TWI591431B - Resist under layer film composition and patterning process - Google Patents

Description

Photoresist underlayer film material and pattern forming method

The present invention relates to a photoresist underlayer film material and a pattern forming method used for microfabrication in a manufacturing process of a semiconductor device or the like.

In recent years, wiring has been formed at a high density in order to utilize a three-dimensional gate such as an ultrafine and high-density Fin-FET (Fin-Field Effect Transistor) and simultaneously form a double damascene of a trench and a via of a copper wiring. It is a double patterning in which lithography and etching (LELE: Litho-Etch-Litho-Etch) is repeated several times, and a material which can fill a high aspect and a high density difference is required. By filling the height difference, the surface of the film is flattened, and the focus of the lithography can be made small, and even when the focus is narrow, the pattern can be patterned with sufficient tolerance.

As a method of flattening the high and low difference substrates, a method of spin coating is generally employed. It is also possible to form an amorphous carbon film by CVD (Chemical Vapor Deposition) and to fill in the height difference. However, since irregularities appear on the surface, it is necessary to cut the surface of the film by CMP (Chemical Mechanical Polishing) to planarize it, which may result in high processing cost. Disadvantages. Further, when the amorphous carbon film formed by the CVD method has an ultra-fine height difference of a pitch of 50 nm or less, voids may occur at the bottom of the step, and there is a problem that it cannot be filled. The ultra-fine height difference of 50 nm or less pitch can be filled by spin coating a material containing a large amount of low molecular weight.

Due to the immersion lithography, the angle between the photoresist and the light incident on the underlying layer becomes small, and the substrate reflection increases. In order to suppress reflection of the substrate, it is effective to make the antireflection film of the lower layer of the photoresist a multilayer film system. a carbon film having a high carbon density (a photoresist underlayer film), a photoreceptor interlayer film containing ruthenium thereon, and a three-layer structure (three layers) on which a photoresist upper film is formed, because hydrocarbons can be used The two layers of the film and the ruthenium-containing interlayer film prevent the substrate from being reflected, so that the application thereof is rapidly expanded with the use of the immersion lithography.

The function of the underlayer film of the photoresist is required to achieve the landfill planarization property by spin coating, the high dry etching resistance when the substrate is dry-etched, and the optimum optical characteristics for obtaining a high anti-reflection effect.

Further, the photoresist underlayer film sometimes requires high heat resistance. The reason is that when p-Si, SiN, SiON, TiN, ZrO ₂ , HfO ₂ or the like is formed as a hard mask layer on the underlayer film of the photoresist, the formation temperature of the films exceeds 300 ° C.

The bis-naphthol compound and its novolak resin described in Patent Document 1, the bis-naphthol quinone and its novolac resin described in Patent Document 2, and the naphthalene described in Patent Document 3 are exemplified. A novolac resin of phenolphthalein and a novolac resin of naphthofluorescein described in Patent Document 4.

Further, when the photoresist underlayer film is formed, the fugitive gas generated during baking becomes a problem. When the fugitive gas component adheres to the top plate of the hot plate and falls onto the wafer, it becomes a defect. In order to improve the filling property of the high and low difference substrates, it is effective to add a monomer component (low molecular weight component) as a photoresist underlayer material, but if the amount of the monomer component is increased, the amount of fugitive gas in high temperature baking increases. . That is, if the landfill property is improved, the fugitive gas is reduced, and the trade-off relationship is required, and the photoresist underlayer film material capable of breaking the trade-off relationship is required. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5, 336, 306 [Patent Document 3] Japanese Patent Laid-Open Publication No. JP-A No. Hei.

[Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object of the invention is to provide a photoresist underlayer film material which is excellent in landfill characteristics, has little occurrence of fugitive gas, and is excellent in dry etching resistance and heat resistance. [How to solve the problem]

In order to solve the above problems, the present invention provides a photoresist underlayer film material, a novolak resin having a repeating unit represented by the following formula (1), and a novolak resin having a repeating unit represented by the following formula (2) and the following One or both of the bisnaphthol derivatives represented by the formula (3). 【化1】 [Chemical 2] In the formula, R ¹ and R ^{2 each} represent a hydrogen atom, or may have a hydroxyl group, alkoxy group, a fluorenyl group, a fluorenylene group, a fluorenyl group, or an ester bond having a linear number of 1 to 10 carbon atoms, a branched form, or a cyclic alkyl group, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, which may have a fluorine atom, and all of R ¹ and all More than 10% of the total number of R ² is a group having at least one fluorine atom. R ³ , R ⁴ , R ¹¹ and R ¹² are any of a hydrogen atom, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms, or may have a hydroxyl group, an alkoxy group, a decyloxy group, an ether group, or The thioether group has a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R ¹⁸ and R ¹⁹ are the same groups as those of R ³ , R ⁴ , R ¹¹ and R ¹² or a halogen atom. R ⁵ , R ⁶ , R ¹³ , R ¹⁴ , R ²⁰ and R ²¹ are a hydrogen atom or an ether bond formed by bonding R ⁵ and R ⁶ , R ¹³ and R ¹⁴ , and R ²⁰ and R ²¹ . R ⁷ and R ¹⁵ are each a hydrogen atom, or may have a hydroxyl group, an alkoxy group, a decyloxy group, an ether group, a thioether group, a chloro group, or a nitro group having 1 to 6 carbon atoms, and a carbon number of 2~ An alkenyl group of 10 or an aryl group having 6 to 10 carbon atoms. R ⁹ , R ¹⁰ , R ¹⁶ and R ¹⁷ are any of a hydrogen atom, an acid labile group, and a glycidyl group, or a linear, branched or cyclic alkane having a carbon number of 1 to 10. A group, a fluorenyl group, or an alkoxycarbonyl group. X ₁ , X ₂ and X ₃ may be a single bond, or may have a linear, branched or cyclic divalent hydrocarbon group having a hydroxyl group, a carboxyl group, an ether group or a lactone ring of 1 to 38 carbon atoms. In the case where X ₁ is a divalent hydrocarbon group, R ⁵ and R ⁶ may also be an ether bond formed by bonding with a carbon atom in X ₁ , and X ₂ is a divalent hydrocarbon group, and R ¹³ and R ¹⁴ may also be and X. _{In the case} where the carbon atom in ₂ is bonded to an ether bond, and X ₃ is a divalent hydrocarbon group, R ²⁰ and R ²¹ may also be an ether bond formed by bonding with a carbon atom in X ₃ . a, b, c, d, g, h, i, j, k, l, m, and n are 1 or 2.

In the case of such a photoresist underlayer film material, the landfill property is good, the generation of the fugitive gas is small, and the dry etching resistance and the heat resistance are excellent.

In addition, the photoresist underlayer film material preferably contains a novolac resin having a repeating unit represented by the above formula (1), a novolac resin having a repeating unit represented by the above formula (2), and the above formula (3). The bisnaphthol derivative represented by the formula is preferred.

As described above, the novolac resin having a repeating unit represented by the formula (1), the novolac resin having a repeating unit represented by the formula (2), and the bisphtholphenol derivative represented by the formula (3) are simultaneously contained. The improvement of the landfill characteristics and the reduction of the fugitive gas can be achieved with a good balance.

In addition, in the novolak resin having a repeating unit represented by the following general formula (1), it is preferred to contain one or more selected from the group consisting of the following general formulae (4)-1 to (4)-5 as the above formula. R ¹ and/or R ^{2 in} (1) are preferred. [化3] In the formula, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁰ is a hydrogen atom, a methyl group, an ethyl fluorenyl group, or a trifluoroethane group. Rf is a fluorine atom or a fluorine atom having at least one or more fluorine atoms, and may further have a linear or branched or cyclic alkyl group having 1 to 9 carbon atoms or a carbon number of 2 to 9 or more. 8 alkenyl group, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms, or alkoxy group having 1 to 10 carbon atoms. R ²² is a hydrogen atom, a methyl group, or an ethyl group. R ²³ and R ²⁴ are a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

By containing such a group, the amount of fugitive gas generated from the photoresist underlayer film material can be further reduced.

In addition, it is preferable that the photoresist lower layer film material contains a novolak resin having a repeating unit represented by the above formula (2), and 1 part by mass of the novolak resin having a repeating unit represented by the above formula (1). The bisnaphthol derivative represented by the above formula (3) is preferably 5 to 100 parts by mass in total.

With such a ratio, the improvement of the landfill property and the reduction of the fugitive gas can be achieved with particularly good balance.

Further, in this case, it is preferable that the photoresist underlayer film material further contains an organic solvent.

In this way, the concentration and viscosity of the photoresist underlayer film material can be adjusted, and the compatibility can be improved.

Further, in this case, it is preferable that the photoresist underlayer film material further contains an acid generator and/or a crosslinking agent.

In this way, the cross-linking hardening reaction of the photoresist underlayer film material can be promoted.

Moreover, the present invention provides a pattern forming method for forming a pattern of a photoresist by using the photoresist underlayer film material on a substrate to be processed by using a lithography method to form a pattern on a substrate, and using a germanium film on the photoresist under the photoresist layer. Forming a ruthenium-containing interlayer film on the interlayer film material, forming a photoresist upper film on the ruthenium-containing interlayer film, exposing the pattern circuit region of the photoresist upper film, and developing the light Forming a photoresist pattern on the upper film, and using the photoresist upper film having the photoresist pattern as a mask to transfer the pattern on the ruthenium-containing interlayer film by etching, and the ruthenium-containing interlayer film of the transferred pattern The pattern is transferred to the photoresist underlayer film by etching as a mask, and the patterned photoresist underlayer film is used as a mask to transfer the pattern onto the substrate to be processed by etching.

Moreover, the present invention provides a pattern forming method for forming a pattern on a substrate by using a lithography method to form a photoresist underlayer film on the substrate to be processed, and forming a photoresist underlayer film on the underlayer film. In the middle of an inorganic hard mask in a tantalum oxide film, a tantalum nitride film, a tantalum oxide film, a tantalum carbonized film, a polycrystalline tantalum film, a titanium nitride film, a titanium oxide film, a titanium carbide film, a zirconium oxide film, or a tantalum oxide film a film, a photoresist upper film is formed on the inorganic hard mask interlayer film, and the patterned circuit region of the photoresist upper film is exposed, and developed to form a photoresist on the photoresist upper film. a pattern, the photoresist upper layer film having the photoresist pattern is formed as a mask, and the pattern is transferred to the inorganic hard mask interlayer film by etching, and the inorganic hard mask interlayer film of the transferred pattern is used as a mask The mask is transferred to the photoresist underlayer film by etching, and the patterned photoresist underlayer film is used as a mask to transfer the pattern onto the substrate to be processed by etching.

Moreover, the present invention provides a pattern forming method for forming a pattern on a substrate by using a lithography method to form a photoresist underlayer film on the substrate to be processed, and forming a photoresist underlayer film on the underlayer film. In the middle of an inorganic hard mask in a tantalum oxide film, a tantalum nitride film, a tantalum oxide film, a tantalum carbonized film, a polycrystalline tantalum film, a titanium nitride film, a titanium oxide film, a titanium carbide film, a zirconium oxide film, or a tantalum oxide film a layer film, an organic anti-reflection film is formed on the inorganic hard mask interlayer film, and a photoresist upper layer film is formed on the organic anti-reflection film to form a photoresist film, and the photoresist layer is obtained. After exposing the pattern circuit region of the upper film, developing a photoresist pattern on the photoresist upper layer film, and using the photoresist upper photoresist film having the photoresist pattern as a mask to transfer the pattern to the organic anti-reflection by etching a film and an inorganic hard mask interlayer film, the inorganic hard mask interlayer film of the transferred pattern is used as a mask, and the pattern is transferred to the photoresist underlayer film by etching, and the transferred pattern light is further Blocking the underlying film as a mask The pattern is transferred to the substrate to be processed by etching.

