# Patent

## Title
Antireflective coating composition, antireflective coating, and patterning process

## Abstract

A composition comprising (A) a polymer having an alcohol structure with plural fluorine atoms substituted at α- and α′-positions and having k=0.01-0.4 and (B) an aromatic ring-containing polymer having k=0.3-1.2 is used to form an antireflective coating. The ARC-forming composition can be deposited by the same process as prior art ARCs. The resulting ARC is effective in preventing reflection of exposure light in photolithography and has an acceptable dry etching rate.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2007-254939 filed in Japan on Sep. 28, 2007, the entire contents of which are hereby incorporated by reference.
TECHNICAL FIELD
This invention relates to a composition suitable for forming an antireflective coating (ARC) on a resist used in micropatterning for the fabrication of semiconductor devices or the like, and more particularly, to a composition suitable for forming an antireflective coating useful in a lithographic process adapted for exposure to KrF excimer laser (248 nm) or ArF excimer laser (193 nm). It also relates to an ARC formed from the composition, and a process for forming a pattern in a substrate by lithography using the ARC. As used in the art, the “antireflective coating” is often abbreviated herein as ARC.
BACKGROUND ART
Traditionally the technology for the fabrication of semiconductor devices depends on lithographic micropatterning using photoresist compositions. Integration of semiconductor devices is effective in improving the performance, function and reliability of devices and reducing the cost. Since the birth of integrated circuits (IC), technical development works have been continued to boost the integration level.
With the target on further device integration, efforts have been made to reduce the pattern rule by reducing the wavelength of exposure light in photolithography. In the mass production process of 64 M-bit DRAM, for example, the exposure light source of i-line (365 nm) was replaced by a KrF excimer laser having a shorter wavelength of 248 nm. For the fabrication of DRAM with an integration density of 1 G or more requiring a finer patterning technology (feature size 0.13 μm or less), photolithography using ArF excimer laser (193 nm) is under investigation.
Increasing the diameter of lens and increasing the numerical aperture (NA) of lithography system by adopting immersion lithography are also effective in reducing the pattern rule. However, as the NA increases, reflection of exposure light by a substrate poses a greater impact. Specifically, a process of providing a bottom antireflective coating (BARC) between a photoresist film and a substrate is generally employed in order to control reflection. Prior art ARCs are difficult to fully avoid the reflection of exposure light by the substrate. This raises a problem that exposure variations, known as standing waves, occur in a resist film thickness direction, resulting in a decline of resolution.
Known prior art ARCs include inorganic ARCs such as Si and TiN, and organic ARCs composed of light absorber-loaded polymers. The inorganic ARCs require deposition equipment such as vacuum evaporation, CVD and sputtering systems whereas the organic ARCs can be formed in a relatively simple manner without a need for any special equipment. The organic ARCs are not only required to suppress the reflection of exposure light, but also required to have a high dry etching rate as compared with resist film and to avoid intermixing with resist film and diffusion of low-molecular-weight fraction into the resist film (see SPIE Vol. 2195, p 225-229 (1994)).
While the immersion lithography is adapted to provide a liquid between the projection lens and the wafer, the use of water having a refractive index of 1.44 at wavelength 193 nm enables to design a projection lens to a numerical aperture (NA) which is 1.44-fold higher than the lithography in air with a refractive index of 1.0. The immersion lithography, when combined with a projection lens having a NA around 1.3, enables pattern formation at a half pitch of 45 nm.
As the NA increases, the incident angle of light on the resist film becomes shallower, with more oblique light entering. It is pointed out that the proportion of oblique incident light is further increased by s-polarized illumination intended for contrast enhancement, so that reflection by the substrate is further increased. In contrast, it is reported that bi-layer BARC (SPIE Vol. 6153, p 61531J (2006)) and a tri-layer process including a silicon-containing intermediate film and an undercoat film having an antireflection effect (SPIE Vol. 6153, p 61530K (2006)) have a high antireflection effect at NA 1.0 or above. At NA 1.2 or above, however, the bi-layer ARC is insufficient and a further reduction of reflection is necessary. In contrast, it is reported in SPIE Vol. 6153, p 61531J (2006) that a graded BARC which becomes more absorptive toward the substrate side is more effective for reflectance reduction than the bi-layer BARC. It is known from the past to use an ARC in the form of a multilayer coating in order to prevent reflection of light over a wide range of wavelength, as implemented on optical lenses and the like. A substrate having a good antireflection effect over a wide range of wavelength can also be an antireflective substrate compliant with varying incident angle. An ARC in which the number of multiple layers is increased infinite, that is, absorption is changed stepwise can be an excellent ARC. One example that applies this principle to BARC is described in JP Patent 3,414,107. The illustrative materials used to provide stepwise absorption changes are photo-bleachable materials such as nitrone.
A multilayer ARC may be formed by iterative application of BARCs with different coefficients of absorption, but this process is impractical because of process complexities and reduced throughputs. It is preferred from the standpoint of process simplicity that an ARC having graded absorption be formed by a single coating step. Although the photo-bleachable materials are proposed in JP Patent 3,414,107, no such materials are available at wavelength 193 nm. It is then difficult to design an ARC which increases its transparency on the resist side upon exposure.
JP-A 2000-53921 discloses a method of forming a two-layer ARC for reducing the reflection of visible light, using an ARC-forming composition comprising a fluorine-containing compound capable of forming a low refractive index cured film and a compound capable of forming a high refractive index cured film with greater surface free energy. It is believed that self-arrangement and collection of molecules proceed at the film formation stage so that the free energy of film surface may become minimum, and a two-layer structure forms due to a phase-separation phenomenon. This method permits two layers to be formed by a single coating step and is thus effective for productivity improvement. However, if careful selection of two polymers having an adequate difference of free energy is not considered, a two-layer structure may not always form due to phase separation and in many cases, phase separation occurs in a direction parallel to the substrate, resulting in a so-called island-in-sea structure in which domains of one phase are distributed in a matrix of the other phase, for example. Thus an optimum combination of compounds exists.
A reduction of pattern feature size entails a thickness reduction of a photoresist film, which encourages to increase the etching rate of BARC. In the past, novolac resins and polyimide resins were used as the polymer to form BARC, but their etching rate is very slow, leaving a problem that the photoresist pattern has been slimmed at the time when the BARC film extinguishes. One effective means for increasing the etching rate is by reducing the number of carbon atoms and increasing a proportion of oxygen atoms. A study was thus made on the use of a (meth)acrylic resin having crosslinking groups and absorptive groups as the base resin. To further accelerate the etching rate, a polyester resin having oxygen atoms incorporated in the polymer backbone was proposed as the base resin.
In the efforts to develop F2 lithography photoresist materials, various fluorine-containing polymers were examined for the purpose of improving transparency at 157 nm. Those polymers having perfluoroalkyl groups had so high water repellency that pattern collapse and stripping occurred due to incomplete development and poor substrate adhesion. On the other hand, alcohols having multiple fluorine atoms substituted at α-position provide hydrophilicity and adhesion because the hydroxyl group is rendered acidic due to electron withdrawal of fluorine, to ensure appropriate alkaline solubility. Thus a number of F2 lithography polymers having —C(CF3)2OH structure were developed.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a composition for forming an ARC suited for use in lithography for the fabrication of semiconductor devices or the like, effective for preventing reflection of exposure light, and having a sufficiently high dry etching rate to reduce the etching time and to prevent the overlying resist film from being slimmed or deformed; an ARC; and a process for forming a pattern in a substrate using the ARC-forming composition.
In one aspect, the invention provides an antireflective coating composition comprising
(A) at least one polymer comprising recurring units of at least one type represented by the general formula (1) and/or (2) and having an extinction coefficient at a preselected imaging radiation wavelength in the range of 0.01 to 0.4, and
(B) at least one polymer containing an aromatic ring and having an extinction coefficient at a preselected imaging radiation wavelength in the range of 0.3 to 1.2.




Herein R1 is hydrogen, fluorine, methyl, or trifluoromethyl, R2 and R3 are each independently hydrogen or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 8 carbon atoms, or R2 and R3 may bond together to form a ring with the carbon atom to which they are attached, R4 is hydrogen or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 30 carbon atoms, in which a constituent unit —CH2— may be replaced by —O— or —C(═O)—, R5 to R7 are each independently hydrogen, halogen, hydroxyl or a straight, branched or cyclic, monovalent organic group of 1 to 15 carbon atoms, or any two of R5 to R7 may bond together to form a ring with the carbon atom(s) to which they are attached.

In a preferred embodiment, the polymer (A) further comprises 3 to 50 mol % of aromatic ring-containing recurring units.
In another preferred embodiment, the polymer (B) comprises 40 to 100 mol % of aromatic ring-containing recurring units.
In a further preferred embodiment, the composition may further comprise at least one member selected from among an organic solvent, an acid generator, and a crosslinker.
In another aspect, the invention provides a lithographic pattern forming process comprising the steps of applying the composition defined above onto a substrate to form an antireflective coating, forming a photoresist layer on the antireflective coating, exposing a pattern circuitry region of the photoresist layer to an imaging radiation, developing the photoresist layer with a developer to form a patterned resist layer, and etching the antireflective coating and the substrate while using the resist pattern as a mask, thereby forming a pattern in the substrate.
In a further aspect, the invention provides an antireflective coating which is prepared by applying the composition defined above onto a substrate by spin coating and baking to form an antireflective coating having an inner surface contiguous to the substrate and an outer surface remote from the substrate, such that polymer (A) and polymer (B) may segregate vertically toward the outer surface and inner surface, respectively.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph plotting the substrate reflectance versus BARC thickness when the extinction coefficient (k value) of BARC is varied from 0 to 1.0 with the refractive index (n value) of BARC fixed at 1.6 under the condition NA=0.85.
FIG. 2 is a graph plotting the substrate reflectance versus BARC thickness when the extinction coefficient (k value) of BARC is varied from 0 to 1.0 with the refractive index (n value) of BARC fixed at 1.6 under the condition NA=1.35.
FIG. 3 is a graph, in connection with two-layer BARC, plotting the substrate reflectance versus lower layer thickness when the extinction coefficient (k value) of lower layer is varied from 0 to 1.0 under the condition NA=1.35 (upper layer having a k value of 0.2 and a thickness of 60 nm).
FIG. 4 is a graph, in connection with two-layer BARC, plotting the substrate reflectance versus upper layer thickness when the extinction coefficient (k value) of upper layer is varied from 0 to 1.0 under the condition NA=1.35 (lower layer having a k value of 0.6 and a thickness of 40 nm).
FIG. 5 is a graph, in connection with three-layer BARC, plotting the substrate reflectance versus intermediate layer thickness when the extinction coefficient (k value) of upper layer is varied from 0 to 1.0 under the condition NA=1.35 (upper layer having a thickness of 45 nm, intermediate layer having a k value of 0.4, lower layer having a k value of 0.6, and upper, intermediate and lower layers summing to a thickness of 95 nm).



DESCRIPTION OF THE PREFERRED EMBODIMENT
It has been found that when the ARC-forming material of the invention is applied onto a substrate by spin coating and then baked to form an ARC on the substrate, polymer (A) segregates vertically toward the outer surface side of the ARC to form a first layer and polymer (B) segregates vertically toward the inner surface side of the ARC to form a second layer and that depending on the particular polymers used, a third layer of a mixture of polymers (A) and (B) can be formed as the intermixing layer between the first and second layers. It has also been found that when an extinction coefficient k of polymer (A) is set lower than that of polymer (B) and the thicknesses of first, second and third layers are adjusted, the ARC becomes fully effective in preventing reflection of exposure light. For regulating reflectance, it is effective to introduce an adequate proportion of aromatic rings into polymer (A).
For example, it is well known that a surfactant having a perfluoroalkyl group or siloxane emerges afloat on the surface of a resist film as spin coated and covers the surface. The perfluoroalkyl group or siloxane having a low level of surface energy orients or localizes at the surface so that the surface energy is stabilized. It is described in JP Appln. 2006-103016 that when a polymer having —C(CF3)2OH structure is added to a photoresist film, it orients or localizes at the film surface.
In the efforts to develop F2 lithography photoresist materials, it was pointed out that inclusion of fluorine atoms lowers etching resistance, and thus transparency at 157 nm and etching resistance trade off. However, a higher etching rate is preferred for BARC. It is thus proposed in JP Appln. 2007-60010 and 2007-63935 to use (meth)acrylate and poly(α-substituted acrylate) with —C(CF3)2OH structure having improved adhesion as the base resin in an ARC.
In the invention, a solution of a blend of polymer (A) having an alcohol structure having plural fluorine atoms substituted at α- and α′-positions and exhibiting a high etching rate and good adhesion to the resist film and polymer (B) having an aromatic ring is coated on a substrate whereby polymer (A) orients or localizes on the outer surface (photoresist film) side and polymer (B) orients or localizes on the inner surface (substrate) side. Since polymer (B) is more absorptive and has a higher k value than polymer (A), there is formed a bi-layer ARC having higher absorption on the inner surface (substrate) side, or a graded absorption ARC whose absorption increases toward the inner surface (substrate) side, achieving higher antireflection effects.
Referring to FIG. 1, for a 65-nm line-and-space pattern exposed using an exposure tool system having NA 0.85, σ 0.93/0.78, 20° dipole illumination, and 6% half-tone phase shift mask, data obtained by computing reflection on a BARC on a SiO2 substrate of 100 nm thick deposited on a Si substrate are plotted. The BARC has a fixed refractive index (n value) of 1.6 while the film thickness is on the abscissa and the k value representative of reflectance is on the ordinate. It is seen that the substrate reflection can be reduced to or below 1% by optimizing the k value and film thickness.
Referring to FIG. 2, for a 38-nm line-and-space pattern exposed using an exposure tool system having NA 1.35, σ 0.95/0.78, 20° dipole illumination, 100% s-polarization, and 6% half-tone phase shift mask, data obtained by computing reflection on a BARC are plotted. The region where reflectance is reduced to or below 1% is lost. It is seen that the substrate reflection is increased when the NA of a lens is increased so that the angle of light incident on the resist becomes shallower.
FIG. 3 illustrates an example where a two-layer ARC is applied under the condition NA=1.35. Herein the upper layer of ARC has a fixed k value of 0.2 and a fixed thickness of 60 nm, while the k value and thickness of the lower layer are varied. In FIG. 4, the lower layer of ARC has a fixed k value of 0.6 and a fixed thickness of 40 nm, while the k value and thickness of the upper layer are varied. In both FIGS. 3 and 4, there exist ranges of k and thickness values within which reflectance is reduced to or below 1%.
Next, in an example where an intermixing layer is present between the upper and lower layers, and the k value of the intermixing layer is intermediate those of the upper and lower layers, data obtained by computing reflectance when the thickness of the intermediate layer is increased are plotted in the diagram of FIG. 5. It is seen that as the thickness of the intermixing layer increases, the reflectance increases so that the effect of two-layer ARC is reduced. It is believed that the intermixing layer is created by mixing of the upper and lower layers. When polymers (A) and (B) are separated in a film depth direction at the end of deposition, an ARC of ideal two layers forms. If both the polymers are fully mixed without symptoms of separation, then the resulting ARC exerts only the effect of a single layer. The acceptable thickness of the mixed layer is less than or equal to about 50% of the total thickness. If the thickness of the mixed layer exceeds 60% of the total thickness, reflection increases, so that the function of a two-layer BARC diminishes.
The polymer (A) used in the ARC-forming composition of the invention essentially comprises recurring units (1) and/or (2) which have a high fluorine atom content and a poly(meth)acrylate structure, and have a high oxygen atom content as well. As a result, polymer (A) has a high dry etching rate. Accordingly, the ARC of the invention is finished as having an overall dry etching rate which is fully practically acceptable and thus functions to reduce the dry etching time and prevent a resist pattern from slimming and deformation during dry etching, eventually allowing a satisfactory pattern to be formed in the substrate.
In the embodiment wherein the ARC-forming composition further contains an acid generator or crosslinker, the polymer undergoes fast crosslinking reaction during baking after spin coating, forming a denser film. The denser film prevents intermixing with the resist film and diffusion of low-molecular-weight components into the resist film, minimizing any profile failure of the resist pattern. Further the ARC-forming composition is improved in application to the substrate when it contains an organic solvent.
In summary, the ARC-forming composition of the invention can be deposited by the same process as prior art ARCs. The resulting ARC is effective in preventing reflection of exposure light in photolithography. The ARC also has a practically acceptable dry etching rate and is thus useful in forming a fine feature-size pattern.
Now, several embodiments of the invention are described in detail although the invention is not limited thereto.
The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
As used herein, the term “coating” is used interchangeably with “film” or “layer.”
The abbreviation “ARC” denotes antireflective coating, “BARC” is bottom antireflective coating, “Me” is methyl, “Ac” is acetyl, and “phr” is parts by weight per 100 parts by Weight of the resin or polymer.
The term “processable substrate” is interchangeable with patternable substrate and refers to a substrate that can be processed such as by etching to form a pattern therein.
Polymer A
The ARC-forming composition of the invention comprises (A) a polymer comprising recurring units of at least one type represented by the general formula (1) and/or (2), and (B) a polymer containing an aromatic ring, at least one species for each polymer. The polymer (A) is first described.




