JP2019113571A - Resist underlay film-forming composition, and lithography underlay film and patterning method using the same - Google Patents

Abstract

To provide a resist underlay film-forming composition having excellent pattern rectangularity, a lithography underlay film, and a patterning method.SOLUTION: A resist underlay film-forming composition contains a compound containing tellurium or a resin containing tellurium, and a silicon-containing compound.SELECTED DRAWING: None

Description

  The present invention relates to a composition for forming a tellurium-containing resist underlayer film used for a multilayer resist method used for microfabrication in a manufacturing process of a semiconductor element or the like, an underlayer film for lithography using the same, and a pattern forming method.

  Conventionally, in the manufacture of a semiconductor device, fine processing by lithography using a photoresist has been performed. In the microfabrication, first, a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and an active light beam such as ultraviolet light is applied and developed through a mask pattern on which a pattern of the semiconductor device is drawn. , Forming the obtained photoresist pattern. Next, the substrate is etched using the photoresist pattern as a protective film to form fine irregularities corresponding to the pattern on the surface of the substrate. However, in recent years, the degree of integration of semiconductor devices has been increased, and the actinic radiation used has also been shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm) and EUV (Extreme ultraviolet) light (13.5 nm). Tend to be Along with this, the influence of reflection of active light from the semiconductor substrate has become a major problem.

  Further, as a lower layer film between a semiconductor substrate and a photoresist, a film known as a hard mask containing a metal element such as silicon is used (for example, see Patent Document 1 below).

Japanese Patent Application Laid-Open No. 7-183194

  Since the components of the photoresist and the hard mask are largely different, the removal rate by dry etching depends largely on the gas species used for the dry etching. Then, by appropriately selecting the gas type, it is possible to remove the hard mask by dry etching without accompanied by a large decrease in the film thickness of the photoresist. As described above, in recent semiconductor device manufacturing, it is difficult to miniaturize only with the upper layer resist (photoresist), and in order to achieve various effects including the antireflection effect, it is formed under the upper layer resist. If a hard mask is not used, the miniaturization process can not be established. Furthermore, various multilayer resist methods have been developed in which a resist underlayer film is provided between the upper layer resist (for example, photoresist, electron beam resist, EUV resist) and the hard mask. Such a resist underlayer film does not intermix with the upper layer resist, has heat resistance, and has a rectangular and excellent pattern because it has an etching rate higher than that of the mask (upper layer resist patterned) at the time of patterning. You can get it. Or when patterning a layer provided on a substrate such as a mask or an organic lower layer film, it is required to exhibit etching resistance because it functions as a mask.

  An object of the present invention is to provide a composition for forming a resist underlayer film excellent in rectangularity of a pattern, an underlayer film for lithography, and a pattern forming method.

  The present inventors have intensively studied to solve the above problems, and as a result, a compound and resin having a specific structure, a silicon-containing compound (for example, hydrolyzable organosilane, its hydrolyzate or its hydrolytic condensate), Since the composition for forming a resist underlayer film containing the above has high heat resistance, it can be used under high temperature bake conditions, has high absorption capability to the above-mentioned actinic light, is highly sensitive, and does not intermix with the resist. It has been found that the present invention can have a large fluorine-based dry etching rate as compared to a resist, and has led to the present invention.

  That is, the present invention is as follows.

（式（Ａ）中、Ｘは、テルルを含む炭素数０〜３０の２ｍ価の基であり、Ｚは、酸素原子、硫黄原子又は無架橋であり、Ｒ⁰は、各々独立して、酸素原子を含む１価の基、硫黄原子を含む１価の基、窒素原子を含む１価の基、炭化水素基、又はハロゲン原子であり、ｍは、１〜４の整数であり、ｐは、各々独立して０〜２の整数であり、ｎは、各々独立して０〜（５＋２×ｐ）の整数である。）
＜４＞ 前記テルルを含有する化合物が、下記式（１）で示される＜３＞のレジスト下層膜形成用組成物。