Moreover, the present invention provides a pattern forming method for forming a pattern on a substrate by using a lithography method to form a photoresist underlayer film on the substrate to be processed, and forming a photoresist underlayer film on the underlayer film. In the middle of an inorganic hard mask in a tantalum oxide film, a tantalum nitride film, a tantalum oxide film, a tantalum carbonized film, a polycrystalline tantalum film, a titanium nitride film, a titanium oxide film, a titanium carbide film, a zirconium oxide film, or a tantalum oxide film a film on which a hydrocarbon film material is spin-coated on the inorganic hard mask interlayer film to form a hydrocarbon film, and a ruthenium-containing interlayer film material is formed on the hydrocarbon film to form a ruthenium-containing interlayer film on the ruthenium-containing interlayer film Forming a photoresist upper layer film by using a photoresist upper layer film material to obtain a five-layer photoresist film, exposing the pattern circuit region of the photoresist upper layer film, and developing a photoresist pattern on the photoresist upper layer film to form a photoresist pattern. The photoresist upper layer film having the photoresist pattern is formed as a mask, and the pattern is transferred to the foregoing ruthenium-containing interlayer film by etching, and the ruthenium-containing interlayer film of the transferred pattern is used as a mask to transfer the pattern by etching. In the aforementioned hydrocarbon film, the transferred pattern The hydrocarbon film is used as an etching mask to transfer the pattern to the inorganic hard mask interlayer film by etching, and the inorganic hard mask interlayer film of the transferred pattern is used as a mask to etch the pattern by etching. The underlayer film is printed on the photoresist, and the photoresist film of the transferred pattern is used as a mask to transfer the pattern onto the substrate to be processed by etching.

By using a photoresist underlayer film material of the present invention which is excellent in landfill properties, has little occurrence of fugitive gas, and is excellent in dry etching resistance and heat resistance, it is possible to greatly reduce defects in microfabrication in a manufacturing process such as a semiconductor device.

Moreover, in this case, it is preferable that the inorganic hard mask intermediate layer film is formed by any of a CVD method, an ALD method, and a sputtering method.

If such a method is used, it is suitable to form an inorganic hard mask interlayer film.

Further, in this case, as the photoresist upper layer film material, the above-mentioned photoresist underlayer film which is formed without using a germanium-containing intermediate layer film or the inorganic hard mask interlayer film as a mask is used. The etching is preferably carried out using an etching gas containing oxygen or hydrogen.

In this way, the removal of the photoresist upper layer film and the etching of the photoresist underlayer film can be simultaneously performed. [Effects of the Invention]

As described above, in the photoresist underlayer film material of the present invention, the barrier property is good and the generation of the fugitive gas is small, and the photoresist underlayer film excellent in dry etching resistance and heat resistance can be formed. Moreover, the film thickness uniformity of the photoresist underlayer film can also be improved. Moreover, in the pattern forming method of the present invention using such a photoresist underlayer film material, the substrate can be sufficiently filled and the generation of the fugitive gas can be suppressed, so that the defects in the microfabrication of the manufacturing steps such as the semiconductor device can be greatly reduced. Therefore, the photoresist underlayer film material and the pattern forming method of the present invention are particularly suitable for filling a fine trench pattern of a common pitch, and suppressing the occurrence of fugitive gas during baking of the photoresist underlying film which is a source of defects. Manufacturing of three-dimensional devices such as FETs.

As described above, it is necessary to develop a photoresist underlayer film material which has good landfill characteristics and a small occurrence of fugitive gas. In order to improve the landfill characteristics, it is effective to add a monomer component to the film material under the photoresist. However, if a monomer component is added, the monomer component evaporates into a fugitive gas during baking and adheres to the top plate of the hot plate. If it has been attached to the top plate, it will become the cause of the defect, so the improvement of the landfill property is in a trade-off relationship with the prevention performance of the fugitive gas. In order to construct a photoresist underlayer film material which is excellent in landfill characteristics and has little occurrence of fugitive gas, the inventors of the present invention have intensively studied and found that there are many monomer components effective for landfill on the high and low substrate side, and there are many surface components on the surface layer. The composition of the photoresist underlayer film having a large amount of polymer component has an effect of improving both the improvement of the landfill property and the occurrence of the fugitive gas.

The present inventors have further studied and found that a novolac resin having a repeating unit represented by the formula (1), a novolak resin having a repeating unit represented by the formula (2), and the following formula (3) The photoresist underlayer film material obtained by one or both of the bisnaphthol derivatives can improve the landfill property and can suppress the generation of fugitive gas even when a large amount of the monomer component is contained, and the present invention has been completed.

That is, the present invention is a photoresist underlayer film material, a novolak resin having a repeating unit represented by the following formula (1), and a novolak resin having a repeating unit represented by the following formula (2) and the following formula (3) Or one or both of the bisphthol derivatives. 【化4】 【化5】 In the formula, R ¹ and R ^{2 each} represent a hydrogen atom or a linear, branched or branched carbon number of 1 to 10 which may have a hydroxyl group, an alkoxy group, a fluorenyl group, a fluorenylene group, a fluorenyl group or an ester bond. a cyclic alkyl group, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, which may have a fluorine atom, and all of R ¹ and all More than 10% of the total number of R ² is a group having at least one or more fluorine atoms. R ³ , R ⁴ , R ¹¹ and R ¹² are any of a hydrogen atom, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms, or may have a hydroxyl group, an alkoxy group, a decyloxy group, an ether group, or sulfur. The ether group has a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R ¹⁸ and R ¹⁹ are the same or a halogen atom as R ³ , R ⁴ , R ¹¹ and R ¹² . R ⁵ , R ⁶ , R ¹³ , R ¹⁴ , R ²⁰ and R ²¹ are a hydrogen atom or an ether bond formed by bonding R ⁵ and R ⁶ , R ¹³ and R ¹⁴ , and R ²⁰ and R ²¹ . R ⁷ and R ¹⁵ are each a hydrogen atom, or may have a hydroxyl group, an alkoxy group, a decyloxy group, an ether group, a thioether group, a chloro group, or a nitro group having 1 to 6 carbon atoms, and a carbon number of 2~ An alkenyl group of 10 or an aryl group having 6 to 10 carbon atoms. R ⁹ , R ¹⁰ , R ¹⁶ and R ¹⁷ are any of a hydrogen atom, an acid labile group, and a glycidyl group, or a linear, branched or cyclic alkyl group having a carbon number of 1 to 10. Mercapto, or alkoxycarbonyl. X ₁ , X ₂ and X ₃ may be a single bond or may have a linear, branched or cyclic divalent hydrocarbon group having a hydroxyl group, a carboxyl group, an ether group or a lactone ring of 1 to 38 carbon atoms. In the case where X ₁ is a divalent hydrocarbon group, R ⁵ and R ⁶ may also be an ether bond formed by bonding with a carbon atom in X ₁ , and X ₂ is a divalent hydrocarbon group, and R ¹³ and R ¹⁴ may also be and X. _{In the case} where the carbon atom in ₂ is bonded to an ether bond, and X ₃ is a divalent hydrocarbon group, R ²⁰ and R ²¹ may also be an ether bond formed by bonding with a carbon atom in X ₃ . a, b, c, d, g, h, i, j, k, l, m, and n are 1 or 2. )

The invention is described in detail below, but the invention is not limited thereto.

<Photoresist underlayer film material> The photoresist underlayer film material of the present invention, the novolak resin having the repeating unit represented by the above formula (1), and the above-mentioned novolac resin having a repeating unit represented by the formula (2) and the above One or both of the bisnaphthol derivatives represented by the formula (3). In the case of such a photoresist underlayer film material, in the spin coating, a novolac resin having a repeating unit represented by the above formula (1) and having a fluorine atom of a predetermined amount or more covers the surface of the film. By the presence of the layer of the fluorine-containing atom, even if the photoresist underlayer material containing the monomer component for improving the landfill property is baked at a high temperature, generation of the fugitive gas can be suppressed.

Further, by adding the bisnaphthol derivative represented by the above formula (3) as a monomer component, the landfill characteristics of the high and low difference substrates are further improved. In general, due to the addition of such a monomer component, the generation of the fugitive gas during baking may increase, but the photoresist underlayer film material of the present invention, as described above, has a repeating unit represented by the above formula (1) and has a predetermined The novolac resin having a fluorine atom or more is moved to the surface of the underlayer film of the photoresist during coating, and a resin layer containing a large amount of the resin is formed on the surface of the film under the photoresist. The surface of the photoresist underlayer film is covered with a resin layer of a bis-naphthol novolak resin having a fluorine atom, and even if it contains a monomer component, the monomer component can be suppressed from evaporating from the surface of the photoresist under the photoresist to a fugitive gas during baking. . This is an effective means of suppressing the occurrence of fugitive gases and improving the landfill characteristics. Further, by increasing the blending amount of the monomer component and using a small molecular weight, the landfill characteristics can be further improved.

Further, in order to prevent the ruthenium-containing interlayer film (SOG film) on the photoresist underlayer film from being peeled off by the hydrofluoric acid aqueous solution, the TiN film and the BPSG (Boron Phosphorus Silicate Glass) film are made of an alkaline stripping solution SC (Standard Clean). When the film is peeled off from the surface of the photoresist under the photoresist, it is effective to form a layer of a fluorine-containing atom in the surface layer of the film under the photoresist. The reason is that the water repellency of fluorine prevents the hydrofluoric acid aqueous solution and SC1 from penetrating into the underlayer of the photoresist.

Further, since the naphthalene ring has a small absorption at a wavelength of 193 nm of the ArF excimer laser, it is possible to suppress reflection from the underlayer film of the photoresist and to condense the aromatic ring, so that dry etching resistance is high.

Further, on the photoresist underlayer film, not only the ruthenium-containing intermediate layer film formed by spin coating but also an inorganic film which is used as an anti-reflection film and a hard mask, such as a SiON film or a TiN film, may be formed. The SiON film is excellent not only in anti-reflection effect but also in dry etching resistance higher than that of the antimony-containing interlayer film formed by spin coating. Further, the TiN film is not only resistant to dry etching, but also has the advantage of being able to be peeled off by an alkaline stripping liquid such as SC1. When the SiON film or the TiN film is formed, the substrate temperature is required to be 300° C. or higher. Therefore, if the film is a low-resistance film having a good dry etching resistance and insufficient heat resistance, a method of forming such an inorganic film cannot be employed. On the other hand, the photoresist underlayer film formed using the photoresist underlayer film material of the present invention is also preferably used because it has sufficient heat resistance to form an inorganic film which is heated to 300 ° C or higher.

Further, for example, when a lower layer film solution is applied onto a high-low-difference substrate on which a hole pattern has been formed, a void is formed at the bottom of the hole immediately after coating, and the bottom portion of the hole is filled after baking at a high temperature. It is shown that the resin flows during baking, and the resin is filled in the bottom of the hole, and the void becomes a void and moves in the direction of the surface of the lower layer film and disappears.

Usually, if the resin-containing solution is rotated at a low speed of 500 rpm or less and then baked to evaporate the solvent, it will become a non-uniform film thickness. On the other hand, when spin coating is performed at a rotation of 700 rpm or more, the film thickness is not uneven. The phenomenon that the baking after low-speed rotary spin coating becomes uneven in film thickness is due to the Marangoni effect.

The same Marangoni effect is believed to occur also during high temperature baking of the underlying film resin. When a resin material composed only of a single body is used, the phenomenon of pullback from the edge of the wafer and uneven film thickness after application can be explained by the Marangoni effect. The surface tension of the high-temperature substance is low, and it moves to the surface of the film and the temperature is lowered, which causes the surface tension to become high. In general, a material having a low surface tension is coated on the surface of the film, and the energy is relatively stable, but the Marangoni effect is reversed, the energy becomes unstable, and the film thickness is uneven.

In contrast, the photoresist underlayer film material of the present invention contains a material having a low surface tension of fluorine (i.e., a novolac resin having a repeating unit represented by the formula (1)), and the surface of the film is covered with a material having a low surface tension. Can eliminate the instability caused by the Marangoni effect. That is, the film thickness uniformity can also be improved.

The photoresist underlayer film material of the present invention, as described above, requires a novolak resin having a repeating unit represented by the formula (1), and contains a novolak resin having a repeating unit represented by the formula (2) and a formula (3) Any of the bisphthol phenol derivatives, or both. Further, a novolac resin having a repeating unit represented by the formula (1) and a novolac resin having a repeating unit represented by the formula (2) may be contained, and the bisphthylphenol derivative represented by the formula (3) may not be contained. A novolak resin which may contain a novolac resin represented by the formula (1) and a bis-naphthol derivative represented by the formula (3), and which does not contain a repeating unit represented by the formula (2), may also contain The novolac resin having a repeating unit represented by the formula (1) and the novolac resin represented by the formula (2) and the bisphthylphenol derivative represented by the formula (3) are all three kinds.

