TWI900562B - Electronic device comprising aromatic underlayer and method of manufacturing electronic device - Google Patents

Abstract

Compounds having three or more alkynyl moieties substituted with an aromatic moiety having one or more of certain substituents are useful in forming underlayers useful in semiconductor manufacturing processes.

Description

Electronic device containing an aromatic substrate and method for manufacturing the same

The present invention relates generally to the field of manufacturing electronic devices, and more particularly to the field of materials used as substrates in semiconductor manufacturing.

It is well known in photolithography that if the resist pattern is too tall (high aspect ratio), the resist pattern may collapse due to surface tension from the developer used. Multi-layer resist processes (such as three-layer and four-layer processes) have been designed to address this problem of pattern collapse when a high aspect ratio is desired. Such multi-layer processes use a top resist layer, one or more intermediate layers, and a bottom layer (or underlayer). In such multi-layer resist processes, the top photoresist layer is imaged and developed in a typical manner to provide the resist pattern. The pattern is then transferred to one or more intermediate layers, typically by etching. Each intermediate layer is selected to utilize a different etching process, such as a different plasma etch. Finally, the pattern is typically transferred to the base layer by etching. Such intermediate layers can be made of a variety of materials, but the base layer is typically made of a high-carbon content material. The base layer material is selected to provide the desired antireflective properties, planarization properties, and etch selectivity.

Previous technologies used for underlayers include chemical vapor deposition (CVD) carbon and solution-processed, high-carbon-content polymers. CVD materials have several significant limitations, including high cost of ownership, an inability to planarize topography on the substrate, and high absorbance at 633nm, which is used for pattern alignment. For these reasons, the industry has turned to solution-processed, high-carbon-content materials as underlayers. The ideal underlayer needs to meet the following properties: be able to be cast onto a substrate via a spin-on process; heat-set upon heating with low outgassing and sublimation; be soluble in common processing solvents with good equipment compatibility; have appropriate n and k values to function in conjunction with currently used silicon hardmasks and bottom antireflective (BARC) layers to impart the low reflectivity necessary for photoresist imaging; and be thermally stable up to >400°C so as not to be damaged during the subsequent silicon oxynitride (SiON) CVD process.

It is well known that materials with relatively low molecular weight have relatively low viscosity and flow into topography in a substrate, such as vias and trenches, to provide a planarization layer. The underlying material must be capable of planarization at relatively low outgassing conditions up to 400°C. For use as a high carbon content underlying layer, any composition must be heat-set upon heating. U.S. Patent No. 9,581,905 B2 discloses a compound having the formula

Wherein R ₁ , R ₂ , and R ₃ each independently represent the formula ^RA -C≡CR ^B -, wherein ^RA can be an aryl group substituted with at least one of a hydroxyl group and an aryl group, and ^RB is a single bond or an aryl group. Such compounds can be used to form an underlayer in semiconductor device fabrication. Such compounds cure at relatively high temperatures. There remains a need for materials that cure at relatively low temperatures and can be used to form an underlayer in semiconductor fabrication processes.

The present invention provides a method comprising: (a) providing an electronic device substrate; (b) coating a coating composition comprising one or more curable compounds on a surface of the electronic device substrate, wherein the one or more curable compounds comprise an aromatic nucleus selected from a C _5-6 aromatic ring and a C _9-30 fused aromatic ring system and three or more substituents having formula (1)

wherein at least two substituents having formula (1) are attached to the aromatic nucleus; and wherein Ar ¹ is an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Z is selected from the following substituents: OR ¹ , protected hydroxyl, carboxyl, protected carboxyl, SR ¹ , protected thiol, -OC(=O)-C _1-6 -alkyl, halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, and C _5-30 aryl; each R ² is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to 4; and * represents a point of attachment to the aromatic nucleus; provided that the substituents of formula (1) are not adjacent to each other on the same ring of the aromatic nucleus; (c) curing the layer of the curable compound to form a base layer; (d) coating a photoresist layer on the base layer; (e) exposing the photoresist layer to actinic radiation through a mask; (f) developing the exposed photoresist layer to form an anti-etching pattern; and (g) transferring the pattern to the base layer to expose a portion of the electronic device substrate.

The present invention also provides an electronic device comprising an electronic device substrate having a polymer layer on a surface of the electronic device substrate, the polymer comprising one or more curable compounds as polymerized units, wherein the one or more curable compounds comprise an aromatic nucleus selected from a C _5-6 aromatic ring and a C _9-30 fused aromatic ring system and three or more substituents having formula (1)

wherein at least two substituents having formula (1) are attached to the aromatic nucleus; and wherein Ar ¹ is an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Z is selected from the following substituents: OR ¹ , protected hydroxyl, carboxyl, protected carboxyl, SR ¹ , protected thiol, -OC(=O)-C _1-6 -alkyl, halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, and C _5-30 aryl; each R ² is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to 4; and * represents the point of attachment to the aromatic nucleus; provided that the substituents of formula (1) are not adjacent to each other on the same ring of the aromatic nucleus.

The present invention further provides a compound having formula (2) wherein Ar ^c is an aromatic nucleus having 5 to 30 carbon atoms; Ar ¹ , Ar ² , and Ar ³ are each independently an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Y is a covalent chemical single bond, a divalent linking group, or a trivalent linking group; Z ¹ and Z ² are independently selected from the following substituents: OR ¹ , a protected hydroxyl group, a carboxyl group, a protected carboxyl group, SR ¹ , a protected thiol group, -OC(=O)-C _1-6 -alkyl, a halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, a C _2-10 unsaturated alkyl group, and a C _5-30 aryl group; each R ² is selected from H, C _1-10 alkyl, a C _2-10 unsaturated alkyl group, a C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x1 = 1 to 4; x2 = 1 to 4; y1 = 2 to 4; each y2 = 0 to 4; y1 + each y2 3; w = 0 to 2; and z is equal to 0 to 2; wherein when Y is a covalent chemical single bond or a divalent linking group, z = 1; and when Y is a trivalent linking group , z = 2; provided that when w = 0, Ar ^c and each Ar ¹ are not phenyl.

Still further, the present invention provides a method comprising: (a) providing an electronic device substrate; (b) coating a coating composition comprising one or more curable compounds having formula (2) on a surface of the electronic device substrate; wherein Ar ^c is an aromatic nucleus having 5 to 30 carbon atoms; Ar ¹ , Ar ² , and Ar ³ are each independently an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Y is a covalent chemical single bond, a divalent linking group, or a trivalent linking group; Z ¹ and Z ² are independently selected from the following substituents: OR ¹ , a protected hydroxyl group, a carboxyl group, a protected carboxyl group, SR ¹ , a protected thiol group, -OC(=O)-C _1-6 -alkyl, a halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, a C _2-10 unsaturated alkyl group, and a C _5-30 aryl group; each R ² is selected from H, C _1-10 alkyl, a C _2-10 unsaturated alkyl group, a C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x1 = 1 to 4; x2 = 1 to 4; y1 = 2 to 4; each y2 = 0 to 4; y1 + each y2 3; w = 0 to 2; and z is equal to 0 to 2; wherein when Y is a covalent chemical single bond or a divalent linking group, z = 1; and when Y is a trivalent linking group, z = 2; (c) curing the layer of the curable compound to form a base layer; (d) coating a photoresist layer on the base layer; (e) exposing the photoresist layer to actinic radiation through a mask; (f) developing the exposed photoresist layer to form an anti-etching pattern; and (g) transferring the pattern to the base layer to expose a portion of the electronic device substrate.