Herein R1 is a hydrogen atom, fluorine atom, methyl group, or trifluoromethyl group. R2 and R3 are each independently a hydrogen atom or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 8 carbon atoms, or R2 and R3 may bond together to form a ring, specifically alicyclic ring, preferably of 5 to 10 carbon atoms, with the carbon atom to which they are attached. R4 is a hydrogen atom or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in which a constituent unit —CH2— may be replaced by —O— or —C(═O)—. R5 to R7 are each independently a hydrogen atom, a halogen atom, a hydroxyl group or a straight, branched or cyclic, monovalent organic group of 1 to 15 carbon atoms, or at least any two of R5 to R7 may bond together to form a ring with the carbon atom(s) to which they are attached.

More specifically, in formula (1), R2 and R3 are each independently a hydrogen atom or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 8 carbon atoms. Alternatively, R2 and R3 may bond together to form a ring with the carbon atom to which they are attached. Examples of straight, branched or cyclic, monovalent C1-C8 hydrocarbon group represented by R2 and R3 include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, and n-octyl. R2 and R3 may be the same or different. When R2 and R3 bond together to form a ring with the carbon atom to which they are attached, examples of the alkylene group formed by R2 bonding with R3 include tetramethylene and pentamethylene.
R4 is a hydrogen atom or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in which a constituent unit —CH2— may be replaced by —O— or —C(═O)—. The monovalent hydrocarbon groups represented by R4 include protective groups for alcoholic hydroxyl group, for example, groups of the general formulae (R1-1) and (R1-2) shown below, tertiary alkyl groups of 4 to 20 carbon atoms, specifically 4 to 15 carbon atoms, trialkylsilyl groups in which each alkyl radical has 1 to 5 carbon atoms, oxoalkyl groups of 4 to 20 carbon atoms, specifically 4 to 15 carbon atoms, and acyl groups of 1 to 10 carbon atoms.




The broken line indicates a valence bond.
In formula (R1-1), RL01 and RL02 are hydrogen or straight, branched or cyclic alkyl groups of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Examples include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl, norbornyl, tricyclodecanyl, tetracyclododecanyl, and adamantyl. RL03 is a monovalent hydrocarbon group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain a hetero atom such as oxygen, examples of which include straight, branched or cyclic alkyl groups and substituted forms of these groups in which some hydrogen atoms are replaced by hydroxyl, alkoxy, oxo, amino, alkylamino or the like. Examples of the straight, branched or cyclic alkyl groups are as exemplified above for RL01 and RL02, and examples of the substituted alkyl groups are shown below.




A pair of RL01 and RL02, RL01 and RL03, or RL02 and RL03 may bond together to form a ring with the carbon and oxygen atoms to which they are attached. Each of RL01, RL02 and RL03 is a straight or branched alkylene group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms when they form a ring.
In formula (R1-2), RL04 is a tertiary alkyl group of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group in which each alkyl moiety has 1 to 6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms, or a group of formula (R1-1). Exemplary tertiary alkyl groups are tert-butyl, tert-amyl, 1,1-diethylpropyl, 2-cyclopentylpropan-2-yl, 2-cyclohexylpropan-2-yl, 2-(bicyclo[2.2.1]heptan-2-yl)propan-2-yl, 2-(adamantan-1-yl)propan-2-yl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, and 2-ethyl-2-adamantyl. Exemplary trialkylsilyl groups are trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl. Exemplary oxoalkyl groups are 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-2-oxooxolan-5-yl. Exemplary acyl groups include formyl, acetyl, ethylcarbonyl, pivaloyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, trifluoroacetyl, and trichloroacetyl. In formula (R1-2), y is an integer of 0 to 6.
Of the protective groups of formula (R1-1), the straight and branched ones are exemplified by the following groups.




Of the protective groups of formula (R1-1), the cyclic ones are, for example, tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl.
Examples of the protective groups of formula (R1-2) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl groups.
In formula (2), R5 to R7 are each independently hydrogen, halogen, hydroxyl or a straight, branched or cyclic, monovalent organic group of 1 to 15 carbon atoms. Alternatively, at least any two of R5 to R7 may bond together to form a ring with the carbon atom(s) to which they are attached. Examples of the straight, branched or cyclic, monovalent organic group of 1 to 15 carbon atoms include monovalent hydrocarbon groups, for example, straight, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, methylcyclohexylmethyl, ethylcyclohexylmethyl, ethylcyclohexylethyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]heptylmethyl, bicyclo[2.2.1]heptylethyl, bicyclo[2.2.1]heptylbutyl, methylbicyclo[2.2.1]heptylmethyl, ethylbicyclo[2.2.1]heptylmethyl, ethylbicyclo[2.2.1]heptylethyl, bicyclo[2.2.2]octyl, bicyclo[2.2.2]octylmethyl, bicyclo[2.2.2]octylethyl, bicyclo[2.2.2]octylbutyl, methylbicyclo[2.2.2]octylmethyl, ethylbicyclo[2.2.2]octylmethyl, ethylbicyclo[2.2.2]octylethyl, tricyclo[5.2.1.02,6]decyl, tricyclo[5.2.1.02,6]decylmethyl, tricyclo[5.2.1.02,6]decylethyl, tricyclo[5.2.1.02,6]decylbutyl, methyltricyclo[5.2.1.02,6]decylmethyl, ethyltricyclo[5.2.1.02,6]decylmethyl, ethyltricyclo[5.2.1.02,6]decylethyl, adamantyl, adamantylmethyl, adamantylethyl, adamantylbutyl, methyladamantylmethyl, ethyladamantylmethyl, ethyladamantylethyl, tetracyclo[4.4.0.12,5.17,10]dodecyl, tetracyclo[4.4.0.12,5.17,10]dodecylmethyl, tetracyclo[4.4.0.12,5.17,10]dodecylethyl, tetracyclo[4.4.0.12,5.17,10]dodecylbutyl, tetracyclo[4.4.0.12,5.17,10]dodecylmethyl, ethyltetracyclo[4.4.0.12,5.17,10]dodecylmethyl, and ethyltetracyclo[4.4.0.12,5.17,10]dodecylethyl, aryl groups such as phenyl, methylphenyl, naphthyl, anthryl, and phenanthryl, and aralkyl groups such as benzyl, diphenylmethyl and phenethyl; alkoxy groups such as methoxy, ethoxy and propoxy, and acyloxy groups such as formyloxy and acetoxy, and substituted forms of the foregoing groups in which some hydrogen atoms are substituted by halogen atoms, alkyl, aryl, alkoxy, alkoxycarbonyl, oxo, alkoxyalkyl, acyloxy, acyloxyalkyl, alkoxyalkoxy or other groups.
At least two of R5 to R7 in any combination may bond together to form a ring with the carbon atom(s) to which they are attached. A typical ring-forming combination is a pair of R5 and R6, a pair of R5 and R7, or a pair of R6 and R7. Exemplary rings thus formed are alicyclic hydrocarbons of 3 to 12 carbon atoms such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, tricyclo[5.2.2.02,6]decane, adamantane, and tetracyclo[4.4.0.12,5.17,10]dodecane, and fused rings containing at least one of the foregoing. Also included are substituted forms of the foregoing alicyclic hydrocarbons in which some hydrogen atoms are replaced by halogen atoms, hydroxyl, alkyl, aryl, alkoxy, alkoxycarbonyl, oxo, alkoxyalkyl, acyloxy, acyloxyalkyl, alkoxyalkoxy or other groups.
Illustrative examples of the recurring units having formulae (1) and (2) are given below, but not limited thereto.
















Herein R1 is as defined above.

While the polymer (A) should comprise recurring units of at least one type having the general formula (1) and/or (2), preferably it may further comprise recurring units of at least one type having an aromatic ring. Examples of recurring units having an aromatic ring are given below, but not limited thereto.










Herein R1 is as defined above.

For the purpose of forming a more densified ARC, preferably the polymer (A) may further comprise recurring units of at least one type capable of crosslinking reaction in the presence of an acid, for example, recurring units of at least one type containing a hydroxyl group, a crosslinking group derived from cyclic ether such as epoxide or oxetane, or a carboxyl group. In the embodiment wherein the polymer (A) contains recurring units capable of crosslinking reaction, the resulting ARC has a more densified surface which is more effective in preventing intermixing with the resist film or preventing low-molecular-weight components from diffusing into the resist film, minimizing any profile degradation of the resist pattern. Examples of such recurring units are given below, but not limited thereto.




Herein R1 is as defined above.

For the purposes of improving adhesion to the resist film and preventing an acid or basic compound from diffusing from the resist film, the polymer (A) may further comprise other recurring units, for example, recurring units of at least one type derived from monomers of substituted (meth)acrylates, substituted norbornenes, unsaturated acid anhydrides, and the like. Examples of the other recurring units are given below, but not limited thereto.







Herein R1 is as defined above.

In the polymer (A), the respective recurring units are preferably incorporated in proportions <1> to <4> shown below, although the invention is not limited to these ranges. The polymer (A) may comprise:

    <1> recurring units of formulae (1) and (2) in a total proportion of 5 to 90 mol %, preferably 8 to 80 mol %, and more preferably 10 to 70 mol %,
    <2> recurring units having an aromatic ring in a total proportion of 3 to 50 mol %, preferably 5 to 30 mol %, and more preferably 8 to 20 mol %,
    <3> recurring units capable of crosslinking reaction in the presence of acid in a total proportion of 5 to 90 mol %, preferably 8 to 80 mol %, and more preferably 10 to 70 mol %, and
    <4> other recurring units in a total proportion of 0 to 60 mol %, specifically 1 to 60 mol %, preferably 3 to 50 mol %, and more preferably 5 to 40 mol %,

with the proviso that the total of <1> to <4> is 100 mol %.