Among them, the novolac resin having a repeating unit represented by the formula (1) and the novolac resin having a repeating unit represented by the formula (2) and the bis-naphthol derivative represented by the formula (3) are all contained in all three. Preferably.

As described above, all of the novolac resin having a repeating unit represented by the formula (1), a novolac resin having a repeating unit represented by the formula (2), and a bis-naphthol derivative represented by the formula (3) It can improve the landfill characteristics and reduce the fugitive gas with better balance.

The linear, branched or cyclic divalent hydrocarbon group having 1 to 38 carbon atoms represented by X ₁ , X ₂ and X ₃ in the above formula, more specifically, a carbon number of 1 to 38 A linear, branched, or cyclic alkyl group, an aryl group, and an aralkyl group.

The bisnaphthol derivative which can be used as a monomer for obtaining the novolac resin having the repeating unit represented by the above formulas (1) and (2) can be specifically exemplified below. Further, the following may be used as the bisnaphthol derivative represented by the above formula (3).

【化6】

【化7】

【化8】

【化9】

【化10】

【化11】

【化12】

【化13】

【化14】

【化15】

Here, R ²⁵ represents R ¹ , R ⁹ and R ¹⁶ , and R ²⁶ represents R ² , R ¹⁰ and R ¹⁷ . Further, a bis naphthol derivative obtained by obtaining a novolak resin having a repeating unit represented by the above formulas (1) and (2), and a bisnaphthol represented by the above formula (3) for improving a landfill property Derivatives may be the same or different.

Further, when R ⁹ , R ¹⁰ , R ¹⁶ and R ¹⁷ are an acid labile group, they may be the same or different, and examples thereof include a group represented by the following formulas (A-1) to (A-3). 【化16】

In the above formula (A-1), R ^L30 is a carbon number of 4 to 20, preferably a tertiary alkyl group of 4 to 15, a trialkylsulfonyl group having an alkyl group having 1 to 6 carbon atoms, and a carbon number of 4~ a pendant oxyalkyl group of 20 or a substituent represented by the above formula (A-3). Specific examples of the tertiary alkyl group include a third butyl group, a third pentyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, and a 1-ethyl ring. Hexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, etc., as trialkylsulfonium Specific examples thereof include a trimethylsulfonyl group, a triethylsulfonyl group, and a dimethyl-tert-butylfluorenyl group. Specific examples of the pendant oxyalkyl group include a 3-oxocyclohexyl group and 4 -methyl-2-oxooxy Alkyl-4-yl, 5-methyl-2-oxooxytetrahydrofuran-5-yl and the like. A1 is an integer from 0 to 6.

The acid restless group represented by the above formula (A-1) specifically includes a third butoxycarbonyl group, a third butoxycarbonylmethyl group, a third pentyloxycarbonyl group, and a third pentyloxycarbonyl group. 1,1,1-diethylpropoxycarbonyl, 1,1-diethylpropoxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonyl Methyl, 2-tetrahydrofuranyloxycarbonylmethyl and the like.

Further, examples of the tertiary alkyl group include a substituent represented by the following formula (A-1)-1 to (A-1)-10. 【化17】

Here, R ^L37 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 17 carbon atoms which is the same or different from each other, and R ^L38 is a hydrogen atom or a carbon number of 1~ A linear, branched, or cyclic alkyl group of 10. Further, R ^L39 is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms which are the same or different from each other. A1 is the same as above.

In the above formula (A-2), R ^L31 and R ^L32 are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group and the like. R ^L33 is a monovalent hydrocarbon group having a carbon number of 1 to 18, preferably a carbon number of 1 to 10, which may have a hetero atom such as an oxygen atom, particularly a linear, branched or cyclic alkyl group, and the like. One of the atoms is substituted with a hydroxyl group, an alkoxy group, a pendant oxy group, an amine group, an alkylamine group or the like, and specific examples thereof include the following substituted alkyl groups. 【化18】

R ^L31 and R ^L32 , R ^L31 and R ^L33 , R ^L32 and R ^L33 may also be bonded and form a ring together with the carbon atom to which they are bonded, and R ^L31 , R ^L32 and R ^L33 each forming a ring are involved in ring formation. It is a linear or branched alkyl group having a carbon number of 1 to 18, preferably a carbon number of 1 to 10. The ring should preferably have a carbon number of 3 to 10, and particularly preferably a carbon number of 4 to 10.

Among the acid labile groups represented by the above formula (A-2), those having a linear or branched shape include the following formulas (A-2)-1 to (A-2)-69.

【化19】

【化20】

【化21】

【化22】

In the acid labile group represented by the above formula (A-2), the ring may be exemplified by tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl or 2-methyltetra Hydroperan-2-yl and the like.

Further, it is also possible to use the crosslinked acetal group represented by the following formula (A-2a) or (A-2b) to carry out the intermolecular reaction of the above-mentioned novolac resin having a repeating unit represented by the formula (2) as a base resin. Or intramolecular crosslinks. 【化23】

In the above formula, R ^L40 and R ^L41 are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or R ^L40 may be bonded to R ^L41 and bonded thereto. The carbon atoms together form a ring. When a ring is formed, R ^L40 and R ^L41 are a linear or branched alkyl group having 1 to 8 carbon atoms. R ^L42 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. B1 and D1 are 0 or 1 to 10, preferably 0 or an integer of 1 to 5. Further, C1 is 1 to 7, preferably an integer of 1 to 3.

In the above formula, A is a (C1+1)-valent aliphatic or alicyclic saturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group having a carbon number of 1 to 50, and a hetero atom may be inserted in the groups. A part of the hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group, or a fluorine atom. Further, A is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group, an alkanetriyl group, an alkanetetrayl group or a aryl group having 6 to 30 carbon atoms. These groups may also have heteroatoms inserted. Further, a part of the hydrogen atoms bonded to the carbon atoms of the groups may be substituted with a hydroxyl group, a carboxyl group, a fluorenyl group or a halogen atom. Further, B is a group represented by -CO-O-, -NHCO-O-, or -NHCONH-.

Specific examples of the crosslinked acetal group represented by the above formulas (A-2a) and (A-2b) include the following formulas (A-2) to 70-(A-2)-77. 【化24】

Then, in the above formula (A-3), R ^L34 , R ^L35 and R ^L36 are a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a carbon number of 2 to 20 A linear, branched, or cyclic alkenyl group. Further, the groups may also contain a hetero atom such as oxygen, sulfur, nitrogen or fluorine, or may be bonded to R ^L34 and R ^L35 , R ^L34 and R ^L36 , R ^L35 and R ^L36 and the carbon atom to which they are bonded. Together, an alicyclic ring having a carbon number of 3 to 20 is formed.

Examples of the tertiary alkyl group represented by the above formula (A-3) include a third butyl group, a triethyl carvyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, and a 1-ethyl group. A cyclopentyl group, a 2-(2-methyl)adamantyl group, a 2-(2-ethyl)adamantyl group, a third pentyl group and the like.

Further, the tertiary alkyl group may specifically be represented by the following formula (A-3)-1 to (A-3)-18. 【化25】

In the above formula (A-3)-1~(A-3)-18, R ^L43 is the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or carbon number 6 ~20 phenyl and other aryl groups. R ^L44 and R ^L46 are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ^L45 is an aryl group such as a phenyl group having 6 to 20 carbon atoms.

Further, as shown by the following formulas (A-3)-19 and (A-3)-20, a divalent or higher alkyl group such as a divalent alkyl group or an ^exoaryl group may be included, and the polymer may be intramolecular or Intermolecular crosslinks. E1 is 0-8, preferably an integer of 0-6. 【化26】

Further, the novolak resin having a repeating unit represented by the above formulas (1) and (2) may be obtained by co-condensation with a monomer other than the above-described bis-naphthol derivative. Specific examples of the monomer which can be used for the co-condensation include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5- Dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-three Methylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5- Diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methyl Hydroquinone, 5-methyl resorcinol, catechol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propane Phenolic, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5 -methylphenol, gallic phenol, thymol, iso-thymol, 4,4'-(9H-茀-9-ylidene)bisphenol, 2,2'dimethyl-4,4'-(9H -茀-9-subunit) bisphenol, 2,2'diallyl-4,4'-(9H-茀-9-ylidene) Phenol, 2,2'difluoro-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'diphenyl-4,4'-(9H-fluorene-9-subunit) Bisphenol, 2,2'dimethoxy-4,4'-(9H-indol-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1')- Spirobi-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spiropyrene- 6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spiropyrene -6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spiroindole-5,5'-diol, 5,5'-dimethyl- 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spiroindole-6,6'-diol, 1,2- Dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxyl Naphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, 6-methoxy-2- Naphthol, 3-methoxy-2-naphthol, 1,4-dimethoxynaphthalene, 1,5-dimethoxynaphthalene, 1,6-dimethoxynaphthalene, 1,7-dimethyl Oxynaphthalene, 1,8-Dimethoxynaphthalene, 2,3-dimethoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 3-hydroxy-naphthalene-2-carboxylic acid Methyl ester, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethyl Naphthalene, 1,6-dimethylnaphthalene, 1,7-dimethylnaphthalene, 1,8-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, 2, 7-Dimethylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 1-propylnaphthalene, 2-propylnaphthalene, 1-butylnaphthalene, 2-butylnaphthalene, 1-phenylnaphthalene, 1 -cyclohexylnaphthalene, 1-cyclopentylnaphthalene, anthracene, hydroxyanthracene, vinylnaphthalene, ethanenaphthalene, biphenyl, bisphenol, phenol, dicyclopentadiene, substituted or unsubstituted phenolphenolphthalein , phenol red, cresol phenolphthalein, cresol red, thymol phenolphthalein, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 4-trifluoromethylphenol, 2,3-difluorophenol, 2, 4-difluorophenol, 2,5-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,3,4-trifluorophenol, 2, 3,6-trifluorophenol, 3,4,5-trifluorophenol, 2-trifluoromethoxyphenol, 3-trifluoromethoxyphenol, 4-trifluoromethoxyphenol, 2-trifluoromethyl sulfur Phenolic, 3-trifluoromethylthiophenol, 4-trifluoromethylthiophenol, 2,3-bis(trifluoromethyl)phenol, 2,4-bis(trifluoromethyl)phenol, 2,5 - bis(trifluoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol, 3,4-bis(trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol, five Fluorophenol, 3-trifluoromethylphenol, 2-trifluoromethylphenol, 4-(1,1,1,3,3,3-hexafluoro-2-propanol)phenol, 3-(1,1 , 1,3,3,3-hexafluoro-2-propanol)phenol, 3,5-di(1,1,1,3,3,3-hexafluoro-2-propanol)phenol, and the like.

When a novolak resin having a repeating unit represented by the above formulas (1) and (2) is synthesized, a substituted or unsubstituted bisnaphthol derivative is added to another monomer as needed, and an aldehyde is added and carried out. The novolac is varnished to polymerize it. By the phenol aldehyde lacquering, the molecular weight is increased, and the generation of fugitive gas and fine particles due to the low molecular weight body during baking can be suppressed.

An aldehyde which can be used for the synthesis of a novolac resin having a repeating unit represented by the above formulas (1) and (2), for example, formaldehyde, three Alkane, polyoxymethylene, benzaldehyde, methoxybenzaldehyde, phenylbenzaldehyde, tritylbenzaldehyde, cyclohexylbenzaldehyde, cyclopentylbenzaldehyde, tert-butylbenzaldehyde, naphthaldehyde, hydroxynaphthaldehyde , furfural, furfural, furfural, methoxynaphthaldehyde, dimethoxynaphthaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, naphthylacetaldehyde, substituted or unsubstituted carboxynaphthalene aldehyde , α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde , m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, furancarboxaldehyde, Thiophene aldehyde and the like. Among these, especially formaldehyde is preferred.

These aldehydes may be used alone or in combination of two or more. Further, the amount of the aldehyde to be used is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per mole of the substituted or unsubstituted bisnaphthol derivative.