The present invention also provides a method for filling gaps (or holes), comprising: (a) providing a semiconductor substrate having a relief image on a surface of the substrate, the relief image comprising a plurality of gaps to be filled; (b) applying a coating of one or more compounds having formula (2) on the relief image; and (c) heating the coating at a temperature sufficient to cure the coating.

It will be understood that when an element is referred to as being "on" another element, it can be directly adjacent to the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

It will also be understood that although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present invention.

As used throughout this specification, the following abbreviations shall have the following meanings, unless the context clearly indicates otherwise: °C = degrees Celsius; g = gram; mg = milligram; L = liter; mL = milliliter; Å = angstrom; nm = nanometer; μm = micron; mm = millimeter; sec. = second; min. = minute; hr. = hour; DI = deionized; and Da = dalton. Unless otherwise indicated, "wt%" refers to weight percent based on the total weight of the referenced composition. Unless otherwise indicated, all amounts are wt% and all ratios are molar ratios. All numerical ranges are inclusive and combinable in any order, except where it is apparent that numerical ranges are limited to add up to 100%. The articles "a/an" and "the" refer to the singular and plural. Unless otherwise indicated, "alkyl" refers to straight chain, branched chain and cyclic alkyl groups. As used herein, "alkyl" refers to alkane groups and includes alkane monovalent groups, divalent groups (alkylene groups), and higher valent groups. "Halogen" refers to fluorine, chlorine, bromine and iodine. Unless otherwise indicated, "alkyl" includes "heteroalkyl". The term "heteroalkyl" refers to an alkyl group in which one or more carbon atoms in the group are replaced by one or more heteroatoms (such as nitrogen, oxygen, sulfur, phosphorus), for example, as in an ether or thioether. In a preferred embodiment, "alkyl" does not include "heteroalkyl". If the number of carbons is not indicated for any alkyl or heteroalkyl group, 1-12 carbons are expected.

"Aryl" includes aromatic carbocyclic rings and aromatic heterocyclic rings. The term "aryl" refers to aromatic groups and includes monovalent groups, divalent groups (arylidene groups), and higher valent groups. Preferably, aryl moieties are aromatic carbocyclic rings. "Substituted aryl" refers to any aryl functional group in which one or more hydrogen atoms are replaced by one or more substituents selected from the group consisting of halogen, C _1-6 -alkyl, halogenated-C _1-6 -alkyl, C _1-6 -alkoxy, halogenated-C _1-6 -alkoxy, phenyl, and phenoxy, preferably selected from the group consisting of halogen, C _1-6 -alkyl, halogenated-C _1-4 -alkyl, C _1-6 -alkoxy, halogenated-C _1-4 -alkoxy, and phenyl, and more preferably selected from the group consisting of halogen, C _1-6 -alkyl, C _1-6 -alkoxy, phenyl, and phenoxy. Preferably, the substituted aryl group has 1 to 3 substituents, and more preferably 1 or 2 substituents. As used herein, the term "polymer" includes oligomers. The term "oligomer" refers to dimers, trimers, tetramers, and other polymeric materials that are capable of further curing. The term "curing" means any process, such as polymerization or condensation, that increases the overall molecular weight of the resins of the present invention or removes solubility-enhancing groups from the oligomers of the present invention, or both. "Curable" refers to any material that can be cured under certain conditions. As used herein, "gap" refers to any hole in a semiconductor substrate that is intended to be filled with a gap-filling composition.

An aromatic underlayer is formed in the manufacture of an electronic device according to the following method, the method comprising: (a) providing an electronic device substrate; (b) coating a coating composition comprising one or more curable compounds on a surface of the electronic device substrate, wherein the one or more curable compounds comprise an aromatic nucleus selected from a C _5-6 aromatic ring and a C _9-30 fused aromatic ring system and three or more substituents having formula (1)

wherein at least two substituents having formula (1) are attached to the aromatic nucleus; and wherein Ar ¹ is an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Z is selected from OR ¹ , a protected hydroxyl group, a carboxyl group, a protected carboxyl group, SR ¹ , a protected thiol group, -OC(=O)-C _1-6 -alkyl, a halogen, and NHR ² ; each R ¹ is selected from H, C _{1-10 alkyl, C 2-10 unsaturated alkyl, and C 5-30 aryl; each R 2 is selected from H, C 1-10 alkyl ,} ^C _{2-10 unsaturated} alkyl, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to 4; and * represents the point of attachment to the aromatic nucleus; provided that the substituents of formula (1) are not adjacent to each other on the same ring of the aromatic nucleus; (c) curing the layer of the curable compound to form a base layer; (d) coating a photoresist layer on the base layer; (e) exposing the photoresist layer to actinic radiation through a mask; (f) developing the exposed photoresist layer to form an anti-etching pattern; and (g) transferring the pattern to the base layer to expose a portion of the electronic device substrate. Next, the substrate is patterned, and the patterned base layer is removed. In a preferred embodiment, the photoresist layer is coated directly on the base layer. In an alternative preferred embodiment, prior to step (d), a layer of one or more of a silicon-containing composition, an organic antireflective composition (BARC), or a combination thereof is directly coated on the base layer to form an intermediate layer, and a photoresist layer is directly coated on the intermediate layer. When a silicon-containing intermediate layer is used, the pattern is transferred to the silicon-containing intermediate layer after step (f) and before step (g).

A wide variety of electronic device substrates can be used in the present invention, including packaging substrates such as multi-chip modules; flat panel display substrates; integrated circuit substrates; substrates for light-emitting diodes (LEDs), including organic light-emitting diodes (OLEDs); semiconductor wafers; polycrystalline silicon substrates; and the like, with semiconductor wafers being preferred. Such substrates are typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used to manufacture integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. As used herein, the term "semiconductor wafer" is intended to encompass semiconductor substrates, semiconductor devices, and various packages used at various interconnect levels, including single-chip wafers, multi-chip wafers, packages used at various levels, or other components requiring solder connections. Such substrates can be of any suitable size. Preferred wafer substrates have a diameter of 200 mm to 300 mm, although wafers with smaller and larger diameters can be suitably used in accordance with the present invention. As used herein, the term "semiconductor substrate" includes any substrate having one or more semiconductor layers or structures, which may optionally include the active or operational portion of a semiconductor device. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic device has been or is being mass-produced.

If desired, an adhesion promoter layer may be applied to the substrate surface prior to depositing the coating composition of the present invention, which is then cured to form a base layer. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as a silane, preferably an organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or an aminosilane coupling agent such as γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names AP 3000, AP 8000, and AP 9000S available from Dow Electronic Materials (Marlborough, Massachusetts).

