Underlayer composition for use in the manufacture of electronic devices

Abstract

The present invention provides a base layer composition for use in the manufacture of electronic devices. [Solution] A coating composition for use with an overcoated photoresist composition, comprising: a thermocrosslinkable resin; a compound of the following general formula (1); and a solvent. TIFF2026089677000011.tif39170

Description

[Technical Field]

[0001] This invention relates to the manufacture of electronic devices, and more specifically, to materials for use in semiconductor manufacturing. [Background technology]

[0002] The underlayer composition (or resist underlayer composition) can be used in the semiconductor industry as an etching mask for lithography of advanced technology nodes for integrated circuit manufacturing. In photolithography in the manufacture of electronic devices, an image is formed and developed on a resist layer, and then the image is transferred to a substrate. Multiple layers can be involved in this process. For example, an underlayer composition (e.g., a bottom anti-reflective coating or BARC) may be applied between the substrate and the photoresist layer.

[0003] As electronic device structures become more intricate and complex, and feature density increases, feature size decreases. These changes make the underlying layers (or resist layers) more important than ever in a variety of applications. Among the various roles of the underlying layers, one key challenge is to fill very narrow trenches, holes, spaces, and other topographic features within the substrate, planarize the surface beneath the resist, and protect intentionally formed trenches from subsequent processes that could damage the structure on the substrate.

[0004] For example, if the underlayer is insufficiently gap-filling and planarized, void formation within the gaps can lead to patterning defects during imaging of the overcoated photoresist layer, even when the resist underlayer serves as a conventional bottom anti-reflective coating (BARC) to minimize substrate reflection. In addition to reduced device yield due to lithography failures, void formation can further increase defects by causing current leakage between adjacent devices, as well as damage to the device and substrate in subsequent processes such as dry etching and wet etching. Conventional resist underlayer formulations cannot fill such gaps with high aspect ratios (depth:width) and narrow widths.

[0005] Formulations having a specific resin structure aimed at achieving such properties have been developed previously, but there remains a need for formulations that can be applied to various resins that need to retain other properties such as optical properties, dry etching rate, heat resistance, etc.

Brief Description of the Drawings

[0006] [Figure 1] Presents photographs of scanning electron microscope scans discussed in the examples.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0008]

Non-Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0009] This specification includes a thermally crosslinkable resin and; the following general formula (1):

Chemical Formula

[0010] Also disclosed is a patterning method comprising: (a) forming a lower layer on a substrate from the lower layer composition described herein; (b) applying a photoresist layer over the lower layer; (c) exposing the photoresist layer to actinic radiation; and (d) developing the exposed photoresist layer to obtain a resist relief image.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] Here, exemplary embodiments are specifically referred to, and examples thereof are illustrated in this description. In this regard, the exemplary embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Therefore, the exemplary embodiments are only described below to explain aspects of this description.

[0012] The underlayer compositions disclosed herein can form a film that can protect the underlying substrate during various pattern transfer and etching processes, and / or provide a film having sufficient planarization properties to provide a relatively flat top surface when the underlayer or substrate includes various pitches, various line / space patterns, and / or various trench depths.

[0013] The lower layer composition comprises a thermocrosslinkable resin, a compound of formula (I), and a solvent.

[0014] A thermally crosslinkable resin may be used in a resist coating composition. The polymeric main chain of the resin is selected from the group consisting of polyester, acrylic polymer, vinyl polymer (such as styrene polymer or vinyl ether polymer), novolac resin, polynorbornene, polyacetal, polyethylene glycol, polyamide, polyacrylamide, polyphenol, polyvinyl alcohol, copolymers thereof, or mixtures thereof. The thermally crosslinkable polymer contains one or more crosslinkable groups, such as hydroxyl, carboxyl, thiol, amine, epoxy, alkoxy, amide, or ethylenically unsaturated groups. The resin may be included in the formulation as a mixture of one or more resins as described above. The thermally crosslinkable resin may have a weight-average molecular weight (Mw) in the range of 500 to 10,000 grams / mol. The molecular weight can be determined by gel permeation chromatography using a polystyrene standard.

[0015] The total amount of such resin can be present in the composition in amounts ranging from, for example, 0.1 to 0.5 to 1 to a maximum of 20, a maximum of 15, and a maximum of 10 weight percent (wt%) based on the total weight of the composition.