A catalyst can be used for the condensation reaction of the above bisnaphthol derivative with the above aldehyde. Specific examples thereof include acidic catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. The amount of the acidic catalyst used is preferably from 1 × 10 ^-5 to 5 × 10 ^-1 mol per mol of the bisnaphthol derivative.

The novolac resin having a repeating unit represented by the above formulas (1) and (2) is preferably a molecular weight of from 400 to 20,000 in terms of a weight average molecular weight. More preferably in the range of 500 to 10,000, and particularly preferably in the range of 600 to 10,000. Those with smaller molecular weight have better landfill characteristics, but they are prone to dissipate gas during baking. Therefore, it is better to optimize the viewpoint of landfill characteristics and dissipative gas generation.

In order to achieve a reduction in the landfill property and the amount of the fugitive gas, it is preferred to use the above-mentioned novolak resin of the repeating unit represented by the formula (2) in an amount of 1 part by mass based on 1 part by mass of the novolac resin having the repeating unit represented by the above formula (1). It is preferable to mix in a ratio of 50 parts by mass, and it is preferable to use the bis-naphthol derivative represented by the above formula (3) at 0 parts by mass relative to 1 part by mass of the novolac resin having the repeating unit represented by the above formula (1). A ratio of ~50 parts by mass is preferably mixed.

Further, in the photoresist underlayer film material of the present invention, it is preferred to use the above-mentioned repeating unit novolac of the formula (2) with respect to 1 part by mass of the novolac resin having the repeating unit represented by the above formula (1). The resin is preferably mixed with the bisnaphthol derivative represented by the above formula (3) in a total amount of 5 to 100 parts by mass. By such a ratio, the reduction of the fugitive gas obtained by the resin layer of the novolac resin having the repeating unit represented by the above formula (1) can be achieved with a particularly good balance, and the dinaphthalene represented by the above formula (3) Improvement in landfill characteristics due to phenolic derivatives.

Further, when a novolac resin having a repeating unit represented by the above formulas (1) and (2) is produced, the reaction solution may contain a monomer such as an unpolymerized substituted or unsubstituted bis-naphthol derivative, and A low molecular weight body such as a polymer or a trimer. Compared with naphthol derivatives, the naphthol derivative has a larger molecular weight, so it is less likely to be a fugitive gas component than a naphthol derivative. However, if it contains a large amount of unpolymerized monomer or a low molecular weight body, it may become a fugitive gas. For one reason, it is preferable to remove as much as possible from the viewpoint of considering the landfill characteristics and the reduction of the dissipative gas. When the monomer component is added in order to improve the landfill characteristics, it is preferred to remove the unpolymerized monomer or the low molecular weight body in the above manner, and it is preferred to additionally add a desired amount of the monomer component.

The photoresist underlayer film material of the present invention contains a novolak resin having a repeating unit represented by the above formula (1), and a novolak resin having the above repeating unit represented by the formula (2) and the following formula (3) One or both of the bisphthylphenol derivatives, but resins other than the novolac resins may be blended. Examples of the blendable resin include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, and 3,4-dimethylphenol. 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2 - tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5 -methyl resorcinol, catechol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4- Propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, Gallic phenol, thymol, isothymol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2 -naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. Hydroxynaphthalene, phenol phenolphthalein, phenol red, cresol phenolphthalein, cresol red, thymol phenolphthalein, methyl 3-hydroxy-naphthalene-2-carboxylate, hydrazine, hydroxy hydrazine, benzofuran, hydroxyanthracene, vinyl naphthalene A novolak resin obtained by the reaction of biphenyl, bisphenol, phenol and aldehyde. Further, a phenol compound may be used instead of dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorphedin-2-ene, α-pinene, A resin synthesized by copolymerization of β-pinene or limonene.

Further, as the monomer component, a hydroxystyrene, an alkoxystyrene, a hydroxyvinylnaphthalene or an alkoxyvinylnaphthalene may be added in addition to the bis-naphthol derivative represented by the above formula (3). A compound such as a methyl acrylate, a vinyl ether, maleic anhydride or itaconic anhydride. Further, a compound of a substituted or unsubstituted naphthol may be added.

Further, a high-carbon resin may be used in combination with the photoresist underlayer film material of the present invention. Examples of such a resin include JP-A-2004-205658, JP-A-2004-205676, JP-A-2004-205685, and 2004-271838. No. 2004-354554, the same as No. 2005-10431, the same as No. 2005-49810, the same as No. 2005-114921, the same as No. 2005-128509, the same as No. 2005-250434, the same as No. 2006-053543 Japanese Patent Publication No. 2006-227391, No. 2006-259249, No. 2006-259482, No. 2006-285095, No. 2006-293207, No. 2006-293298, and No. 2007-140461 And 2007-171895, the same as 2007-199653, the same as 2007-316282, the same as 2008-26600, the same as 2008-65303, the same as 2008-96684, the same as 2008-257188, the same The use of the photoresist underlayer film material described in the publication of the Japanese Patent Publication No. 2010-170539, the same as that of the Japanese Patent Publication No. 2010-170, pp. Resin.

Further, in the photoresist underlayer film material of the present invention, the novolac resin having the repeating unit represented by the above formula (1) preferably includes one or more selected from the group consisting of the following general formulae (4)-1 to (4)-5. The group is preferably R ¹ and/or R ² in the above formula (1). 【化27】 In the formula, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁰ is a hydrogen atom, a methyl group, an ethyl fluorenyl group, or a trifluoroethane group. Rf is a fluorine atom or a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms or a carbon number of 2 to 8 having at least one or more fluorine atoms and further having a hydroxyl group or an alkoxy group. The alkenyl group, the aryl group having 6 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, or the alkoxy group having 1 to 10 carbon atoms. R ²² is a hydrogen atom, a methyl group, or an ethyl group. R ²³ and R ²⁴ are a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

By containing such a group, the amount of fugitive gas generated from the underlying film material of the photoresist can be further reduced.

Specific examples of the group represented by the above formula (4)-1 to (4)-5 are as follows.

【化28】

【化29】

【化30】

【化31】

【化32】

【化33】

The novolac resin having the repeating unit represented by the above formula (1) is preferably 10% or more, more preferably 20% or more, and more preferably 20% or more, based on the total of all R ¹ and all R ^{2 in} the above formula (1). More than 30% is preferably selected from the group consisting of the above formula (4)-1 to (4)-5. Further, the novolac resin having the repeating unit represented by the above formula (1) may contain a plurality of groups selected from the fluorine atom in the above formula (4)-1 to (4)-5.

In addition, as a method for synthesizing the novolac resin having the repeating unit represented by the above formula (1), a bis-naphthol derivative having a fluorine-containing group of R ¹ and/or R ² may be used as a monomer, and an aldehyde may be used. A method of performing novolak reaction by a reaction or using a bis-naphthol derivative having a hydrogen atom such as R ¹ and/or R ² as a monomer, and reacting with an aldehyde to carry out novolak-forming, and obtaining a novolac resin A method of adding a fluorine-containing group, a method of substituting a hydrogen atom of a hydroxyl group possessed by a novolac resin into a fluorine-containing group, or the like.

Further, a method in which a fluorine-containing group is added to a novolak resin, for example, a method in which a hydroxyl group possessed by a novolac resin and a fluorine-containing compound having a carbon-carbon double bond are subjected to an addition reaction may be mentioned. Further, a method in which a hydrogen atom of a hydroxyl group possessed by a novolac resin is substituted with a fluorine-containing group, for example, a method in which an epoxy compound having one or more fluorine atoms, an acid anhydride, or hydrazine chloride is used is substituted.

(Organic solvent) An organic solvent can also be further used in the photoresist underlayer film material of the present invention. The organic solvent which can be used for the photoresist underlayer film material of the present invention is not particularly limited as long as it is soluble in a base resin such as the above-described novolac resin, a monomer component, and an additive such as an acid generator or a crosslinking agent to be described later. Specifically, the solvent described in paragraphs (0091) to (0092) of JP-A-2007-199653 can be added.

(Crosslinking agent) In the case of a photoresist underlayer film, it is necessary to dissolve the yttrium-containing interlayer film material or the photoresist upper layer film material when the yttrium-containing interlayer film material or the photoresist upper layer film material is distributed on the photoresist underlayer film. And the property of not mixing with the ruthenium containing interlayer film or the photoresist upper layer film. Therefore, it is preferred to add a crosslinking agent for crosslinking the coating under the coating to be crosslinked in the photoresist underlayer film material of the present invention.

The crosslinking agent which can be used in the present invention may, for example, be a melamine compound, a guanamine compound or a glycoluril compound which is substituted with at least one selected from the group consisting of a methylol group, an alkoxymethyl group and a fluorenyloxymethyl group. A urea compound, an epoxy compound, an isocyanate compound, or an azide compound, or a compound containing a double bond such as an ethylenic group or the like. They can be used as additives or can be introduced into the polymer side chains as pendants. Further, a compound having a hydroxyl group can also be used as a crosslinking agent.

In the specific examples of the crosslinking agent, examples of the epoxy compound include gin(2,3-epoxypropyl)isocyanurate, trimethylolethanetrisole, and trimethylolpropane. Glycidyl ether, trishydroxyethylethane triglycidyl ether, and the like. Examples of the melamine compound include a compound obtained by methoxymethylation of hexamethylenemethyl melamine, hexamethoxymethyl melamine, hexamethylol melamine, or a mixture of hexamethylenemethyl melamine, or a mixture thereof A compound obtained by methylation of 1 to 6 methylol groups of oxyethyl melamine, hexamethoxymethyl melamine or hexamethylol melamine, or a mixture thereof. The guanamine compound may be a compound obtained by methoxymethylation of 1 to 4 methylol groups of tetramethylol decylamine, tetramethoxymethyl decylamine or tetramethylol decylamine, or A compound obtained by methylating a mixture of 1 to 4 methylol groups of tetramethoxyethylguanamine, tetradecyloxyguanamine or tetrahydroxymethylguanamine, or a mixture thereof, or the like. Examples of the glycoluril compound include methoxymethylation of 1 to 4 methylol groups of tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl glycoluril, and tetramethylol glycoluril. Further, the obtained compound, or a mixture thereof, a compound of 1 to 4 methylol groups of tetramethylol glycoluril which is methylated by a methoxy group, or a mixture thereof. Examples of the urea compound include a compound obtained by methoxymethylation of 1 to 4 methylol groups of tetramethylolurea, tetramethoxymethylurea or tetramethylolurea, or a mixture thereof, Methoxyethyl urea and the like. Examples of the isocyanate compound include tolyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. Examples of the azide compound include 1,1'-biphenyl-4,4'. - Biazide, 4,4'-methylidene diazide, 4,4'-oxybis azide.

Further, examples of the crosslinking agent which forms a crosslinking by an acetal group include a compound having a plurality of enol ether groups in the molecule. Examples of the crosslinking agent having at least two or more enol ether groups in the molecule include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, and 1,4-butylene. Glycol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol Divinyl ether, neopentyl alcohol trivinyl ether, neopentyl alcohol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol dipropylene ether, triethylene glycol dipropylene ether, 1, 2 -propylene glycol dipropylene ether, 1,4-butanediol dipropylene ether, tetramethylene glycol dipropylene ether, neopentyl glycol dipropylene ether, trimethylolpropane tripropylene ether, hexanediol dipropylene Ether, 1,4-cyclohexanediol dipropylene ether, neopentyl alcohol tripropylene ether, neopentyl alcohol tetrapropylene ether, sorbitol tetrapropylene ether, sorbitol pentapropylene ether, and the like.

Further, examples of the crosslinking agent of the compound having a plurality of enol ether groups in the molecule include the compounds shown below. 【化34】

Since the enol ether group forms an acetal bond with a hydroxyl group by heat, it is possible to carry out thermal crosslinking using an acetal group by adding a compound having a plurality of enol ether groups in the molecule.

Further, a crosslinking agent having at least two or more ethylene oxide-containing acid-removing tertiary ester groups in the molecule may be added. Specific examples of such a crosslinking agent include those described in JP-A-2006-96848. When such a crosslinking agent is used, as shown in JP-A-2001-226430, ethylene oxide is crosslinked by heat, and the tertiary ester moiety is decomposed by an acid.