The coating composition useful in the present invention comprises one or more curable compounds comprising an aromatic nucleus selected from a C _5-6 aromatic ring and a C _9-30 fused aromatic ring system and three or more substituents having formula (1)

wherein at least two substituents having formula (1) are attached to the aromatic nucleus; and wherein Ar ¹ is an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Z is selected from OR ¹ , a protected hydroxyl group, a carboxyl group, a protected carboxyl group, SR ¹ , a protected thiol group, —OC(═O)—C _1-6 -alkyl, a halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 -alkyl, C _2-10 -unsaturated alkyl, and C _5-30 -aryl; each R ² is selected from H, C _1-10 -alkyl, C _2-10 -unsaturated alkyl, C _5-30 -aryl, C(═O)—R ¹ , and S(═O) ₂ -R ¹ ; x is an integer from 1 to 4; and * represents the point of attachment to the aromatic nucleus; provided that the substituents of formula (1) are not located adjacent to each other on the same ring of the aromatic nucleus. Thus, substituents of formula (1) bonded to the same aromatic ring of the nucleus will not be bonded to adjacent carbon atoms of the aromatic ring, for example, at the 1 and 2 positions of the benzene nucleus. Preferably, each Z is independently selected from OR ¹ , a protected hydroxyl group, a carboxyl group (C(═O)OH), a protected carboxyl group, SH, fluorine, and NHR ² . More preferably, each Z is independently selected from hydroxyl (OH), protected hydroxyl, _OCH2C≡CH , C(=O)OH, protected carboxyl, and ^NHR2 , yet more preferably selected from OH, protected hydroxyl, _OCH2C≡CH , carboxyl, and protected carboxyl, and still more preferably selected from OH and protected hydroxyl. Each ^R1 is independently selected from H, _C1-10 alkyl, _C2-10 unsaturated alkyl, and _C5-30 aryl, and more preferably selected from H, _C1-10 -alkyl, _C2-10 -alkenyl, _C2-10 -alkynyl, and _C5-30 aryl. In a preferred embodiment, ^R1 is H. Preferably, R ² is selected from H, C _1-10 -alkyl, C _2-10 -unsaturated alkyl, and C _5-30 -aryl, and more preferably is selected from H, C _1-10 -alkyl, C _2-10 -alkenyl, and C _2-10 -alkynyl. As used herein, the term "aromatic core" refers to a single aromatic ring or a fused aromatic ring system to which at least two functional groups of formula (1) are attached. The aromatic core may be substituted as needed with one or more substituents selected from the following: C _1-20 -aliphatic or alicyclic functional groups and C _5-30 -aryl functional groups. Preferably, the aromatic core is selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylene, (chrysene), phenanthracene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, more preferably selected from benzene, naphthalene, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, , phenanthracene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, In formula (1), preferably, each Ar ¹ is independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, and benzo[a]pyrene, preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, , phenanthracene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and even more preferably is selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, , and 萉. Preferably, x = 1 or 2, and more preferably x = 1. The curable compound of the present invention has at least three functional groups having formula (1), wherein at least two substituents having formula (1) are directly attached to the aromatic core. The curable compound of the present invention may have any suitable number of functional groups having formula (1), such as 3 to 10, preferably 3 to 8, more preferably 3 to 6, and even more preferably 3 or 4. Further preferably, the curable compound of the present invention has 2 to 4 functional groups having formula (1) directly attached to the aromatic core.

In one embodiment, preferred curable compounds useful in the coating composition of the present invention are those having formula (2)

wherein Ar ^c is an aromatic nucleus having 5 to 30 carbon atoms; Ar ¹ , Ar ² , and Ar ³ are each independently an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Y is a covalent chemical single bond, a divalent linking group, or a trivalent linking group; Z ¹ and Z ² are independently selected from OR ¹ , a protected hydroxyl group, a carboxyl group, a protected carboxyl group, SR ¹ , a protected thiol group, -OC(=O)-C _1-6 -alkyl, a halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, a C _2-10 unsaturated alkyl group, and a C _5-30 aryl group; each R ² is selected from H, C _1-10 alkyl, a C _2-10 unsaturated alkyl group, a C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x1 = 1 to 4; x2 = 1 to 4; y1 = 2 to 4; each y2 = 0 to 4; y1 + each y2 3; w = 0 to 2; and z is equal to 0 to 2; wherein when Y is a covalent chemical single bond or a divalent linking group, z = 1; and when Y is a trivalent linking group, z = 2. Preferably, Ar ^c is an aromatic nucleus having 5 to 25 carbon atoms, and more preferably 5 to 20 carbon atoms. Suitable aromatic nuclei for Ar ^c include, but are not limited to, pyridine, benzene, naphthalene, quinoline, isoquinoline, carbazole, anthracene, phenanthrene, pyrene, coronene, terphenyl, , benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, preferably benzene, naphthalene, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, , phenanthrene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, Preferably, Ar ¹ is selected from benzene, pyridine, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, More preferably, Ar ¹ , Ar ² , and Ar ³ are each independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthracene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, , phenanthracene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, More preferably, Ar ^c is selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylmethane, , phenanthrene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and Ar ¹ , Ar ² , and Ar ³ are each independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthrene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene. Preferably, Z ¹ and Z ² are each independently selected from OR ¹ , a protected hydroxyl group, a carboxyl group (C(=O)OH), a protected carboxyl group, SH, fluorine, and NHR ² , more preferably selected from a hydroxyl group (OH), a protected hydroxyl group, OCH ₂ C≡CH, C(=O)OH, a protected carboxyl group, and NHR ² , yet more preferably selected from OH, a protected hydroxyl group, OCH ₂ C≡CH, a carboxyl group, and a protected carboxyl group, and still more preferably selected from OH and a protected hydroxyl group. Each ^R is independently selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, and C _5-30 aryl, and is more preferably selected from H, C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, and C _5-30 aryl. In a preferred embodiment, ^R is H. Preferably, ^R is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, and C _5-30 aryl, and is more preferably selected from H, C _1-10 alkyl, C _2-10 alkenyl, and C _2-10 alkynyl. Preferably, each ^Z is the same. Even more preferably, each ^Z is the same. More preferably, Z ¹ = Z ² . Preferably, x 1 and x 2 are each independently selected from 1 to 3, more preferably independently 1 or 2, and even more preferably each 1. Preferably, each y 2 = 0 to 2. Preferably, y 1 + each y 2 = 3 to 8, more preferably 3 to 6, and even more preferably 3 or 4. Preferably, w = 0 to 1. In a preferred embodiment, the substituents comprising Ar ¹ and Ar ³ are not adjacent to each other on the same ring of the aromatic nucleus. In a preferred embodiment, when w = 0, Ar ^c and each Ar ¹ are not phenyl. In a preferred embodiment, Y is a single covalent bond. In another preferred embodiment, Y is a divalent or trivalent linking group. For Y, exemplary linking groups include but are not limited to O, S, N(R ³ ) _r , S(═O) ₂ , CR ⁴ R ⁵ , bis-imide functional groups, bis-etherimide functional groups, bis-ketimide functional groups, bis-benzo Azole functional groups, bis-benzimidazole functional groups, and bis-benzothiazole functional groups, wherein r = 0 or 1, and preferably the linking group of Y is O, N(R ³ ) _w , and CR ⁴ R ^5. R ³ is **-C(=O)-C _5-30 -aryl or **-S(=O) ₂ -C _5-30 -aryl, where ** is the point of attachment to N. R ⁴ and R ⁵ are independently selected from H, C _1-10 -alkyl and C _5-10 -aryl, and R ⁴ and R ⁴ can form a 5-membered or 6-membered ring together with the carbon to which they are attached, which ring can be fused to one or more aromatic rings. When Y=CR ⁴ R ⁵ , a suitable linking group is a fluorenyl functional group having the following formula (A):

