in delamination and delamination occurring between the BARC layer 105 and the substrate 101, which can adversely affect the performance of the BARC layer 105 during further processing .

Although all of the above occurs to form voids in the BARC layer 105 and delamination, eventually the combination of the crosslinking reaction and the elimination of the solvent will also cause the materials in the BARC layer 105 to cure and solidify. This curing prevents the materials from flowing into the voids or delaminations, which prevents the BARC layer 105 materials from patching the voids and delaminations.

However, with the inclusion of the buoyant crosslinking agent and the formation of the buoyant region 201, the buoyant crosslinking agent becomes localized along the top surface of the BARC layer 105. Therefore, the crosslinking reaction will primarily take place in the floating area 201, with the rest of the BARC layer 105, which is not in the floating area 201, having fewer crosslinking reactions and thus fewer crosslinking polymers.

In these circumstances, the crosslinking reaction will occur primarily along the top surface of the BARC layer 105, thereby providing the desired protection against the photoresist 401 that is subsequently applied, as well as the desired anti-reflective properties. However, elsewhere in the BARC layer 105, the crosslinking response is throttled, resulting in an alleviation of any subsequent problems caused by the overcrosslinking. In particular, there is no significant film shrinkage outside of the flotation region 201 and there are no significant by-products of the crosslinking reaction for outgassing outside of the flotation region 201, thereby avoiding void formation. In addition, by avoiding the crosslinking reactions along the interface of the BARC layer 105 and the substrate 101, the hydrophilic properties of the BARC layer 105 remain unchanged, whereby the adhesion remains the same and adhesion problems between the BARC layer 105 and the substrate 101 are avoided or reduced . Finally, because the remainder of the BARC layer 105 has fewer crosslinked polymers, the BARC layer 105 may still be able to flow during the course of the crosslinking reactions, creating a few voids that form at an early stage of the crosslinking reaction before completion of preheating 301 may have formed.

The use of a floating crosslinking agent is not the only method or material that can be used to form the floating region 201, however. Rather, any suitable material that is involved in the crosslinking reaction and that can be caused to float toward the top surface of the BARC layer 105 and form the floating region 201 may alternatively be used.

For example, in an alternative example, instead of using a buoyant crosslinking agent, a buoyant polymer resin can be employed. In this example, the floating polymeric resin may comprise a polymeric resin as described above with reference to FIG 1 was reported, but in which a fluorine atom was substituted into the structure. For example, in an example where the floating polymer resin has an alkyl group, the fluorine atom can be substituted for a hydrogen atom in one or more of the polymer's alkyl groups.

In another example, the fluorine atom can be part of a fluoroalkyl group substituted into the polymer of the polymeric resin. As a specific example, the fluorine atom can be incorporated into one of the fluoroalkyl groups, such as the fluoroalkyl groups discussed above with reference to the floating crosslinking agent (eg, CF ₃ , C ₂ F ₅ , C ₃ F _{7 ,} etc.). In an example where the polymeric resin has an alkyl group, the fluoroalkyl group can be substituted into the polymeric resin to form the buoyant polymeric resin by replacing one of the alkyl groups with the fluoroalkyl group to form the buoyant polymeric resin.

Instead of the floating crosslinking agent described above with reference to 1 in this example, the crosslinking agent can be similar to the crosslinking agent described above for the floating crosslinking agent (without the addition of the fluorine atom). Alternatively, the crosslinking agent may be a melamine-based agent, a urea-based agent, an ethylene urea-based agent, a propylene urea-based agent, a glycoluril-based agent, an aliphatic cyclic hydrocarbon containing a hydroxyl group, a hydroxyalkyl group, or a combination thereof comprises, oxygen-containing aliphatic cyclic hydrocarbon derivatives, glycoluril compounds, etherified amino resins, combinations thereof, or the like.

Specific examples of materials that can be used as the crosslinking agent include melamine, acetoguanamine, benzoguanamine, urea, ethylene urea or glycoluril with formaldehyde, glycoluril with a combination of formaldehyde and a lower alcohol, hexamethoxymethylmelamine, bismethoxymethyl urea, bismethoxymethylbismethoxyethylene urea, tetramethoxymethyl glycoluril and tetrabutoxymethyl glycoluril, mono- , di-, tri- or tetrahydroxymethylated glycoluril, mono-, di-, tri- and/or tetramethoxyethylated glycoluril, mono-, di-, tri- and/or tetraethoxymethylated glycoluril, mono-, di-, tri- and/or tetrapropoxymethylated Glycoluril and mono-, di-, tri- and/or tetrabutoxymethylated glycoluril, 2,3-dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis(hydroxymethyl)norbornane, cyclohexanedimethanol, 3,4,8(or 9 )-trihydroxytricyclodecane, 2-methyl-2-adamantanol, 1,4-dioxane-2,3-diol and 1,3,5-trihydroxycyclohexane, tetramethoxymethylglycoluril, methylpropyltetramethoxymethylglycoluril and methylphenyltetramethoxymethylglycoluril, 2,6-bis(hydroxymethyl)p-cresol, N-methoxymethyl or N-butoxymethyl melamine. Also, compounds obtained by reacting formaldehyde or formaldehyde and lower alcohols with amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea and glycoluril, and substituting the hydrogen atoms of the amino group with the hydroxymethyl group or the lower alkoxymethyl group, whereby hexamethoxymethylmelamine , bismethoxymethyl urea, bismethoxymethyl bismethoxyethylene urea, tetramethoxymethyl glycoluril and tetrabutoxymethyl glycoluril, copolymers of 3-chloro-2-hydroxypropyl methacrylate and methacrylic acid, copolymers of 3-chloro-2-hydroxypropyl methacrylate and cyclohexyl methacrylate and methacrylic acid, copolymers of 3-chloro-2-hydroxypropyl methacrylate and benzyl methacrylate and methacrylic acid, bisphenol A-di(3-chloro-2-hydroxypropyl) ether, Poly(3-chloro-2-hydroxypropyl) ether of a phenol novolak resin, pentaerythritol tetra(3-chloro-2-hydroxypropyl) ether, trimethylolmethane tri(3- chloro-2-hydroxypropyl) ether phenol, bisphenol A di(3-acetoxy-2-hydroxypropyl) ether, poly(3-acetoxy-2-hydroxypropyl) ether of a phenol novolak resin, pentaerythritol tetra(3-acetoxy-2- hydroxypropyl)ether, pentaerythritol poly(3-chloroacetoxy-2-hydroxypropyl)ether, trimethylolmethane tri( _3- acetoxy- ₂ -hydroxypropyl)ether, combinations thereof or the like are examples.

In this example where the buoyant polymeric resin is used in place of the buoyant crosslinking agent, the buoyant polymeric resin can have an initial concentration in the material for the BARC layer 105 between about 0.1% and about 60%, while the buoyant crosslinking agent has an initial concentration between about 0.01% and about 30%. The BARC layer 105 material can be distributed as described above with reference to FIG 1 (eg, a spin-on process) such that the BARC layer 105 initially has a constant concentration as it is distributed.

Similar to the one referred to above 2 However, in the example described, with the addition of the fluorine atom, the floating polymer resin, once dispersed, will rise toward the top of the BARC layer 105, with the floating region 201 (see Fig 2 ) forms during the delivery process. With the floating region 201 at the top of the BARC layer 105, the preheating process initiates the crosslinking reaction predominantly in the floating region 201 and any crosslinking reactions outside of the floating region 201 are restricted. By performing the crosslinking reaction adjacent to the top surface of the BARC layer 105, defects created by voids and delamination can be reduced or avoided.

In yet another embodiment, the buoyant region 201 may be formed by using a buoyant catalyst instead of using the buoyant crosslinking agent or the buoyant polymer. In this embodiment, the floating catalyst may comprise a trifluoro catalyst, as referred to above with reference to FIG 1 was reported, but in which a fluorine atom was substituted into the structure. For example, in an embodiment in which the levitating catalyst has an alkyl group, the fluorine atom can be substituted for a hydrogen atom in one or more of the catalyst's alkyl groups.

In another embodiment, the fluorine atom can be part of a fluoroalkyl group substituted into the catalyst. As a specific example, the fluorine atom can be incorporated into one of the fluoroalkyl groups, such as the fluoroalkyl groups discussed above with reference to the floating crosslinking agent (eg, CF ₃ , C ₂ F ₅ , C ₃ F _{7 ,} etc.). In an embodiment where the catalyst has an alkyl group, the fluoroalkyl group can be substituted into the catalyst to form the levitating catalyst by replacing one of the alkyl groups with the fluoroalkyl group to form the levitating catalyst.