Further, the photoresist underlayer film material of the present invention can be crosslinked by heating at 300 ° C or higher after spin coating without adding the above-mentioned crosslinking agent. In this case, the polymers are bonded to each other by an oxidative coupling reaction.

(Acid generator) Further, in the photoresist underlayer film material of the present invention, an acid generator for further promoting the crosslinking reaction by heat may be added. Acid generators may be added if they are acid-decomposed by acid decomposition or acid-produced by light irradiation. Specific examples of the acid generator include the materials described in paragraphs (0061) to (0085) of JP-A-2007-199653.

When the photoresist underlayer film material of the present invention as described above is used, a resin layer having a novolak resin having a repeating unit of the above formula (1) and having a fluorine atom of a predetermined amount or more is formed on the surface of the underlayer film. From the layer in which the fluorine-containing atom is present, the generation of the fugitive gas can be suppressed even if the photoresist underlayer film material is baked at a high temperature. Further, by adding the monomer component represented by the above formula (3) to the underlayer film material of the photoresist, it is possible to improve the filling property of the substrate of the level difference in a state in which the generation of the fugitive gas is suppressed.

<Pattern Forming Method> The present invention provides a pattern forming method for forming a photoresist underlayer film using the above-described photoresist underlayer film material of the present invention on a substrate to be processed by lithography on a substrate, and a film under the photoresist Forming a ruthenium-containing intermediate layer film using a ruthenium-containing interlayer film material, forming a photoresist upper layer film on the ruthenium-containing interlayer film using the photoresist upper layer film material, exposing the patterned circuit region of the photoresist upper layer film, and developing And forming a photoresist pattern on the photoresist upper layer film, and using the photoresist upper resist film having the photoresist pattern as a mask to transfer the pattern to the ruthenium-containing interlayer film by etching, and the transferred pattern is included The interlayer film is transferred as a mask to the photoresist underlayer film by etching, and the patterned photoresist underlayer film is used as a mask to transfer the pattern onto the substrate to be processed by etching.

Hereinafter, an example of the pattern forming method of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

Fig. 1 is a flow chart showing an example of a pattern forming method of the three-layer process of the present invention using a ruthenium-containing interlayer film material. In the pattern forming method shown in the flow chart of FIG. 1, first, (A) the photoresist underlayer film material of the present invention is applied on the processed layer 2 on the substrate 1 to form the photoresist underlayer film 3, in the photoresist The underlayer film 3 is coated with a ruthenium-containing interlayer film material to form a ruthenium-containing interlayer film 4, and a photoresist upper layer film material is applied onto the ruthenium-containing interlayer film 4 to form a photoresist upper layer film 5. Then, (B) the pattern circuit region 6 of the photoresist upper film 5 is exposed, (C) developed to form a photoresist pattern on the photoresist upper film 5 (in the case of a positive photoresist), (D) The photoresist upper layer film 5 forming the photoresist pattern is transferred as a mask to transfer the pattern to the ruthenium containing interlayer film 4, E) the transferred pattern ruthenium containing interlayer film 4 is used as a mask to etch the pattern The film is transferred to the underlayer film 3, and (F) is formed as a mask with the photoresist pattern of the transferred pattern as a mask, and the pattern is formed on the layer 2 to be processed by etching.

[Substrate to be processed] The substrate to be processed is not particularly limited, and for example, a layer to be processed on the substrate can be used. The substrate is not particularly limited, and Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, etc., and the processed layer are preferably used. Further, Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and various Low-k films (low dielectric films) are preferably used for the layer to be processed. And the etching barrier film, or the Fin-FET high and low difference substrate, etc., the thickness of the processed layer is preferably 10 to 10,000 nm, preferably 20 to 5,000 nm.

A hard mask for processing the substrate to be processed may be formed between the substrate to be processed and the underlayer film, and the substrate to be processed is a SiO ₂ -based insulating film substrate. SiN, SiON, and p may be used. -Si, α-Si, W, W-Si, amorphous carbon, and the like. In the case where the substrate to be processed is a gate electrode such as p-Si, W-Si or Al-Si, SiO ₂ , SiN, SiON or the like is used.

On the photoresist underlayer film formed by using the photoresist underlayer film material of the present invention, a photoresist upper film can be formed, and a photoresist layer selected from the group consisting of germanium, titanium, zirconium, hafnium, etc. is disposed between the photoresist upper film and the photoresist underlayer film. The three-layer treatment of the interlayer film of the elements in the metal is also desirable. The element contained in the intermediate layer film for the three layers is preferably yttrium.

[The ruthenium-containing intermediate layer film] The material of the ruthenium-containing intermediate layer film is not particularly limited, and a sesquiterpene-based material having absorption at the exposure wavelength described in JP-A-2007-302873 can be used. Further, the ruthenium containing interlayer film is formed by spin coating. The ruthenium-containing interlayer film material is spin-coated and baked at a temperature of 150 to 300 ° C to form a ruthenium-containing interlayer film composed of a ruthenium oxide film.

When using the three-layer treatment, the optical constant (n, k値) most suitable for the anti-reflection effect of the yttrium-containing interlayer film is n 値 1.5 to 1.9, k 値 0.15 to 0.3, and film thickness 20 to 130 nm. range. Further, in the case of the photoresist underlayer film, n 値 is 1.3 to 1.8, k 値 is 0.2 to 0.8, and film thickness is 50 nm or more.

[Resistance upper layer film] The photoresist upper layer film material is not particularly limited, and a base polymer composed of a known hydrocarbon system as disclosed in JP-A-H09-73173 and JP-A-2000-336121 can be used. Further, the thickness of the photoresist upper layer film is not particularly limited, and is preferably 20 to 500 nm, particularly preferably 30 to 400 nm.

When the photoresist upper layer film is formed using the above-mentioned photoresist upper layer film material, the spin coating method or the like is preferable as in the case of forming the photoresist underlayer film. The pre-baking after forming the photoresist upper layer film by spin coating or the like is preferably carried out at 80 to 180 ° C for a range of 10 to 300 seconds.

Further, when the interlayer film containing the tantalum is not formed but replaced with the intermediate layer film forming the inorganic hard mask, a film selected from the group consisting of a tantalum oxide film and a tantalum nitride film may be formed between the photoresist underlayer film and the photoresist upper layer film. An inorganic hard mask interlayer film of a tantalum oxide film, a tantalum carbonized film, a polycrystalline tantalum film, a titanium nitride film, a titanium oxide film, a titanium carbide film, a zirconium oxide film, or a hafnium oxide film.

[Inorganic Hard Mask Interlayer Film] The material of the inorganic hard mask interlayer film is not particularly limited. An inorganic hard mask interlayer film containing an element selected from the group consisting of a metal such as ruthenium, titanium, zirconium or hafnium, in particular, an intermediate film containing titanium, and a material described in JP-A-2014-178602 can be used. An inorganic hard mask intermediate layer film may be formed on the photoresist underlayer film and a photoresist upper layer film may be disposed thereon as a three-layer process. The inorganic hard mask interlayer film material is particularly preferably p-Si, SiN, SiON, SiC, TiN, TiO ₂ , TiC, ZrO ₂ , HfO ₂ . The formation of the inorganic hard mask interlayer film can be performed by a CVD method, an ALD method, a sputtering method, or the like.

Further, when an organic anti-reflection film is formed on the inorganic hard mask interlayer film to form a 4-layer photoresist film, the organic anti-reflection film material can be coated on the inorganic hard mask interlayer film to form an organic anti-reflection film. membrane. In this case, it becomes a 4-layer process.

[Organic Antireflection Film] The organic antireflection film material is not particularly limited, and a known product can be used.

Further, when a hydrocarbon film is formed and a ruthenium-containing interlayer film is formed thereon to obtain a 5-layer photoresist film, a hydrocarbon film material can be used on the inorganic hard mask interlayer film to form a hydrocarbon film by spin coating, and A ruthenium-containing interlayer film is formed using a ruthenium-containing interlayer film material. In this case, it becomes a 5-layer process.

[Carbon Film] The hydrocarbon film material is not particularly limited, and a known product can be used.

[Pattern Formation] (3-layer treatment) First, a method of forming a photoresist underlayer film using the photoresist underlayer film material of the present invention will be described. It can be formed on a substrate by spin coating or the like in the same manner as the formation of a usual photoresist film. Coating the photoresist underlayer film material on the substrate to be processed by spin coating or the like to form a photoresist underlayer film, evaporating the organic solvent, and in order to prevent mixing with the photoresist upper layer film or to promote crosslinking reaction, It is preferred to perform baking. The baking temperature is in the range of 80 to 1000 ° C, preferably in the range of 10 to 300 seconds. Further, the thickness of the underlayer film of the photoresist can be appropriately selected, but it is preferably from 5 to 100,000 nm, particularly preferably from 10 to 50,000 nm. If it is such a thickness, a high anti-reflection effect can be obtained.

The baking method is most commonly used on a hot plate. Further, it is also possible to perform baking by irradiating infrared rays. High-temperature baking at temperatures above 400 °C can also be carried out using hot plates, but the method of batch heating hundreds of wafers in the furnace has the advantage of increasing productivity.

In the case of the three-layer treatment, as shown in FIG. 1(A), after the photoresist underlayer film 3 is formed on the processed layer 2 laminated on the substrate 1, a germanium-containing interlayer film 4 is formed, and light is formed thereon. The upper film 5 is blocked.

Further, a photoresist protective film may be formed on the photoresist upper film. The photoresist film may be provided to prevent elution of an additive such as an acid generator from the photoresist upper film and to improve water slidability in order to perform wet exposure. Further, the photoresist film may also be an anti-reflective function. The photoresist film is water-soluble and water-insoluble. The water-insoluble resistive protective film is preferably one which is soluble in an alkali developing solution and which is insoluble in an alkali developing solution and which is peeled off by an organic solvent. The former has an advantage in that it can be peeled off while developing a photoresist, and is preferable. When applied to a negative pattern formed by development with an organic solvent, the latter solvent release type can be peeled off while developing. When the alkali developing solution is soluble, the polymer compound having an α-trifluoromethyl group is a compound having a carbon number of 4 or more and an ether compound having 8 to 12 carbon atoms.

The photoresist protective film is formed by spin-coating a protective film material on a pre-baked photoresist film and pre-baking. The film thickness of the photoresist film is preferably in the range of 10 to 200 nm. After dry or infiltrated exposure, post-exposure bake (PEB) is carried out and developed with an alkali developer for 10 to 300 seconds. The alkali developer is generally used in an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide. When the photoresist film which is soluble in the developer is used, the peeling of the photoresist film and the development of the photoresist film can be simultaneously performed.

The formation of the photoresist pattern of the photoresist upper layer film can be carried out according to a usual method. The pattern circuit region of the photoresist upper film is exposed, and PEB and development are performed to obtain a photoresist pattern. When a ruthenium-containing interlayer film to which an acid generator has been added is used in a polymer containing an acid-containing unstable group containing ruthenium, a pattern of a ruthenium-containing interlayer film can be obtained by exposure and development to a resist pattern.

At this time, if there is water remaining on the photoresist upper layer film before PEB, in PEB, water will absorb the acid in the photoresist upper layer film and there is no possibility of pattern formation. Therefore, in order to completely remove the water on the photoresist film before PEB, it is preferable to use the spin-drying before PEB, the surface of the film by dry air or nitrogen, or the water on the pedestal after exposure. The shape of the nozzle, the optimization of the water recovery treatment, and the like are preferably performed by drying or recovering the water on the film.

First, the pattern circuit region 6 of the photoresist upper film 5 is exposed (Fig. 1, (B)), PEB and development are performed, and a photoresist pattern is formed on the photoresist upper film 5 (Fig. 1, (C)). Using the obtained photoresist pattern as a mask, the ruthenium-containing interlayer film 4 was etched using a CF-based gas, and the pattern was transferred to the ruthenium-containing interlayer film 4 (Fig. 1, (D)).

Here, the development can be carried out by a dipping method using an alkali aqueous solution, a dipping method, or the like, and in particular, a dipping method using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide is preferred. First, it is treated with a developing solution at a temperature ranging from 10 seconds to 300 seconds, and then rinsed with pure water, and dried by spin drying or nitrogen blowing. Because of the alkali development, the exposed portion of the positive photoresist is partially dissolved, and in the case of a negative photoresist, the exposed portion becomes insoluble.