wherein * represents the point of attachment to ^Arc and Ar ^2. Suitable bis-imide functional linking groups for Y are shown by formula (B) and formula (C), wherein Y ¹ is a covalent single bond or a C _5-30 -arylene group, wherein * represents the point of attachment to ^Arc and Ar ^2. Suitable bis-etherimide and bis-ketoimide functional groups are those of formula (C), wherein Y ¹ is =O or -C(=O)-, respectively, and wherein * represents the point of attachment to ^Arc and Ar ^2. Suitable bis-benzo Azole, bis-benzimidazole, and bis-benzothiazole functional groups are those having formula (D) wherein G = O, NH, and S, respectively, and wherein Y ² is a covalent single bond or a C _5-30 -arylene group, and wherein * indicates the point of attachment to Ar ^c and Ar ² .

For Z, ^Z1 and ^Z2 of formulas (1) and (2), the protected carboxyl group is any group that can be cleaved under certain conditions to produce a carboxyl group. Such protected carboxyl groups can be cleaved by heat, acid, base or a combination thereof, preferably by heat, acid or a combination thereof, and more preferably by heat. Exemplary protected carboxyl groups include esters, such as benzyl esters and esters having a quaternary carbon directly bonded to the alkoxy oxygen of the ester group. Preferably, the protected carboxyl group is an ester having a quaternary carbon directly bonded to the alkoxy oxygen of the ester group, and more preferably the ester has the formula YC(O)-O-CR'R"R'", wherein Y is an organic residue and R', R" and R'" are each independently selected _{from C1-10} alkyl. Preferred protected carboxyl groups include: tertiary butyl esters; 1-alkylcyclopentyl esters such as 1-methylcyclopentyl ester and 1-ethylcyclopentyl ester; 2,3-dimethyl-2-butyl ester; 3-methyl-3-pentyl ester; 2,3,3-trimethyl-3-butyl ester; 1,2-dimethylcyclopentyl ester; 2,3,4-trimethyl-3-pentyl ester; 2,2,3,4,4-pentamethyl-3-pentyl ester; and adamantyl esters such as hydroxyadamantyl esters and C _1-12 alkyl adamantyl esters. Each of the above-mentioned protected carboxyl groups can be cleaved by one or more of heat, acid or base. Preferably, heat, acid or a combination of heat and acid is used, and more preferably, the protected carboxyl groups are cleaved by heat. For example, the protected carboxyl groups can be cleaved in 4 and preferably 1. Such protected carboxyl groups can be cleaved at room temperature when exposed to a pH of 1 to 4. When the pH is <1, such protected carboxyl groups are typically heated to about 90°C to 110°C, and preferably to about 100°C. Alternatively, when the protected carboxyl group is an ester having a quaternary carbon directly bonded to the alkoxy oxygen of the ester group, the protected carboxyl group can be cleaved by heating to a suitable temperature, such as 125° C. to 125° C., preferably 125° C. to 250° C., and more preferably 150° C. to 250° C. Such protected carboxyl groups and conditions for their use are well known in the art, such as U.S. Patent No. 6,136,501, which discloses various ester groups having a quaternary carbon directly bonded to the alkoxy oxygen of the ester group.

For Z, Z ¹ and Z ² in formulas (1) and (2), suitable protected hydroxy groups are any groups that can be cleaved under certain conditions to produce a hydroxy group. Such protected hydroxy groups can be cleaved by heat, acid, base or a combination thereof. Exemplary protected hydroxy groups include: ethers such as methoxymethyl ether, tetrahydropyranyl ether, tertiary butyl ether, allyl ether, benzyl ether, tertiary butyldimethylsilyl ether, tertiary butyldiphenylsilyl ether, acetonide, and benzyl acetal; esters such as trimethylacetate and benzoate; and carbonates such as tertiary butyl carbonate. Each of the above-mentioned protected hydroxy groups can be cleaved under acidic or alkaline conditions, and preferably under acidic conditions. More preferably, the protected hydroxyl groups are cleaved using an acid or a combination of acid and heat. For example, the protected hydroxyl groups may be cleaved in 4 and preferably 1. Such protected hydroxyl groups can be cleaved at room temperature when exposed to a pH of 1 to 4. When the pH is <1, such protected hydroxyl groups are typically heated to about 90°C to 110°C, and preferably to about 100°C. Such protected hydroxyl groups and conditions for their use are well known in the art.

For Z, Z ¹ and Z ² in formulas (1) and (2), suitable protected thiol groups are any groups that can be cleaved under certain conditions to produce thiol groups. Such protected thiol groups can be cleaved by heat, acid, base or a combination thereof. Exemplary protected thiol groups include: ethers such as methoxymethyl sulfide, tetrahydropyranyl sulfide, tertiary butyl sulfide, allyl sulfide, benzyl sulfide, tertiary butyldimethylsilyl sulfide, tertiary butyldiphenylsilyl sulfide, thioacetonide, and benzylthioacetal; thioesters such as trimethylacetic acid thioester and benzoic acid thioester; and thiocarbonates such as tertiary butyl thiocarbonate. Each of the above-mentioned protected thiol groups can be cleaved under acidic or alkaline conditions, and preferably under acidic conditions. More preferably, the protected thiol groups are cleaved using an acid or a combination of acid and heat. For example, the protected thiol groups may be cleaved in 4 and preferably 1. Such thiol groups can be cleaved at room temperature when exposed to a pH of 1 to 4. When the pH is <1, such protected thiol groups are typically heated to about 90°C to 110°C, and preferably to about 100°C. Such protected thiol groups and conditions for their use are well known in the art.

In addition to the one or more curable compounds described above, the coating composition of the present invention may optionally contain, and preferably contains, one or more organic solvents. Suitable organic solvents are any organic solvents that dissolve the one or more curable compounds, and are preferably organic solvents conventionally used in the manufacture of electronic devices. The organic solvents may be used alone or as a mixture of organic solvents. Suitable organic solvents include, but are not limited to, ketones such as cyclohexanone and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol methyl ether (PGME), propylene glycol ethyl ether (PGEE), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and dimethoxypropanol. Ethylene glycol dimethyl ether, anisole; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; lactones such as γ-butyrolactone; and any combination of the foregoing. Preferred solvents are PGME, PGEE, PGMEA, EL, HBM, and combinations thereof.

The coating composition of the present invention may also contain one or more coating additives typically used in such coatings, such as curing agents, crosslinking agents, and surface leveling agents. The selection of such optional additives and their amounts are well within the skill of those skilled in the art. The curing agent is typically present in an amount of 0 to 20 wt %, and preferably 0 to 3 wt %, based on total solids. The crosslinking agent is typically used in an amount of 0 to 30 wt %, and preferably 3 to 10 wt %, based on total solids. The surface leveling agent is typically used in an amount of 0 to 5 wt %, and preferably 0 to 1 wt %, based on total solids. The selection of such optional additives and their amounts are well within the skill of those skilled in the art.