In specific embodiments, the fluorine atom or fluoroalkyl groups can be substituted into the catalysts as follows:

In this embodiment, where the buoyant catalyst is used in place of the buoyant crosslinking agent or the buoyant polymer resin, the buoyant catalyst may have an initial concentration in the BARC layer 105 material of between about 0.01% and about 10%. The material for the BARC layer 105 can be distributed as referenced above in FIG 1 (eg, a spin-on process) such that the BARC layer 105 material initially has a constant concentration as it is dispersed.

Similar to the one referred to above 2 However, in the described embodiment, with the addition of the fluorine atom, the floating polymer resin, once dispersed, will rise toward the top of the BARC layer 105, with the floating region 201 (see Fig 2 ) forms during the delivery process. With the floating region 201 at the top of the BARC layer 105, the preheating process initiates the crosslinking reaction only in the floating region 201 and any crosslinking reactions outside of the floating region 201 are limited or prevented, thereby reducing or avoiding voids or delamination problems.

The 4A-4B 12 show applying, exposing, and developing a photoresist 401 over the BARC layer 105. In one embodiment, the photoresist 401 comprises a photoresist polymer resin along with one or more photoactive compounds (PACs) in a photoresist solvent. In one embodiment, the photoresist polymer resin may comprise a hydrocarbon structure (such as an alicyclic hydrocarbon structure) containing one or more groups that cleave (eg, an acid labile group) or otherwise react when mixed with acids, bases, or free radicals generated by the PACs (as further described below). In one embodiment, the hydrocarbon structure has a repeating unit that forms a skeletal backbone of the photoresist polymer resin. This repeating unit may contain acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth)acrylonitrile, (meth)acrylamides, styrenes, vinyl ethers, combinations thereof, and the like.

Specific structures that can be employed for the repeating unit of the hydrocarbon structure include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-Methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-alkyl-2-adamantyl (meth)acrylate or dialkyl(1-adamantyl)methyl (meth)acrylate, methyl methacrylate, ethyl methacrylate, n -Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, acetoxyethyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-acetoxy-2-hydroxypropyl methacrylate, 3-chloroacetoxy-2-hydroxypropyl methacrylate, butyl crotonate, hexyl crotonate and the like. Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butylate, vinyl methoxyacetate, vinyl benzoate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, n-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide , 2-Methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, phenylacrylamide, benzylacrylamide, methacrylamide, methylacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, 2-methoxyethyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, phenyl methacrylamide, benzyl methacrylamide, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl methyl benzoate, α-methyl styrene, maleimide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, combinations thereof or the like.

In one embodiment, the hydrocarbon structure repeating unit may also have either a monocyclic or a polycyclic hydrocarbon structure substituted into it, or else the monocyclic or polycyclic hydrocarbon structure may be the repeating unit to form an alicyclic hydrogen structure. Specific examples of monocyclic structures that can be used include bicycloalkane, tricycloalkane, tetracycloalkane, cyclopentane, cyclohexane, or the like.

The group which will decompose, otherwise known as a leaving group or - in one embodiment where the PAC is a photoacid generator - an acid labile group, is attached to the hydrocarbon structure so that it interacts with the acid/base/free Responds to radicals generated by PACs during exposure. In one embodiment, the group which will decompose, a carboxylic acid group, fluoroalcohol group, phenol alcohol group, sulfone group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, tris(alkylsulfonyl)methylene group, combinations thereof, or the like. Specific groups that can be used for the fluoroalcohol group include fluorohydroxyalkyl groups such as hexafluoroisopropanol group. Specific groups that can be used for the carboxylic acid groups include acrylic acid groups, methacrylic acid groups or the like.

In one embodiment, the photoresist polymeric resin may also have other groups attached to the hydrocarbon structure that help improve various properties of the polymerizable resin. For example, including a lactone group in the hydrocarbon structure helps reduce the level of line edge roughness after developing the photoresist 401, which helps reduce the number of defects that occur during development. In one embodiment, the lactone groups can contain rings that are five to seven members, although any suitable lactone structure can alternatively be used for the lactone group.

The photoresist polymeric resin may also contain groups that can help increase the adhesion of the photoresist 401 to underlying structures (e.g., the BARC layer 105). In one embodiment, polar groups that can help increase adhesion can be used, and polar groups that can be used in this embodiment include hydroxyl groups, cyano groups, or the like, although any suitable polar group can alternatively be employed.

Optionally, the photoresist polymer resin may further comprise one or more alicyclic hydrocarbon structures that also do not contain a group that will decompose. In one embodiment, the hydrocarbon structure that does not contain a group that will break down can contain structures such as 1-adamantyl (methacrylate), tricyclodecanyl (meth)acrylate, cyclohexyl (methacrylate), combinations thereof, or the like.

In addition, the photoresist 401 also includes one or more PACs. The PACs can be photoactive ingredients such as photoacid generators, photobase generators, free radical generators or the like, and the PACs can be positive-acting or negative-acting. In an embodiment where the PACs are a photoacid generator, the PACs can be halogenated triazines, onium salts, diazonium salts, aromatic diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, o-nitrobenzyl sulfonate, sulfonated esters, halogenated sulfonyloxydicarboximides, diazodisulfones , α-cyanoxyamine sulfonates, imide sulfonates, ketodiazosulfones, sulfonyldiazoesters, 1,2-di(arylsulfonyl)hydrazines, nitrobenzyl esters and the s-triazine derivatives, suitable combinations thereof, and the like.

Specific examples of photoacid generators that can be used include: α-(trifluoromethylsulfonyloxy)bicyclo[2.2.i]hept-5-ene-2,3-dicarboximide (MDT), N-hydroxynaphthalimide (DDSN), benzoin tosylate, t -butylphenyl-α-(p-toluenesulfonyloxy)-acetate and t-butyl-α-(p-toluenesulfonyloxy)-acetate, triarylsul fonium and diaryliodonium hexafluoroantimonate, hexafluoroarsenates, trifluoromethanesulfonates, iodonium perfluorooctanesulfonates, N-camphorsulfonyloxynaphthalimide, N-pentafluorophenylsulfonyloxynaphthalimide, ionic iodonium sulfonates such as diaryliodonium (alkyl or aryl) sulfonate and bis-(di-t-butylphenyl)iodonium camphorylsulfonate, perfluoroalkanesulfonates, how eg perfluoropentanesulfonate, perfluorooctanesulfonate, perfluoromethanesulfonate, aryl (eg phenyl or benzyl) triflates such as triphenylsulfonium triflate or bis-(t-butylphenyl)iodonium triflate, pyrogallol derivatives (eg trimesylate of pyrogallol), trifluoromethanesulfonate esters of hydroxyimides, α,α' -bis-sulfonyl-diazomethanesulfonate esters of nitrogen-substituted benzyl alcohols, naphthoquinone-4-diazides, alkyl disulfones and the like.

In an embodiment where the PACs are a free radical generator, the PACs can be n-phenylglycine, aromatic ketones such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4 ,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 3,3'-dimethyl-4'-methoxybenzophenone, p,p'-bis(dimethylamino)benzophenone, p,p`-bis(diethylamino)benzophenone, anthraquinone , 2-ethylanthraquinone, naphthaquinone and phenanthraquinone, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, methyl benzoin and ethyl benzoin, benzyl derivatives such as dibenzyl, benzyl diphenyl disulfide and benzyl dimethyl ketal, acridine derivatives such as 9-phenyl acridine and 1,7-bis(9-aeridinyl)heptane, thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone and 2-isopropylthioxanthone, acetophenones such as 1,1-dichloroacetophenone , p-t-butyldichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and 2,2-dichloro-4-phenoxyacetophenone, 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di-(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2- (o-Metoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-Metoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-Di(p-metoxyphenyl)-5-phenylimidazole dimer, 2-( 2,4-dimetoxyphenyl)-4,5-diphenylimidazole dimer and 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer, suitable combinations thereof, or the like.

In an embodiment where the PACs are a photobase generator, the PACs may include quaternary ammonium dithiocarbamates, α-aminoketones, oximurethane-containing molecules such as dibenzophenone oxime hexamethylenediurethane, ammonium tetraorganylborate salts, and cyclic N-(2-nitrobenzyloxycarbonyl)amines, suitable combinations thereof, or the like . As will be appreciated by those skilled in the art, the chemical compounds listed herein are intended only as illustrative examples of the PACs and are not intended to limit the embodiments to only those PACs specifically described. Rather, any suitable PAC may alternatively be employed, and all such PACs are fully intended to be included within the scope of the embodiments.