It is also possible to develop a negative pattern by using an organic solvent. The developer used at this time may be selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, Methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, propyl formate, butyl formate , isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxy Ethyl propyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, 2-hydroxyisobutylate Ethyl acetate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate One or more solvents selected from the group consisting of esters, ethyl phenylacetate and 2-phenylethyl acetate.

Then, the pattern of the photoresist pattern and the ruthenium-containing interlayer film is used as a mask, and the pattern is transferred to the photoresist underlayer film 3 by dry etching such as oxygen plasma (Fig. 1, (E)). The dry etching of the photoresist underlayer film formed using the photoresist underlayer film material of the present invention is preferably carried out using an etching gas containing oxygen or hydrogen. Further, in addition to oxygen or hydrogen, a passive gas such as He or Ar, CO, CO ₂ , NH ₃ , SO ₂ , N ₂ or NO ₂ gas may be added.

Further, when etching a photoresist underlayer film using a polymer containing no ruthenium atom as the above-mentioned photoresist upper layer film material, it is preferred to use an etching gas containing oxygen or hydrogen. By using such an etching gas, the removal of the photoresist upper layer film and the etching of the photoresist underlayer film can be simultaneously performed.

Further, after the pattern of the ruthenium-containing intermediate layer film was removed, the processed layer 2 was etched using the pattern of the photoresist underlayer film as a mask to form a pattern (Fig. 1, (F)). When the layer to be processed 2 is SiO ₂ or SiN, the etching gas of the fluorine-containing gas is preferable, and if it is polycrystalline germanium (p-Si), Al or W, an etching gas containing a chlorine-based or bromine-based gas is contained. More ideal. When implanting ions, the processing of the substrate to be processed is not necessarily required, and the pattern of the underlying film of the photoresist is used as a mask to perform ion implantation. The ruthenium-containing interlayer film is peeled off from the photoresist underlayer film before or after the ion implantation. This peeling can be carried out by dry peeling of a CF-based gas or an O ₂ -based gas, and wet peeling using sulfuric acid hydrogen peroxide water or ammonia hydrogen peroxide water.

Further, when the ruthenium-containing intermediate layer film is not formed but replaced with the inorganic hard mask intermediate layer film, the etching of the inorganic hard mask intermediate layer film can be carried out by a usual method.

Further, in the case of the four-layer treatment, the etching of the organic anti-reflection film can be carried out in accordance with a usual method. Further, the etching of the organic anti-reflection film may be performed continuously with the etching of the inorganic hard mask interlayer film, or the etching of the inorganic hard mask interlayer film may be performed by etching the organic anti-reflection film only after changing the etching device or the like. .

Further, in the case of the 5-layer treatment, the etching of the hydrocarbon film can be carried out in accordance with a usual method.

As described above, according to the pattern forming method of the present invention using the photoresist underlayer film material of the present invention, the substrate can be sufficiently filled and the generation of the fugitive gas can be suppressed, so that the microfabrication of the manufacturing process such as the semiconductor device can be greatly reduced. defect. Therefore, the photoresist underlayer film and the pattern forming method of the present invention are particularly suitable for the filling of a fine trench pattern requiring a common pitch, and the Fin- which occurs when the photoresist of the underlying film which is the source of the defect is baked. Manufacturing of three-dimensional devices such as FETs. [Examples]

The following examples and comparative examples are specifically described for the present invention, but the present invention is not limited to the description.

<Synthesis of the above-mentioned novolac resin having a repeating unit represented by the general formula (2)> [Synthesis Example 1-1] Addition of 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol) 45g, 37% by mass of formalin aqueous solution 120g, oxalic acid 5g, two 50 g of alkane was stirred at 100 ° C for 24 hours. After the reaction, it was dissolved in 500 mL of methyl isobutyl ketone, and the catalyst and metal impurities were removed by washing with sufficient water, and the pressure was reduced to 2 mmHg at 150 ° C, and the water and the solvent were distilled off under reduced pressure to obtain a novolak resin 2 shown below. 1.

Novolak resin 2-1 Molecular weight (Mw) = 3,100 Dispersity (Mw / Mn) = 3.88 [Chem. 35]

[Synthesis Example 1-2] In the same manner as in Synthesis Example 1-1, 45 g of α-naphthol phenolphthalein, 120 g of a 37% by mass aqueous solution of Formalin, and 5 g of oxalic acid were added. 50 g of alkane obtained the novolak resin 2-2 shown below.

Novolac resin 2-2 Molecular weight (Mw) = 2,100 Dispersity (Mw / Mn) = 3.67 [Chem. 36]

[Synthesis Example 1-3] In the same manner as in Synthesis Example 1-1, 45 g of naphthalene fluorescein, 120 g of a 37% by mass aqueous solution of formalin, and 5 g of oxalic acid were added. 50 g of alkane obtained the novolac resin 2-3 shown below.

Novolak resin 2-3 Molecular weight (Mw) = 2,600 Dispersity (Mw / Mn) = 3.55 [Chem. 37]

[Synthesis Example 1-4] 45 g of 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol), 60 g of a 37% by mass aqueous solution of formalin, 5 g of oxalic acid, and two 50 g of alkane was stirred at 80 ° C for 24 hours. After the reaction, it was dissolved in 500 ml of methyl isobutyl ketone, and the catalyst and metal impurities were removed by washing with sufficient water, and then the pressure was reduced to 2 mmHg at 150 ° C, and the water and the solvent were distilled off under reduced pressure to obtain a novolac resin 2 as shown below. -4.

Novolak resin 2-4 Molecular weight (Mw) = 1,100 Dispersity (Mw / Mn) = 3.86 [Chem. 38]

<Synthesis of a novolac resin having a repeating unit represented by the above formula (1)> [Synthesis Example 2-1] A novolac resin 2-1 4.6 g, 4,5-epoxy-1,1,1-three A mixture of 2.2 g of fluoropentane, 40 g of 1-methoxy-2-propanol, and 0.2 g of 25% by mass of caustic soda was stirred at room temperature for 24 hours. After diluting with ethyl acetate and washing with dilute nitric acid and ultrapure water, the solvent was distilled off under reduced pressure to obtain 6.8 g of the novolak resin 1-1 shown below. The novolac resin 1-1 thus obtained was analyzed by ¹³ C, ¹ H-NMR (nuclear magnetic resonance) and GPC (gel permeation chromatography) to obtain the following analysis results.

Novolac resin 1-1 Molecular weight (Mw) = 4,000 Dispersity (Mw / Mn) = 3.95 [Chem. 39]

[Synthesis Example 2-2] A mixture of 4.6 g of a novolac resin 2-1, 4.3 g of 3,3,3-trifluoropropionic anhydride, 30 g of ethyl acetate and 0.2 g of methanesulfonic acid was stirred at 70 ° C for 24 hours. After cooling, it was washed with dilute ammonia water and ultrapure water, and the solvent was distilled off under reduced pressure to obtain 6.6 g of the novolak resin 1-2 shown below. The novolac resin 1-2 thus obtained was analyzed in the same manner as above to obtain the following analysis results.

Novolac resin 1-2 Molecular weight (Mw) = 3,600 Dispersity (Mw / Mn) = 3.90 [Chemical 40]

[Synthesis Example 2-3] A mixture of 4.6 g of novolak resin 2-1, 5.0 g of trifluoromethanesulfinic anhydride, 40 g of N,N-dimethylformamide, and 3.0 g of triethylamine was stirred at 70 ° C. 24 hours. After cooling, it was diluted with ethyl acetate, and after washing with ultrapure water, the solvent was distilled off under reduced pressure to obtain 6.9 g of the novolak resin 1-3 shown below. The novolac resin 1-3 thus obtained was analyzed in the same manner as above to obtain the following analysis results.

Novolac resin 1-3 Molecular weight (Mw) = 3,400 Dispersity (Mw / Mn) = 3.89 [Chem. 41]

[Synthesis Example 2-4] In the same manner as in Synthesis Example 2-1, 4.6 g of novolak resin 2-1, hexafluorobutanesulfonyl chloride 6.4 g, N,N-dimethylformamide 40 g, and three A mixture of 3.0 g of ethylamine gave 10.2 g of the novolac resin 1-4 shown below. With respect to the obtained novolac resin 1-4 and the same analysis as described above, the following analysis results were obtained.

Novolak resin 1-4 Molecular weight (Mw) = 4,200 Dispersity (Mw / Mn) = 4.25 [Chem. 42]

[Synthesis Example 2-5] 4.0 g of novolak resin 2-1 was dissolved in 40 mL of tetrahydrofuran, and then 0.01 g of methanesulfonic acid and 1.7 g of 2,2,2-trifluoroethyl vinyl ether were added, and the mixture was reacted at room temperature. After 1 hour, 0.25 g of 30% by mass aqueous ammonia was added to stop the reaction. The obtained reaction solution was crystallized and precipitated in 1 L of acetic acid water, washed twice with water and filtered, and the obtained white solid was dried under reduced pressure at 40 ° C to obtain white polymer shown below. The polymer obtained was named as novolak resin 1-5, and analyzed in the same manner as above to obtain the following analysis results.

Novolac resin 1-5 Molecular weight (Mw) = 3,800 Dispersity (Mw / Mn) = 4.00 [Chem. 43]

<Examples 1-1 to 1-10, Comparative Examples 1-1 and 1-2> [Preparation of photoresist underlayer film material] The above-mentioned novolak resins 1-1 to 1-5 and novolac resin 2-1~ 2-4, and the monomers 1 to 6 shown below are dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in a ratio shown in Table 1, and filtered with a fluororesin filter having a pore size of 0.1 μm. Prepared as a photoresist underlayer film material (lower film material 1~10, comparative lower layer film material 1, 2).

Monomer 1~6 【化44】

(Measurement of Refractive Index) The photoresist underlayer film materials (underlayer film materials 1 to 10 and comparative underlayer film materials 1 and 2) prepared above were applied onto a cerium (Si) substrate, and baked at 350 ° C for 60 seconds to form respective The underlayer film is a photoresist having a film thickness of 100 nm. After the formation of the photoresist underlayer film, the refractive index (n, k) at a wavelength of 193 nm was obtained by a spectroscopic ellipsometer (VASE) manufactured by J.A. Woollam Inc., whose incident angle was variable. The results are shown in Table 1.

[Table 1] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Polymer 1 (parts by mass) </td ><td> Polymer 2 (parts by mass) </td><td> Additive (parts by mass) </td><td> Organic solvent (parts by mass) </td><td> n value</td>< Td> k value </td></tr><tr><td> underlayer film material 1 </td><td> novolak resin 1-1 (7) </td><td> novolac resin 2- 1 (43) </td><td> Monomer 1 (50) </td><td> PGMEA(2500) </td><td> 1.38 </td><td> 0.46 </td></ Tr><tr><td> Lower Membrane Material 2 </td><td> Novolak Resin 1-2 (7) </td><td> Novolak Resin 2-1 (43) </td><td > Monomer 1 (50) </td><td> PGMEA(2500) </td><td> 1.40 </td><td> 0.45 </td></tr><tr><td> Lower Membrane Material 3 </td><td> Novolak Resin 1-3 (7) </td><td> Novolak Resin 2-1 (43) </td><td> Monomer 1 (50) </td ><td> PGMEA(2500) </td><td> 1.41 </td><td> 0.46 </td></tr><tr><td> Lower Membrane Material 4 </td><td> Phenolic Varnish Resin 1-4 (7) </td><td> Novolak Resin 2-1 (43) </td><td> Monomer 1 (50) </td><td> PGMEA(2500) </ Td><td> 1.37 </td><td> 0.45 </td></tr><tr><td> Film material 5 </td><td> Novolak resin 1-5 (15) </td><td> Novolak resin 2-2 (25) </td><td> Monomer 2 (60) < /td><td> PGMEA(2500) </td><td> 1.44 </td><td> 0.43 </td></tr><tr><td> Lower Membrane Material 6 </td><td > Novolak Resin 1-1 (20) </td><td> Novolak Resin 2-3 (20) </td><td> Monomer 3 (60) </td><td> PGMEA(2500) </td><td> 1.44 </td><td> 0.42 </td></tr><tr><td> Lower Membrane Material 7 </td><td> Novolak Resin 1-1 (15) </td><td> Novolak Resin 2-4 (85) </td><td> - </td><td> PGMEA(2500) </td><td> 1.40 </td><td> 0.45 </td></tr><tr><td> Lower Membrane Material 8 </td><td> Novolak Resin 1-1 (20) </td><td> - </td><td> Monomer 4 (80) </td><td> PGMEA(2500) </td><td> 1.38 </td><td> 0.46 </td></tr><tr><td> Lower Membrane Material 9 </td><td> Novolak Resin 1-2 (7) </td><td> - </td><td> Monomer 5 (80) </td><td> PGMEA(2500) < /td><td> 1.40 </td><td> 0.45 </td></tr><tr><td> Lower Membrane Material 10 </td><td> Novolak Resin 1-2 (7) < /td><td> - </td><td> Monomer 6 (30) Monomer 1 (50) </td><td> PGMEA(2500) </td><td> 1.41 < /td><td> 0.45 </td></tr><tr><td> Comparing the underlying film material 1 </td><td> - </td><td> Novolac resin 2-1 (50) </td><td> monomer 5 (50) </td><td> PGMEA(4000) </td><td> 1.40 </td><td> 0.48 </td></tr><tr ><td> Comparing the underlying film material 2 </td><td> - </td><td> Novolac resin 2-1 (100) </td><td> - </td><td> PGMEA( 4000) </td><td> 1.39 </td><td> 0.49 </td></tr></TBODY></TABLE> PGMEA: propylene glycol monomethyl ether acetate