The monomers from which the recurring units of formula (1) essential for the polymer (A) are derived may be prepared by well-known organic chemical techniques, and in particular, by the technique described in JP-A 2007-204385. Likewise the monomers from which the recurring units of formula (2) essential for the polymer (A) are derived may be prepared by well-known organic chemical techniques, and in particular, by the technique described in JP-A 2006-152255.
The monomers from which the recurring units having an aromatic ring, the recurring units capable of crosslinking reaction in the presence of acid, and the other recurring units are derived may be commercially available monomers or prepared by well-known organic chemical techniques.
The polymer (A) may be prepared through various polymerization reactions, preferably radical polymerization.
For radical polymerization, preferred reaction conditions include (1) a solvent selected from hydrocarbon solvents such as benzene, toluene and xylene, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone, ester solvents such as ethyl acetate, propyl acetate, butyl acetate and ethyl lactate, lactone solvents such as γ-butyrolactone, and alcohol solvents such as ethanol and isopropyl alcohol; (2) a polymerization initiator selected from well-known radical polymerization initiators including azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylisobutyronitrile, dimethyl2,2′-azobisisobutyrate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile), and 4,4′-azobis(4-cyanovaleric acid), and peroxides such as lauroyl peroxide and benzoyl peroxide; (3) a radical chain transfer agent, if necessary for molecular weight control, selected from thiol compounds including 1-butanethiol, 2-butanethiol, 2-methyl-1-propanethiol, 1-octanethiol, 1-decanethiol, 1-tetradecanethiol, cyclohexanethiol, 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, 6-mercapto-1-hexanol, 1-thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, and thiolactic acid; (4) a reaction temperature in the range of about 0° C. to about 140° C.; and (5) a reaction time in the range of about 0.5 to about 48 hours. Reaction parameters outside these ranges need not be excluded.
The polymer (A) has a weight average molecular weight (Mw) of 1,000 to 200,000, and preferably 2,000 to 180,000, as measured by gel permeation chromatography (GPC) versus polystyrene standards. Outside the range, poor separation in a coating thickness direction between polymers (A) and (B) or an extremely low dry etching rate may occur.
The polymer (A) should have an extinction coefficient (k value) at a preselected imaging radiation wavelength in the range of 0.01 to 0.4, preferably 0.02 to 0.38, and more preferably 0.03 to 0.35. With a k value of less than 0.01 or more than 0.4, no satisfactory antireflection effect is achievable (see FIGS. 4 and 5). It is understood that the polymer (A) may be endowed with a k value in the range by properly selecting the type and proportion of recurring units having an aromatic ring.
Polymer B
Also included in the inventive composition is the polymer (B) containing an aromatic ring. It is preferably selected from those polymers containing a hydroxyl group, a crosslinking group derived from cyclic ether such as epoxide or oxetane, or a carboxyl group and having a molecular weight of 1,000 to 100,000.
Suitable polymers include polymers from monomers having a polymerizable unsaturated bond such as styrene or its derivatives, indene, indole, methyleneindane, acenaphthylene, aromatic ring-bearing (meth)acrylic acid derivatives, vinyl naphthalene or its derivatives, vinyl anthracene or its derivatives, and vinyl carbazole. Polyester resins, polyvinyl phenolic resins, polyether resins, and bisphenol A resins having an aromatic ring are also useful.
Also included are novolac resins obtained through condensation of phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, pyrogallol, thymol, glycidyl 2-methylphenyl ether, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, dihydroxynaphthalenes (e.g., 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene), methyl3-hydroxy-naphthalene-2-carboxylate, indene, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, isothymol, polyindene, polyacenaphthylene, polystyrene, 4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-dimethyl-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-diallyl-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-difluoro-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-diphenyl-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-dimethoxy-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 3,3,3′,3′,4,4′-hexamethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-5,5′-diol, and 5,5′-dimethyl-3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, with aldehydes.
The polymer (B) may further comprise recurring units free of aromatic ring, for example, recurring units containing a hydroxyl group, a crosslinking group derived from cyclic ether such as epoxide or oxetane, or a carboxyl group and capable of crosslinking reaction in the presence of an acid, for preventing diffusion of an acid or basic compound from the resist film, or recurring units for increasing a dry etching rate. In order to form a multilayer ARC having a higher extinction coefficient (k value) on the substrate side, the content of aromatic ring-free recurring units must be determined such that the polymer (B) may have an extinction coefficient (k value) of at least 0.3. Examples of aromatic ring-free recurring units include those exemplified above as the other recurring units in conjunction with polymer (A) and the recurring units shown below.







In the polymer (B), the total of aromatic ring-containing recurring units is preferably 40 to 100 mol %, and more preferably 50 to 100 mol %. If the proportion of aromatic ring-containing recurring units is less than 40 mol %, the polymer (B) may have an extinction coefficient (k value) of less than 0.3.
Preferred examples of the polymer (B) include polyhydroxystyrene, copolymers of hydroxyvinylnaphthalene and indene:




copolymers obtained through condensation with aldehydes of cresol and naphthol, hydroxypyrene, hydroxyfluorene, hydroxyindene or 4,4′-(9H-fluoren-9-ylidene)bisphenol as shown by the following formulae:





polymers of hydroxystyrene and anthracenealkyl(meth)acrylates such as anthracenemethyl methacrylate, polymers comprising recurring units as shown by the following formula:





copolymers of acenaphthylene and hydroxystyrene:





copolymers of glycidyl(meth)acrylate, hydroxystyrene and indene:





copolymers of indene and N-hydroxyethyl maleimide:





polymers comprising recurring units as shown by the following formulae:





(wherein n is such a number that the polymer may have a Mw within the above-specified range)





polymers obtained through polyaddition of acid anhydrides and polyhydric alcohols or polycondensation of carboxylic acids and polyhydric alcohols, for example, combinations of recurring units (i) and (ii), recurring units (i) and (iii), or recurring units (i), (ii) and (iii):





The polymer (B) has a weight average molecular weight (Mw) of 1,000 to 100,000, and preferably 1,500 to 90,000, as measured by GPC versus polystyrene standards. Outside the range, separation in a coating depth direction between polymers (A) and (B) may be compromised.
The polymer (B) should have an extinction coefficient (k value) at a preselected imaging radiation wavelength in the range of 0.3 to 1.2, preferably 0.32 to 1.18, and more preferably 0.35 to 1.15. With a k value of less than 0.3 or more than 1.2, no satisfactory antireflection effect is achievable.
For a better antireflection effect, it is necessary that the k value of polymer (B) be greater than the k value of polymer (A). Specifically the k value of polymer (B) is preferably greater than the k value of polymer (A) by at least 0.1, and more preferably by at least 0.2. It is understood that the polymer (B) may be endowed with a k value in the range by properly selecting the type and proportion of aromatic ring-containing recurring units.
In the ARC-forming composition of the invention, polymers (A) and (B) are preferably present in a weight ratio between 30:70 and 80:20, and more preferably between 40:60 and 77:23.
In a preferred embodiment, the ARC-forming composition of the invention further comprises at least one member selected from an organic solvent, an acid generator and a crosslinker.
To the ARC-forming composition of the invention, an organic solvent is preferably added in order to facilitate coating to substrates. Where the ARC-forming composition contains an acid generator or crosslinker, crosslinking reaction of the polymers during the heating or baking step following spin coating is facilitated to form a more densified film. This reduces a likelihood of intermixing with the resist film or diffusion of low-molecular-weight components into the resist film, minimizing profile degradation of the resist pattern.
Acid Generator
To the ARC-forming composition of the invention, an acid generator may be added in order to facilitate thermally or otherwise induced crosslinking reaction. The acid generators include thermal acid generators capable of generating an acid through pyrolysis and photoacid generators capable of generating an acid upon exposure to light, and both are useful.
The acid generators used herein include
(i) onium salts of the formula (P1a-1), (P1a-2), (2) or (P1b),
(ii) diazomethane derivatives of the formula (P2),
(iii) glyoxime derivatives of the formula (P3),
(iv) bissulfone derivatives of the formula (P4),
(v) sulfonic acid esters of N-hydroxyimide compounds of the formula (P5),
(vi) β-ketosulfonic acid derivatives,
(vii) disulfone derivatives,
(viii) nitrobenzylsulfonate derivatives, and
(ix) sulfonate derivatives.
These acid generators are described in detail.
(i) Onium salts of formula (P1a-1), (P1a-2) or (2):




Herein, R101a, R101b, and R101c independently represent straight, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl groups of 1 to 12 carbon atoms, aryl groups of 6 to 20 carbon atoms, or aralkyl or aryloxoalkyl groups of 7 to 12 carbon atoms, wherein some or all hydrogen atoms may be replaced by alkoxy or other groups. Also, R101b and R101c, taken together, may form a ring with the sulfur atom to which they are attached. R101b and R101c each are alkylene groups of 1 to 6 carbon atoms when they form a ring. R101d, R101e, R101f, and R101g stand for hydrogen atoms or straight, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl groups of 1 to 12 carbon atoms, aryl groups of 6 to 20 carbon atoms, or aralkyl or aryloxoalkyl groups of 7 to 12 carbon atoms, wherein some or all hydrogen atoms may be replaced by alkoxy groups. A pair of R101d and R101e or a combination of R101d, R101e and R101f may form a ring with the nitrogen atom to which they are attached, and in this event, R101d and R101e or R101d, R101e and R101f together represent an alkylene group of 3 to 10 carbon atoms or a hetero-aromatic ring having the nitrogen atom incorporated therein. K− is a non-nucleophilic counter ion.
R101a, R101b, R101c, R101d, R101e, R101f, and R101g may be the same or different and are illustrated below. Exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Exemplary alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Exemplary oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl as well as 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Exemplary oxoalkenyl groups include 2-oxo-4-cyclohexenyl and 2-oxo-4-propenyl. Exemplary aryl groups include phenyl and naphthyl; alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl; alkoxynaphthyl groups such as methoxynaphthyl and ethoxynaphthyl; dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl; and dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl. Exemplary aralkyl groups include benzyl, phenylethyl, and phenethyl. Exemplary aryloxoalkyl groups are 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl.
Examples of the non-nucleophilic counter ion represented by K− include halide ions such as chloride and bromide ions, fluoroalkylsulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate, arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate, alkylsulfonates such as mesylate and butanesulfonate, imide acids such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide, methide acids such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide, and sulfonates having fluorine substituted at α-position as represented by the following general formula (K-1) and sulfonates having fluorine substituted at α- and β-positions as represented by the following general formula (K-2).




In formula (K-1), R102 is a hydrogen atom, straight, branched or cyclic C1-C20 alkyl or acyl group, C2-C20 alkenyl group, or C6-C20 aryl or aryloxy group. In formula (K-2), R103 is a hydrogen atom, straight, branched or cyclic C1-C20 alkyl group, C2-C20 alkenyl group, or C6-C20 aryl group.

Of the non-nucleophilic counter ions represented by K−, those sulfonates having fluorine substituted at α-position are most preferred because of high acid strength and quick crosslinking reaction.
Examples of the hetero-aromatic ring having the nitrogen atom (in formula (2)) incorporated therein, represented by R101d, R101e, R101f, and R101g include imidazole derivatives (e.g., imidazole, 4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline and 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline and 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.
The salts of (P1a-1) and (P1a-2) have both the functions of a photoacid generator and a thermal acid generator while the salts of (2) function as a thermal acid generator.




Herein, R102a and R102b independently represent straight, branched or cyclic alkyl groups of 1 to 8 carbon atoms. R103 represents a straight, branched or cyclic alkylene group of 1 to 10 carbon atoms. R104a and R104b independently represent 2-oxoalkyl groups of 3 to 7 carbon atoms. K− is a non-nucleophilic counter ion.
Illustrative of the alkyl groups represented by R102a and R102b are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, and cyclohexylmethyl. Illustrative of the alkylene groups represented by R103 are methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, 1,4-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclooctylene, and 1,4-cyclohexanedimethylene. Illustrative of the 2-oxoalkyl groups represented by R104a and R104b are 2-oxopropyl, 2-oxocyclopentyl, 2-oxocyclohexyl, and 2-oxocycloheptyl. Illustrative examples of the counter ion represented by K− are the same as exemplified for formulae (P1a-1), (P1a-2) and (2).
Among the onium salts of formulae (P1a-1), (P1a-2), (2) and (P1b), the salts of formulae (P1a-1), (P1a-2) and (P1b) generate acid in response to light or heat, and the salts of (2) generate acid in response to heat. Among the onium salts of formulae (P1a-1), (P1a-2), (2) and (P1b), the ammonium salts of formula (2) are most preferred as the acid generator to be added to the ARC-forming composition of the invention. Since the ammonium salts of formula (2) are thermally decomposed into amine and acid, the risk of evaporation by heat becoming a source of particulate emission is minimized. Accordingly, during pattern formation, the risk of the substrate being contaminated is minimized and the substrate is maintained at a high level of cleanness.
(ii) Diazomethane Derivatives of Formula (P2)




Herein, R105 and R106 independently represent straight, branched or cyclic C1-C12 alkyl or halogenated alkyl groups, C6-C20 aryl or halogenated aryl groups, or C7-C12 aralkyl groups.
Of the groups represented by R105 and R106, exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, amyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, and adamantyl. Exemplary halogenated alkyl groups include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl. Exemplary aryl groups include phenyl; alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl; and alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Exemplary halogenated aryl groups include fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Exemplary aralkyl groups include benzyl and phenethyl.
(iii) Glyoxime Derivatives of Formula (P3)




Herein, R107, R108, and R109 independently represent straight, branched or cyclic C1-C12 alkyl or halogenated alkyl groups, C6-C20 aryl or halogenated aryl groups, or C7-C12 aralkyl groups. Also, R108 and R109, taken together, may form a ring with the carbon atoms to which they are attached. R108 and R109 each are straight or branched C1-C6 alkylene groups when they form a ring. R105 is as defined in formula (P2).
Illustrative examples of the alkyl, halogenated alkyl, aryl, halogenated aryl, and aralkyl groups represented by R107, R108, and R109 are the same as exemplified for R105 and R106. Examples of the alkylene groups represented by R108 and R109 include methylene, ethylene, propylene, butylene, and hexylene.
(iv) Bissulfone Derivatives of Formula (P4)




Herein, R101a and R101b are as defined above.
(v) Sulfonic Acid Esters of N-Hydroxyimide Compounds of Formula (P5)