The individual components of the photoresist 401 can be added to a photoresist solvent to aid in the mixing and application of the photoresist 401. To aid in the mixing and application of the photoresist 401, the photoresist solvent is selected based at least in part on the materials selected for the photoresist polymer resin as well as the PACs. In particular, the photoresist solvent is selected such that the photoresist polymer resin and the PACs can be evenly dissolved in the photoresist solvent and distributed onto the BARC layer 105.

In one embodiment, the photoresist solvent can be an organic solvent and can be any suitable solvent such as ketones, alcohols, polyalcohols, ethers, glycol ethers, cyclic ethers, aromatic hydrocarbons, esters, propionates, lactates, lactic esters, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxy propionates, cyclic lactones, ring-containing monoketone compounds, alkylene carbonates, alkyl alkoxy acetate, alkyl pyrovates, lactate esters, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol alkyl ether acetates, alkylene glycol alkyl ether esters, alkylene glycol monoalkyl esters, or the like.

Specific examples of materials that can be used as the photoresist solvent for Photoresist 401 include acetone, methanol, ethanol, toluene, xylene, 4-hydroxy-4-methyl-2-pentanone, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2- Heptanone, ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoetheryl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethyl 2-hydroxypropionate, methyl-2 -hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl -3-ethoxypropionate, ethyl acetate, butyl acetate, Methyl lactate and ethyl lactate, propylene glycol, propylene glycol monoacetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl methyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl lactate, ethyl lactate, propyl lactate and butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate, β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanolactone, α-hydroxy-γ-butyrolactone, 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-methyl- 3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl- 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone, pylene carbonate, vinylene carbonate, ethylene carbonate and butylene carbonate, acetate 2-methoxyethyl, acetate 2-ethoxyethyl, acetate 2-(2-ethoxyethoxy)ethyl, acetate 3-methoxy-3-methylbutyl, acetate -1-methoxy-2-propyl, dipropylene glycol, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, dipropylene glycol monoacetate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl puruvate, ethyl puruvate, propyl puruvate, methyl methoxypropionate, ethyl ethoxypropionate, n-methylpyrrolidone (NMP ), 2-Methoxymethyl Ether (Diglyme), Ethylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether, Ethyl Lactate or Methyl Lactate, Methyl Propionate, Ethyl Propionate and Ethyl Ethoxypropionate, Methyl Ethyl Ketone, Cyclohexanone, 2-Heptanone, Carbon Dioxide, Cyclopentanone, Cyclohexanone, Ethyl 3-Ethoxypropionate, Ethyl Lactate, Propylene Glycol Methyl Acetate (PGMEA), Methylene cellosolve, butyl acetate and 2-ethoxyethanol, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate or the like.

However, as one skilled in the art will appreciate, the materials listed and described above as examples of materials that may be employed for the photoresist solvent component of photoresist 401 are for purposes of illustration only and are not intended to limit the embodiments. Rather, any suitable material capable of dissolving the photoresist polymer resin and PACs may alternatively be employed to aid in the mixing and application of the photoresist 401. All such materials are fully intended to be included within the scope of the embodiments.

Furthermore, although any one of the materials described above may be used as the photoresist solvent for photoresist 401, in alternative embodiments more than one of the materials described above may be used. For example, the photoresist solvent may contain a combination mixture of two or more of the materials described. All such combinations are fully intended to be included within the scope of the embodiments.

Optionally, a photoresist crosslinking agent can also be added to the photoresist 401 . The photoresist crosslinking agent reacts with the photoresist polymer resin in the photoresist 401 after exposure, supporting the increase in crosslinking density of the photoresist, which helps to improve the resist pattern and dry etch resistance, in one embodiment, the photoresist crosslinking agent can be an agent Melamine base, a urea-based agent, an ethylene urea-based agent, a propylene urea-based agent, a glycoluril-based agent, an aliphatic cyclic hydrocarbon having a hydroxyl group, a hydroxyalkyl group or a combination thereof, oxygen-containing derivatives of the aliphatic cyclic hydrocarbon, glycoluril compounds, etherified amino resins, combinations thereof, or the like.

Specific examples of materials that can be used as a photoresist crosslinking agent include melamine, acetoguanamine, benzoguanamine, urea, ethylene urea or glycoluril with formaldehyde, glycoluril with a combination of formaldehyde and a lower alcohol, hexamethoxymethylmelamine, bismethoxymethyl urea, bismethoxymethylbismethoxyethylene urea, tetramethoxy methylglycoluril and tetrabutoxymethylglycoluril, mono-, di-, tri- or tetrahydroxymethylated glycoluril, mono-, di-, tri- and/or tetramethoxymethylated glycoluril, mono-, di-, tri- and/or tetraethoxymethylated glycoluril, mono-, di-, tri- and/or tetrapropoxymethylated glycoluril and mono-, di-, tri- and/or tetrabutoxymethylated glycoluril, 2,3-dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis(hydroxymethyl)norbornane, cyclohexanedimethanol, 3, 4,8(or 9)-trihydroxytricyclodecane, 2-methyl-2-adamantanol, 1,4-dioxane-2,3-diol and 1,3,5-trihydroxycyclohexane, tetramethoxymethyl glycoluril, methylpropyltetramethoxymethyl glycoluril and methylphenyltetramethoxymethyl glycoluril, 2,6-bis( hydroxymethyl)p-cresol, N-methoxymethyl- or N-butoxymethylmelamine. Also, compounds obtained by reacting formaldehyde or formaldehyde and lower alcohols with amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea and glycoluril, and substituting the hydrogen atoms of the amino group with the hydroxymethyl group or the lower alkoxymethyl group, whereby hexamethoxymethylmelamine , bismethoxymethyl urea, bismethoxymethyl bismethoxyethylene urea, tetramethoxymethyl glycoluril and tetrabutoxymethyl glycoluril, copolymers of 3-chloro-2-hydroxypropyl methacrylate and methacrylic acid, copolymers of 3-chloro-2-hydroxypropyl methacrylate and cyclohexyl methacrylate and methacrylic acid, copolymers of 3-chloro-2-hydroxypropyl methacrylate and benzyl methacrylate and methacrylic acid, bisphenol A-di(3-chloro-2-hydroxypropyl) ether, Poly(3-chloro-2-hydroxypropyl) ether of a phenol novolak resin, pentaerythritol tetra(3-chloro-2-hydroxypropyl) ether, trimethylolmethane tri(3- chloro-2-hydroxypropyl) ether phenol, bisphenol A di(3-acetoxy-2-hydroxypropyl) ether, poly(3-acetoxy-2-hydroxypropyl) ether of a phenol novolak resin, pentaerythritol tetra(3-acetoxy-2- hydroxypropyl) ether, pentaerythritol poly(3-chloroacetoxy-2-hydroxypropyl) ether, trimethylolmethane tri(3-acetoxy-2-hydroxypropyl) ether, combinations thereof or the like are examples.

In addition to the photoresist polymer resins, PACs, photoresist solvents, and photoresist crosslinking agents, photoresist 401 may also contain a number of other additives that help photoresist 401 achieve the highest resolution. For example, photoresist 401 may also contain wetting agents that help improve the ability of photoresist 401 to cover the surface to which it is applied. In one embodiment, the wetting agents may include nonionic wetting agents, polymers having fluorinated aliphatic groups, wetting agents containing at least one fluorine atom and/or at least one silicon atom, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters.

Specific examples of materials that can be used as wetting agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyethylene glycol distearate, polyethylene glycol dilaurate , polyethylene glycol, polypropylene glycol, polyoxyethylene stearyl ether and polyoxyethylene cetyl ether; fluorine-containing cationic wetting agents, fluorine-containing nonionic wetting agents, fluorine-containing anionic wetting agents, cationic wetting agents and anionic wetting agents, polyethylene glycol, polypropylene glycol, polyoxyethylene cetyl ether, combinations thereof, or the like.

Another additive that can be added to the photoresist 401 is a scavenger that can be used to prevent the diffusion of the generated acids/bases/free radicals in the photoresist, which helps the configuration of the resist pattern and the stability of the photoresist 401 in Improved timing. In one embodiment, the scavenger is an amine, such as a secondary lower aliphatic amine, a tertiary lower aliphatic amine, or the like. Specific examples of amines that can be used include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine and triethanolamine, alkanolamine, combinations thereof, or the like.