A curing agent may be optionally used in the coating composition to account for the cure of the deposited curable compound. A curing agent is any component that causes the curable compound to cure on the surface of the substrate. Preferred curing agents are acids and thermal acid generators. Suitable acids include, but are not limited to: arylsulfonic acids, such as p-toluenesulfonic acid; alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid; perfluoroalkylsulfonic acids, such as trifluoromethanesulfonic acid; and perfluoroarylsulfonic acids. A thermal acid generator is any compound that releases an acid when exposed to heat. Thermal acid generators are well known in the art and are generally commercially available, such as from King Industries, Norwalk, Connecticut. Exemplary thermal acid generators include, but are not limited to, amine-terminated strong acids, such as amine-terminated sulfonic acids, such as amine-terminated dodecylbenzenesulfonic acid. Those skilled in the art will also appreciate that certain photoacid generators are capable of releasing acid upon heating and can be used as thermal acid generators.

Any suitable crosslinking agent may be used in the composition of the present invention, provided that such crosslinking agent has at least two, and preferably at least three, functional groups capable of reacting with the aromatic resin reaction product of the present invention under suitable conditions (e.g., under acidic conditions). Exemplary crosslinking agents include, but are not limited to, novolac resins, epoxy-containing compounds, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, and the like. Preferably, such crosslinking agents have two or more, preferably three or more, and more preferably four, substituents selected from the group consisting of hydroxymethyl, _C1 - _C10 alkoxymethyl, and _C2 - _C10 acyloxymethyl groups. Examples of suitable crosslinking agents are those shown by formulas (3) and (4).

Such crosslinking agents are well known in the art and are commercially available from a variety of sources.

The coating composition of the present invention may optionally include one or more surface leveling agents (or surfactants). While any suitable surfactant may be used, such surfactants are typically non-ionic. Exemplary non-ionic surfactants include those containing alkyleneoxy linkages (e.g., ethyleneoxy, propyleneoxy, or a combination of ethyleneoxy and propyleneoxy linkages).

The coating composition of the present invention can be applied to the electronic device substrate by any suitable means, such as spin coating, slot-die coating, doctor blading, curtain coating, roller coating, spray coating, dip coating, and the like. Spin coating is preferred. In a typical spin coating method, the composition of the present invention is applied to a substrate rotating at a speed of 500 to 4000 rpm for a period of 15 to 90 seconds to obtain the desired coating composition layer on the electronic device substrate. Those skilled in the art will appreciate that the height of the coating composition layer can be adjusted by varying the rotation speed.

After the coating composition layer is applied to the substrate, it is optionally baked at a relatively low temperature to remove any organic solvents and other relatively volatile components from the layer. Typically, the substrate is baked at a temperature of 80°C to 150°C, although other suitable temperatures may be used. The baking time is typically 10 seconds to 10 minutes, and preferably 30 seconds to 5 minutes, although longer or shorter times may be used. When the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate. After solvent removal, a layer, film, or coating of the curable compound is obtained on the substrate surface.

The layer of curable compound is then cured sufficiently to form the aromatic underlayer so that the film does not intermix with subsequently applied coatings, such as photoresist layers or other layers applied directly on the aromatic underlayer. The underlayer can be cured in an oxygen-containing atmosphere, such as air, or in an inert atmosphere, such as nitrogen, and preferably in an oxygen-containing atmosphere. The curing conditions used are those that are sufficient to cure the film so that it does not intermix with subsequently applied organic layers, such as photoresist layers, while still maintaining the desired antireflective properties (n and k values) and etch selectivity of the underlayer film. This curing step is preferably carried out on a hot plate apparatus, although oven curing can be used to obtain equivalent results. Typically, this curing is performed by 150℃, preferably 170℃, and preferably The curing step is performed by heating the base layer at a curing temperature of 200°C. The curing temperature selected should be sufficient to cure the aromatic base layer. Suitable temperatures for curing aromatic base layers range from 150°C to 400°C, preferably from 170°C to 350°C, and more preferably from 200°C to 250°C. This curing step can take from 10 seconds to 10 minutes, preferably from 1 to 3 minutes, and more preferably from 1 to 2 minutes, although other suitable times may be used.

If the curing step is carried out in such a way that the rapid release of solvents and curing by-products does not allow the quality of the underlying film to be damaged, then an initial baking step may not be necessary. For example, starting at a relatively low temperature and then gradually increasing to A ramp bake at a temperature of 200°C may produce acceptable results. In some cases, it may be preferable to have a two-stage curing process, where the first stage is a lower bake temperature of less than 150°C, and the second stage is A high bake temperature of 200°C and a two-stage curing process promote uniform filling and planarization of pre-existing substrate surface topography, such as trench and via filling.

After curing the base layer, one or more processing layers, such as a photoresist, a silicon-containing layer, a hard mask layer, a bottom antireflective coating (or BARC) layer, etc., can be applied to the cured base layer. For example, the photoresist can be applied (e.g., by spin coating) directly to the surface of the silicon-containing layer or other intermediate layer directly on the resin base layer, or alternatively, the photoresist can be applied directly to the cured base layer. A variety of photoresists can be suitably used, such as those used for 193 nm photolithography, such as those sold under the Epic ^™ brand available from Dow Electronic Materials (Marysburg, Massachusetts). Suitable photoresists can be positive-acting or negative-acting etchants. After coating, the photoresist layer is then imaged (exposed) using patterned actinic radiation, and the exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the underlying layer by a suitable etching technique. Typically, the photoresist is also removed during this etching step. Next, the pattern is transferred to the substrate and the underlying layer is removed by a suitable etching technique known in the art (such as by plasma etching). After patterning the substrate, the underlying layer is removed using conventional techniques. The electronic device substrate is then processed according to conventional means.

The cured base layer can be used as the bottom layer of a multi-layer resist process. In this process, a coating composition is applied to a substrate and cured as described above. Next, one or more intermediate layers are applied to the aromatic base layer. For example, a silicon-containing layer or hard mask layer is applied directly to the aromatic base layer. An exemplary silicon-containing layer, such as silicon-BARC, can be deposited on the base layer by spin coating and subsequently cured, or an inorganic silicon layer, such as SiON or _SiO2, can be deposited on the base layer by chemical vapor deposition (CVD). Any suitable hard mask can be used and can be deposited on the underlying layer by any suitable technique and cured (as appropriate). Optionally, an organic BARC layer can be placed directly on the silicon-containing layer or the hard mask layer and cured as appropriate. Next, a photoresist (such as those used in 193nm photolithography) is applied directly on the silicon-containing layer (in a three-layer process) or directly on the organic BARC layer (in a four-layer process). The photoresist layer is then imaged (exposed) using patterned actinic radiation, and the exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the layer directly below it using a suitable etching technique known in the art (e.g., plasma etching), resulting in a patterned silicon-containing layer in a three-layer process and a patterned organic BARC layer in a four-layer process. If a four-layer process is used, the pattern is then transferred from the organic BARC layer to the silicon-containing layer or hardmask layer using a suitable pattern transfer technique (e.g., plasma etching). After patterning the silicon-containing layer or hardmask layer, the aromatic base layer is then patterned using a suitable etching technique (e.g., _O₂ or _CF₄ plasma). During the etching of the aromatic underlayer, any remaining patterned photoresist layer and organic BARC layer are removed. Next, the pattern is transferred to the substrate, such as by a suitable etching technique, which also removes any remaining silicon-containing layer or hard mask layer, followed by the removal of any remaining patterned aromatic underlayer to provide a patterned substrate.