Herein, R110 is a C6-C10 arylene group, C1-C6 alkylene group, or C2-C6 alkenylene group wherein some or all hydrogen atoms may be replaced by straight or branched C1-C4 alkyl or alkoxy groups, nitro, acetyl, or phenyl groups. R111 is a straight, branched or cyclic C1-C8 alkyl group, alkenyl, alkoxyalkyl, phenyl or naphthyl group wherein some or all hydrogen atoms may be replaced by C1-C4 alkyl or alkoxy groups, phenyl groups (which may have substituted thereon a C1-C4 alkyl, alkoxy, nitro, or acetyl group), hetero-aromatic groups of 3 to 5 carbon atoms, or chlorine or fluorine atoms.
Of the groups represented by R110, exemplary arylene groups include 1,2-phenylene and 1,8-naphthylene; exemplary alkylene groups include methylene, ethylene, trimethylene, tetramethylene, phenylethylene, and norbornane-2,3-diyl; and exemplary alkenylene groups include 1,2-vinylene, 1-phenyl-1,2-vinylene, and 5-norbornene-2,3-diyl. Of the groups represented by R111, exemplary alkyl groups are as exemplified for R101a to R101c; exemplary alkenyl groups include vinyl, 1-propenyl, allyl, 1-butenyl, 3-butenyl, isoprenyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 3-heptenyl, 6-heptenyl, and 7-octenyl; and exemplary alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, methoxyhexyl, and methoxyheptyl.
Of the substituents on these groups, the C1-C4 alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; the C1-C4 alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy; the phenyl groups which may have substituted thereon a C1-C4 alkyl or alkoxy group, nitro, or acetyl group include phenyl, tolyl, p-tert-butoxyphenyl, p-acetylphenyl and p-nitrophenyl; the hetero-aromatic groups of 3 to 5 carbon atoms include pyridyl and furyl.
Illustrative examples of the acid generator include:
onium salts such as

    tetramethylammonium trifluoromethanesulfonate,
    tetramethylammonium nonafluorobutanesulfonate,
    triethylammonium nonafluorobutanesulfonate,
    pyridinium nonafluorobutanesulfonate,
    triethylammonium camphorsulfonate,
    pyridinium camphorsulfonate,
    tetra-n-butylammonium nonafluorobutanesulfonate,
    tetraphenylammonium nonafluorobutanesulfonate,
    tetramethylammonium p-toluenesulfonate,
    (p-methoxyphenylmethyl)dimethylphenylammonium trifluoro-methanesulfonate,
    diphenyliodonium trifluoromethanesulfonate,
    bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate,
    bis(p-tert-butylphenyl)iodonium nonafluorobutanesulfonate,
    (p-tert-butylphenyl)phenyliodonium trifluoromethanesulfonate,
    diphenyliodoniump-toluenesulfonate,
    (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate,
    triphenylsulfonium trifluoromethanesulfonate,
    (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethane-sulfonate,
    bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethane-sulfonate,
    tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate,
    triphenylsulfonium p-toluenesulfonate,
    (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate,
    bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate,
    tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate,
    triphenylsulfonium nonafluorobutanesulfonate,
    triphenylsulfonium butanesulfonate,
    trimethylsulfonium trifluoromethanesulfonate,
    trimethylsulfonium p-toluenesulfonate,
    cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethane-sulfonate,
    cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate,
    dimethylphenylsulfonium trifluoromethanesulfonate,
    dimethylphenylsulfonium p-toluenesulfonate,
    dicyclohexylphenylsulfonium trifluoromethanesulfonate,
    dicyclohexylphenylsulfonium p-toluenesulfonate,
    trinaphthylsulfonium trifluoromethanesulfonate,
    (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoro-methanesulfonate,
    ethylenebis[methyl(2-oxocyclopentyl)sulfonium trifluoro-methanesulfonate],
    1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate,
    triethylammonium nonaflate, tributylammonium nonaflate,
    tetraethylammonium nonaflate, tetrabutylammonium nonaflate,
    triethylammonium bis(trifluoromethylsulfonyl)imide, and
    triethylammonium tris(perfluoroethylsulfonyl)methide;


diazomethane derivatives such as

    bis(benzenesulfonyl)diazomethane,
    bis(p-toluenesulfonyl)diazomethane,
    bis(xylenesulfonyl)diazomethane,
    bis(cyclohexylsulfonyl)diazomethane,
    bis(cyclopentylsulfonyl)diazomethane,
    bis(n-butylsulfonyl)diazomethane,
    bis(isobutylsulfonyl)diazomethane,
    bis(sec-butylsulfonyl)diazomethane,
    bis(n-propylsulfonyl)diazomethane,
    bis(isopropylsulfonyl)diazomethane,
    bis(tert-butylsulfonyl)diazomethane,
    bis(n-amylsulfonyl)diazomethane,
    bis(isoamylsulfonyl)diazomethane,
    bis(sec-amylsulfonyl)diazomethane,
    bis(tert-amylsulfonyl)diazomethane,
    1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane,
    1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, and
    1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane;


glyoxime derivatives such as

    bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime,
    bis-O-(p-toluenesulfonyl)-α-diphenylglyoxime,
    bis-O-(p-toluenesulfonyl)-α-dicyclohexylglyoxime,
    bis-O-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime,
    bis-O-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,
    bis-O-(n-butanesulfonyl)-α-dimethylglyoxime,
    bis-O-(n-butanesulfonyl)-α-diphenylglyoxime,
    bis-O-(n-butanesulfonyl)-α-dicyclohexylglyoxime,
    bis-O-(n-butanesulfonyl)-2,3-pentanedioneglyoxime,
    bis-O-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,
    bis-O-(methanesulfonyl)-α-dimethylglyoxime,
    bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime,
    bis-O-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime,
    bis-O-(tert-butanesulfonyl)-α-dimethylglyoxime,
    bis-O-(perfluorooctanesulfonyl)-α-dimethylglyoxime,
    bis-O-(cyclohexanesulfonyl)-α-dimethylglyoxime,
    bis-O-(benzenesulfonyl)-α-dimethylglyoxime,
    bis-O-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime,
    bis-O-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime,
    bis-O-(xylenesulfonyl)-α-dimethylglyoxime, and
    bis-O-(camphorsulfonyl)-α-dimethylglyoxime;


bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane;
β-ketosulfonic acid derivatives such as

    2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and
    2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane;


disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone;
nitrobenzyl sulfonate derivatives such as

    2,6-dinitrobenzylp-toluenesulfonate and
    2,4-dinitrobenzylp-toluenesulfonate;


sulfonic acid ester derivatives such as

    1,2,3-tris(methanesulfonyloxy)benzene,
    1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and
    1,2,3-tris(p-toluenesulfonyloxy)benzene; and


sulfonic acid esters of N-hydroxyimides such as

    N-hydroxysuccinimide methanesulfonate,
    N-hydroxysuccinimide trifluoromethanesulfonate,
    N-hydroxysuccinimide ethanesulfonate,
    N-hydroxysuccinimide 1-propanesulfonate,
    N-hydroxysuccinimide 2-propanesulfonate,
    N-hydroxysuccinimide 1-pentanesulfonate,
    N-hydroxysuccinimide 1-octanesulfonate,
    N-hydroxysuccinimide p-toluenesulfonate,
    N-hydroxysuccinimide p-methoxybenzenesulfonate,
    N-hydroxysuccinimide 2-chloroethanesulfonate,
    N-hydroxysuccinimide benzenesulfonate,
    N-hydroxysuccinimide 2,4,6-trimethylbenzenesulfonate,
    N-hydroxysuccinimide 1-naphthalenesulfonate,
    N-hydroxysuccinimide 2-naphthalenesulfonate,
    N-hydroxy-2-phenylsuccinimide methanesulfonate,
    N-hydroxymaleimide methanesulfonate,
    N-hydroxymaleimide ethanesulfonate,
    N-hydroxy-2-phenylmaleimide methanesulfonate,
    N-hydroxyglutarimide methanesulfonate,
    N-hydroxyglutarimide benzenesulfonate,
    N-hydroxyphthalimide methanesulfonate,
    N-hydroxyphthalimide benzenesulfonate,
    N-hydroxyphthalimide trifluoromethanesulfonate,
    N-hydroxyphthalimide p-toluenesulfonate,
    N-hydroxynaphthalimide methanesulfonate,
    N-hydroxynaphthalimide benzenesulfonate,
    N-hydroxy-5-norbornene-2,3-dicarboxyimide methanesulfonate,
    N-hydroxy-5-norbornene-2,3-dicarboxyimide trifluoromethane-sulfonate, and
    N-hydroxy-5-norbornene-2,3-dicarboxyimide p-toluenesulfonate.


Preferred among these acid generators are onium salts such as triethylammonium nonafluorobutanesulfonate,

    (p-methoxyphenylmethyl)dimethylphenylammonium trifluoro-methanesulfonte,
    bis(p-tert-butylphenyl)iodonium nonafluorobutanesulfonate,
    triphenylsulfonium trifluoromethanesulfonate,
    (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethane-sulfonate,
    tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate,
    triphenylsulfonium p-toluenesulfonate,
    (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate,
    tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate,
    trinaphthylsulfonium trifluoromethanesulfonate,
    cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethane-sulfonate,
    (2-norbornyl)methyl(2-oxocylohexyl)sulfonium trifluoro-methanesulfonate, and
    1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate;

diazomethane derivatives such as

    bis(benzenesulfonyl)diazomethane,
    bis(p-toluenesulfonyl)diazomethane,
    bis(cyclohexylsulfonyl)diazomethane,
    bis(n-butylsulfonyl)diazomethane,
    bis(isobutylsulfonyl)diazomethane,
    bis(sec-butylsulfonyl)diazomethane,
    bis(n-propylsulfonyl)diazomethane,
    bis(isopropylsulfonyl)diazomethane, and
    bis(tert-butylsulfonyl)diazomethane;
    glyoxime derivatives such as
    bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and
    bis-O-(n-butanesulfonyl)-α-dimethylglyoxime;
    bissulfone derivatives such as bisnaphthylsulfonylmethane;

and sulfonic acid esters of N-hydroxyimide compounds such as

    N-hydroxysuccinimide methanesulfonate,
    N-hydroxysuccinimide trifluoromethanesulfonate,
    N-hydroxysuccinimide 1-propanesulfonate,
    N-hydroxysuccinimide 2-propanesulfonate,
    N-hydroxysuccinimide 1-pentanesulfonate,
    N-hydroxysuccinimide p-toluenesulfonate,
    N-hydroxynaphthalimide methanesulfonate, and
    N-hydroxynaphthalimide benzenesulfonate.