Alternatively, an organic acid can be used as the scavenger. Specific embodiments of organic acids that can be employed include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, phosphoric oxo acid and their derivatives such as phosphoric acid and their derivatives such as their esters such as phosphoric acid, phosphoric acid Di-n-butyl ester and phosphoric acid diphenyl ester, phosphonic acid and derivatives thereof such as their esters such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester, and phosphinic acid and their derivatives such as their esters including phosphinic acid and phenylphosphinic acid.

Another additive that can be added to photoresist 401 is a stabilizer to help prevent unwanted diffusion of the acids generated during photoresist 401 exposure. In one embodiment, the stabilizer can be nitrogen compounds such as aliphatic primary, secondary and tertiary amines, cyclic amines such as piperidines, pyrrolidines, morpholines, aromatic heterocycles such as pyridines, pyrimidines, purines, imines such as diazobicycloundecene, guanidines, imides, Amides and others included. Alternatively, ammonium salts including ammonium, primary, secondary, tertiary and quaternary alkyl and aryl ammonium salts of alkoxides including hydroxide, phenates, carboxylates, aryl and alkyl sulfonates, sulfonamides and others can also be used for the stabilizer. Other cationic nitrogen compounds including pyridinium salts and salts of other heterocyclic nitrogen compounds with anions such as alkoxides including hydroxide, phenates, carboxylates, aryl and alkyl sulfonates, sulfonamides and the like can also be used.

Yet another additive that can be added to photoresist 401 can be a dissolution inhibitor to help control dissolution of photoresist 401 during development. In one embodiment, bile salt esters can be used as the dissolution inhibitor. Specific examples of materials that can be used include cholic acid (IV), deoxycholic acid (V), lithocholic acid (VI), t-butyl deoxycholate (VII), t-butyl lithocholate (VIII), and t-butyl 3-α-acetyllithocholate ( ix) a.

Another additive that can be added to the photoresist 401 can be a plasticizer. Plasticizers can be used to reduce delamination and gapping between the photoresist 401 and underlying layers (e.g., the BARC layer 105), and they can include monomeric, oligomeric, and polymeric plasticizers such as oligo-polyethylene glycol ethers, cycloaliphatic ethers, and acid-free reactives steroidally derived materials. Specific examples of materials that can be used for the plasticizers include dioctyl phthalate, diisodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerol, and the like.

Yet another additive that can be added includes a colorant that helps viewers inspect the photoresist 401 and find any defects that may need to be corrected before further processing. In one embodiment, the colorant can be either a triarylmethane dye or, alternatively, a fine particle organic pigment. Specific examples of materials that can be used as the colorant include Crystal Violet, Methyl Violet, Ethyl Violet, Oil Blue #603, Victoria Pure Blue BOH, Malachite Green, Diamond Green, Phthalocyanine Pigments, Azo Pigments, Carbon Black, Titanium Oxide, Brilliant Green Dye (C.I. 42020) , Victoria Pure Blue FGA (Linebrow), Victoria BO (Linebrow) (C.I. 42595), Victoria Blue BO (C.I.44045), Rhodamine 6G (C.I. 45160), benzophenone compounds such as 2,4-dihydroxybenzophenone and 2,2' ,4,4'-Tetrahydroxybenzophenone, salicylic acid compounds such as phenyl salicylate and 4-t-butylphenyl salicylate, phenyl acrylate compounds such as ethyl 2-cyano-3,3-diphenyl acrylate, 2'-ethylhexyl-2-cyano-3,3 -diphenyl acrylate, benzotriazole compounds such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole and 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole , coumarin compounds such as 4-methyl-7-diethylamino-1-benzopyran-2-one, thioxanthone compounds such as diethylthioxanthone, stilbene compounds, naphthalic acid compounds, azo dye, phthalocyanine blue, phthalocyanine green, Victoria blue, crystal violet, titanium oxide , Carbon Black, Naphthalene Black, Photopia Methyl Violet, Bromophenol Blue and Bromocresol Green, Laser dyes such as Rhodamine G6, Coumarin 500, DCM (4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran), Kiton Red 620, Pyrromethene 580 or the like. In addition, one or more colorants can be used in combination to achieve the desired hue.

Adhesion additives may also be added to photoresist 401 to promote adhesion between photoresist 401 and an underlying layer to which photoresist 401 has been applied (eg, BARC layer 105). In one embodiment, the adhesion additives include a silane compound having at least one reactive substituent such as a carboxyl group, methacryloyl group, isocyanate group, and/or epoxy group. Specific examples of the adhesion components include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, benzimidazoles and polybenzimidazoles, pyridine substituted with a lower hydroxyalkyl derivative, a heterocyclic nitrogen compound, urea, thiourea, an organophosphorus compound, 8-oxyquinoline, 4-hydroxypteridine and derivatives, 1,10-phenanthroline and derivatives, 2,2'-bipyridine and derivatives, benzotriazoles; organophosphorus compounds, phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethylethanolamine and derivatives, benzothiazole and benzothiazole amine salt having a cyclohexyl ring and a morpholine ring, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, combinations thereof or the like.

Surface leveling agents can be added to the photoresist 401 to help the top surface of the photoresist 401 be flat so that incident light is not adversely affected by an uneven surface. In one embodiment, the surface leveling agents may include fluoroaliphatic esters, hydroxyl terminated fluorinated polyethers, fluorinated ethylene glycol polymers, silicones, acrylic polymer leveling agents, combinations thereof, or the like.

In one embodiment, the photoresist polymer resin and PACs are added to the photoresist solvent for coating along with any desired additives or other agents. Once added, the mixture is then mixed to achieve uniform composition across the photoresist 401 to ensure that there are no defects caused by uneven mixing or non-constant composition of the photoresist 401. Once mixed together, the photoresist 401 can either be stored prior to use or used immediately.

Once complete, the photoresist 401 can be deployed by first applying the photoresist 401 to the BARC layer 105 . The photoresist 401 may be applied to the BARC layer 105 such that the photoresist 401 covers an upper exposed surface of the BARC layer 105 and may be coated using a process such as a spin coating process, dip coating process, air knife coating process, curtain coating process, wire bar coating process, gravure coating method, lamination method, extrusion coating method, combinations thereof or the like. In one embodiment, the photoresist 401 can be applied to have a thickness over the surface of the BARC layer 105 between about 10 nm and about 300 nm, such as about 150 nm.

Once the photoresist 401 is coated on the semiconductor substrate, a preheating of the photoresist 401 is performed to cure and dry the photoresist 401 prior to exposure to complete the application of the photoresist 401. The curing and drying of the photoresist 401 eliminates the photoresist solvent component but leaves behind the polymer resin, PACs, photoresist crosslinking agents, and other selected additives. In one embodiment, the preheating can be performed at a temperature suitable to vaporize the photoresist solvent, such as between about 40°C and 150°C, although the exact temperature depends on the materials chosen for the photoresist 401. The pre-bake is performed for a time sufficient to cure and dry the photoresist 401, such as from about 10 seconds to about 5 minutes, such as about 90 seconds.

Once applied, the photoresist 401 can be exposed to form an exposed area 403 and an unexposed area 405 in the photoresist 401 . In one embodiment, exposure may be initiated by placing the substrate 101 and photoresist 401, once cured and dried, in a photoresist imaging tool 400 for exposure. The photoresist imaging device 400 may include a photoresist backing plate 404 , a photoresist energy source 407 , a patterned mask 409 between the photoresist backing plate 404 and the photoresist energy source 407 , and photoresist optics 413 . In one embodiment, photoresist backing plate 404 is a surface onto which semiconductor device 100 and photoresist 401 can be placed or attached and which provides support and control to substrate 101 during exposure of photoresist 401 . Additionally, the photoresist support plate 404 may be moveable along one or more axes as well as provide arbitrary heating or cooling for the substrate 101 and photoresist 401 to prevent temperature gradients from affecting the exposure process.

In one embodiment, photoresist energy source 407 applies photoresist energy 411, such as light, to photoresist 401 to cause reaction of the PACs, which in turn react with the photoresist polymer resin to chemically alter those portions of photoresist 401 which the photoresist energy 411 impinges. In one embodiment, photoresist energy 411 may be electromagnetic radiation, such as g-rays (having a wavelength of about 436 nm), i-rays (having a wavelength of about 365 nm), ultraviolet radiation, far ultraviolet radiation, x-rays , electron beams or the like. The photoresist energy source 407 can be a source of electromagnetic Radiation may be KrF excimer laser light (having a wavelength of 248 nm), ArF excimer laser light (having a wavelength of 193 nm), F2 excimer laser light (having a wavelength of 157 nm), and the like although any other suitable source of photoresist energy 411, such as mercury vapor lamps, xenon lamps, carbon arc lamps, or the like, may alternatively be employed.