[0016] The composition is further, formula (I): [ka] (In the formula, W1, W2, W3, and W4 are independently single bonds or substituted or unsubstituted C) 1~5is an alkylene; L1 and L2 are each an ester group; L3 and L4 are independently a group selected from a single bond, or a carbonyl or ester group; R1 and R2 are independently hydrogen, halogen, substituted or unsubstituted C 1~10 alkyl, or substituted or unsubstituted C 3~10 cycloalkyl; R3 and R4 are independently hydrogen, halogen, hydroxyl, substituted or unsubstituted C 1~10 alkyl, or substituted or unsubstituted C3~10 cycloalkyl). The additional compound contains groups. When the group is substituted, specific examples of the substituent include nitro, cyano, amino, thio, C1-6 alkylthio or C1-6 haloalkyl group. R3 is preferably hydroxyl. In a specific embodiment, W3 and L3 are preferably each a single bond. In another preferred embodiment, L3 is an ester group. The compound of general formula (1) can be present in the composition in an amount from 0.1 to, from 0.5 to, from 1 to a maximum of 20, a maximum of 15, a maximum of 12, or a maximum of 10 wt% based on the total weight of the coating composition.

[0017] Specific examples of the compound of formula (1) include formulas (2)-(60):

Chemical formula

[0018] The lower layer composition contains a solvent. The solvent component may be a single solvent or a mixture of two or more distinct solvents. Preferably, each of the solvents may be miscible with the others. Suitable solvents include, for example, one or more oxyisobutyrate esters, particularly methyl-2-hydroxyisobutyrate, 2-hydroxyisobutyrate, and ethyl lactate; one or more glycol ethers, particularly 2-methoxyethyl ether (diglym), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; one or more solvents having both an ether moiety and a hydroxyl moiety, particularly methoxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; one or more alkyl esters, particularly methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate, as well as other solvents such as one or more dibasic esters; and / or other solvents such as one or more propylene carbonate, cyclohexanone, and gamma butyrolactone.

[0019] The amount of solvent in the composition can range from, for example, 60, 65, 70 to a maximum of 99.9, or up to 99% by weight, based on the total weight of the composition.

[0020] In some embodiments, the underlying composition may further include one or more curing agents to help cure the underlying composition, for example, after the underlying composition has been applied to a surface. The curing agents are any components that cause the underlying composition to cure on the surface of the substrate.

[0021] It may be beneficial to include acid-generating compounds, such as photoacid-generating (PAG) compounds and / or thermoacid-generating (TAG) compounds, in the underlying composition. A preferred curing agent is a thermoacid-generating (TAG).

[0022] Suitable PAGs are known in the field of chemically amplified photoresists and include, for example: onium salts, e.g., triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2 3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, e.g., bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, e.g., N-hydroxysuccinimodomethanesulfonic acid, N-hydroxysuccinimodotrifluoromethanesulfonic acid; and halogen-containing triazine compounds, e.g., 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. One or more such PAGs can be used.

[0023] A TAG compound is any compound that releases acid when exposed to heat. Exemplary thermal acid generators include, but are not limited to, amine-blocked strong acids, such as amine-blocked dodecylbenzenesulfonic acid and other amine-blocked sulfonic acids. It will also be well understood by those skilled in the art that certain photoacid generators can release acid upon heating and thus function as thermal acid generators.

[0024] Suitable TAG compounds may include, for example, nitrobenzyl tosylates such as 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, and 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl-4-chlorobenzenesulfonate and 2-trifluoromethyl-6-nitrobenzyl-4-nitrobenzenesulfonate; phenolic sulfonate esters such as phenyl-4-methoxybenzenesulfonate; alkylammonium salts of organic acids such as triethylammonium salts of 10-camphorsulfonic acid, trifluoromethylbenzenesulfonic acid, and perfluorobutanesulfonic acid; certain onium salts, and p-toluenesulfonic acid-trimethylpyridinium salt (disclosed in Patent Document 1). Various aromatic (anthracene, naphthalene, or benzene derivative) sulfonic acid amine salts, such as those disclosed in Patent Documents 2, 3, 4, and 5, can be used as TAGs. Examples of tags include those sold by King Industries, Norwalk, Conn., USA, under the names NACURE, CDX, and K-PURE, such as NACURE 5225, CDX-2168E, K-PURE2678, and KPURE2700. One or more of these tags may be used.

[0025] The amount of such curing agent in this composition (if used) may be, for example, greater than 0, 0.01, 0.02, 0.03 to a maximum of 5, a maximum of 3, or a maximum of 1 percent by weight, based on the total weight of the underlying composition.

[0026] In some embodiments, the lower layer composition does not contain a photoacid generator. Therefore, in these embodiments, the lower layer composition may not substantially contain PAG compounds and / or polymeric PAG, for example, it may not contain PAG compounds or polymeric PAG.