The cured base layer of the present invention can also be used in a self-aligned double patterning process. In this process, a coating composition of the present invention is applied to a substrate, such as by spin coating. Any remaining organic solvent is removed and the coating composition layer is cured to form a cured base layer. A suitable intermediate layer, such as a silicon-containing layer, is applied to the cured base layer. A suitable photoresist layer is then applied to the intermediate layer, such as by spin coating. The photoresist layer is then imaged (exposed) using patterned actinic radiation, and the exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the intermediate layer and the cured bottom layer by means of a suitable etching technique to expose a portion of the substrate. Typically, the photoresist is also removed during this etching step. Next, a conformal silicon-containing layer is placed over the patterned cured bottom layer and the exposed portion of the substrate. Such a silicon-containing layer is typically an inorganic silicon layer, such as SiON or _SiO2 , conventionally deposited by CVD. Such a conformal coating results in a silicon-containing layer on the exposed portion of the substrate surface and on top of the bottom layer pattern, i.e., such a silicon-containing layer substantially covers the sides and top of the patterned bottom layer. Next, the silicon-containing layer is partially etched (trimmed) to expose the top surface of the patterned polyarylene resin base layer and a portion of the substrate. After this partial etching step, the pattern on the substrate comprises a plurality of features, each of which comprises lines or pillars of the cured base layer, wherein the silicon-containing layer is directly adjacent to the sides of each cured base layer feature. Next, the cured base layer is removed, such as by etching, to expose the substrate surface beneath the cured base layer pattern and provide a patterned silicon-containing layer on the substrate surface, wherein such patterned silicon-containing layer is doubled (i.e., having twice as many lines and/or pillars) as the patterned cured base layer.

The coating compositions of the present invention can also be used to form planarization layers, gapfill layers, and protective layers in the fabrication of integrated circuits. When used as such planarization layers, gapfill layers, or protective layers, one or more intervening material layers (e.g., a silicon-containing layer, other aromatic resin layers, hardmask layers, etc.) are typically present between the cured layer of the coating composition of the present invention and any photoresist layers. These planarization layers, gapfill layers, and protective layers are typically ultimately patterned. The gap filling process according to the present invention comprises: (a) providing a semiconductor substrate having a relief image on a surface of the substrate, the relief image comprising a plurality of gaps to be filled; (b) applying a gap filling composition on the relief image, wherein the gap filling composition comprises: one or more curable compounds, the one or more curable compounds comprising an aromatic nucleus selected from a C _5-6 aromatic ring and a C _9-30 fused aromatic ring system and three or more substituents having formula (1)

wherein at least two substituents having formula (1) are attached to the aromatic nucleus; and wherein Ar ¹ is an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Z is selected from the following substituents: OR ¹ , protected hydroxyl, carboxyl, protected carboxyl, SR ¹ , protected thiol, -OC(=O)-C _1-6 -alkyl, halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, and C _5-30 aryl; each R ² is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to 4; and * represents a point of attachment to the aromatic nucleus; provided that the substituents of formula (1) are not adjacent to each other on the same ring of the aromatic nucleus; and (ii) one or more organic solvents; and (c) heating the gap-filling composition at a temperature to cure the one or more curable compounds. The composition of the present invention substantially fills, preferably fills, and more preferably completely fills a plurality of gaps in a semiconductor substrate.

The compounds of the present invention exhibit excellent gap-filling properties. Compared to the compounds disclosed in U.S. Patent No. 9,581,905, films formed from the compounds of the present invention exhibit excellent planarization, solvent resistance, and reduced defect formation.

Example 1. 1,3,5-Tribromobenzene (2.36 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dibromobenzene at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70° C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dihydroquinone. (14 g) and then slowly added the solution to the reaction mixture via an addition funnel. After the addition was complete, the reaction mixture was stirred at 70 ° C under nitrogen overnight. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by column chromatography to obtain 3.5 g (84% yield) of 1,3,5-tris((4-acetyloxyphenyl)ethynyl)benzene (Compound I1) as a light yellow solid. The reaction is shown in the following reaction scheme.

Example 2. 1,3,5-Tribromobenzene (2.36 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dibromobenzene at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70° C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dihydroquinone. (14g), and then the solution was slowly added to the reaction mixture by an addition funnel. After the addition was completed, the reaction mixture was stirred at 70°C under nitrogen overnight. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by column chromatography to obtain a light yellow solid. The obtained solid was then dissolved in THF (35g) under nitrogen. Lithium hydroxide monohydrate (0.94g) and water (8g) were added, and the reaction mixture was stirred at 60°C for 1 hour. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum to obtain 2.6 g (81% yield) of 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (Compound I2) as a light yellow solid. The reaction is shown in the following reaction scheme.

Example 3. 4-Iodophenyl acetate (24.75 g), cuprous iodide (0.17 g) and triethylamine (27.32 g) were added to 22.82 g of 1,4-dimethoxybenzene at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.63 g) was added to the reaction mixture, and the mixture was heated to 70° C. 1,3,5-triethynylbenzene (4.5 g) was then added to the degassed 1,4-dihydroquinone via a syringe pump. The solution in (20g) is slowly added to the reaction mixture. After the addition is completed, the reaction is stirred at 70°C under nitrogen overnight. After the reaction is complete, the reaction mixture is cooled to room temperature and the solvent is evaporated. The residue is diluted with ethyl acetate and filtered to remove the solid. The solution is evaporated and the residue is purified by column chromatography to obtain a light yellow solid. The obtained solid is then dissolved in THF (38g) under nitrogen. Lithium hydroxide monohydrate (3.81g) and water (16g) are added, and the mixture is stirred at 60°C for 1 hour. The mixture is then cooled to room temperature and the solvent is removed. The residue was diluted with ethyl acetate and water and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to obtain 7.7 g (61% yield) of 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (Compound I2) as a light yellow solid. The reaction is shown in the following reaction scheme.

Example 4. 1,3,5-Tribromobenzene (3.12 g), cuprous iodide (0.29 g) and triethylamine (4.55 g) were added to 22 g of 1,4-dibromobenzene at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.70 g) was added to the reaction mixture, and the mixture was heated to 70° C. 1-Ethynyl-4-methoxybenzene (5.28 g) was dissolved in degassed 1,4-dichlorobenzene. (20 g) and then slowly added the solution to the reaction mixture via an addition funnel. After the addition was complete, the reaction mixture was stirred at 70 ° C under nitrogen overnight. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by column chromatography to obtain 4.0 g (85% yield) of 1,3,5-tris((4-methoxyphenyl)ethynyl)benzene (Compound I3) as a light yellow solid. The reaction is shown in the following reaction scheme.