Patterned mask 409 is positioned between photoresist energy source 407 and photoresist 401 to block portions of photoresist energy 411 to form patterned energy 415 before photoresist energy 411 actually impinges photoresist 401 . In one embodiment, the patterned mask 409 may include a number of layers (e.g., substrate, absorption layers, anti-reflective coating layers, shielding layers, etc.) to reflect, absorb, or otherwise block portions of the photoresist energy 411 that those portions of the photoresist 401 , where illumination is not desired, can be achieved. The desired pattern can be formed in the patterned mask 409 by forming openings through the patterned mask 409 in the desired illumination contour.

An optics (in 4A represented by the trapezoid labeled 413) can be used to focus, expand, the photoresist energy 411 as it emanates from the photoresist energy source 407, is patterned through the patterned mask 409 and directed towards the photoresist 401, to reflect or otherwise control. In one embodiment, photoresist optics 413 includes one or more lenses, mirrors, filters, combinations thereof, or the like to control photoresist energy 411 along its path. Although in 4A Also, while photoresist optics 413 are shown as being between patterned mask 409 and photoresist 401, elements of photoresist optics 413 (eg, individual lenses, mirrors, etc.) can also be placed anywhere between the photoresist power source 407 (where the photoresist energy 411 is generated) and the photoresist 401 may be located.

In one embodiment, the semiconductor device 100 is arranged with the photoresist 401 on the photoresist carrier plate 404 . Once the pattern is aligned with the semiconductor device 100, the photoresist energy source 407 generates the desired photoresist energy 411 (e.g., light) that passes through the patterned mask 409 and photoresist optics 413 on its way to the photoresist 401. The structured energy 415 triggers a reaction of the PACs in the photoresist 401 when it hits portions of the photoresist 401 . The chemical reaction products of the PAC absorption of the patterned energy 415 (e.g. acids/bases/free radicals) then react with the photoresist polymer resin, chemically altering the photoresist 401 in those portions that were exposed through the patterned mask 409.

In a specific example where the structured energy 415 is 193 nm wavelength light, the PAC is a photoacid generator and the group to be decomposed is a carboxylic acid group on the hydrocarbon structure and a crosslinking agent is used, the structured energy 415 impinges on the photoacid generator and the photoacid generator will absorb the incident structured energy 415. This absorption initiates the photoacid generator to produce a proton (e.g., an H+ atom) in the photoresist 401. When the proton encounters the carboxylic acid group on the hydrocarbon structure, the proton reacts with the carboxylic acid group, chemically altering the carboxylic acid group and generally changing the properties of the photoresist polymer resin. The carboxylic acid group then reacts with the photoresist crosslinking agent to crosslink with other photoresist polymer resins in photoresist 401.

Optionally, the exposure of the photoresist 401 can be done using an immersion lithography technique. In such a technique, an immersion medium (in 2 not shown individually) between the photoresist imager 400 (and in particular between an exit lens of the photoresist optics 413) and the photoresist 401. With this immersion medium in place, the photoresist 401 can be patterned with the patterned energy 415 passing through the immersion medium.

In this embodiment, a protective layer (in 4A also not shown individually) may be formed over the photoresist 401 to prevent the immersion medium from coming into direct contact with the photoresist 401 and leaching or otherwise adversely affecting the photoresist 401. In one embodiment, the protective layer is insoluble in the immersion medium such that the immersion medium will not dissolve it and is immiscible in the photoresist 401 such that the Protective layer will not adversely affect the photoresist 401. In addition, the protective layer is transparent, allowing the structured energy 415 to freely pass through the protective layer.

In one embodiment, the protective layer comprises a protective layer resin in a protective layer solvent. The material used for the protective coating solvent is dependent, at least in part, on the ingredients chosen for the photoresist 401, since the protective coating solvent should not dissolve the materials of the photoresist 401 so as to prevent deterioration of the photoresist 401 during application and to avoid using the protective layer. In one embodiment, the protective layer includes alcohol solvents, fluorinated solvents, and hydrocarbon solvents.

Specific examples of materials that can be used for the protective layer solvent include methanol, ethanol, 1-propanol, isopropanol, n-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 3-methyl-1- Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, n-hexanol, cyclohexanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 2- Methyl-1-Pentanol, 2-Methyl-2-Pentanol, 2-Methyl-3-Pentanol, 3-Methyl-1-Pentanol, 3-Methyl-2-Pentanol, 3-Methyl-3-Pentanol, 4-Methyl- 1-Pentanol, 4-Methyl-2-Pentanol, 2,2,3,3,4,4-Hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-Octafluoro-1- pentanol, 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2, 2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1, 8-diol, 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoroheptane, perfluoro-2-pentanone, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, perfluorotributylamine, perfluorotetrapentylamine, toluene, xylene and anisole and aliphatic hydrocarbon solvents such as n-heptane , n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3,3-dimethylhexane, 2,3,4-trimethylpentane, combinations thereof, or the like.

Similar to the photoresist 401, the protective layer resin may have a protective layer repeating unit. In one embodiment, the protective layer repeating unit may be an acrylic resin having a hydrogen repeating structure having a carboxyl group, an alicyclic structure, an alkyl group having one to five carbon atoms, a phenol group, or a group containing a fluorine atom. Specific examples of the alicyclic structure include cyclohexyl group, adamantyl group, norbornyl group, isobornyl group, tricyclodecyl group, tetracyclodecyl group and the like. Specific examples of the alkyl group include n-butyl group, isobutyl group or the like. However, any suitable protective coating resin may alternatively be used.

The protective coating composition may also include additional additives to aid in such things as adhesion, surface leveling, hiding, and the like. For example, the protective layer composition may further comprise a protective layer wetting agent, although other additives may also be added, and all such additives are fully intended to be included within the scope of the embodiment. In one embodiment, the protective layer wetting agent may be an alkyl cationic wetting agent, an amide-type quaternary cationic wetting agent, an ester-type quaternary cationic wetting agent, an amine oxide wetting agent, a betaine wetting agent, an alkoxylate wetting agent, a fatty acid ester wetting agent, an amide wetting agent, an alcohol wetting agent, an ethylenediamine wetting agent, or a fluorine and/or silicon containing wetting agent.

Specific examples of materials which can be used for the protective layer wetting agent include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate; and polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate.

Before applying the resist to the photoresist 401, the resist resin and desired additives are first added to the resist solvent to form a resist assembly. The protective coating solvent is then mixed to ensure that the protective coating composition has a uniform concentration throughout the protective coating composition.

Once the protective layer composition is ready for application, the protective layer composition can be applied over the photoresist 401 . In one embodiment, the application may be performed using a process such as a spin coating process, dip coating process, air knife coating process, curtain coating process, wire bar coating process, gravure coating process, lamination process, extrusion coating process, combinations thereof, or the like. In one embodiment, the photoresist 401 can be applied to have a thickness over the surface of the photoresist 401 of about 100 nm.

After the resist composition has been applied to the photoresist 401, a resist prebake may be performed to remove the resist solvent. In one embodiment, the resist preheat can be performed at a temperature suitable to vaporize the resist solvent, such as between about 40°C and 150°C, although the exact temperature depends on the materials selected for the resist composition . The protective layer pre-bake is performed for a time sufficient to cure and dry the protective layer composition, such as from about 10 seconds to about 5 minutes, such as about 90 seconds.

Once the protective layer has been placed over the photoresist 401, the semiconductor device 100 with the photoresist 401 and protective layer is placed on the photoresist backing plate 404, and the immersion medium can be placed between the protective layer and the photoresist optic 413. In one embodiment, the immersion medium is a liquid that has a refractive index greater than that of the surrounding atmosphere, such as a refractive index greater than 1. Examples of the immersion medium include water, oil, glycerine, glycerol, cycloalkanols, or the like, though alternatively any suitable medium can be used.

The placement of the immersion medium between the protective layer and the photoresist optic 413 can be done, for example, using an air knife method, whereby fresh immersion medium is introduced into an area between the protective layer and the photoresist optic 413 and controlled using pressurized gas that is directed towards the protective layer to form a barrier and prevent the immersion medium from spreading. In this embodiment, the immersion medium can be introduced, used and detached from the protective layer for reprocessing, so that there is a fresh immersion medium that is used for the respective imaging process.