These acid generators may be used singly or in combinations of two or more thereof. The acid generator is preferably added in an amount of 0.1 to 50 parts by weight, and more preferably 0.5 to 40 parts by weight, per 100 parts by weight of the polymers combined. At least 0.1 phr of the acid generator generates a sufficient amount of acid to induce crosslinking reaction. Up to 50 phr of the acid generator minimizes the occurrence of a mixing phenomenon that acid migrates to the overlying resist layer.
Crosslinker
Suitable crosslinkers which can be used herein include melamine compounds, guanamine compounds, glycoluril compounds and urea compounds having substituted thereon at least one group selected from among methylol, alkoxymethyl and acyloxymethyl groups, epoxy compounds, isocyanate compounds, azide compounds, and compounds having a double bond such as an alkenyl ether group. Acid anhydrides are also useful as the crosslinker.
Of the foregoing crosslinkers, examples of suitable epoxy compounds include tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine compounds having 1 to 6 methylol groups methoxymethylated and mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine compounds having 1 to 6 methylol groups acyloxymethylated and mixtures thereof. Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethylol guanamine compounds having 1 to 4 methylol groups methoxymethylated and mixtures thereof, tetramethoxyethyl guanamine, tetraacyloxyguanamine, tetramethylol guanamine compounds having 1 to 4 methylol groups acyloxymethylated and mixtures thereof. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds having 1 to 4 methylol groups methoxymethylated and mixtures thereof, tetramethylol glycoluril compounds having 1 to 4 methylol groups acyloxymethylated and mixtures thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds having 1 to 4 methylol groups methoxymethylated and mixtures thereof, and tetramethoxyethyl urea.
Suitable isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and cyclohexane diisocyanate. Suitable azide compounds include 1,1′-biphenyl-4,4′-bisazide, 4,4′-methylidenebisazide, and 4,4′-oxybisazide.
Examples of the alkenyl ether group-containing compound include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylol propane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylol propane trivinyl ether.
Examples of the acid anhydride include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4′-(isopropylidene)-diphthalic anhydride, and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, and alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylene-tetrahydrophthalic anhydride, dodecenylsuccinic anhydride, trialkyltetrahydrophthalic anhydrides.
In the embodiment of the ARC-forming composition wherein one polymer comprises recurring units having a glycidyl group, addition of a hydroxyl-containing compound is effective. In particular, compounds having at least two hydroxyl groups in a molecule are preferred. Examples of suitable hydroxyl-containing compounds include alcoholic group-containing compounds such as naphthol novolac, m- and p-cresol novolac, naphthol-dicyclopentadiene novolac, m- and p-cresol-dicyclopentadiene novolac, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]-decane, pentaerythritol, 1,2,6-hexanetriol, 4,4′,4′′-methylidene triscyclohexanol, 4,4′-[1-[4-[1-(4-hydroxycyclohexyl)-1-methylethyl]phenyl]-ethylidene]biscyclohexanol, [1,1′-bicyclohexyl]-4,4′-diol, methylenebiscyclohexanol, decahydronaphthalene-2,6-diol, and [1,1′-bicyclohexyl]-3,3′,4,4′-tetrahydroxyl; and
low-nuclear phenol compounds such as bisphenol, methylene bisphenol, 2,2′-methylenebis[4-methylphenol], 4,4′-methylidene-bis[2,6-dimethylphenol], 4,4′-(1-methyl-ethylidene)bis[2-methylphenol], 4,4′-cyclohexylidene bisphenol, 4,4′-(1,3-dimethylbutylidene)bisphenol, 4,4′-(1-methylethylidene)bis[2,6-dimethylphenol], 4,4′-oxybisphenol, 4,4′-methylenebisphenol, bis(4-hydroxyphenyl)methanone, 4,4′-methylene bis[2-methylphenol], 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisphenol, 4,4′-(1,2-ethanediyl)bisphenol, 4,4′-(diethylsilylene)bisphenol, 4,4′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenol, 4,4′,4′′-methylidene trisphenol, 4,4′-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]-bisphenol, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 4,4′,4′′-ethylidyne tris[2-methylphenol], 4,4′,4′′-ethylidyne trisphenol, 4,6-bis[(4-hydroxyphenyl)methyl]-1,3-benzenediol, 4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol], 4,4′,4′′,4′′-(1,2-ethanediylidene)tetrakisphenol, 4,4′,4′′,4′′-(1,2-ethanediylidene)tetrakis[2-methylphenol], 2,2′-methylenebis[6-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol], 4,4′,4′′,4′′-(1,4-phenylenedimethylidyne)tetrakisphenol, 2,4,6-tris(4-hydroxyphenylmethyl)-1,3-benzenediol, 2,4′,4′′-methylidenetrisphenol, 4,4′,4′′′-(3-methyl-1-propanyl-3-ylidene)trisphenol, 2,6-bis[(4-hydroxy-3-fluorophenyl)methyl]-4-fluorophenol, 2,6-bis[4-hydroxy-3-fluorophenyl]methyl]-4-fluorophenol, 3,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2-benzenediol, 4,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,3-benzenediol, p-methylcalix[4]arene, 2,2′-methylenebis[6-[(2,5/3,6-dimethyl-4/2-hydroxyphenyl)methyl]-4-methylphenol, 2,2′-methylenebis[6-[(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-methylphenol, 4,4′,4′′,4′′′-tetrakis[(1-methylethylidene)bis(1,4-cyclo-hexylidene)]phenol, 6,6′-methylenebis[4-(4-hydroxyphenylmethyl)-1,2,3-benzene-triol, and 3,3′,5,5′-tetrakis[(5-methyl-2-hydroxyphenyl)methyl]-[(1,1′-biphenyl)-4,4′-diol].
In the ARC-forming composition, the crosslinker is preferably compounded in an amount of 1 to 50 parts by weight, more preferably 2 to 40 parts by weight per 100 parts by weight of the polymers combined. At least 1 phr of the crosslinker minimizes the risk of mixing with the resist film. Up to 50 phr of the crosslinker minimizes the risk that the antireflection effect is reduced or the crosslinked film cracks. The crosslinkers may be used alone or in admixture of two or more.
The organic solvent used in the ARC-forming composition of the invention may be any organic solvent in which the base polymers, acid generator, crosslinker and other components are soluble. Illustrative, non-limiting, examples of the organic solvent include ketones such as cyclohexanone and methyl-2-n-amylketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate. These solvents may be used alone or in combinations of two or more thereof. Of the above organic solvents, preferred are diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, ethyl lactate and propylene glycol monomethyl ether acetate, and mixtures thereof.
The organic solvent is preferably added in an amount of 200 to 10,000 parts by weight, especially 300 to 8,000 parts by weight per 100 parts by weight of the polymers combined.
Basic Compound
In the ARC-forming material of the invention, a basic compound may be compounded for improving the storage stability. The basic compound plays the role of an acid quencher for preventing a minute amount of acid generated from the acid generator from promoting crosslinking reaction during shelf storage.
Examples of suitable basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having carboxyl group, nitrogen-containing compounds having sulfonyl group, nitrogen-containing compounds having hydroxyl group, nitrogen-containing compounds having hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives.
Examples of suitable primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, iso-butylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine. Examples of suitable secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine. Examples of suitable tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, trilsopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,N′,N′-tetramethylmethylenediamine, N,N,N′,N′-tetramethylethylenediamine, and N,N,N′,N′-tetramethyltetraethylenepentamine.
Examples of suitable mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.
Examples of suitable aromatic and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, and diaminonaphthalene; and pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazole derivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g., thiazole and isothiazole), imidazole derivatives (e.g., imidazole, 4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline and 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline and 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.
Examples of suitable nitrogen-containing compounds having carboxyl group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (e.g., nicotinic acid, alanine, alginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine). Examples of suitable nitrogen-containing compounds having sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate. Examples of suitable nitrogen-containing compounds having hydroxyl group, nitrogen-containing compounds having hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidine ethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N-(2-hydroxyethyl)phthalimide, and N-(2-hydroxyethyl)isonicotinamide.
Examples of suitable amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide. Suitable imide derivatives include phthalimide, succinimide, and maleimide.
The basic compounds may be used alone or in admixture of two or more. The basic compound is preferably formulated in an amount of 0.001 to 2 parts by weight, and especially 0.01 to 1 part by weight, per 100 parts by weight of the polymers combined. At least 0.001 phr of the basic compound provides the desired effect whereas up to 2 phr of the basic compound minimizes the risk of trapping the entirety of thermally generated acid to inhibit crosslinking reaction.
Process
Another aspect of the invention is a process for forming a pattern in a substrate by lithography. Specifically, the patterning process involves at least the steps of applying the ARC-forming composition onto a substrate to form an ARC, applying a photoresist composition over the ARC to form a photoresist layer, exposing a pattern circuitry region of the photoresist layer to an imaging radiation, developing the photoresist film with a liquid developer to form a patterned photoresist layer, and etching the ARC and substrate through the resist pattern as a mask for thereby forming a pattern in the substrate.
Using the ARC-forming composition of the invention, an ARC can be formed on a processable substrate. The processable substrate is formed on a (support) substrate. The processable substrate may be selected from low dielectric constant films of Si, SiO2, SiON, SiN, polycrystalline silicon (p-Si), amorphous silicon (α-Si), W, W—Si, Al, Cu, Al—Si and the like and etching stop films thereof, and typically formed to a thickness of 10 to 10,000 nm, especially 20 to 5,000 nm. The support substrate is not particularly limited and is typically made of a material different from the processable substrate material, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, TiN, Al or the like.
In another embodiment, a hard mask may be laid on the processable substrate for facilitating processing of the processable substrate. When the processable substrate is a dielectric layer of SiO2 based material, the hard mask is selected from SiN, SiON, p-Si, α-Si, W, and W—Si. When the processable substrate is a gate electrode of p-Si, W—Si, Al—Si or the like, the hard mask is selected from SiO2, SiN, SiON and the like. In this embodiment, an ARC may be formed on the hard mask using the ARC-forming composition.
In a further embodiment, an organic film may be formed on the processable substrate, and a silicon-containing film formed on the organic film. In this embodiment, an ARC may be formed on the Si-containing film using the ARC-forming composition. The patterning process thus involves the steps of applying a photoresist composition over the ARC to form a photoresist layer, exposing a pattern circuitry region of the photoresist layer to an imaging radiation, developing the photoresist film with a liquid developer to form a patterned resist layer, etching the ARC and Si-containing film through the resist pattern as a mask, etching the organic film through the patterned Si-containing film as a mask, and further etching the processable substrate for thereby forming a pattern in the substrate.
To accelerate the migration phenomenon that allows polymer (A) to move afloat and polymer (B) to settle down by utilizing a difference of surface energy, a hydrophilic substrate is preferably used as the substrate. For example, a SiO2 substrate is originally hydrophilic, but is converted, through HMDS treatment, into a water repellent substrate which may impede separation between polymers (A) and (B). Also, Si, SiON and SiN substrates are highly hydrophilic when their surface is covered with an autoxidation film, but become highly water repellent immediately after treatment with hydrofluoric acid, which nature may impede separation between polymers (A) and (B).
It is now described how to form an ARC according to the invention. From the ARC-forming composition of the invention, an ARC may be formed on a substrate by spin coating and other standard techniques as used in forming photoresist films. After the ARC-forming composition is applied by spin coating or the like, desirably the organic solvent is evaporated off and the coating is baked to promote crosslinking reaction to prevent mixing with an overlying resist film. The baking is preferably performed at a temperature of 80 to 300+ C. for a time of 10 to 300 seconds. The thickness of the ARC is determined so as to enhance the antireflection effect and falls preferably in the range of 10 to 200 nm, and more preferably 20 to 150 nm. Once the ARC is formed, a resist film is formed thereon.
The photoresist composition from which the resist film is formed may be any of well-known compositions as described in JP-A 9-73173 and JP-A 2000-336121, for example. The thickness of the resist film is not particularly limited, but falls preferably in the range of 30 to 500 nm, and more preferably 50 to 400 nm. When the resist film is formed from the photoresist composition, spin coating and other standard techniques may be preferably used as in the case of ARC formation. After the resist composition is applied by spin coating or the like, the resist coating is desirably pre-baked at 80 to 180° C. for 10 to 300 seconds.
Thereafter, in accordance with the standard procedure, the resist coating in a pattern circuitry region is exposed to radiation, post-exposure baked (PEB), and developed, yielding a resist pattern.
A resist protective coating may be formed on top of the resist film. The resist protective coating may have an antireflection function and be formed of either water-soluble or water-insoluble materials. The water-insoluble materials include those which are dissolvable in alkaline developer and those which are not dissolvable in alkaline developer, but strippable with fluorochemical solvents. The former is advantageous from the process standpoint in that it can be stripped at the same time as the development of the resist. In the case of immersion lithography, a protective film may be provided for the purpose of preventing additives like acid generator from being leached out of the resist film and for the purpose of improving water slippage. The protective film is preferably made of a material which is not dissolvable in water, but in alkali, typically a solution of a polymer of alcohol structure having plural fluorine atoms substituted at α-position, in a higher alcohol of at least 4 carbon atoms or an ether compound of 8 to 12 carbon atoms. A protective film is typically formed by applying a protective film solution onto the resist film as pre-baked by spin coating, and pre-baking the coating. The protective film preferably has a thickness in the range of 10 to 200 nm.
Where the protective coating is used, the resultant multilayer structure is exposed to radiation by dry or immersion lithography, post-exposure baked (PEB), and developed in an alkaline developer for 10 to 300 seconds to form a resist pattern. A typical alkaline developer is a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH). Where a protective coating which is soluble in the developer is used, stripping of the protective coating and development of the resist film occur simultaneously.
In the case of immersion lithography, to fully remove water on the protective coating prior to PEB, the water on the resist should preferably be dried or recovered by suitable means, for example, spin drying prior to PEB, purging of the film surface with dry air or nitrogen, or optimizing the water recovery nozzle configuration or process on a stage after the exposure. Full removal of residual water on the protective coating prior to PEB minimizes the risk that water can penetrate into the resist film to suck up the acid in the resist, impeding pattern formation.
Development is carried out by a puddle, dip or similar technique using an aqueous alkaline solution, typically by a puddle technique using a 2.38 wt % aqueous solution of TMAH, at room temperature for 10 to 300 seconds. The resist coating as developed is then rinsed with deionized water and dried by spin drying or nitrogen blowing.
Next, the ARC is etched by dry etching or the like while using the resist pattern as a mask. This etching may be carried out by a standard technique. In the case of dry etching with an oxygen-based gas, an inert gas such as He or Ar and another gas such as CO, CO2, NH3, SO2, N2 or NO2 may be added to oxygen gas. Etching with fluorochemical gases is employed where the substrate is SiO2 or SiN, and etching with chlorine or bromine based gases is employed where the substrate is polysilicon (p-Si), Al or W. The ARC of the invention is characterized by a high etching rate during etching of the substrate. As a result of etching, a pattern is formed in the substrate.
Although the foregoing description refers to a photoresist composition as the overcoat layer material, the ARC-forming composition may also be used in an application other than photolithography, for example, in an application where electron beam exposure is used, for the purpose of forming a resist undercoat layer for preventing the resist film from footing or undercutting.
Example
Synthesis Examples and Examples are given below together with Comparative Examples for further illustrating the invention although the invention is not limited thereby.
The weight average molecular weight (Mw) and number average molecular weight (Mn) of a polymer are determined by gel permeation chromatography (GPC) versus polystyrene standards, and a dispersity (Mw/Mn) is computed therefrom. The abbreviation AIBN denotes 2,2′-azobisisobutyronitrile, MEK denotes methyl ethyl ketone, and THF denotes tetrahydrofuran.
Monomers 1 to 7 used in Synthesis Examples are identified below.




Synthesis of Polymer A-1

In a nitrogen atmosphere, a flask was charged with 24.1 g of Monomer 1, 11.6 g of Monomer 4, 4.3 g of Monomer 6, 0.672 g of AIBN, 10.0 g of MEK, and 30.0 g of toluene to form a monomer solution. In a nitrogen atmosphere, another flask was charged with 5.0 g of MEK and 15.0 g of toluene and heated to 80° C. with stirring, after which the monomer solution was added dropwise over 4 hours. After the completion of dropwise addition, the polymerization solution was stirred for a further 2 hours while maintaining it at the temperature of 80° C. The polymerization solution was cooled down to room temperature and added dropwise to 800 g of hexane, whereupon the precipitating polymer was filtered. The polymer precipitate was washed twice with a solvent mixture of 12.0 g MEK and 228.0 g hexane and vacuum dried at 50° C. for 20 hours, obtaining 36.0 g of a polymer in white powder solid form, designated Polymer A-1. The yield was 90%. The polymer had a Mw of 16,400 and a dispersity Mw/Mn of 1.98. On 13C-NMR analysis, it had a copolymer compositional ratio of Monomer 1/Monomer 4/Monomer 6=43/36/21 mol %.
Synthesis of Polymer A-2
In a nitrogen atmosphere, a flask was charged with 22.3 g of Monomer 1, 14.0 g of Monomer 5, 3.9 g of Monomer 6, 0.619 g of AIBN, 20.7 g of MEK, and 41.5 g of toluene to form a monomer solution. In a nitrogen atmosphere, another flask was charged with 10.4 g of MEK and 20.7 g of toluene and heated to 80° C. with stirring, after which the monomer solution was added dropwise over 4 hours. After the completion of dropwise addition, the polymerization solution was stirred for a further 2 hours while maintaining it at the temperature of 80° C. The polymerization solution was cooled down to room temperature and added dropwise to 400 g of hexane, whereupon the precipitating polymer was filtered. The polymer precipitate was washed twice with a solvent mixture of 24.0 g MEK and 216.0 g hexane and vacuum dried at 50° C. for 20 hours, obtaining 32.6 g of a polymer in white powder solid form, designated Polymer A-2. The yield was 82%. The polymer had a Mw of 12,900 and a dispersity Mw/Mn of 1.75. On 13C-NMR analysis, it had a copolymer compositional ratio of Monomer 1/Monomer 5/Monomer 6=43/34/23 mol %.
Synthesis of Polymer A-3
In a nitrogen atmosphere, a flask was charged with 22.6 g of Monomer 1, 10.8 g of Monomer 4, 6.7 g of Monomer 7, 0.626 g of AIBN, 10.0 g of MEK, and 30.0 g of toluene to form a monomer solution. In a nitrogen atmosphere, another flask was charged with 5.0 g of MEK and 15.0 g of toluene and heated to 80° C. with stirring, after which the monomer solution was added dropwise over 4 hours. After the completion of dropwise addition, the polymerization solution was stirred for a further 2 hours while maintaining it at the temperature of 80° C. The polymerization solution was cooled down to room temperature and added dropwise to 800 g of hexane, whereupon the precipitating polymer was filtered. The polymer precipitate was washed twice with a solvent mixture of 12.0 g MEK and 228.0 g hexane and vacuum dried at 50° C. for 20 hours, obtaining 37.6 g of a polymer in white powder solid form, designated Polymer A-3. The yield was 94%. The polymer had a Mw of 14,700 and a dispersity Mw/Mn of 1.94. On 13C-NMR analysis, it had a copolymer compositional ratio of Monomer 1/Monomer 4/Monomer 7=43/33/24 mol %.
Synthesis of Polymer A-4
In a nitrogen atmosphere, a flask was charged with 9.9 g of Monomer 2, 3.7 g of Monomer 4, 1.4 g of Monomer 6, 0.214 g of AIBN, and 15.0 g of toluene to form a monomer solution. In a nitrogen atmosphere, another flask was charged with 7.5 g of toluene and heated to 80° C. with stirring, after which the monomer solution was added dropwise over 4 hours. After the completion of dropwise addition, the polymerization solution was stirred for a further 2 hours while maintaining it at the temperature of 80° C. The polymerization solution was cooled down to room temperature and added dropwise to 150 g of hexane, whereupon the precipitating polymer was filtered. The polymer precipitate was washed twice with a solvent mixture of 9.0 g DIISOPROPYL ETHER and 81.0 g hexane and vacuum dried at 70° C. for 20 hours, obtaining 9.2 g of a polymer in white powder solid form, designated Polymer A-4. The yield was 61%. The polymer had a Mw of 16,400 and a dispersity Mw/Mn of 1.61. On 13C-NMR analysis, it had a copolymer compositional ratio of Monomer 2/Monomer 4/Monomer 6=33/42/25 mol %.
Synthesis of Polymer A-5
In a nitrogen atmosphere, a flask was charged with 22.1 g of Monomer 3, 14.0 g of Monomer 5, 4.0 g of Monomer 6, 0.624 g of AIBN, 10.0 g of MEK, and 30.0 g of toluene to form a monomer solution. In a nitrogen atmosphere, another flask was charged with 5.0 g of MEK and 15.0 g of toluene and heated to 80° C. with stirring, after which the monomer solution was added dropwise over 4 hours. After the completion of dropwise addition, the polymerization solution was stirred for a further 3.5 hours while maintaining it at the temperature of 80° C. The polymerization solution was cooled down to room temperature and added dropwise to 400 g of hexane, whereupon the precipitating polymer was filtered. The polymer precipitate was washed twice with a solvent mixture of 12.0 g MEK and 228.0 g hexane and vacuum dried at 50° C. for 20 hours, obtaining 39.4 g of a polymer in white powder solid form, designated Polymer A-5. The yield was 98%. The polymer had a Mw of 17,600 and a dispersity Mw/Mn of 1.88. On 13C-NMR analysis, it had a copolymer compositional ratio of Monomer 3/Monomer 5/Monomer 6=42/35/23 mol %.
Synthesis of Polymer A-6
In a nitrogen atmosphere, a flask was charged with 8.8 g of Monomer 1, 5.7 g of Monomer 4, 3.1 g of Monomer 6, and 20.0 g of tetrahydrofuran to form a monomer solution. The reactor was subjected to three cycles of cooling to −70° C. in the nitrogen atmosphere, vacuum evacuation, and nitrogen flow. The reactor was warmed to room temperature, fed with 0.1 g of AIBN as the polymerization initiator, and heated at 60° C., whereupon reaction occurred for 15 hours. The reaction solution was added dropwise to 100 ml of isopropyl alcohol, whereupon the precipitating polymer was filtered. The polymer precipitate was vacuum dried at 60° C., obtaining a white polymer, designated Polymer A-6. The polymer had a Mw of 10,500 and a dispersity Mw/Mn of 1.76. On 13C-NMR analysis, it had a copolymer compositional ratio of Monomer 1/Monomer 4/Monomer 6=30/40/30 mol %.
Synthesis of Comparative Polymers 1 to 3
Comparative Polymers 1 to 3, identified below, were prepared by similar radical polymerization.