Example 5. 1,3,5-Tribromobenzene (3.12 g), cuprous iodide (0.29 g) and triethylamine (4.55 g) were added to 22 g of 1,4-dibromobenzene at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.70 g) was added to the reaction mixture, and the mixture was heated to 70° C. 4-Ethynylaniline (4.68 g) was dissolved in degassed 1,4-dichlorobenzene. (20 g) and then slowly added the solution to the reaction mixture via an addition funnel. After the addition was complete, the reaction mixture was stirred at 70 ° C under nitrogen overnight. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by column chromatography to obtain 1.5 g (36% yield) of 1,3,5-tris((4-aminophenyl)ethynyl)benzene (Compound I4) as a yellow solid. The reaction is shown in the following reaction scheme.

Reaction Scheme 5

Example 6. 1,3,5-Tribromobenzene (15.0 g) was added to 40.0 g of 1,4-dibromobenzene at room temperature. to produce a clear solution. Triethylamine (14.5 g) and cuprous iodide (0.91 g) were added to the reaction mixture. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (1.00 g) was added to the reaction mixture. Next, 22.9 g of 4-fluorophenylacetylene was slowly added to the reaction mixture via an addition funnel. After the addition was complete, the reaction was stirred at 55° C. under nitrogen for 24 hours. The reaction mixture was filtered and the solvent was evaporated. The residue was dissolved in heptane and filtered through a silica plug. After filtration, the solvent was removed to yield 1,3,5-tris((4-fluorophenyl)ethynyl)benzene (Compound I5) as a light yellow solid (8.0 g) (39% yield). The reaction is shown in the following reaction scheme.

Example 7. 5,5'-oxybis(1,3-dibromobenzene) (3.61 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dibromobenzene at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70° C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dihydroquinone. (17g), and then the solution was slowly added to the reaction mixture by an addition funnel. After the addition was completed, the reaction mixture was stirred at 70°C under nitrogen overnight. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by chromatography to obtain a light yellow solid. The obtained solid was then dissolved in THF (40g) under nitrogen. Lithium hydroxide monohydrate (1.26g) and water (10g) were added, and the mixture was stirred at 60°C for 1 hour. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to obtain 3.1 g (65% yield) of 5,5'-oxybis(1,3-bis((4-hydroxyphenyl)ethynyl)benzene) (Compound I6) as a light yellow solid. The reaction is shown in the following reaction scheme.

Example 8. 9,9-bis(6-(3,5-dibromophenoxy)naphthalen-2-yl)-9H-fluorene (6.85 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 25 g of 1,4-dibromophenoxy-1,2-diol at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70° C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dichloromethane. (22g), and then the solution was slowly added to the reaction mixture by an addition funnel. After the addition was completed, the reaction mixture was stirred at 70°C under nitrogen overnight. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by chromatography to obtain a light yellow solid. The obtained solid was then dissolved in THF (40g) under nitrogen. Lithium hydroxide monohydrate (1.26g) and water (10g) were added, and the mixture was stirred at 60°C for 1 hour. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to obtain 4.7 g (59% yield) of 9,9-bis(6-(3,5-bis((4-hydroxyphenyl)ethynyl)phenoxy)naphthalen-2-yl)-9H-fluorene (Compound I7) as a light yellow solid. The reaction is shown in the following reaction scheme.

Example 9. 1,3,5-Tribromobenzene (2.83 g), cuprous iodide (0.17 g) and triethylamine (4.10 g) were added to 20 g of 1,4-dibromobenzene at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.32 g) was added to the reaction mixture, and the mixture was heated to 70° C. 2-((6-ethynylnaphthalen-2-yl)oxy)tetrahydro-2H-pyran (6.81 g) was dissolved in degassed 1,4-dihydro- (13g), and then the solution was slowly added to the reaction mixture via an addition funnel. After the addition was complete, the reaction mixture was stirred at 70°C under nitrogen overnight. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by chromatography to obtain a white solid. The obtained solid was then dispersed in MeOH (54g) under nitrogen. 12N HCl (4.5g) and water (54g) were added, and the mixture was refluxed at 60°C overnight. The reaction mixture was then cooled to room temperature, and the solvent was removed under vacuum. The residue was diluted with ethyl acetate, and the organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to give 1.1 g (21% yield) of 1,3,5-tris((2-hydroxynaphthyl-6-ethynyl)benzene (Compound I8) as a white solid. The reaction is shown in the following reaction scheme.

Compound I2 (6.0 g) was stirred in 46 g of anhydrous DMF at room temperature for 15 minutes. The mixture was heated to 30°C and then 10.34 g _{of K2CO3} was added. The reaction was then heated to 50°C and 8.63 g of bromopropyne (80% in toluene) solution was added dropwise via an additional funnel. The reaction mixture was heated at 50°C for 24 hours. The reaction was then cooled to room temperature and filtered to remove most of _{the K2CO3} . The organic phase was precipitated into 2 L of water and stirred at room temperature for 0.5 hours. The precipitated polymer was collected by filtration and dried under vacuum at 35°C for 1 day to obtain a solid (17.8 g).

Comparative Example 1. 1,3,5-tris(4-bromophenyl)benzene (4.05 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dibromophenyl at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70° C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dihydroquinone. (14g), and then the solution was slowly added to the reaction mixture by an addition funnel. After the addition was completed, the reaction mixture was stirred at 70°C under nitrogen overnight. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by chromatography to obtain a light yellow solid. The obtained solid was then dissolved in THF (35g) under nitrogen. Lithium hydroxide monohydrate (0.94g) and water (8g) were added, and the mixture was stirred at 60°C for 1 hour. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to give 2.2 g (44% yield) of 1,3,5-tris((4-(4-hydroxyphenyl)ethynyl)phenyl)benzene (Comparative 1) as a light yellow solid. The reaction is shown in the following reaction scheme.

Reaction Scheme 10

Example 10. Solubility was evaluated by mixing the compounds of the present invention at 5% solids with each of PGME and PGMEA. The mixtures were inspected visually and using a turbidity meter (Orbeco-Hellige). If the turbidity value was less than 1, the compound was rated as soluble ("S"), and if the turbidity value was greater than 1, it was rated as non-soluble ("NS"). The results are reported in Table 1. As can be seen from the data, the compounds of the present invention and the comparative compound were soluble in each of PGME and PGMEA.

Example 11. The thermal stability of compounds of the present invention was evaluated using a TA-Instruments thermogravimetric analyzer (TGA) Q500 under the following conditions: ramping to 700°C at 10°C/min under _N2 and ramping to 700°C at 10°C/min under air. The temperature at which the material lost 5% of its weight ("Td _5% ") is reported in Table 2.