However, the air knife method described above is not the only method by which the photoresist 401 can be exposed using an immersion method. Any other suitable method for imaging the photoresist 401 using an immersion medium may also be employed, such as burying the entire substrate 101 along with the photoresist 401 and protective layer, using solid barriers instead of gaseous barriers, or using a Immersion medium without a protective layer. Any suitable method of exposing the photoresist 401 through the immersion medium may be used, and all such methods are fully intended to be included within the scope of the embodiments.

After the photoresist 401 has been exposed to the patterned energy 415, a post-exposure bake can be used to induce the generation, distribution, and reaction of the acid/base/free radicals generated by the patterned energy 415 impinging on the PACs during exposure were to support. Such assistance helps initiate or enhance chemical reactions that produce chemical differences between the exposed area 403 and the unexposed area 405 in photoresist 401 . These chemical differences also cause differences in solubility between the exposed area 403 and the unexposed area 405. In one embodiment, this post-exposure bake can be performed at temperatures between about 50°C and about 160°C and for a time period of between about 40 seconds and take place about 120 seconds.

4B 12 shows developing photoresist 401 using developer 417 after photoresist 401 has been exposed. After development of the photoresist 401 and after the post-exposure bake has taken place, the photoresist 401 can be developed using either a positive developer or a negative developer depending on the desired pattern for the photoresist 401. In an embodiment where it is desired that the exposed area 403 of the Photoresist 401 is removed to form a positive image, a positive developer such as a basic aqueous solution can be used to remove portions of the photoresist 401 that have been exposed to the structured energy 415 and have their solubility modified by the chemical reactions and was changed. Such basic aqueous solutions may include tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, aqueous ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, monoethanolamine , diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, ammonium, caustic soda, caustic potash, sodium metasilicate, potassium metasilicate, sodium carbonate, tetraethylammonium hydroxide, combinations thereof, or the like.

If negative development is desired, then an organic solvent or critical fluid can be used to remove those portions of the photoresist 401 that have not been exposed to the energy and therefore retain their original solubility. Specific examples of materials that can be employed include hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, critical fluids, combinations thereof, and the like. Specific examples of materials that can be used for the negative solvent include hexane, heptane, octane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, methanol, ethanol, propanol, butanol, critical carbon dioxide, diethyl ether, dipropyl ether, dibutyl ether, ethyl vinyl ether , dioxane, propylene oxide, tetrahydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pyridine, formamide, N,N-dimethylformamide, or the like a.

However, as one skilled in the art will appreciate, the above description of positive developers and negative developers is for illustrative purposes only and is not intended to limit the embodiments to the developers listed above alone. Rather, any suitable type of developer, including acid developer and even water developer, capable of selectively eliminating a portion of photoresist 401 that has a different property (e.g., solubility) than another portion of photoresist 401 may alternatively be employed, and all such developers are fully intended to be included within the scope of the embodiments.

In an embodiment in which immersion lithography is used to expose the photoresist 401 and a protective layer is used to shield the photoresist 401 from the immersion medium, the developer 417 can be chosen such that only the portions of the photoresist 401 where it is desired to remove it, but it can also be chosen so that the protective layer is removed in the same development step. Alternatively, the protective layer can be removed in a separate process, such as using a separate solvent from the developer 417 or even an etch process to remove the protective layer from the photoresist 401 prior to development.

4B 12 shows an application of developer 417 to photoresist 401 using, for example, a spin-on process. In this process, the developer 417 is applied to the photoresist 401 from above the photoresist 401 while the semiconductor device 100 (and the photoresist 401) is rotated. In one embodiment, the developer 417 can be supplied at a flow rate of between about 300 ml/min and about 1000 ml/min, such as about 500 ml/min, while the semiconductor device 100 is fed at a speed of between about 500 rpm and about 2500 rpm revolutions per minute, such as about 1500 revolutions per minute. In one embodiment, developer 417 can have a temperature between about 10°C and about 80°C, such as about 50°C, and development can take between about 1 minute and about 60 minutes, such as about 30 minutes.

Although the spin-on process described herein is a suitable method for developing the photoresist 401 after exposure, it is provided for purposes of illustration and is not intended to limit the embodiments. Rather, any suitable method of development may alternatively be used, including dipping processes, puddle processes, spraying processes, combinations thereof, or the like. All such development processes are fully intended to be included within the scope of the embodiments.

4B FIG. 4 shows a cross-section of the development process in an embodiment in which a negative developer is used to eliminate the unexposed areas of the photoresist 401. FIG. As shown, the developer 417 is applied to the photoresist 401 and dissolves the unexposed one Portion 405 of the photoresist 401 on. This dissolution and removal of the unexposed portion 405 of the photoresist 401 leaves a void in the photoresist 401 that patterns the photoresist 401 in the form of the patterned energy 415, thereby transferring the pattern of the patterned mask 409 to the photoresist 401.
Once the photoresist 401 has been patterned, the pattern can be transferred to the BARC layer 105. FIG. In an embodiment where the BARC layer 105 remains insoluble to the developer 417, the BARC layer 105 can be removed using an etch process that employs the photoresist 401 (now patterned) as a mask layer. The etching process may be a dry etching process in which an etchant such as oxygen, nitrogen, hydrogen, ammonium, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, carbon monoxide, carbon dioxide, helium, boron dichloride, argon, fluorine, trifluoromethane, tetrafluoromethane, perfluorocyclobutane, perfluoropropane, combinations thereof or the like is employed. Alternatively, however, any other suitable etching process, such as wet etching, and any other suitable etchant may be used.

Alternatively, in an embodiment in which the BARC layer 105 has an acid labile group that can react to uncrosslink the crosslinked polymers in the BARC layer 105 and alter the solubility of the BARC layer 105, the BARC layer 105 can be used , to be structured by the developer 417 during the development process. In particular, the generators can generate an acid in the BARC layer 105 during exposure, which acts to break the crosslink bonds and alter the solubility of the BARC layer 105. Then, in a positive development process, a positive developer can be used to remove both the photoresist 401 that has been exposed and the BARC layer 105 in the same process. Any suitable patterning process with any suitable number of steps may be employed to pattern and eliminate both photoresist 401 and BARC layer 105, and all such processes and steps are fully intended to be within the scope of the embodiments are included.

5 12 shows another embodiment in which the BARC layer 105 is used in a physical planarization process such as chemical polishing (CMP). In a CMP process, a combination of etch materials and abrasive materials are brought into contact with BARC layer 105 (or a layer overlying BARC layer 105, such as photoresist 401) and an abrasive pad 501 is used. to abrade BARC layer 105 (or any layers overlying BARC layer 105) until a desired thickness is achieved.

In this embodiment, the floating region 201 along the top surface of the BARC layer 105 causes the polymeric resin in the floating region 201 to crosslink more than in the rest of the BARC layer 105. As such, the rest of the BARC layer 105 (the portion outside of the Floating area 201) have a lower crosslinking density and remain more flexible than the floating area 201. This flexibility can better withstand the shear forces associated with the physical abrasion of chemical mechanical polishing without failure, such as delamination.

6 12 illustrates removing photoresist 401 and BARC layer 105 with floating region 201. In one embodiment, photoresist 401 may be removed using, for example, an ashing process wherein the temperature of photoresist 401 is increased until photoresist 401 undergoes a thermal undergoes decomposition. Once thermally decomposed, the photoresist 401 can be physically removed using one or more washes.

Once the photoresist 401 has been removed, the BARC layer 105 (with the floating area 201) can be removed using a fluid 601 that acts on the BARC layer 105 to remove both the floating area 201 and the rest of the BARC - Eliminate layer 105. In one embodiment, the fluid 601 is a fluid that acts either physically, chemically, or via Coulomb forces to cause the BARC layer 105 to be eliminated. In a specific embodiment, the fluid 601 may include an aqueous solution. When the fluid is an aqueous solution, the fluid can be either acidic (e.g., having a pH between about -1 and 4) or basic (e.g., having a pH between about 9 and 14). The pH in these embodiments can be adjusted as desired using either organic or inorganic acids or bases (as described below).

Alternatively, a wet cleaning process can be used to remove the BARC layer 105 . In an embodiment employing a wet cleaning process, a solution such as an SC-1 or SC-2 cleaning solution may be used, although other solutions such as eg a mixture of H ₂ SO ₄ and H ₂ O ₂ (known as SPM) or a solution of hydrogen fluoride (HF) can be used. Any suitable solution or process that can be employed to eliminate the BARC layer 105 is fully intended to be within the scope of the embodiments.

Alternatively, the fluid 601 can be an organic solvent. In this embodiment, the fluid 601 can be an ester, ether, amide, alcohol, anhydride, or alkane having between 2 and 30 carbon atoms. However, any other suitable organic solvent such as the BARC solvent or the photoresist solvent discussed above may alternatively be employed.