(Sublimation measurement) The obtained underlayer film materials (lower film materials 1 to 10 and lower layer film materials 1 and 2) were respectively applied onto a Si substrate, and fired under the conditions described in Table 2, using Reon Co., Ltd. The particle counter KR-11A measures the number of particles occurring in the hot plate oven during baking for the number of particles of 0.3 μm and 0.5 μm. The results are shown in Table 2.

[Table 2] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist underlayer film material</td>< Td> Baking temperature (°C) </td><td> 0.3μm particles (number) </td><td> 0.5μm particles (number) </td></tr><tr><td> Example 1-1 </td><td> Lower film material 1 </td><td> 350 </td><td> 15 </td><td> 2 </td></tr><tr ><td> Example 1-2 </td><td> Lower Membrane Material 2 </td><td> 350 </td><td> 12 </td><td> 1 </td></ Tr><tr><td> Example 1-3 </td><td> Lower Membrane Material 3 </td><td> 350 </td><td> 16 </td><td> 1 </ Td></tr><tr><td> Example 1-4 </td><td> Lower Membrane Material 4 </td><td> 320 </td><td> 6 </td><td > 0 </td></tr><tr><td> Example 1-5 </td><td> Lower Membrane Material 5 </td><td> 320 </td><td> 13 </ Td><td> 2 </td></tr><tr><td> Example 1-6 </td><td> Lower Membrane Material 6 </td><td> 360 </td><td > 11 </td><td> 2 </td></tr><tr><td> Example 1-7 </td><td> Lower Membrane Material 7 </td><td> 400 </ Td><td> 5 </td><td> 1 </td></tr><tr><td> Example 1-8 </td><td> Lower Membrane Material 8 </td><td > 350 </td><td> 19 </td><td> 6 </td></tr><tr>< Td> Example 1-9 </td><td> Lower Membrane Material 9 </td><td> 350 </td><td> 21 </td><td> 5 </td></tr> <tr><td> Example 1-10 </td><td> Underlayer film material 10 </td><td> 350 </td><td> 24 </td><td> 7 </td> </tr><tr><td> Comparative Example 1-1 </td><td> Comparison of Lower Membrane Material 1 </td><td> 350 </td><td> 102 </td><td> 29 </td></tr><tr><td> Comparative Example 1-2 </td><td> Comparison of Lower Membrane Material 2 </td><td> 350 </td><td> 25 </ Td><td> 8 </td></tr></TBODY></TABLE>

As a result of the above, the lower film materials 1 to 10 and the lower film material 2 were less likely to be in the baking than in the lower film material 1, so that the occurrence of the fugitive gas was reduced, and the baking oven was less likely to be contaminated. It can be seen that any of the underlying film materials has sufficient heat resistance.

(Evaluation of landfill on high and low difference substrates) <Examples 2-1 to 2-10, Comparative Examples 2-1 and 2-2> SiO having a film thickness of 500 nm, a size of 160 nm, and a pitch of 320 nm was formed for the high and low difference substrates. ₂ Si film of dense film pattern of film. The obtained photoresist lower layer film material (lower film material 1 to 10, comparative lower layer film materials 1, 2) is applied onto the SiO ₂ film of the high and low difference substrate so that the film thickness on the flat Si substrate becomes 95 nm, after which The wafer was cut and observed by SEM to see if the photoresist underlayer film material had been buried in the bottom of the hole. The results are shown in Table 3.

[Table 3] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist underlayer film material</td>< Td> Baking temperature (°C) </td><td> Filling condition of hole pattern</td></tr><tr><td> Example 2-1 </td><td> Lower film material 1 </td><td> 350 </td><td> The underlying film is buried until the bottom of the hole, no holes occur.</td></tr><tr><td> Example 2-2 </td ><td> Lower Membrane Material 2 </td><td> 350 </td><td> Same as above</td></tr><tr><td> Example 2-3 </td><td> Underlayer film material 3 </td><td> 350 </td><td> Same as above</td></tr><tr><td> Example 2-4 </td><td> Lower film material 4 </td><td> 320 </td><td> Same as above</td></tr><tr><td> Example 2-5 </td><td> Lower Membrane Material 5 </td> <td> 320 </td><td> Same as above</td></tr><tr><td> Example 2-6 </td><td> Lower Membrane Material 6 </td><td> 360 </td><td> Same as above</td></tr><tr><td> Example 2-7 </td><td> Lower Membrane Material 7 </td><td> 400 </td> <td> Same as above</td></tr><tr><td> Example 2-8 </td><td> Lower Membrane Material 8 </td><td> 360 </td><td> Ibid. </td></tr><tr><td> Example 2-9 </td><td> Lower Membrane Material 9 </t d><td> 360 </td><td> Same as above</td></tr><tr><td> Example 2-10 </td><td> Lower Membrane Material 10 </td><td > 360 </td><td> Same as above</td></tr><tr><td> Comparative Example 2-1 </td><td> Comparison of Lower Membrane Material 1 </td><td> 350 < /td><td> Same as above</td></tr><tr><td> Comparative Example 2-2 </td><td> Comparison of Lower Membrane Material 2 </td><td> 350 </td> <td> Holes appear at the bottom of the hole</td></tr></TBODY></TABLE>

According to the results shown in the above Table 3, the underlying film materials 1 to 10 have good landfill characteristics even in the high-level retardation substrate, and as a result of the combination of Table 2, it is understood that the generation of the fugitive gas can be suppressed. On the other hand, it is understood that the comparison of the underlayer film materials 1 and 2 cannot achieve both the securing of the landfill characteristics and the reduction of the fugitive gas.

<Examples 3-1 to 3-10, Comparative Examples 3-1 and 3-2> [Preparation of ruthenium-containing interlayer film material] The ruthenium-containing polymer and acid generator PAG1 shown below were shown in Table 4. The ratio was dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), and filtered through a fluororesin filter having a pore size of 0.1 μm to prepare a ruthenium-containing interlayer film material. The ruthenium-containing interlayer film material prepared above was applied onto a Si substrate and baked at 200 ° C for 60 seconds to form a ruthenium-containing interlayer film each having a film thickness of 40 nm. After the formation of the ruthenium-containing interlayer film, the refractive index (n, k) at a wavelength of 193 nm was determined by a JAWoollam Corporation Spectroscopic Ellipsometer (VASE) having an incident angle, and the results are shown in Table 4. 【化45】

[Table 4] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Polymer (parts by mass) </td> <td> Acid generator (parts by mass) </td><td> Organic solvent (parts by mass) </td><td> Water (parts by mass) </td><td> n value</td><td > k value </td></tr><tr><td> 矽 interlayer film material </td><td> 矽-containing polymer (100) </td><td> PAG1(2.0) </td ><td> PGEE(4000) </td><td> Water (60) </td><td> 1.62 </td><td> 0.21 </td></tr></TBODY></TABLE > PGEE: propylene glycol ether

[Preparation of the photoresist upper layer film material] The photoresist polymer, the acid generator PAG2, and the quencher shown below were dissolved in a ratio of the amount shown in Table 5 to contain 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.). In the organic solvent, a filter made of a fluororesin having a pore diameter of 0.1 μm was filtered to prepare a photoresist upper layer film material (a photoresist film material for ArF).

[Table 5] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Photoresist film material </td><td> Polymer (mass parts </td><td> Acid generator (parts by mass) </td><td> Quencher (parts by mass) </td><td> Organic solvent (parts by mass) </td></tr> <tr><td> Photoresist film material for ArF</td><td> Photoresist polymer (100) </td><td> PAG2(6.0) </td><td> Quencher (5.0) </td><td> PGMEA(2000) </td></tr></TBODY></TABLE>

Photoresist polymer molecular weight (Mw) = 7,500 Dispersity (Mw / Mn) = 1.92 [Chem. 46]

【化47】

[Pattern etching test] The obtained photoresist underlayer film forming materials (underlayer film materials 1 to 10 and comparative underlayer film materials 1 and 2) were applied onto a 300 mm Si wafer substrate on which a SiO ₂ film having a film thickness of 80 nm was formed. The film was baked at 350 ° C for 60 seconds to form a photoresist film having a film thickness of 100 nm. Further, the baking gas atmosphere of the photoresist underlayer film is in the air. On the above, the above-prepared yttrium-containing interlayer film material was coated and baked at 200 ° C for 60 seconds to form an intermediate layer film having a film thickness of 35 nm, and a photoresist film material for ArF was coated thereon, and baked at 105 ° C. Bake for 60 seconds to form a photoresist film for ArF having a film thickness of 100 nm.

Next, a three-layer Si wafer substrate was formed in the above manner by an ArF infiltration exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98/0.65, 35-degree dipole s polarized illumination, 6% and a half). Exposure to the phase shift mask), baking at 100 ° C for 60 seconds (PEB), developing with a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, obtaining a positive shape of 43 nm 1:1 Line and spacing pattern.

Next, dry etching was performed using the etching apparatus Telius manufactured by Tokyo Wealth Co., Ltd., and the pattern was transferred to the ruthenium containing interlayer film using the photoresist pattern formed as a mask. Then, the dry etching is also used to transfer the pattern of the yttrium-containing interlayer film of the transferred pattern as a mask to the underlayer film of the photoresist, and the underlying film of the photoresist having the transferred pattern is used as a mask to transfer the pattern. In the SiO ₂ film.

The etching conditions are as follows. Conditional chamber pressure transfer to the ruthenium containing interlayer film 10.0 Pa RF power 1,500 W CF ₄ gas flow rate 15 sccm (mL/min) O ₂ gas flow rate 75 sccm (mL/min) Time 15 sec

Transfer condition to photoresist underlayer film chamber pressure 2.0Pa RF power 500W Ar gas flow rate 75sccm (mL/min) O ₂ gas flow rate 45sccm (mL/min) Time 120sec

Transfer condition to SiO ₂ film chamber pressure 2.0 Pa RF power 2,200 WC ₅ F ₁₂ gas flow rate 20 sccm (mL/min) C ₂ F ₆ gas flow rate 10 sccm (mL/min) Ar gas flow rate 300 sccm (mL/min) O ₂ gas flow rate 60sccm (mL/min) time 90sec

The wafer was cut, and the pattern profile was observed by an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the pattern shape after etching in each etching step and the distortion of the pattern after etching of the SiO ₂ film were compared. The results are shown in Table 6.