Example 12. Measurement of Solvent Stripping Resistance as an Indicator of Film Crosslinking. Compositions of the compounds of the present invention and comparative compound 1 at 4.5% solids in a mixture of PGMEA and benzyl benzoate were prepared. Each composition was spin-coated onto an 8" (200 mm) silicon wafer using an ACT-8 Clean Track (Tokyo Electron Co.) at 1500 rpm and then baked for 60 seconds at the temperatures reported in Table 3 to form a film. The film was obtained using an OptiProbe from Therma-Wave Corporation. ^TM to measure the initial film thickness. Next, a commercial remover, OK73 (PGME/PGMEA=70/30), was applied to each film for 90 seconds, followed by a post-stripping bake step at 105°C for 60 seconds. The thickness of each film after the post-stripping bake was measured again to determine the amount of film thickness loss. The difference in film thickness before and after contact with the remover is reported in Table 3 as a percentage of the remaining film thickness. As can be seen from the data, after contact with the remover, the film formed by the compound of the present invention retained greater than 99% of its thickness, whereas the film formed by Comparative Compound 1 retained only 12% of its film thickness (i.e., it lost 88% of its thickness).

Example 13. Compositions of the present invention compound and comparative compound 1 at 4.5% solids in a mixture of PGMEA and benzyl benzoate were prepared. Each composition was spin-coated onto an 8" (200 mm) silicon wafer at 1500 rpm using an ACT-8 Clean Track (Tokyo Electron Co.) and then baked for 60 seconds at the temperature specified in Table 4 to form a cured film. Optical constants were measured at 193 nm using a Vacuum Ultra-Violet Variable Angle Ellipsometer (VUV-VASE, Woollam Co.) and are reported in Table 4.

Example 14. The compounds of the present invention were evaluated to determine their gapfill properties. Gapfill templates were created at CNSE Nano-FAB (Albany, NY). The templates had a _SiO2 film thickness of 100 nm and various spacings and patterns. Before coating the samples with the compositions of the present invention, the template samples were baked at 150°C for 60 seconds as a dehydration bake. Each coating composition (4.5% solids in a mixture of PGMEA, benzyl benzoate, and PolyFox PF656) was coated on the template samples using an ACT-8 Clean Track (Tokyo Electron Co., Ltd.) spin coater and a spin rate of 1500 rpm +/- 200 rpm. The target film thickness after curing was 100 nm, and the component dilutions were adjusted accordingly to approximately achieve the target film thickness after curing. The films were cured by placing the wafer on a hot plate at the temperature determined in Table 5 for 60 seconds. Cross-sectional scanning electron microscopy (SEM) images of the coated samples were collected using a Hitachi S4800 SEM (from Hitachi High Technologies). The planarization quality of the film was obtained from the SEM images by measuring the thickness difference (ΔFT) between the dense trenches and the open areas of the film using Hitachi offline CD measurement software or CDM software. Films with ΔFT < 20 nm were considered to have "good" planarization and films with ΔFT > 20 nm were considered to have "poor" planarization. Gap filling was evaluated by visually inspecting SEM images to observe whether there were any voids or air bubbles in the trench pattern. Films with no voids in the trench pattern were considered to have "good" gap filling, and films with voids in the trench pattern were considered to have "poor" gap filling. These results are reported in Table 5.

Example 15. Compositions of the present invention's compound and comparative compound 1 in PGMEA at 4.5% solids were prepared. Each composition was spin-coated onto an 8" (200 mm) silicon wafer at 1500 rpm using an ACT-8 Clean Track (Tokyo Electron Co., Ltd.) and then baked for 60 seconds at the temperature reported in Table 6 to form a cured film. Coating quality was evaluated by visual inspection of the film, and the results are reported in Table 6.

Example 16. Each primer solution (4.5% solids in a mixture of PGMEA and benzyl benzoate) was spin-coated onto a 200 mm silicon wafer using an ACT-8 Clean Track at 1500 rpm, with a target film thickness of 100 nm after curing. The pristine silicon wafer was inverted on top of the coated wafer with three (2 mm) spacers on the edge. The wafer stack was baked on a hot plate (with the coated wafer on the bottom) at the temperature specified in Table 7 for 60 seconds. The top wafer was inspected for haze (indicating sublimation) and defects using an SP2 defect tool with 500 nm sensitivity (from KLA-Tencor Corporation). As can be seen from the data in Table 7, comparative compound 1 gives significantly higher defect counts and defect densities than compound I2 of the present invention.

Claims (9)

A method for manufacturing an electronic device, comprising: (a) providing an electronic device substrate; (b) coating a coating composition comprising one or more curable compounds on a surface of the electronic device substrate, wherein the one or more curable compounds comprise an aromatic nucleus selected from a C _5-6 aromatic ring and a C _9-30 fused aromatic ring system and three or more substituents having formula (1) wherein at least two substituents having formula (1) are attached to the aromatic nucleus; and wherein Ar ¹ is an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Z is selected from the following substituents: OR ¹ , protected hydroxyl, carboxyl, protected carboxyl, SR ¹ , protected thiol, -OC(=O)-C _1-6 -alkyl, halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, and C _5-30 aryl; each R ² is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to 4; and * represents a point of attachment to the aromatic nucleus; provided that the substituents of formula (1) are not adjacent to each other on the same ring of the aromatic nucleus; (c) curing the layer of the curable compound to form an underlayer; (d) coating a photoresist layer on the underlayer; (e) exposing the photoresist layer to actinic radiation through a mask; (f) developing the exposed photoresist layer to form an anti-etching pattern; and (g) transferring the pattern to the underlayer to expose a portion of the electronic device substrate. The method as described in claim 1 further comprises the steps of patterning the substrate and then removing the patterned bottom layer. The method as described in claim 1 further comprises the step of coating one or more of a silicon-containing layer, an organic anti-reflective coating layer, and a combination thereof on the base layer before step (d). The method as described in claim 3 further comprises, after step (f) and before step (g), a step of transferring the pattern onto one or more of the silicon-containing layer, the organic anti-reflective coating, and a combination thereof. The method of claim 1, wherein each Z is independently selected from OR ¹ , a protected hydroxyl group, a carboxyl group, a protected carboxyl group, SH, fluorine, and NHR ² . The method as described in claim 1, wherein the aromatic nucleus is selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene. The method of claim 1, wherein each Ar ¹ is independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene. The method as described in claim 1, wherein the coating composition further comprises one or more of an organic solvent, a curing agent, and a surface leveling agent. An electronic device comprising an electronic device substrate having a polymer layer on a surface of the electronic device substrate, the polymer comprising one or more curable compounds as polymerized units, wherein the one or more curable compounds comprise an aromatic nucleus selected from a C _5-6 aromatic ring and a C _9-30 fused aromatic ring system and three or more substituents having formula (1) wherein at least two substituents having formula (1) are attached to the aromatic nucleus; and wherein Ar ¹ is an aromatic ring or fused aromatic ring system having 5 to 30 carbon atoms; Z is selected from the following substituents: OR ¹ , protected hydroxyl, carboxyl, protected carboxyl, SR ¹ , protected thiol, -OC(=O)-C _1-6 -alkyl, halogen, and NHR ² ; each R ¹ is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, and C _5-30 aryl; each R ² is selected from H, C _1-10 alkyl, C _2-10 unsaturated alkyl, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to 4; and * represents the point of attachment to the aromatic nucleus; provided that the substituents of formula (1) are not adjacent to each other on the same ring of the aromatic nucleus.