[0027] The lower layer composition may further contain one or more additives. Any suitable crosslinking agent can be further used in the coating composition, provided that such crosslinking agent has at least two, preferably at least three, sites that can react with functional groups in the lower layer composition. Exemplary crosslinking agents include novolac resins, acrylate resins, vinyl resins, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, etc., typically methylol, C1~ 10 Alkoxymethyl, and C2~ 10 Examples of suitable crosslinking agents include those described above having two or more substituents, more typically three or more, selected from acyloxymethyl. Suitable crosslinking agents include tetramethoxyglycoluryl (TMGU) and those listed below: [ka]

[0028] Additional crosslinking agents are well known in the art and are commercially available from various suppliers. The amount of such additional crosslinking agent in the coating composition (if present) may range, for example, from more than 0 to 0.1, 0.2, or 0.3 to a maximum of 5, 4, or 3 percent by weight of the total weight of the coating composition.

[0029] The lower composition may contain one or more optional additives, such as surfactants. If present, each optional additive may be used in the lower composition in small amounts, such as 0.01, 0.05, 0.1 to a maximum of 5, a maximum of 4, a maximum of 3, a maximum of 2, or a maximum of 1 percent by weight, based on the total weight of the lower composition.

[0030] Typical surfactants exhibit amphiphilic properties. This means they can be both hydrophilic and hydrophobic at the same time. Amphiphilic surfactants have a hydrophilic head group with a strong affinity for water and a long, hydrophobic tail that is organically hydrophilic and repels water. Preferred surfactants may be ionic (i.e., anionic, cationic) or nonionic. Further examples of surfactants include silicone surfactants, poly(alkylene oxide) surfactants, and fluorochemical surfactants. Preferred nonionic surfactants include, but are not limited to, octyl and nonylphenol ethoxylates such as TRITON® X-114, X-100, X-45, and X-15, and branched secondary alcohol ethoxylates such as TERGITOL TMN-6 (The Dow Chemical Company, Midland, Mich, USA). Further exemplary surfactants include alcohol (primary and secondary) ethoxylates, amine ethoxylates, glucosides, glucamine, polyethylene glycol, poly(ethylene glycol-co-propylene glycol), or other surfactants disclosed in Non-Patent Literature 1, published by Manufacturers Confectioners Publishing Co. of Glen Rock, NJ. Nonionic surfactants that are acetylenediol derivatives may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc. of Allentown, Pa., and are sold under the trade names SURFYNOL and DYNOL. Additional suitable surfactants include other polymer compounds such as the triblock EO-PO-EO copolymers PLURONIC® 25R2, L121, L123, L31, L81, L101, and P123 (BASF, Inc.).

[0031] The desired total solids content of the underlayer composition will depend on factors such as the desired final layer thickness. Typically, the total solids content of the underlayer composition may be 0.1 to 20% by weight, e.g., 0.1 to 10% by weight, or more typically, 0.11 to 8% by weight, based on the total weight of the coating composition. The solids content in the composition refers to the components remaining in the film after the solvent has been removed (e.g., by evaporation) after the underlayer film or coating has been formed. The solids content may include resins, crosslinking agents, and optional components such as TAG, PAG, and surfactants.

[0032] The base layer composition can be prepared according to known procedures. For example, the base layer composition can be prepared by mixing a resin, a compound of formula (I), a solvent, and any optional components in any order. The base layer composition can be used as is, or it can be purified or diluted before being coated onto a substrate. Purification may include one or more methods such as centrifugation, filtration, distillation, decantation, evaporation, or treatment with ion exchange beads.

[0033] The pattern formation method of the present invention includes coating a layer of a base layer composition onto a substrate, curing the coated base layer composition to form a coated base layer, and forming a photoresist layer on the coated base layer. The method may further include the steps of exposing the photoresist layer to activation radiation in a patterned manner and developing the exposed photoresist layer to obtain a resist relief image. In some embodiments, the method may further include forming a silicon-containing layer, an organic anti-reflective coating layer, or a combination thereof on the coated base layer before forming the photoresist layer. In some embodiments, the method may further include transferring a pattern to the silicon-containing layer, an organic anti-reflective coating layer, or a combination thereof after developing the exposed photoresist layer and before transferring the pattern to the coated base layer.

[0034] A wide variety of substrates can be used in pattern formation methods, with electronic device substrates being typical. Suitable substrates include, for example, packaging substrates such as multi-chip modules; flat panel display substrates; integrated circuit substrates; substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs); semiconductor wafers; and polycrystalline silicon substrates. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. As used herein, the term “semiconductor wafer” is intended to encompass “electronic device substrates,” “semiconductor substrates,” “semiconductor devices,” and various packages for various levels of interconnection, such as single-chip wafers, multiple-chip wafers, packages for various levels, or other assemblies requiring solder connections. Such substrates may be of any suitable size. Typical wafer substrate diameters are 200 mm to 300 mm, but wafers with smaller and larger diameters can be suitably used according to the present invention. As used herein, the term “semiconductor substrate” includes any substrate having one or more semiconductor layers or structures that may optionally contain an effective or operational portion of a semiconductor device. A semiconductor device means a semiconductor substrate on which at least one microelectronic device is batch manufactured or in the process of being manufactured.