Synthesis of Polymer B-1

Polymer B-1 is poly(4-hydroxystyrene) having a Mw of 8,000, available from Aldrich.
Synthesis of Polymer B-2
A 200-ml flask was charged with 7.0 g of indene, 6.9 g of 6-hydroxy-2-vinylnaphthalene, and 20 g of 1,2-dichloroethane as a solvent. In a nitrogen atmosphere, 0.5 g of boron trifluoride as a polymerization initiator was added to the reactor, which was heated to 60° C., whereupon reaction occurred for 15 hours. The reaction solution was concentrated to 1⁄2, and poured into a mixture of 2.5 L methanol and 0.2 L water for precipitation. The resulting white solids were filtered and vacuum dried at 60° C., yielding a white polymer, designated Polymer B-2. The polymer had a Mw of 15,000 and a dispersity Mw/Mn of 1.92. On 13C-NMR analysis, it had a copolymer compositional ratio of 6-hydroxy-2-vinylnaphthalene/indene=40/60 mol %.




Synthesis of Polymer B-3

A 300-ml flask was charged with 160 g of m-cresol, 50 g of 1-naphthol, 75 g of 37% formalin, and 5 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 500 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted-monomers, yielding 188 g of a polymer, designated Polymer B-3. The polymer had a Mw of 12,000 and a dispersity Mw/Mn of 4.60. On 1H-NMR analysis, it had a copolymer compositional ratio of a1/b1=80/20 mol %.




Synthesis of Polymer B-4

A 300-ml flask was charged with 160 g of m-cresol, 70 g of 1-hydroxypyrene, 75 g of 37% formalin, and 5 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 500 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, yielding 193 g of a polymer, designated Polymer B-4. The polymer had a Mw of 12,700 and a dispersity Mw/Mn of 4.80. On 1H-NMR analysis, it had a copolymer compositional ratio of a1/b2=83/17 mol %.




Synthesis of Polymer B-5

A 300-ml flask was charged with 160 g of m-cresol, 60 g of 2-hydroxyfluorene, 75 g of 37% formalin, and 5 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 500 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, yielding 190 g of a polymer, designated Polymer B-5. The polymer had a Mw of 10,800 and a dispersity Mw/Mn of 4.30. On 1H-NMR analysis, it had a copolymer compositional ratio of a1/b3=75/25 mol %.




Synthesis of Polymer B-6

A 300-ml flask was charged with 160 g of m-cresol, 50 g of 6-hydroxyindene, 75 g of 37% formalin, and 5 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 500 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, yielding 175 g of a polymer, designated Polymer B-6. The polymer had a Mw of 9,800 and a dispersity Mw/Mn of 5.30. On 1H-NMR analysis, it had a copolymer compositional ratio of a1/b4=68/32 mol %.




Synthesis of Polymer B-7

A 100-ml flask was charged with 2 g of Compound 1, shown below, 0.75 g of 37% formalin, and 0.05 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 10 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, yielding 1.8 g of a polymer, designated Polymer B-7. The polymer had a Mw of 4,000 and a dispersity Mw/Mn of 2.60.




Synthesis of Polymer B-8

A 500-ml flask was charged with 82 g of 4-hydroxystyrene, 85 g of 2-methacrylic acid-1-anthracene-methyl, and 40 g of toluene as a solvent. The reactor was subjected to three cycles of cooling to −70° C. in a nitrogen atmosphere, vacuum evacuation, and nitrogen flow. The reactor was warmed to room temperature, fed with 4.1 g of AIBN as the polymerization initiator, and heated at 80° C., whereupon reaction occurred for 24 hours. The reaction solution was concentrated to 1⁄2, and poured into a solvent mixture of 300 ml methanol and 50 ml water for precipitation. The resulting white solids were filtered and vacuum dried at 60° C., yielding 133 g of a white polymer, designated Polymer B-8. The polymer had a Mw of 14,400 and a dispersity Mw/Mn of 1.77. On 1H-NMR analysis, it had a copolymer compositional ratio of 4-hydroxystyrene/2-methacrylic acid-1-anthracenemethyl=56/44 mol %.
Synthesis of Polymer B-9
A 300-ml flask was charged with 200 g of Compound 2, shown below, 75 g of 37% formalin, and 5 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 500 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, yielding 163 g of a polymer, designated Polymer B-9. The polymer had a Mw of 13,000 and a dispersity Mw/Mn of 4.60.




Synthesis of Polymer B-10

A 200-ml flask was charged with 15.2 g of acenaphthylene, 3.3 g of 4-hydroxystyrene, and 60 g of 1,2-dichloroethane as a solvent. Then, 1 g of boron trifluoride as a polymerization initiator was added to the reactor, which was heated to 60° C., whereupon reaction occurred for 25 hours. To the reaction solution, 1 L of methanol and 500 g of water were added for precipitation. The resulting white solids were filtered and dried, yielding 12 g of a white polymer, designated Polymer B-10. The polymer had a Mw of 8,800 and a dispersity Mw/Mn of 1.82. On 13C- and 1H-NMR analysis, it had a copolymer compositional ratio of acenaphthylene/4-hydroxystyrene=75/25 mol %.




Synthesis of Polymer B-11

A 2-L flask was charged with 56.8 g of glycidyl methacrylate, 48.0 g of 4-hydroxystyrene, 25.5 g of indene, and 150 g of THF as a solvent. The reactor was subjected to three cycles of cooling to −70° C. in a nitrogen atmosphere, vacuum evacuation, and nitrogen flow. The reactor was warmed to room temperature, fed with 2.6 g of AIBN as the polymerization initiator, and heated at 60° C., whereupon reaction occurred for 15 hours. The reaction solution was poured into 1500 ml of isopropyl alcohol for precipitation. The resulting white solids were filtered and vacuum dried at 60° C., yielding 110.1 g of a white polymer, designated Polymer B-11. The polymer had a Mw of 8,400 and a dispersity Mw/Mn of 1.83. On 13C- and 1H-NMR analysis, it had a copolymer compositional ratio of glycidyl methacrylate/4-hydroxy-styrene/indene=42/38/20 mol %.




Synthesis of Polymer B-12

A 200-ml flask was charged with 11.5 g of indene, 14.1 g of N-hydroxyethylmaleimide, and 15 g of THF as a solvent. The reactor was subjected to three cycles of cooling to −70° C. in a nitrogen atmosphere, vacuum evacuation, and nitrogen flow. The reactor was warmed to room temperature, fed with 2.5 g of 2,2′-azobis(2,4-dimethylvaleronitrile) as the polymerization initiator, and heated at 55° C., whereupon reaction occurred for 25 hours. The reaction solution was diluted with 5 ml of acetone and poured into 2 L of isopropyl alcohol for precipitation. The resulting white solids were filtered and vacuum dried at 40° C., yielding 13 g of a white polymer, designated Polymer B-12. The polymer had a Mw of 6,500 and a dispersity Mw/Mn of 1.66. On 13C- and 1H-NMR analysis, it had a copolymer compositional ratio of indene/N-hydroxyethylmaleimide=50/50 mol %.




Synthesis of Polymer B-13

A 300-ml flask was charged with 120 g of m-cresol, 150 g of 4,4′-(9H-fluoren-9-ylidene)bisphenol, 75 g of 37% formalin, and 5 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 500 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, yielding 255 g of a polymer, designated Polymer B-13. The polymer had a Mw of 6,000 and a dispersity Mw/Mn of 3.70. On 1H-NMR analysis, it had a copolymer compositional ratio of a1/b5=67/33 mol %.




Synthesis of Polymer B-14

A 300-ml flask was charged with 120 g of m-cresol, 54 g of 37% formalin, and 3 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 300 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, leaving a novolac resin.
A 300-ml flask was charged with 120 g of the novolac resin and 41 g of 9-anthracenemethanol in THF. Tosylic acid, 0.5 g, was added to the solution which was stirred at 80° C. for 24 hours for reaction. By washing the solution with water to remove the catalyst and metal impurities and distilling off the THF under reduced pressure, 155 g of a polymer, designated Polymer B-14, was recovered from the solution. The polymer had a Mw of 6,000 and a dispersity Mw/Mn of 2.70. On 1H-NMR analysis, it had a copolymer compositional ratio of a1/b6=65/35 mol %.




Synthesis of Polymer B-15

A 300-ml flask was charged with 120 g of poly(p-hydroxystyrene) with a Mw of 14,000 and a dispersity Mw/Mn of 1.67 and 41 g of 9-anthracenemethanol in THF. Tosylic acid, 0.5 g, was added to the solution which was stirred at 80° C. for 24 hours for reaction. By washing the solution with water to remove the catalyst and metal impurities and distilling off the THF under reduced pressure, 155 g of a polymer, designated Polymer B-15, was recovered from the solution. The polymer had a Mw of 15,000 and a dispersity Mw/Mn of 1.70. On 1H-NMR analysis, it had a copolymer compositional ratio of a2/b7=20/80 mol %.




Synthesis of Polymer B-16

A 300-ml flask was charged with 180 g of 4,4,′-(9H-fluoren-9-ylidene)bisphenol, 75 g of 37% formalin, and 5 g of oxalic acid, which were stirred at 100° C. for 24 hours for reaction. The reaction solution was dissolved in 500 ml of methyl isobutyl ketone. The solution was thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was distilled off under reduced pressure. The system was kept under a vacuum of 2 mmHg at 150° C. for removing the water and unreacted monomers, yielding 163 g of a polymer, designated Polymer B-16. The polymer had a Mw of 11,000 and a dispersity Mw/Mn of 4.40.




Synthesis of Polymer B-17

Polymer B-17 is poly[(o-cresol glycidyl ether)-co-formaldehyde] having a Mw of 2,000, available from Aldrich.




Synthesis of Polymer B-18

In a nitrogen atmosphere, a flask was charged with 15.05 g of bisphenol A, 22.16 g of bisphenol AF, 46.40 g of 25% NaOH aqueous solution, 97.02 g of water, and 200 mg of benzyltriethylammonium chloride, which were heated at 70° C. and stirred to form a homogeneous solution. To the flask was added 12.81 g of epichlorohydrin in 124.83 g of cyclopentyl methyl ether. The internal temperature of the flask was raised to 84° C. whereupon stirring was continued for 5.5 hours. The reaction solution was cooled to room temperature, after which 26.43 g of 20% aqueous hydrochloric acid and 108.57 g of water were added. Further, 300 g of ethyl acetate was added to the solution, from which the water layer was separated off. The organic layer was washed 4 times with 300 g of water, and the solvent was distilled off in vacuum. Cyclopentyl methyl ether was added to the residue to form 300 g of a solution. The solution was added dropwise to 1,500 g of hexane whereupon the precipitating polymer was filtered. The polymer precipitate was washed twice with 300 g of hexane and vacuum dried at 50° C. for 2 hours and then at 90° C. for 22 hours, obtaining 41.01 g of a polymer in white solid form, designated Polymer B-18. The polymer had a Mw of 6,430 and a dispersity Mw/Mn of 1.76. On 1H-NMR analysis, it had a copolymer compositional ratio of a3/b8=51/49 mol %.