The fluid 601 may be applied to the BARC layer 105 using, for example, a wet etch process. In one embodiment, the BARC layer 105 and the flotation region 201 are submerged in the fluid 601 using, for example, a dipping process, puddle process, spray-on process, combinations thereof, or the like. The fluid 601 can have a temperature between about 30°C and about 150°C, such as about 50°C.

However, because the floating region within itself 201 has a higher degree of cross-linking than the rest of the BARC layer 105, the floating region 201 also has a greater density than the rest of the BARC layer 105. As such, the buoyant region 201 will also have a different removal rate from the fluid 601 than the rest of the BARC layer 105. In a specific embodiment, the floating region 201 will have a lower clearance rate than the rest of the BARC layer 105. FIG.

Provided the remainder of BARC layer 105 has a faster clearance rate than floatation area 201, then BARC layer 105 (which contains floatation area 201) can at a far faster rate than other BARC layers that do not have floatation area 201 can be eliminated. These other BARC layers (excluding the floating region 201) may have a constant crosslinking and constant density with no apparent removal until at least 10 minutes after sunk. As such, in an embodiment where the BARC layer 105 and the buoyancy region 201 are immersed in the fluid 601, the immersion may occur for a time of less than about 1 minute.

In an embodiment where the fluid 601 uses chemical reactions to eliminate the BARC layer 105 and the buoyancy region 201, the fluid 601 can react with the BARC layer 105 in a number of methods to effect the elimination. For example, the chemical reaction can be an oxidation/reduction reaction, an acid/base reaction, a substitution reaction, an addition reaction, combinations thereof, or the like. For example, the fluid 601 can be an inorganic acid (e.g. sulfonic acid, hydrochloric acid, sulfuric acid), an organic acid (e.g. acetic acid), an inorganic base (e.g. sodium hydroxide or potassium hydroxide), or an organic base (e.g. triethylamine, pyridine, methylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide , choline, guanidine, imidazole, lithium organyls or Grignard reagent) to react with the BARC layer 105. Any suitable type of chemical reaction can be used to eliminate the BARC layer 105 and the buoyant region 201 .

Alternatively, in an embodiment where the removal process uses the fluid 601 to apply physical forces to remove the BARC layer 105 and the buoyancy region 201, the physical forces could be Coulomb forces, with the fluid 601 being used to calculate the surface energy of the BARC layer 105 to change. By changing the surface energy, the adhesion between the BARC layer 105 and the underlying layers (e.g. the substrate and the fins 103) can be reduced or eliminated, thereby at least partially freeing the BARC layer 105 from its adhesion to the underlying layers and it allowing the BARC layer 105 to be removed from the underlying layers.

The fluid 601 may also include additives that either enhance the physical properties of the fluid 601 or otherwise enhance the chemical reactions between the fluid 601 and the BARC layer 105 . In one embodiment, the fluid 601 can additionally contain a wetting agent. In one embodiment, the wetting agent may contain nonionic wetting agents, polymers having fluorinated aliphatic groups, wetting agents containing at least one fluorine atom and/or at least one silicon atom, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters.

Specific examples of materials that can be used as wetting agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyethylene glycol distearate, polyethylene glycol dilaurate , polyethylene glycol, polypropylene glycol, polyoxyethylene stearyl ether and polyoxyethylene cetyl ether; fluorine-containing cationic wetting agents, fluorine-containing nonionic wetting agents, fluorine-containing anionic wetting agents, cationic wetting agents and anionic wetting agents, polyethylene glycol, polypropylene glycol, polyoxyethylene cetyl ether, combinations thereof, or the like.

In addition, the fluid 601 may also contain additional components that may help stabilize or control the physical properties of the fluid 601 . For example, the fluid 601 can include an ingredient such as ozone, which can be used to stabilize the fluid 601 as well as act as a wetting agent, hydrogen peroxide, and/or carbon dioxide, which can be useful in changing a surface charge. Any suitable materials may be included in the fluid 601 to help regulate the fluid 601, and all such materials are fully intended to be included within the scope of the embodiments.

In specific embodiments, the fluid 601 may be a solution in a Standard Clean 1 (SC-1) cleaning process or a sulfuric acid peroxide mixture (SPM). For example, in the embodiment where the fluid 601 is an SC-1 fluid, the fluid 601 may be a solution of ammonium hydroxide (NH ₄ OH), hydrogen peroxide (H ₂ O ₂ ), and water in a suitable ratio (such as a ratio 1:1:5). Such a solution will dissolve both the floating region 201 and the remainder of the BARC layer 105.

By using the fluid 601 to dissolve the BARC layer 105 with the floating area 201, the overall removal rate of the BARC layer 105 relative to a BARC layer without the floating area 201 can be reduced. For example, without the floating region 201, when the BARC layer can be of constant density and constant crosslinking, removal can be significantly more difficult and significantly more time consuming, sometimes taking well over 10 minutes to effectively remove the BARC layer. ensure shift. However, by including the flotation region 201, the removal of the entire BARC layer 105 (which has regions of different densities) can be achieved at a far greater rate, such that effective removal of the BARC layer 105 occurs in a far shorter time, such as less than can be reached in about 1 minute.

Furthermore, as one skilled in the art will appreciate, the above-described embodiments in which the BARC layer 105 is used to fill voids between the fins 103 over the substrate 101 are intended for illustration only and are not intended to limit the embodiments. Rather, any suitable type of substrate 101 with any suitable type of structures on the substrate 101 can alternatively be used. For example, in an embodiment where the substrate 101 is conductive, the substrate 101 may be formed from a conductive material using processes similar to the processes used for the metallization layers (eg, damascene, dual damascene , separation, etc.). In a specific embodiment where the substrate 101 is conductive, the conductive material for the substrate 101 comprises at least one metal, metal alloy, metal nitride, metal sulfide, metal selenide, metal oxide, or metal silicide. For example, the conductive material may have the formula MX _a where M is a metal and X is nitrogen, silicon, selenium, oxygen or silicon and where a is between 0.4 and 2.5. Specific examples include copper, titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride (WN ₂ ), and tantalum nitride, although any suitable material may alternatively be used.

In yet another embodiment, the substrate 101 is a dielectric layer having a dielectric constant between about 1 and about 40. In this embodiment, the substrate 101 comprises silicon, a metal oxide, or a metal nitride having a formula MX _b , where M is a metal or silicon, X is nitrogen or oxygen and b is between about 0.4 and 2.5. In specific examples, the dielectric layer for the substrate 101 formed using such processes as deposition, oxidation, or the like may be silicon oxide, silicon nitride, aluminum oxide, hafnium oxide, lanthana, or the like.

7 Figure 12 illustrates fluid 601 removal after BARC layer 105 (including floatation area 201) has been removed. As can be seen, after removing the fluid 601 and the BARC layer 105, the substrate 101 and fins 103 remain. Once the BARC layer 105 has been eliminated, additional processing may be performed on the fins 103, such as forming multi-gate transistors from the fins 103.

8th 14 shows another embodiment in which the BARC layer 105 (with the floating region 201) is used together with a middle layer 801 that was placed on the BARC layer 105 after the floating region 201 was formed. In an embodiment, the middle layer 801 can be an organic layer or an inorganic layer that has a different etch resistance than the photoresist 401 . In one embodiment, the middle layer 801 comprises at least one etch resist molecule, such as a low Onishi number structure, a double bond structure, a triple bond structure, titanium, titanium nitride, aluminum, aluminum oxide, silicon oxynitride, or the like.

In another specific embodiment, the middle layer 801 is a hard mask material such as silicon, silicon nitride, oxides, oxynitrides, silicon carbide, combinations thereof, or the like. The hard mask material for the middle layer 801 may be formed using a process such as chemical vapor deposition (CVD), although other processes such as plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), spin coating or even forming silicon oxide followed by nitriding can alternatively be used. Any suitable method or combination of methods for forming or otherwise placing the hardmask material may be employed, and all such methods or combinations are fully intended to be included within the scope of the embodiments. The middle layer 801 can be formed to a thickness between about 10 nm and about 80 nm, such as about 30 nm.

Once a layer of the middle layer hardmask material 801 has been formed, the photoresist 401 can be placed over the middle layer hardmask material 801 and patterned. Placing the photoresist 401 over the middle layer hardmask material 801 and patterning the photoresist 401 may be similar to placing the photoresist 401 and developing the photoresist 401 as described with reference to FIG 1-4B have been described. For example, photoresist 401 may be applied using a spin coating process, exposed using photoresist imager 400 and then developed using developer 417 .