[Table 6] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist underlayer film material</td>< Td> pattern shape after development </td><td> intermediate layer transfer etched shape </td><td> underlayer film transfer etched shape</td><td> substrate transfer etched shape</td ><td> Reversed pattern of substrate transfer after etching</td></tr><tr><td> Example 3-1 </td><td> Lower film material 1 </td><td> Vertical Shape</td><td> Vertical Shape</td><td> Vertical Shape</td><td> Vertical Shape</td><td> None</td></tr><tr><td> Example 3-2 </td><td> Lower Membrane Material 2 </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical shape </td><td> none</td></tr><tr><td> Example 3-3 </td><td> Lower film material 3 </td><td> Vertical shape < /td><td> Vertical Shape</td><td> Vertical Shape</td><td> Vertical Shape</td><td> None</td></tr><tr><td> Example 3-4 </td><td> Lower Membrane Material 4 </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical Shape </td><td> no</td></tr><tr><td> Example 3-5 </td><td> Lower Membrane Material 5 </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical shape </td><td> none</td></tr><tr><td> Example 3-6 </td><td> Lower film material 6 </td><td> Vertical shape < /td><td> Vertical Shape</td><td> Vertical Shape</td><td> Vertical Shape</td><td> None</td></tr><tr><td> Example 3-7 </td><td> Lower Membrane Material 7 </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical Shape </td><td> Vertical Shape </td><td> None</td></tr><tr><td> Example 3-8 </td><td> Lower Membrane Material 8 </td><td> Vertical Shape </td ><td> Vertical shape</td><td> Vertical shape</td><td> Vertical shape</td><td> None</td></tr><tr><td> Example 3- 9 </td><td> Lower Membrane Material 9 </td><td> Vertical Shape</td><td> Vertical Shape</td><td> Vertical Shape</td><td> Vertical Shape</ Td><td> none</td></tr><tr><td> Example 3-10 </td><td> Lower Membrane Material 10 </td><td> Vertical Shape</td>< Td> vertical shape</td><td> vertical shape</td><td> vertical shape</td><td> none</td></tr><tr><td> Comparative Example 3 1 </td><td> Comparing the underlying film material 1 </td><td> Vertical shape</td><td> Vertical shape</td><td> Vertical shape</td><td> Vertical shape< /td><td> None</td></tr><tr><td> Comparative Example 3-2 </td><td> Comparison of Underlying Membrane Material 2 </td><td> Vertical Shape </td ><td> Vertical Shape</td><td> Vertical Shape</td><td> Vertical Shape</td><td> None</td></tr></TBODY></TABLE>

According to the results shown in the above Table 6, if the photoresist underlayer film material of the present invention is used, a good pattern can be formed even after dry etching as in the conventional photoresist underlayer film. Further, it is understood that any of the underlayer film materials has sufficient dry etching resistance.

1‧‧‧Substrate
2‧‧‧Processed layer
3‧‧‧Photoresist underlayer film
4‧‧‧矽 interlayer film
5‧‧‧Photoresist upper film
6‧‧‧pattern circuit area

1(A) to (F) are flow charts showing an example of a pattern forming method of the three-layer process of the present invention using a ruthenium containing interlayer film.

no

Claims (11)

A photoresist underlayer film material comprising: a novolac resin having a repeating unit represented by the following formula (1); and a novolak resin having a repeating unit represented by the following formula (2) and represented by the following formula (3) Any one or both of the bisnaphthol derivatives; and the novolak resin having the repeating unit represented by the following formula (1) contains a compound selected from the following formula (4)-1 to (4)-5 One or more groups are as R ¹ and/or R ² in the formula (1); [Chemical 2] In the formula, R ¹ and R ^{2 each} represent a hydrogen atom or a linear, branched or branched carbon number of 1 to 10 which may have a hydroxyl group, an alkoxy group, a fluorenyl group, a fluorenylene group, a fluorenyl group or an ester bond. a cyclic alkyl group, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, which may have a fluorine atom, and all of R ¹ and all 10% or more of the total number of R ² is a group having at least one fluorine atom; and R ³ , R ⁴ , R ¹¹ and R ¹² are each a hydrogen atom, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms; Or a linear, branched or cyclic alkyl group having a carbon number of 1 to 10, or a carbon number of 2 to 10, which may have a hydroxyl group, an alkoxy group, a decyloxy group, an ether group or a thioether group. An alkenyl group or an aryl group having 6 to 10 carbon atoms; R ¹⁸ and R ¹⁹ represent a group similar to R ³ , R ⁴ , R ¹¹ and R ¹² or a halogen atom; R ⁵ , R ⁶ , R ¹³ and R ¹⁴ , R ²⁰ and R ²¹ are a hydrogen atom, or an ether bond formed by the combination of R ⁵ and R ⁶ , R ¹³ and R ¹⁴ , and R ²⁰ and R ²¹ ; R ⁷ and R ¹⁵ are a hydrogen atom, or may have a hydroxyl group or an alkane. An oxy group, a decyloxy group, an ether group, a thioether group, a chloro group, or a nitro group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon number of 6 An aryl group of ~10; R ⁹ , R ¹⁰ , R ¹⁶ and R ¹⁷ are any of a hydrogen atom, an acid labile group, and an epoxy group, or a linear or branched carbon number of 1 to 10. Or a cyclic alkyl group, a mercapto group, or an alkoxycarbonyl group; X ₁ , X ₂ , and X ₃ are a single bond, or may have a hydroxyl group, a carboxyl group, an ether group, or a lactone ring having a carbon number of 1 to 38. a linear, branched or cyclic divalent hydrocarbon group; wherein X ₁ is a divalent hydrocarbon group, R ⁵ and R ⁶ may be an ether bond formed by bonding with a carbon atom in X ₁ , and X ₂ is In the case of a divalent hydrocarbon group, R ¹³ and R ¹⁴ may be an ether bond formed by bonding with a carbon atom in X ₂ , and X ₃ is a divalent hydrocarbon group, and R ²⁰ and R ²¹ may be a carbon in X ₃ An ether bond formed by atomic bonding; a, b, c, d, g, h, i, j, k, l, m, and n are 1 or 2; In the formula, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ⁰ is a hydrogen atom, a methyl group, an ethyl fluorenyl group or a trifluoroethyl fluorenyl group; Rf is a fluorine atom or has at least one fluorine The atom may also have a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydroxyl group or an alkoxy group. An aralkyl group having 7 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; R ²² being a hydrogen atom, a methyl group or an ethyl group; and R ²³ and R ²⁴ being a hydrogen atom or a carbon number of 1 to 5 A chain or branched alkyl group. The photoresist underlayer film material according to the first aspect of the invention, wherein the photoresist underlayer film material contains a novolak resin having a repeating unit represented by the formula (1), and a repeating unit represented by the formula (2) The novolak resin and the bisnaphthol derivative represented by the formula (3). The photoresist underlayer film material according to the second aspect of the invention, wherein the photoresist underlayer film material contains one part of the novolac resin having a repeating unit represented by the formula (1) The novolak resin of the repeating unit represented by the formula (2) and the bisnaphthol derivative represented by the formula (3) are 5 to 100 parts by mass in total. The photoresist underlayer film material of claim 1 or 2, wherein the photoresist underlayer film material further contains an organic solvent. The photoresist underlayer film material of claim 1 or 2, wherein the photoresist underlayer film material further comprises an acid generator and/or a crosslinking agent. A pattern forming method is a method for forming a pattern by using a lithography on a substrate, characterized in that a photoresist underlayer film is formed on the substrate to be processed by using the photoresist underlayer film material according to any one of claims 1 to 5, Forming a ruthenium-containing intermediate layer film on the underlayer film using the ruthenium-containing interlayer film material, forming a photoresist upper layer film on the ruthenium-containing interlayer film using the photoresist upper layer film material, and patterning the photoresist upper layer film After exposing the region, developing a photoresist pattern on the photoresist upper layer film, and using the photoresist upper resist film having the photoresist pattern as a mask to transfer the pattern onto the germanium containing interlayer film by etching, The ruthenium-containing interlayer film of the transferred pattern is transferred as a mask to transfer the pattern under the photoresist under the mask, and the photoresist pattern underlayer of the transferred pattern is used as a mask to transfer the pattern by etching. The substrate to be processed. A pattern forming method for forming a pattern on a substrate by using a lithography on a substrate, characterized in that the photoresist underlayer film is formed by using the photoresist underlayer film material according to any one of claims 1 to 5, Forming on the underlayer film of the photoresist is selected from the group consisting of a tantalum oxide film, a tantalum nitride film, a tantalum oxide film, a tantalum carbonization film, a polysilicon film, a titanium nitride film, a titanium oxide film, a titanium carbide film, a zirconium oxide film, Or an inorganic hard mask interlayer film in the ruthenium oxide film, wherein a photoresist upper layer film is formed on the inorganic hard mask interlayer film, and the patterned circuit region of the photoresist upper film is exposed; Developing a resist pattern on the photoresist upper layer film, and using the photoresist upper resist film having the photoresist pattern as a mask to transfer the pattern on the inorganic hard mask interlayer film by etching, and transferring the pattern The inorganic hard mask interlayer film of the pattern is transferred as a mask to transfer the pattern to the underlayer film of the photoresist, and the photoresist film of the transferred pattern is used as a mask to transfer the pattern by etching. The substrate to be processed. A pattern forming method is a method for forming a pattern by using a lithography on a substrate, characterized in that a photoresist underlayer film is formed on the substrate to be processed by using the photoresist underlayer film material according to any one of claims 1 to 5. Forming on the underlayer film of the photoresist is selected from the group consisting of a tantalum oxide film, a tantalum nitride film, a tantalum oxide film, a tantalum carbonization film, a polysilicon film, a titanium nitride film, a titanium oxide film, a titanium carbide film, a zirconium oxide film. Or an inorganic hard mask interlayer film in the ruthenium oxide film, an organic anti-reflection film is formed on the inorganic hard mask interlayer film, and a photoresist upper layer film is formed on the organic anti-reflection film to form a photoresist upper film A four-layer photoresist film is obtained, and the patterned circuit region of the photoresist upper layer film is exposed, developed, and a resist pattern is formed on the photoresist upper layer film, and the photoresist resistive upper layer film having the photoresist pattern is formed as a mask. And the pattern is transferred to the organic anti-reflection film and the inorganic hard mask interlayer film by etching, and the inorganic hard mask interlayer film of the transferred pattern is used as a mask to transfer the pattern to the photoresist by etching. Underlayer film, and then the photoresist of the transferred pattern -Layer film as a mask and etching to transfer the pattern to the substrate to be processed. A pattern forming method is a method for forming a pattern by using a lithography on a substrate, characterized in that a photoresist underlayer film is formed on the substrate to be processed by using the photoresist underlayer film material according to any one of claims 1 to 5. Forming on the underlayer film of the photoresist is selected from the group consisting of a tantalum oxide film, a tantalum nitride film, a tantalum oxide film, a tantalum carbonization film, a polysilicon film, a titanium nitride film, a titanium oxide film, a titanium carbide film, a zirconium oxide film. Or an inorganic hard mask interlayer film in the ruthenium oxide film, wherein a hydrocarbon film material is spin-coated on the inorganic hard mask interlayer film to form a hydrocarbon film, and a ruthenium-containing interlayer film material is used on the hydrocarbon film to form a film a ruthenium intermediate film, wherein a photoresist upper layer film is formed on the ruthenium containing interlayer film to form a photoresist film, and a photoresist layer is formed by exposing the pattern circuit region of the photoresist upper film to development Forming a photoresist pattern on the photoresist upper layer film, and using the photoresist upper layer film having the photoresist pattern as a mask to transfer the pattern on the germanium containing interlayer film by etching, The ruthenium-containing interlayer film of the transferred pattern is transferred as a mask to transfer the pattern to the hydrocarbon film, and the hydrocarbon film of the transferred pattern is used as an etch mask to transfer the pattern to the inorganic layer by etching. Hard masking the interlayer film, using the inorganic hard mask interlayer film of the transferred pattern as a mask, transferring the pattern to the photoresist underlayer film by etching, and then lowering the photoresist of the transferred pattern The film is used as a mask to transfer the pattern onto the substrate to be processed by etching. The pattern forming method according to any one of claims 7 to 9, wherein the inorganic hard mask interlayer film is formed by any one of a CVD method, an ALD method, and a sputtering method. The pattern forming method according to any one of claims 6 to 9, wherein the photoresist upper layer film material uses a polymer which does not contain a germanium atom, and the inner layer film or the inorganic hard mask is used. The etching of the underlayer film of the photoresist is performed as a mask, and the etching is performed using an etching gas containing oxygen or hydrogen.