Synthesis of Polymer B-19

In a nitrogen atmosphere, a flask was charged with 77.58 g of bisphenol AF, 81.22 g of 25% NaOH aqueous solution, 169.83 g of water, and 400 mg of benzyltriethylammonium chloride, which were heated at 50° C. and stirred to form a homogeneous solution. To the flask was added 26.69 g of epichlorohydrin in 218.50 g of cyclopentyl methyl ether. The internal temperature of the flask was raised to 84° C. whereupon stirring was continued for 15 hours. The reaction solution was cooled to room temperature, after which 100 g of THF was added. The water layer was separated off. The organic layer was washed with 200 g of water and 200 g of 2.1% aqueous hydrochloric acid. It was further washed three times with 200 g of water, and the solvent was distilled off in vacuum. Cyclopentyl methyl ether was added to the residue to form 220 g of a solution. The solution was added dropwise to 2,000 g of hexane whereupon the precipitating polymer was filtered. The polymer precipitate was washed twice with a solvent mixture of 30 g cyclopentyl methyl ether and 570 g hexane and vacuum dried at 50° C. for 1 hour and then at 70° C. for 21 hours, obtaining 79.76 g of a polymer in white solid form, designated Polymer B-19. The polymer had a Mw of 5,750 and a dispersity Mw/Mn of 1.74.




Synthesis of Polymer B-20

In a nitrogen atmosphere, a flask was charged with 24.25 g of 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride, 3.52 g of glycerol, 2.75 g of 2,6-bishydroxymethyl-p-cresol, and 117.90 g of acetonitrile, which were stirred for 48 hours at an internal temperature of 83° C. The reaction solution was added dropwise to 3,050 g of water whereupon the precipitating polymer was filtered. The polymer precipitate was washed three times with 240 g water and vacuum dried at 60° C. for 27.5 hours, obtaining 28.91 g of a polymer in solid form, designated Polymer B-20. The polymer had a Mw of 15,300 and a dispersity Mw/Mn of 29.6. On 13C-NMR analysis, it had a copolymer compositional ratio of a4/b9/c1=52/33/15 mol %.
Synthesis of Polymer B-21
In a nitrogen atmosphere, a flask was charged with 36.00 g of 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride, 5.22 g of glycerol, 4.09 g of 2,6-bishydroxymethyl-p-cresol, and 175.03 g of acetonitrile, which were stirred for 50 hours at an internal temperature of 83° C. Water, 22.66 g, was added to the solution, which was stirred for a further 4 hours at an internal temperature of 77° C. The reaction solution was added dropwise to 4,500 g of water whereupon the precipitating polymer was filtered. The polymer precipitate was washed three times with 360 g water and vacuum dried at 60° C. for 26 hours, obtaining 38.92 g of a polymer in solid form, designated Polymer B-21. The polymer had a Mw of 6,800 and a dispersity Mw/Mn of 47.6. On 13C-NMR analysis, it had a copolymer compositional ratio of a4/b9/c1=52/33/15 mol %.




Synthesis of Comparative Polymer 4

A 500-ml flask was charged with 40 g of 4-hydroxystyrene, 160 g of 2-methacrylic acid-1-adamantane, and 40 g of toluene as a solvent. The reactor was subjected to three cycles of cooling to −70° C. in a nitrogen atmosphere, vacuum evacuation, and nitrogen flow. The reactor was warmed up to room temperature, fed with 4.1 g of AIBN as a polymerization initiator, and then heated to 80° C., whereupon reaction occurred for 24 hours. The reaction solution was concentrated to 1⁄2, and poured into a solvent mixture of 300 ml methanol and 50 ml water for precipitation. The resulting white solids were filtered and vacuum dried at 60° C., yielding 188 g of a white polymer, designated Comparative Polymer 4. The polymer had a Mw of 10,900 and a dispersity Mw/Mn of 1.77. On 1H-NMR analysis, it had a copolymer compositional ratio of 4-hydroxystyrene/2-methacrylic acid-1-adamantane=32/68 mol %.




Measurement of Optical Parameters of Polymers

Solutions for measuring optical parameters were prepared by mixing selected components in accordance with the formulation shown in Tables 1 and 2. The components used included polymers (A) designated Polymers A-1 to A-6, Comparative Polymers 1 to 4, aromatic ring-bearing polymers (B) designated Polymers B-1 to B-21, acid generators AG1, AG2, and AG3, identified below, crosslinkers CR1 and CR2, identified below, a surfactant FC-430 (3M-Sumitomo Co., Ltd.), and a solvent. Filtration through a fluoroplastic filter having a pore size of 0.1 μm gave coating solutions.
The coating solutions thus prepared (Polymers A-1 to A-6, Polymers B-1 to B-21, Comparative Polymers 1 to 4, Examples 1 to 27, Comparative Examples 1 to 4) were coated on Si substrates, and baked at 220° C. for 60 seconds in the case of Examples 1 to 6, 23 to 27 and Comparative Examples 1 to 3, or at 200° C. for 60 seconds in the case of Polymers A-1 to A-6, Polymers B-1 to B-21, Comparative Polymers 1 to 4, Examples 7 to 12, 14, 16 to 22, and Comparative Example 4, or at 300° C. for 60 seconds in the case of Examples 13 and 15, to form coating films for measuring optical parameters.
Using a variable angle spectroscopic ellipsometer (VASE®) of J. A. Woollam Co., the refractive index (n) and extinction coefficient (k) at wavelength 193 nm of the coating films were determined. The results are shown in Tables 1 and 2.















TABLE 1








Acid


Organic
Refractive
Extinction



Polymer
generator
Crosslinker
Surfactant
solvent
index
coefficient



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)
(n)
(k)























Polymer A-1
Polymer A-1
—
—
—
PGMEA
1.66
0.22



(100)



(2400)


Polymer A-2
Polymer A-2
—
—
—
PGMEA
1.65
0.21



(100)



(2400)


Polymer A-3
Polymer A-3
—
—
—
PGMEA
1.74
0.17



(100)



(2400)


Polymer A-4
Polymer A-4
—
—
—
PGMEA
1.67
0.24



(100)



(2400)


Polymer A-5
Polymer A-5
—
—
—
PGMEA
1.65
0.18



(100)



(2400)


Polymer A-6
Polymer A-6
—
—
—
PGMEA
1.63
0.29



(100)



(2400)


Comparative
Comparative
—
—
—
PGMEA
1.70
0.13


Polymer 1
Polymer 1



(2400)



(100)


Comparative
Comparative
—
—
—
PGMEA
1.72
0.05


Polymer 2
Polymer 2



(2400)



(100)


Comparative
Comparative
—
—
—
PGMEA
1.66
0.22


Polymer 3
Polymer 3



(2400)



(100)


Polymer B-1
Polymer B-1
—
—
—
PGMEA
1.62
0.59



(100)



(2400)


Polymer B-2
Polymer B-2
—
—
—
PGMEA
1.45
0.40



(100)



(2400)


Polymer B-3
Polymer B-3
—
—
—
PGMEA
1.48
0.53



(100)



(2400)


Polymer B-4
Polymer B-4
—
—
—
PGMEA
1.48
0.54



(100)



(2400)


Polymer B-5
Polymer B-5
—
—
—
PGMEA
1.49
0.52



(100)



(2400)


Polymer B-6
Polymer B-6
—
—
—
PGMEA
1.48
0.52



(100)



(2400)


Polymer B-7
Polymer B-7
—
—
—
PGMEA
1.53
0.32



(100)



(2400)


Polymer B-8
Polymer B-8
—
—
—
PGMEA
1.39
0.35



(100)



(2400)


Polymer B-9
Polymer B-9
—
—
—
PGMEA
1.45
0.52



(100)



(2400)


Polymer B-10
Polymer B-10
—
—
—
PGMEA
1.45
0.32



(100)



(2400)


Polymer B-11
Polymer B-11
—
—
—
PGMEA
1.41
0.54



(100)



(2400)


Polymer B-12
Polymer B-12
—
—
—
PGMEA
1.53
0.39



(100)



(2400)


Polymer B-13
Polymer B-13
—
—
—
PGMEA
1.45
0.54



(100)



(2400)


Polymer B-14
Polymer B-14
—
—
—
PGMEA
1.54
0.58



(100)



(2400)


Polymer B-15
Polymer B-15
—
—
—
PGMEA
1.52
0.59



(100)



(2400)


Polymer B-16
Polymer B-16
—
—
—
PGMEA
1.34
0.64



(100)



(2400)


Polymer B-17
Polymer B-17
—
—
—
PGMEA
1.42
0.58



(100)



(2400)


Polymer B-18
Polymer B-18
—
—
—
PGMEA
1.49
0.60



(100)



(2400)


Polymer B-19
Polymer B-19
—
—
—
PGMEA
1.45
0.71



(100)



(2400)


Polymer B-20
Polymer B-20
—
—
—
PGMEA
1.36
0.53



(100)



(2400)


Polymer B-21
Polymer B-21
—
—
—
PGMEA
1.36
0.50



(100)



(2400)


Comparative
Comparative
—
—
—
PGMEA
1.71
0.22


Polymer 4
Polymer 4



(2400)



(100)
























TABLE 2








Acid


Organic
Refractive
Extinction



Polymer
generator
Crosslinker
Surfactant
solvent
index
coefficient



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)
(n)
(k)























Example 1
Polymer A-1
AG1
—
—
PGMEA
1.66
0.22



(100)
(5)


(2400)


Example 2
Polymer A-2
AG3
—
—
PGMEA
1.66
0.22



(100)
(7)


(2400)


Example 3
Polymer A-3
AG1
—
—
PGMEA
1.73
0.17



(100)
(5)


(2400)


Example 4
Polymer A-4
AG1
—
—
PGMEA
1.67
0.24



(100)
(5)


(2400)


Example 5
Polymer A-5
AG3
—
—
PGMEA
1.65
0.19



(100)
(7)


(2400)


Example 6
Polymer A-6
AG3
—
—
PGMEA
1.63
0.30



(100)
(3)


(2400)


Comparative
Comparative
AG1
—
—
PGMEA
1.70
0.15


Example 1
Polymer 1
(5)


(2400)



(100)


Comparative
Comparative
AG1
CR1
—
PGMEA
1.72
0.06


Example 2
Polymer 2
(5)
(10)

(2400)



(100)


Comparative
Comparative
AG1
—
—
PGMEA
1.67
0.24


Example 3
Polymer 3
(5)


(2400)



(100)


Example 7
Polymer B-1
AG2
CR1
FC-430
PGMEA
1.62
0.58



(28)
(1)
(10)
(0.1)
(100)


Example 8
Polymer B-2
AG1
CR1
FC-430
PGMEA
1.45
0.40



(28)
(1)
(4)
(0.1)
(100)


Example 9
Polymer B-3
AG1
CR1
FC-430
PGMEA
1.49
0.53



(20)
(0.1)
(2)
(0.1)
(100)


Example 10
Polymer B-4
AG1
CR1
FC-430
PGMEA
1.48
0.55



(20)
(0.1)
(2)
(0.1)
(100)


Example 11
Polymer B-5
AG1
CR1
FC-430
PGMEA
1.50
0.51



(20)
(0.1)
(2)
(0.1)
(100)


Example 12
Polymer B-6
AG1
CR1
FC-430
PGMEA
1.48
0.52



(20)
(0.1)
(2)
(0.1)
(100)


Example 13
Polymer B-7
—
—
FC-430
PGMEA
1.53
0.32



(20)


(0.1)
(100)


Example 14
Polymer B-8
AG1
CR1
FC-430
PGMEA
1.38
0.35



(28)
(1)
(2)
(0.1)
(100)


Example 15
Polymer B-9
—
—
FC-430
PGMEA
1.44
0.52



(20)


(0.1)
(100)


Example 16
Polymer B-10
AG3
CR1
FC-430
PGMEA
1.46
0.31



(26)
(2)
(5)
(0.1)
(100)


Example 17
Polymer B-11
AG1
—
FC-430
PGMEA
1.40
0.55



(28)
(1)

(0.1)
(100)


Example 18
Polymer B-12
AG1
CR1
FC-430
PGMEA
1.52
0.38



(28)
(1)
(5)
(0.1)
(100)


Example 19
Polymer B-13
AG1
CR1
FC-430
PGMEA
1.46
0.53



(28)
(1)
(10)
(0.1)
(100)


Example 20
Polymer B-14
AG1
CR1
FC-430
PGMEA
1.53
0.58



(28)
(1)
(10)
(0.1)
(100)


Example 21
Polymer B-15
AG1
CR1
FC-430
PGMEA
1.52
0.60



(28)
(5)
(10)
(0.1)
(100)


Example 22
Polymer B-16
AG2
CR1
FC-430
PGMEA
1.35
0.64



(28)
(1)
(10)
(0.1)
(100)


Example 23
Polymer B-17
AG1
—
—
PGMEA
1.42
0.60



(100)
(5)


(2400)


Example 24
Polymer B-18
AG1
CR1
—
PGMEA
1.48
0.57



(100)
(5)
(10)

(2400)


Example 25
Polymer B-19
AG1
CR2
—
PGMEA
1.44
0.69



(100)
(5)
(10)

(2400)


Example 26
Polymer B-20
AG3
CR1
—
PGMEA
1.39
0.49



(100)
(3)
(10)

(2400)


Example 27
Polymer B-21
AG3
CR1
—
PGMEA
1.40
0.47



(100)
(3)
(10)

(2400)


Comparative
Comparative
AG1
CR1
FC-430
PGMEA
1.70
0.22


Example 4
Polymer 4
(1)
(4)
(0.1)
(100)



(22)









The components in Tables 1 and 2 are identified below. Acid generators AG1, AG2, and AG3 have the following structural formulae.




Crosslinkers CR1 and CR2 have the following structural formulae.





Organic Solvent:

PGMEA: propylene glycol monomethyl ether acetate
As seen from Tables 1 and 2, polymers (A) in Examples 1 to 6 and polymers (B) in Examples 7 to 27 have appropriate extinction coefficients (k values) at wavelength 193 nm, suggesting that a satisfactory antireflection effect can be attained by properly combining polymers (A) and (B) and controlling the thickness of upper, lower and mixed layers.
Dry Etching Resistance
Solutions for evaluating dry etching resistance were prepared by mixing selected components in accordance with the formulation shown in Table 3. The components used included polymers (A) designated Polymers A-1 to A-5, polymer (B) designated Polymer B-18, acid generators AG1 and AG3, crosslinker CR1, a surfactant FC-4430 (3M-Sumitomo Co., Ltd.), and an organic solvent. Filtration through a Teflon® filter having a pore size of 0.2 μm gave coating solutions.
The coating solutions thus prepared were coated on Si substrates and baked at 220° C. for 60 seconds to form coating films.
Similarly, an ArF single-layer resist material to be described later was coated on a Si substrate and baked at 110° C. for 60 seconds to form a coating film.
These films were examined by a test of etching with CHF3/CF4 gas using a dry etching instrument TE-8500P by Tokyo Electron, Ltd. A difference in thickness of the film before and after the etching test was determined. The results are shown in Table 3.