8th 8 also shows that once the photoresist 401 has been patterned into the desired pattern, the photoresist 401 can be used as a mask to pattern the middle layer 801 hardmask material. For example, the photoresist 401 pattern may be transferred to the middle layer 801 using an anisotropic etch process such as reactive ion etching (RIE), wherein ions of a suitable etchant such as CF ₄ -O ₂ may be employed in a dry etch to eliminate portions of the middle layer 801 exposed by the patterned photoresist 401. However, any other suitable etchant, such as CHF ₂ /O _{2 ,} CH ₂ F ₂ , CH ₃ F, or the like, and any other suitable method of removal, such as a wet strip, may alternatively be used.

8th 10 further shows that once the photoresist 401 pattern has been transferred to the middle layer 801, the middle layer 801 can be used to transfer the photoresist 401 pattern to the BARC layer 105. FIG. In one embodiment, BARC layer 105 may be removed using an etch process that employs photoresist 401 and middle layer 801 (now patterned) as mask layers. The etching process may be a dry etching process using an etchant such as oxygen, nitrogen, hydrogen, ammonium, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, carbon monoxide, carbon dioxide, helium, boron dichloride, argon, fluorine, trifluoromethane, tetrafluoromethane, perfluorocyclobutane, perfluoropropane , combinations thereof or the like is used. Alternatively, however, any other suitable etch process, such as wet etching, or even a wet etch performed simultaneously on the middle layer 801, and any other suitable etchant may be used.

However, as one skilled in the art will appreciate, placing the middle layer 801 over the BARC layer 105 is provided for illustration and is not intended to limit the embodiments. Rather, the middle layer 801 can be in any relationship to the BARC layer 105, such as eg lying between the BARC layer 105 and the substrate 101. Any suitable layer sequence is fully intended to be included within the scope of the embodiments.

By using the BARC layer 105 together with the floating region 201 and the middle layer 801, the pattern of the photoresist 401 in the middle layer 801 and the BARC layer 105 can be formed. This pattern can then be used for additional processing of the substrate 101 and the fins 103.

9 FIG. 12 shows a process flow that can be used to deposit and remove the BARC layer 105 with the floating area 201. FIG. In one embodiment, in a first step 901, the BARC layer 105 is spread or applied. Once distributed, the floating region 201 is formed in the BARC layer 105. FIG. Once used, the BARC layer 105 and the flotation area 201 are eliminated by applying a fluid to the BARC layer 105 and the flotation area 201 .

According to one embodiment, there is provided a method of manufacturing a semiconductor device comprising dispensing an anti-reflective material over a substrate to form an anti-reflective coating layer, the anti-reflective material having a first concentration of a floating component, the floating component being a floating crosslinking agent or a floating catalyst of a crosslinking reaction includes. A floating region is formed adjacent a top surface of the anti-reflective layer, the floating region having a second concentration of the floating component that is greater than the first concentration.

According to another embodiment, there is provided a method of manufacturing a semiconductor device comprising applying an anti-reflective coating to a substrate, the anti-reflective coating including at least one component having a fluorine atom, the component comprising a buoyant crosslinking agent or a buoyant catalyst of a crosslinking reaction. A floating region is formed along a top surface of the anti-reflective coating, the floating region having a higher concentration of the at least one component than the remainder of the anti-reflective coating. The anti-reflective coating is baked to initiate a crosslinking reaction in the floating area.

According to yet another embodiment, there is provided an antireflective material comprising a polymeric resin and a crosslinking agent, wherein the crosslinking agent contains a fluorine atom. The anti-reflective material also includes a catalyst.

According to yet another embodiment, there is provided a method of manufacturing a semiconductor device, comprising dispensing an anti-reflective material over a substrate to form an anti-reflective coating layer, the anti-reflective material having a first concentration of a buoyant component, the first component being a buoyant crosslinking agent or a buoyant Catalyst of a crosslinking reaction comprises. A floating region is formed adjacent a top surface of the anti-reflective coating, the floating region having a second concentration of the floating constituent that is greater than the first concentration. A fluid is applied to the anti-reflective material to remove the anti-reflective material and the floating area.

According to yet another example, there is provided a method of manufacturing a semiconductor device, comprising applying an anti-reflective coating to a substrate and forming the anti-reflective coating into a first region having a first removal rate along a top surface of the anti-reflective coating, a second region of the anti-reflective coating has a second removal rate that is different than the first removal rate. The first area and the second area are eliminated by applying a fluid to the anti-reflective coating. According to yet another embodiment, there is provided a method of manufacturing a semiconductor device, comprising applying an anti-reflective coating to a substrate, wherein the anti-reflective coating includes at least one component that has a fluorine atom. A floating region is formed along an upper surface of the anti-reflective coating, the floating region having a higher concentration of the at least one component than the remainder of the anti-reflective coating, and the floating region and the remainder of the anti-reflective coating stratification can be eliminated by applying a fluid to the anti-reflective coating for less than one minute.

Although the present embodiments and advantages thereof have been described in detail, it should be understood that various changes, substitutions and alterations can be made therein without departing from the spirit and scope of the disclosure as defined in the appended claims. For example, many different monomers can be used to form the BARC layer material, and many different processes can be used to form, apply, and develop the photoresist.

Claims (20)

A method of manufacturing a semiconductor device (100), the method comprising: dispensing an antireflective material over a substrate (101) to form an antireflective coating layer (105), the antireflective material having a first concentration of a buoyant component, the buoyant component comprising a buoyant crosslinking agent or a buoyant catalyst of a crosslinking reaction; forming a floating region (201) adjacent a top surface of the anti-reflective coating (105), the floating region (201) having a second concentration of the floating component that is greater than the first concentration; and applying a fluid (601) to the anti-reflective material to eliminate the anti-reflective material and the floating area (201). procedure after claim 1 , wherein when applying the fluid (601) an aqueous solution is applied. procedure after claim 2 , wherein the aqueous solution has a pH between about -1 and about 4. procedure after claim 2 , wherein the aqueous solution has a pH between about 9 and about 14. A method according to any one of the preceding claims, wherein when applying the fluid (601) an organic solvent is applied. A method according to any one of the preceding claims, wherein the fluid (601) contains an inorganic acid. A method according to any one of the preceding claims, wherein applying the fluid (601) is for less than one minute to eliminate the anti-reflective material. A method of manufacturing a semiconductor device (100), the method comprising: applying an anti-reflective coating (105) to a substrate (101), said anti-reflective coating (105) having a first concentration of a buoyant component, said buoyant component comprising a buoyant crosslinking agent or a buoyant catalyst of a crosslinking reaction; forming a first area of the anti-reflective coating (105) having a first removal rate along a top surface of the anti-reflective coating (105), a second area of the anti-reflective coating (105) having a second removal rate different from the first removal rate; and eliminating the first area and the second area by applying a fluid (601) to the anti-reflective coating (105). procedure after claim 8 , further comprising patterning the anti-reflective coating (105) before eliminating the first region and the second region. procedure after claim 8 or 9 , wherein when applying the fluid (601) an aqueous solution is applied. procedure after claim 10 , wherein the aqueous solution has a pH between about -1 and about 4. procedure after claim 10 , wherein the aqueous solution has a pH between about 9 and about 14. Procedure according to one of Claims 8 until 12 , wherein when applying the fluid (601) an organic solvent is applied. Procedure according to one of Claims 8 until 13 , wherein the fluid (601) contains an inorganic acid. Procedure according to one of Claims 8 until 14 , wherein the elimination of the first area and the second area is completed within one minute. A method of manufacturing a semiconductor device (100), the method comprising: applying an anti-reflective coating (105) to a substrate (101), said anti-reflective coating (105) including at least a first component having a fluorine atom, said first component comprising a buoyant crosslinking agent or a buoyant catalyst of a crosslinking reaction; forming a floating region (201) along a top surface of the anti-reflective coating (105), the floating region (201) having a higher concentration of the at least one first component than a remainder of the anti-reflective coating (105); and eliminating the floating area (201) and the remainder of the anti-reflective coating (105) by applying a fluid (601) to the anti-reflective coating (105) for less than one minute. procedure after Claim 16 , wherein the fluid (601) is an aqueous solution. procedure after Claim 17 , wherein the aqueous solution has a pH between about -1 and about 4. procedure after Claim 17 , wherein the aqueous solution has a pH between about 9 and about 14. Procedure according to one of Claims 16 until 19 , wherein the fluid (601) is an organic solvent.

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