[0035] The substrate is typically composed of one or more of the following: silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. The substrate may include one or more layers and patterned features. The layers may include, for example, one or more conductive layers such as layers of aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys of such metals, nitrides or silicides, doped amorphous silicon or doped polysilicon; one or more dielectric layers such as layers of silicon oxide, silicon nitride, silicon oxynitride, or metal oxides or metal nitrides; semiconductor layers such as single-crystal silicon; and combinations thereof. In some embodiments, the substrate includes titanium nitride. The layers can be formed by various techniques, such as chemical vapor deposition (CVD) including plasma-enhanced CVD (PECVD), low-pressure CVD (LPCVD), or epitaxial growth; physical vapor deposition (PVD) including sputtering or evaporation; or electroplating.

[0036] In a particular pattern formation method of the present invention, it may be desirable to provide one or more lithography layers on the upper surface of the substrate before forming the underlying layer of the present invention, such as a hard mask layer, for example, a CVD layer such as a spin-on-carbon (SOC), amorphous carbon, or metal hard mask layer, a silicon nitride (SiN) layer, a silicon oxide (SiO) layer, or a silicon oxynitride (SiON) layer, an organic or inorganic BARC layer, or a combination thereof. Such layers, together with the layers of the underlying composition of the present invention and the photoresist layer, form a lithography material stack. Typical lithography stacks that can be used in the pattern formation method of the present invention include, for example, the following: bottom layer / photoresist; bottom layer / metal hard mask layer / photoresist; bottom layer / metal hard mask layer / bottom layer / photoresist; bottom layer / SOC layer / photoresist layer; SOC layer / bottom layer / photoresist layer; SOC layer / SiON layer / bottom layer / photoresist layer; SOC layer / SiARC layer / bottom layer / photoresist layer; SOC layer / metal hard mask layer / bottom layer / photoresist layer; amorphous carbon layer / bottom layer / photoresist layer; and amorphous carbon layer / SiON layer / bottom layer / photoresist layer.

[0037] As used herein, “underlying layer” should be understood to refer to one or more layers placed between the substrate and the photoresist layer (i.e., “on top of the substrate”). Accordingly, the coated underlying layer (i.e., layer of the underlying composition) of the present invention can be used alone as an underlying layer, or the coated underlying layer (i.e., layer of the underlying composition) of the present invention can be used in combination with other underlying layers.

[0038] The underlayer composition can be coated onto a substrate by any suitable means, such as spin coating, slot die coating, doctor braiding, curtain coating, roller coating, spray coating, immersion coating, etc. In the case of semiconductor wafers, spin coating is preferred. In a typical spin coating method, the composition is applied to a substrate that is rotating at a speed of 500 to 4000 revolutions per minute (rpm) for a period of 15 to 90 seconds to obtain the desired layer of condensation polymer on the substrate. It will be well understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and the solid content of the composition. The underlayer formed from the underlayer composition typically has a dry layer thickness of 1 to a maximum of 500, a maximum of 400, a maximum of 300, or a maximum of 200 nanometers (nm).

[0039] The coated underlayer composition is optionally soft-baked at a relatively low temperature to remove any solvents and other relatively volatile components. Typically, the substrate is baked at a temperature of 150°C or less, preferably 60–125°C, more preferably 90–115°C. The baking time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 60–90 seconds. If the substrate is a wafer, such a baking step may be performed by heating the wafer on a hot plate. Such a soft baking step may be performed as part of the curing of the coating layer or may be omitted entirely.

[0040] The underlayer composition is then cured to form a coated underlayer. The coating composition needs to be cured sufficiently so that the coated underlayer film does not mix with, or mixes minimally with, any other underlayer components or photoresist layers formed on the underlayer. The coating composition can be cured in an oxygen-containing atmosphere such as air, or in an inert atmosphere such as nitrogen, and under conditions such as heating sufficient to obtain a cured coating layer. This curing process is preferably carried out on a hot plate type apparatus, but oven curing may be used to obtain equivalent results. Typically, curing may be carried out at a temperature of 150°C or higher, preferably 150 to 450°C. The curing temperature is more preferably 180°C or higher, more preferably 200°C or higher, and even more preferably 200 to 400°C. The curing time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 45 seconds to 2 minutes, and even more preferably 45 to 90 seconds. Optionally, a gradient or multi-stage curing process may be used. Gradient baking typically begins at a relatively low (e.g., ambient) temperature, and the temperature is increased at a constant or variable gradient rate up to a higher target temperature. Multistage curing processes involve curing in two or more temperature planes, typically a first stage at a lower bake temperature and one or more additional stages at higher temperatures. Conditions for such gradient or multistage curing processes are known to those skilled in the art and may allow for the omission of a prior soft bake process.