CHF3/CF4 gas etching test



















Chamber pressure
300
mTorr



RF power
1000
W



Gap
9
mm



CHF3 gas flow rate
50
sccm



CF4 gas flow rate
50
sccm



He gas flow rate
200
sccm



O2 gas flow rate
7
sccm



Time
60
sec

























TABLE 3













Thickness









difference




Acid


Organic
Coating
before and



Polymer
generator
Crosslinker
Surfactant
solvent
thickness
after etching



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)
(nm)
(nm)























Example 28
Polymer A-1
AG1
—
FC-4430
PGMEA
500
159



(100)
(5)

(0.1)
(500)


Example 29
Polymer A-2
AG3
—
FC-4430
PGMEA
500
152



(100)
(5)

(0.1)
(500)


Example 30
Polymer A-3
AG1
—
FC-4430
PGMEA
500
171



(100)
(5)

(0.1)
(500)


Example 31
Polymer A-4
AG1
—
FC-4430
PGMEA
500
155



(100)
(5)

(0.1)
(500)


Example 32
Polymer A-5
AG3
—
FC-4430
PGMEA
500
151



(100)
(5)

(0.1)
(500)


Example 33
Polymer B-18
AG1
CR1
FC-4430
PGMEA
500
120



(100)
(5)
(10)
(0.1)
(500)


Example 34
Polymer A-3
AG1
CR1
FC-4430
PGMEA
140
No film left



(67)
(5)
(10)
(0.1)
(500)

after etching



Polymer B-18





(>140)



(33)


ArF single-
(described later)




140
122


layer resist









As seen from Table 3, the polymer (A) used in the ARC-forming composition of the invention is characterized by a high etching rate as compared with the ArF single-layer resist material. ARC-forming compositions comprising both polymers (A) and (B) have a higher etching rate than the ArF single-layer resist material.
Measurement of Thickness of ARC
Solutions for film thickness measurement were prepared by mixing selected components in accordance with the formulation shown in Tables 4 and 5. The components used included polymers (A) designated Polymers A-1 to A-5, Comparative Polymers 1 to 4, aromatic ring-bearing polymers (B) designated Polymers B-1 to B-21, acid generators AG1, AG2, and AG3, crosslinkers CR1 and CR2, and a solvent. Filtration through a Teflon® filter having a pore size of 0.2 μm gave coating solutions.
The coating solutions thus prepared were spin coated on Si substrates and baked at 220° C. for 60 seconds to form test films. Using a variable angle spectroscopic ellipsometer (VASE®) of J. A. Woollam Co., the thickness of the films was determined. The results are shown in Tables 4 and 5.
















TABLE 4













Intermixing






Acid

Organic
Upper layer
layer
Lower layer



Polymer A
Polymer B
generator
Crosslinker
solvent
thickness
thickness
thickness



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)
(nm)
(nm)
(nm)

























Example
35
Polymer A-1
Polymer B-1
AG1
CR1
PGMEA
46.7
11.3
38.5




(67)
(33)
(5)
(10)
(2400)



36
Polymer A-1
Polymer B-1
AG1
CR1
PGMEA
18.8
22.2
20.2




(50)
(50)
(5)
(10)
(3520)



37
Polymer A-1
Polymer B-2
AG1
CR1
PGMEA
45.3
13.0
36.0




(67)
(33)
(5)
(10)
(2400)



38
Polymer A-1
Polymer B-3
AG1
CR1
PGMEA
47.2
11.9
38.4




(67)
(33)
(5)
(10)
(2400)



39
Polymer A-1
Polymer B-4
AG1
CR1
PGMEA
48.0
11.1
37.7




(67)
(33)
(5)
(10)
(2400)



40
Polymer A-1
Polymer B-5
AG1
CR1
PGMEA
45.8
12.0
35.9




(67)
(33)
(5)
(10)
(2400)



41
Polymer A-1
Polymer B-6
AG1
CR1
PGMEA
44.5
12.4
37.2




(67)
(33)
(5)
(10)
(2400)



42
Polymer A-1
Polymer B-7
AG1
CR1
PGMEA
35.9
31.6
24.1




(67)
(33)
(5)
(10)
(2400)



43
Polymer A-1
Polymer B-8
AG1
CR1
PGMEA
48.9
21.6
27.8




(67)
(33)
(5)
(10)
(2400)



44
Polymer A-1
Polymer B-9
AG1
CR1
PGMEA
47.4
14.7
35.1




(67)
(33)
(5)
(10)
(2400)



45
Polymer A-1
Polymer B-10
AG3
CR1
PGMEA
46.4
14.1
34.3




(67)
(33)
(5)
(15)
(2400)



46
Polymer A-1
Polymer B-11
AG1
—
PGMEA
48.1
13.0
32.4




(67)
(33)
(5)

(2400)



47
Polymer A-1
Polymer B-12
AG1
CR1
PGMEA
36.5
30.2
25.8




(67)
(33)
(5)
(10)
(2400)



48
Polymer A-1
Polymer B-13
AG1
CR1
PGMEA
38.1
22.6
31.1




(67)
(33)
(5)
(10)
(2400)



49
Polymer A-1
Polymer B-14
AG1
CR1
PGMEA
39.3
25.3
29.9




(67)
(33)
(5)
(10)
(2400)



50
Polymer A-1
Polymer B-15
AG1
CR1
PGMEA
40.4
24.2
30.6




(67)
(33)
(5)
(10)
(2400)



51
Polymer A-1
Polymer B-16
AG1
CR1
PGMEA
44.2
18.0
33.5




(67)
(33)
(5)
(10)
(2400)



52
Polymer A-1
Polymer B-17
AG1
—
PGMEA
27.2
32.1
29.3




(50)
(50)
(5)

(2400)



53
Polymer A-1
Polymer B-18
AG1
CR1
PGMEA
24.3
40.4
26.5




(50)
(50)
(5)
(10)
(2340)



54
Polymer A-2
Polymer B-1
AG3
CR1
PGMEA
31.2
0.0
45.5




(50)
(50)
(5)
(10)
(3520)



55
Polymer A-2
Polymer B-17
AG3
—
PGMEA
21.1
18.8
22.1




(50)
(50)
(5)

(3520)



56
Polymer A-2
Polymer B-18
AG3
CR1
PGMEA
40.3
23.1
31.1




(67)
(33)
(5)
(10)
(3440)



57
Polymer A-2
Polymer B-19
AG3
CR2
PGMEA
31.5
43.0
22.0




(67)
(33)
(5)
(10)
(3440)



58
Polymer A-3
Polymer B-1
AG1
CR1
PGMEA
20.4
10.0
33.1




(50)
(50)
(5)
(10)
(3520)



59
Polymer A-3
Polymer B-18
AG1
CR1
PGMEA
18.3
27.5
14.4




(67)
(33)
(5)
(10)
(3440)



60
Polymer A-4
Polymer B-1
AG1
CR1
PGMEA
19.6
8.2
30.5




(50)
(50)
(5)
(10)
(3520)



61
Polymer A-4
Polymer B-18
AG1
CR1
PGMEA
18.9
24.2
14.1




(67)
(33)
(5)
(10)
(3440)



62
Polymer A-5
Polymer B-11
AG3
—
PGMEA
30.2
6.5
26.8




(50)
(50)
(5)

(3520)



63
Polymer A-5
Polymer B-17
AG3
—
PGMEA
21.1
20.2
22.3




(50)
(50)
(5)

(3520)



64
Polymer A-5
Polymer B-18
AG3
CR1
PGMEA
25.3
15.2
18.6




(67)
(33)
(5)
(10)
(3440)



65
Polymer A-1
Polymer B-20
AG1
CR1
PGMEA
28.4
41.2
26.2




(50)
(50)
(3)
(10)
(2400)



66
Polymer A-1
Polymer B-21
AG1
CR1
PGMEA
28.9
41.0
27.3




(50)
(50)
(3)
(10)
(2400)



67
Polymer A-3
Polymer B-21
AG1
CR1
PGMEA
17.6
30.3
17.3




(50)
(50)
(3)
(10)
(3440)



68
Polymer A-4
Polymer B-21
AG1
CR1
PGMEA
27.7
40.4
26.2




(50)
(50)
(3)
(10)
(2400)

























TABLE 5













Intermixing






Acid

Organic
Upper layer
layer
Lower layer



Polymer A
Polymer B
generator
Crosslinker
solvent
thickness
thickness
thickness



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)
(nm)
(nm)
(nm)

























Comparative Example
5
Comparative
Polymer B-1
AG1
CR1
PGMEA
0.0
74.0
4.8




Polymer 1
(50)
(5)
(10)
(3520)




(50)



6
Comparative
Polymer B-1
AG1
CR1
PGMEA
0.5
57.2
10.1




Polymer 2
(50)
(5)
(10)
(3520)




(50)



7
Comparative
Polymer B-1
AG1
CR1
PGMEA
island-in-sea




Polymer 3
(50)
(5)
(10)
(3520)
structure




(50)



8
Polymer A-1
Comparative
AG1
CR1
PGMEA
16.0 
16.8
17.4




(50)
Polymer 4
(5)
(10)
(3820)





(50)









As seen from Tables 4 and 5, when the ARC-forming composition of the invention is spin coated onto a substrate and baked to form an ARC, polymers (A) and (B) localize in the ARC so as to form an upper layer having a low extinction coefficient (k) and a lower layer having a high extinction coefficient (k). Depending on particular polymers used, a intermixing layer of polymers (A) and (B) forms as an intermediate layer. By selecting the combination and blend ratio of polymers (A) and (B) so as to control the thickness of the upper, intermixing and lower layers, an ARC that is effective in preventing reflection of exposure light by the substrate can be formed.
Resist Patterning Test
An ArF single-layer resist composition solution was prepared by dissolving a polymer (ArF single-layer resist polymer 1), an acid generator and a basic compound in an organic solvent containing 0.1 wt % of FC-4430 (3M-Sumitomo Co., Ltd.) according to the formulation shown in Table 6, and passing through a Teflon® filter having a pore size of 0.2 μm.












TABLE 6








Acid
Basic
Organic



Polymer
generator
compound
solvent



(pbw)
(pbw)
(pbw)
(pbw)




















ArF single-layer
ArF single-layer
PAG1
Quencher
PGMEA


resist composition
resist polymer 1
(10.0)
1 (1.2)
(1350)



(100)









The components in Table 6 are identified below.
Polymer, ArF single-layer resist polymer 1 has the following structural formula.




Acid generator, PAG1 has the following structural formula.





Basic compound, Quencher 1 has the following structural formula.





Each of the ARC-forming solutions prepared above (Examples 36, 52; 60, 62, Comparative Examples 1, 4) was coated onto a Si substrate and baked at 220° C. for 60 seconds to form an ARC of 60 nm thick. Onto the ARC, the ArF single-layer resist composition solution prepared above was coated and pre-baked at 110° C. for 60 seconds to form a photoresist film of 160 nm thick. Thereafter, the resist film was exposed using an ArF exposure tool S307E (Nikon Corporation, NA 0.85, σ 0.93, 2⁄3 annular illumination, 6% half-tone phase shift mask), then baked (PEB) at 110° C. for 60 seconds, and developed for 60 seconds with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH), thereby giving a positive 80 nm line-and-space pattern. The cross-sectional shape of the resist pattern was observed. The results are shown in Table 7.










TABLE 7







ARC
Cross-sectional shape of resist pattern









Example 36
Rectangular, no footing



Example 52
Rectangular, no footing



Example 60
Rectangular, no footing



Example 62
Rectangular, no footing



Comparative Example 1
Reversely tapered



Comparative Example 4
Standing waves, footing










As seen from Table 7, the ARCs formed from the ARC-forming compositions of the invention ensure that the photoresist films on the ARCs are processed into resist patterns of rectangular shape without footing.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Japanese Patent Application No. 2007-254939 is incorporated herein by reference.
Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

## Claims

1. An antireflective coating composition comprising
(A) at least one polymer comprising recurring units of at least one type represented by the general formula (1) and/or (2) and having an extinction coefficient at a preselected imaging radiation wavelength in the range of 0.01 to 0.4, and
(B) at least one polymer containing an aromatic ring and having an extinction coefficient at a preselected imaging radiation wavelength in the range of 0.3 to 1.2,





wherein R1 is hydrogen, fluorine, methyl, or trifluoromethyl, R2 and R3 are each independently hydrogen or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 8 carbon atoms, or R2 and R3 may bond together to form a ring with the carbon atom to which they are attached, R4 is hydrogen or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 30 carbon atoms, in which a constituent unit —CH2— may be replaced by —O— or —C(═O)—, R5 to R7 are each independently hydrogen, halogen, hydroxyl or a straight, branched or cyclic, monovalent organic group of 1 to 15 carbon atoms, or any two of R5 to R7 may bond together to form a ring with the carbon atom(s) to which they are attached.

2. The composition of claim 1 wherein the polymer (A) further comprises 3 to 50 mol % of aromatic ring-containing recurring units.

3. The composition of claim 1 wherein the polymer (B) comprises 40 to 100 mol % of aromatic ring-containing recurring units.

4. The composition of claim 1, further comprising at least one member selected from the group consisting of an organic solvent, an acid generator, and a crosslinker.

5. A lithographic pattern forming process comprising the steps of:
applying the composition of claim 1 onto a substrate to form an antireflective coating,
forming a photoresist layer on the antireflective coating,
exposing a pattern circuitry region of the photoresist layer to an imaging radiation,
developing the photoresist layer with a developer to form a patterned resist layer, and
etching the antireflective coating and the substrate while using the resist pattern as a mask, thereby forming a pattern in the substrate.

6. An antireflective coating which is prepared by applying the composition of claim 1 onto a substrate by spin coating and baking to form an antireflective coating having an inner surface contiguous to the substrate and an outer surface remote from the substrate, such that polymer (A) and polymer (B) may segregate vertically toward the outer surface and inner surface, respectively.