[0041] After the coated underlayer composition has cured, a photoresist layer is formed on the coated underlayer. As described above, other intervening layers may be provided between the coated underlayer and the overcoated photoresist layer. In some embodiments, the method may further include forming a silicon-containing layer, an organic anti-reflective coating layer, or a combination thereof on the coated underlayer before forming the photoresist layer.

[0042] A wide variety of photoresists can be appropriately used in the method of the present invention, and these are typically positive-type materials. The specific photoresist used depends on the exposure wavelength used and usually comprises an acid-sensitive matrix polymer, a photoactive component such as a photoacid generator, a solvent, and optional additional components. Suitable photoresists are various photoresist materials known to those skilled in the art and commercially available, for example, the UV® and EPIC® product lines from DuPont Electronics & Industrial. The photoresist can be applied to the substrate by known coating techniques such as those described above in relation to the underlying composition, with spin coating being typical. A typical thickness for the photoresist layer is 10 to 300 nm. The photoresist layer is typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking can be done on a hot plate or in an oven, with a hot plate being typical. A typical soft bake is performed at a temperature of 70 to 150°C and for a time of 30 to 90 seconds.

[0043] The photoresist layer is then exposed to activating radiation through a photomask to create a difference in solubility between exposed and unexposed areas. The reference herein to exposing a photoresist composition to activating radiation for the composition indicates that the radiation can form a latent image in the photoresist composition. The photomask has optically transparent and optically impermeable areas corresponding to the areas of the resist layer that are exposed and unexposed by the activating radiation, respectively. The exposure wavelength is typically less than 400 nm, more commonly less than 300 nm, e.g., 248 nm (KrF), 193 nm (ArF), or EUV wavelength (e.g., 13.5 nm). In a preferred embodiment, the exposure wavelength is 193 nm or EUV wavelength. The exposure energy is typically 10 to 100 millijoules (mJ / cm²) per square centimeter, depending, for example, the exposure tool and the components of the photosensitive composition. 2 )

[0044] Following the exposure of the photoresist layer, a post-exposure bake (PEB) is typically performed. PEB can be performed, for example, on a hot plate or in an oven. PEB is typically performed at a temperature of 70–150°C and for 30–90 seconds. This forms a latent image defined by the boundary between polarity-switched and non-switched regions (corresponding to the exposed and unexposed regions, respectively). The photoresist layer is then developed to remove the exposed regions of the layer, leaving the unexposed regions to form a patterned photoresist layer. The developer is typically an aqueous alkaline developer, such as a tetramethylammonium hydroxide (TMAH) solution, typically a tetraalkylammonium hydroxide solution such as a 0.26 N (N) (2.38 wt%) TMAH solution. The developer can be applied by known techniques, such as spin coating or paddle coating.

[0045] The pattern of the photoresist layer can be transferred to one or more underlying layers, including coated underlayers, and to the substrate by appropriate etching techniques, such as plasma etching using the appropriate gas species for each layer being etched. Depending on the number of layers and the materials involved, pattern transfer may involve multiple etching steps using different etching gases. The patterned photoresist layer, coated underlayer, and other optional layers in the lithography stack can be removed after pattern transfer to the substrate using conventional techniques. Optionally, one or more layers in the stack can be removed after pattern transfer to the lower layers and before pattern transfer to the substrate, or consumed during and before pattern transfer to the substrate. For example, pattern transfer to one or more silicon-containing layers, organic anti-reflective coating layers, etc., can be performed after the exposed photoresist layer has been developed and before pattern transfer to the coated underlayer. The substrate is then further processed according to methods known in the art to form an electronic device.

[0046] A coated substrate is also provided, comprising a layer of the underlying composition of the present invention on a substrate and a photoresist layer disposed on the layer of the photoresist underlying composition. As used herein, the term “cured layer” refers to a layer derived from the underlying composition after the composition has been disposed on the substrate and subsequently cured to form a coating layer or film. In other words, curing of the underlying composition forms a cured layer derived from the underlying composition.

[0047] Another embodiment provides a layered article comprising a coated underlayer obtained from the underlayer composition of the present invention. In one embodiment, the layered article may include a substrate, a coated underlayer disposed on the substrate, and a photoresist layer disposed on the coated underlayer.

[0048] A base layer including a coated base layer made from the base layer composition of the present invention exhibits good gap filling and peel resistance. For example, the composition can provide good gap filling (complete or substantially complete filling, or only very small voids with a width of less than 50 nm and less than 10% voids) of an aspect ratio of at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, or at least 2 and a width of less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, or less than 100 nm. The aspect ratio may be less than 100, less than 90, or less than 80, and the width may be at least 0.1 nm, at least 0.5 nm, or at least 1 nm. The preferred base layer composition of the present invention may, as a result, be useful in a variety of semiconductor manufacturing processes.

[0049] The concept of the present invention is further illustrated by the following examples, which are intended to be non-limiting. The compounds and reagents used herein are commercially available unless the procedure is given below. [Examples]

[0050] Example 1 - Polymer Synthesis Polymer 1 A 250 mL three-necked round-bottom flask equipped with a mechanical stirrer, temperature control box and probe, heating mantle, condenser, Dean-Stark trap, and nitrogen purge inlet was charged with dimethyl terephthalate (22.3 g), dimethyl 5-hydroxyisophthalate (18 g), 1,3,5-tris(2-hydroxyethyl) isocyanurate (53 g), 2-hydroxyisobutyric acid (18 g), p-toluenesulfonic acid (2.1 g), and anisole (80 g). The reaction was heated to substantially reflux (120-150°C), and then gradually increased to a peak temperature of 150°C over 6 hours. The cooled solution was diluted with 355 g of tetrahydrofuran (THF) and then precipitated with isopropanol. The polymer was recovered by filtration through a Buchner funnel, air-dried, and then vacuum-dried at 40-70°C. The dried polymer had the following characteristics: weight-average molecular weight (Mw): 2620, polydispersity (PDI): 1.3.

[0051] Polymer 2 In a 500 mL round-bottom flask, tris(2-hydroxyethyl) isocyanurate (37.8 g), tris(2-carboxyethyl) isocyanurate (16.6 g), dibutylnaphthalenedicarboxylate (30.5 g), para-toluenesulfonic acid (1.1 g), anisole (80 g), and 1-butanol (100 g) were charged. The mixture was then heated to 140-160°C and the contents were vigorously stirred. Butanol and anisole were slowly distilled from the reaction flask. The polymer solution was then diluted by adding tetrahydrofuran (100 g), and isopropanol was added to precipitate the mixture. The precipitated polymer solid was collected and dried overnight under vacuum at 40-60°C. The dried polymer had the following characteristics: weight-average molecular weight (Mw): 6570, polydispersity (PDI): 1.6.

[0052] Example 2 - Preparation of the formulation Each composition was prepared by placing the components in a clean bottle, regardless of the order of addition. Tetramethoxyglycoluryl (TMGU) and p-toluenesulfonic acid-trimethylpyridinium salt ("pTSA-TMP"; disclosed in Patent Document 1) were used as crosslinking agents and thermoacid generators (TAGs) in amounts of 0.6 g TMGU and 0.05 g pTSA-TMP for all samples. The polymer was used in an amount of 3.35 g. Table 1 shows the polymer type used, the additive used, the amount of additive used, and the amount of solvent used. The samples were placed on a shaker for at least 4 hours until all materials were completely dissolved. Then, before coating, each sample was passed through a 0.45 μm PTFE membrane filter and placed in a clean bottle. The examples were formulated using methyl 2-hydroxyisobutyrate (HBM). The additives used were purchased through commercial sources such as Tokyo Chemical Industry Co., Ltd. Additives 12, 22, 34, 42, 51, and 55 have the structures shown herein. Comparative additives 61 and 62 are, [ka] It has the structure of [the object].

[0053] [Table 1]

[0054] [Table 2]

[0055] Example 3 - Evaluation of solvent peel resistance and gap filling performance The prepared composition was spin-coated onto an 8-inch silicon wafer using a spinner at 1500 rpm, and the wafer was heated on a hot plate at 205°C for 60 seconds to form a thin film with a thickness of 100 nm. The thin film was then exposed to a 30 mL mixture of 70 / 30 wt / wt% propylene glycol methyl ether (PGME) 1-methoxy-2-propanyl acetate (PGMEA) for 90 seconds, or to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, spin-dried at 4000 rpm for 60 seconds, and post-baked on a hot plate at 110°C for 60 seconds. Thickness measurements were performed using a Therma-wave Opti-probe 5250. The film thickness lost due to delamination from the organic solvent (delamination loss) was calculated as the difference in thickness between the initially coated film and the exposed and post-baked films. The results summarized in Table 2 demonstrate that the introduction of additives into the formulation does not cause significant loss of the crosslinked film due to the solvent.

[0056] A 12-inch wafer was provided having a silicon substrate with a trench pattern deposited with TiN (by LPCVD). The pattern contained trenches with a width of 40 nm and a height of 100 nm. The underlayer composition described above was spin-coated onto the pattern surface of the wafer at 1500 rpm and cured at 205°C for 1 minute to obtain a film thickness of 100 nm. The cured trench pattern was inspected using a vertical scanning electron microscope (V-SEM) to evaluate the void-filling performance of the formulations, and the results are shown in Figures 1(a) to (c) and Table 2. Figure 1(a) is Comparative Example 1, which shows a considerable number of voids in the trenches, and Figure 1(b) is an example showing improved filling with some small residual voids. Figure 1(c) is Example 3, which shows completely filled trenches. The comparative example without additives showed voids in the trenches, but the addition of ester-based additives improved the trench filling.

[0057] [Table 3]

[0058] [Table 4]

[0059] As used herein, the term "and / or" encompasses all combinations of one or more of the related enumerated items. Expressions such as "at least one" qualify the entire list of elements when preceding a list of elements, but not the individual elements of the list.

[0060] As used herein, the terms “a,” “an,” and “the” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically stated herein or clearly contradicted by the context. “Or” means “and / or” unless otherwise specified. All scopes disclosed herein include endpoints, which can be independently combined with one another. The suffix “(s)” is intended to include both singular and plural forms of the term it modifies, thereby including at least one of those terms. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both the cases in which the event occurs and the cases in which it does not occur. Terms such as “first,” “second,” etc., do not imply order, quantity, or importance herein, but rather are used to distinguish one element from another. When an element is said to be "on" another element, it may be in direct contact with the other element, or an intervening element may exist between them. In contrast, when an element is said to be "directly on" another element, no intervening element is present. It should be understood that the components, elements, limitations and / or features described in the embodiments may be combined in any preferred manner in various embodiments. The terms "about," "substantially," "approximately," and their variations are intended to include the degree of error associated with the measurement of a particular quantity based on equipment available at the time of filing. For example, "about" and / or "substantially" and / or "approximately" may include a range of ±8% of a given value.

[0061] All ranges disclosed herein include endpoints, and endpoints can be independently combined with each other (for example, the range “up to 25% by weight, more specifically 5% to 20% by weight” includes the endpoint and all intermediate values ​​of the range “5% to 25% by weight”). Furthermore, the upper and lower limits described can be combined to form ranges (for example, “at least 1% by weight or at least 2% by weight” and “up to 10% or 5% by weight” can be combined to form ranges of “1 to 10% by weight,” “1 to 5% by weight,” “2 to 10% by weight,” or “2 to 5% by weight”).

[0062] This disclosure may include, consist of, or be essentially composed of, any suitable components disclosed herein. This disclosure may be additionally, or instead, formulated to be substantially free of any components, materials, raw materials, auxiliaries, or species used in prior art compositions or not necessary for achieving the functions and / or purposes of this disclosure.

[0063] Unless otherwise specified herein, all test standards are the most current standards in effect as of the filing date of this application, or, if priority is claimed, the most current standards in effect as of the filing date of the earliest priority application in which the test standard appears.

[0064] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which the invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as those defined in the relevant art and in relation to this disclosure, and it will be further understood that unless explicitly defined herein, they should not be interpreted in an ideal or overly formal sense.

[0065] As used herein, the terms “hydrocarbon group” means an organic compound having at least one carbon atom and at least one hydrogen atom, optionally substituted with one or more substituents shown; “alkyl group” means a linear or branched saturated hydrocarbon having the specified number of carbon atoms and a valency of 1; “alkylene group” means an alkyl group having a valency of 2; “hydroxyalkyl group” means an alkyl group substituted with at least one hydroxyl group (-OH); “alkoxy group” means “alkyl-O "-" refers to a group having the formula "-C(=O)-OH"; "Cycloalkyl group" refers to a monovalent group having one or more saturated rings where all ring members are carbon; "Cycloalkylene group" refers to a cycloalkyl group with a valency of 2; "Alkenyl group" refers to a monovalent hydrocarbon group that is straight-chain or branched and has at least one carbon-carbon double bond; "Alkenoxy group" refers to "alkenyl-O-"; "Alkenylene group" refers to an alkenyl group with a valency of at least 2; "Cycloalkenyl group" " refers to a cycloalkyl group having at least one carbon-carbon double bond; "alkynyl group" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic aromatic ring system that includes carbon atoms in one or more rings and may optionally include one or more heteroatoms independently selected from N, O, and S instead of one or more carbon atoms in one or more rings; "aryl group" refers to, This refers to a monovalent monocyclic or polycyclic aromatic group containing only carbon atoms in one or more aromatic rings, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene group" refers to at least a divalent aryl group; "alkylaryl group" refers to an aryl group substituted with an alkyl group; "arylalkyl group" refers to an alkyl group substituted with an aryl group; "aryloxy group" refers to "aryl-O-"; and "arylthio group" refers to "aryl-S-".

[0066] The prefix "hetero" means that a compound or group contains at least one ring-forming atom (e.g., 1, 2, 3 or 4 or more heteroatoms) that is a heteroatom instead of a carbon atom, in which case the heteroatom is independently selected from N, O, S, Si or P. A "heteroatom-containing group" refers to a substituent containing at least one heteroatom; a "heteroalkyl group" refers to an alkyl group having 1 to 4 heteroatoms instead of a carbon atom; a "heterocycloalkyl group" refers to a cycloalkyl group having 1 or more N, O, or S atoms instead of a carbon atom; a "heterocycloalkylene group" refers to a heterocycloalkyl group having at least 2 valencies; a "heteroaryl group" refers to an aryl group having 1 to 3 separate or fused rings having 1 or more N, O, or S atoms as ring-forming atoms instead of a carbon atom; and a "heteroarylene group" refers to a heteroaryl group having at least 2 valencies.

[0067] "Substituted" or "substituted" means that at least one hydrogen atom on a group is replaced by another group, provided that the valence does not exceed the normal valence of the specified atom. If the substituent is oxo (i.e., =O), two hydrogens on the carbon atom are replaced. Two or more substituents or combinations of variables are permitted. For example, the term "substituted" may refer to a mentioned hydrocarbon moiety having two, three, or four identical or different substituents. Exemplary groups that may be present in a "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C) 1~6 ) Alkylamino, alkanoyl (acyl, etc.) 2~6 Alkanoyl groups, for example, formyl (-C(=O)H), carboxylic acids or their alkali metal or ammonium salts, C 2~6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl), C 7~13 Aryl esters (-C(=O)O-aryl or -OC(=O)-aryl), amides (-C(=O)NR2 (wherein R is hydrogen or C) 1~6Alkyl), carboxamide (-CH2C(=O)NR2 (where R is hydrogen or C) 1~6 Alkyl, halogen, thiol (-SH), C 1~6 Alkylthio(-S-alkyl), thiocyano(-SCN), C 1~6 Alkyl, C 2~6 Alkenil, C 2~6 Alkinyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, a C2 compound having at least one aromatic ring. 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is either substituted or unsubstituted aromatic), 1 to 3 separate rings or fused rings, and C having 6 to 18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1 to 3 separate rings or fused rings and 6 to 18 ring carbon atoms, C 7~12 Alkylaryl, C 4~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Examples include arylsulfonyl (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-). When a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding the carbon atoms of any substituents. For example, the group -CH2CH2CN is a C2 alkyl group substituted with a cyano group.

[0068] As used herein, the terms “polymer” and “polymeric” refer to polymeric materials comprising one or more repeating units, which may be the same or different from one another. Accordingly, the polymers and polymeric materials disclosed in the present invention may be referred to herein as “polymer” or “copolymer.” It should be further understood that the terms “polymer” and “polymeric” further include oligomers. In this specification, each of the one or more different repeating units is present at least twice in the polymeric material. In other words, a polymeric material comprising one repeating unit comprises a first repeating unit present in two or more quantities; for example, a polymeric material comprising two repeating units comprises a first repeating unit present in two or more quantities and a second repeating unit present in two or more quantities.

[0069] While this disclosure has been described in relation to what is currently considered to be a practical and exemplary embodiment, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass various modifications and equivalent arrangements that fall within the spirit and scope of the appended claims.

Claims

1. A coating composition for use with an overcoated photoresist composition, With a thermocrosslinkable resin; The following general formula (1): 【Chemistry 1】 (wherein W １ , W ２ , W ３ , and W ４ are independently a single bond or a substituted or unsubstituted C １～５ alkylene; L １ and L ２ are each an ester group; L ３ and L ４ are independently a group selected from a single bond, or a carbonyl or ester group; R １ and R ２ are independently hydrogen, halogen, substituted or unsubstituted C １～１０ alkyl, or substituted or unsubstituted C ３～１０ cycloalkyl; R ３ and R ４ are independently hydrogen, halogen, hydroxyl, substituted or unsubstituted C １～１０ alkyl, or substituted or unsubstituted C ３～１０ cycloalkyl), and a compound of; solvent and A coating composition for use with an overcoated photoresist composition, including the above.

2. R ３ The coating composition according to claim 1, wherein is hydroxyl.

3. W ３ and L ３ The coating composition according to claim 1 or 2, wherein each of them is a single bond.

4. L ３ The coating composition according to claim 1 or 2, wherein is an ester group.

5. The coating composition according to claim 1 or 2, wherein the compound of general formula (1) is present in the composition in an amount of 0.5 to 20 wt% based on the total solid content of the coating composition.

6. The coating composition according to claim 1 or 2, wherein the solvent is an organic solvent.

7. The coating composition according to claim 1 or 2, further comprising a crosslinking agent component, a thermal acid generating agent compound, or both, different from the thermal crosslinkable resin and the compound of general formula (1).

8. A pattern formation method, (a) forming a lower layer on a substrate from the coating composition according to claim 1 or 2; (b) Forming a photoresist layer on the lower layer; (c) Exposing the photoresist layer to activating radiation; (d) Develop the exposed photoresist layer to provide a resist relief image. A pattern formation method including the following.

9. The pattern forming method according to claim 8, wherein the substrate includes gaps having an aspect ratio of 2 or more and a width of 100 nanometers or less.

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