（式（１）中、Ｘ、Ｚ、ｍ、ｐは前記式（Ａ）と同義であり、Ｒ¹は、各々独立して、アルキル基、アリール基、アルケニル基又はハロゲン原子であり、Ｒ²は、各々独立して、水素原子又は酸解離性反応基であり、ｎ¹は各々独立して、０〜（５＋２×ｐ）の整数であり、ｎ²は各々独立して、０〜（５＋２×ｐ）の整数である。但し、少なくとも一つのｎ²は１〜（５＋２×ｐ）の整数である。）
＜５＞ 前記テルルを含有する化合物が、下記式（２）で示される＜４＞のレジスト下層膜形成用組成物。

（式（２）中、Ｚ、Ｒ¹、Ｒ²、ｐ、ｎ¹、ｎ²は前記式（１）と同義であり、Ｘ¹はハロゲン原子である。）
＜６＞ 前記テルルを含有する化合物が、下記式（３）で示される＜５＞のレジスト下層膜形成用組成物。

（式（３）中、Ｒ¹、Ｒ²、Ｘ¹、ｎ¹、ｎ²は前記式（２）と同義である。）
＜７＞ 前記テルルを含有する化合物が、下記式（４）で示される＜６＞のレジスト下層膜形成用組成物。

（式（４）中、Ｒ¹、Ｒ²、Ｘ¹は前記式（３）と同義である。）
＜８＞ 前記テルルを含有する化合物は、前記式（１）におけるＲ²として、少なくとも一つの酸解離性反応基を有する＜４＞のレジスト下層膜形成用組成物。
＜９＞ 前記テルルを含有する化合物は、前記式（１）におけるＲ²が全て水素原子である＜４＞のレジスト下層膜形成用組成物。
＜１０＞ 前記テルルを含有する樹脂が、下記式（Ａ）で示される化合物に由来する構成単位を含む樹脂である＜１＞又は＜２＞のレジスト下層膜形成用組成物。

（式（Ａ）中、Ｘは、テルルを含む炭素数０〜３０の２ｍ価の基であり、Ｚは、酸素原子、硫黄原子又は無架橋であり、Ｒ⁰は、各々独立して、酸素原子を含む１価の基、硫黄原子を含む１価の基、窒素原子を含む１価の基、炭化水素基、又はハロゲン原子であり、ｍは、１〜４の整数であり、ｐは、各々独立して０〜２の整数であり、ｎは、各々独立して０〜（５＋２×ｐ）の整数である。）
＜１１＞ 溶媒を更に含むことを特徴とする＜１＞〜＜１０＞のいずれか１つのレジスト下層膜形成用組成物。
＜１２＞ 酸を更に含有する＜１＞〜＜１１＞のいずれか１つのジスト下層膜形成用組成物。
＜１３＞ 酸架橋剤を更に含有する＜１＞〜＜１２＞のいずれか１つのレジスト下層膜形成用組成物。
＜１４＞ 前記ケイ素含有化合物が、下記式（Ａ１）及び（Ａ２）からなる群より選ばれた少なくとも一種の加水分解性オルガノシラン、それらの加水分解物、又はそれらの加水分解縮合物である＜１〜＜１３＞のいずれか１つのレジスト下層膜形成用組成物。

式（Ａ１）： （Ｒ³）_aＳｉ（Ｒ⁴）_4-a

（式（Ａ１）中、Ｒ³はアルキル基、アリール基、アラルキル基、ハロゲン化アルキル基、ハロゲン化アリール基、ハロゲン化アラルキル基、アルケニル基、エポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アルコキシアリール基、アシルオキシアリール基、イソシアヌレート基、ヒドロキシ基、環状アミノ基、又はシアノ基を有する有機基；或いは、それらの組み合わせを表し、且つＳｉ−Ｃ結合によりケイ素原子と結合しているものであり、Ｒ⁴はアルコキシ基、アシルオキシ基又はハロゲン基を表し、ａは０〜３の整数を表す。）

式（Ａ２）： ［（Ｒ⁵）_cＳｉ（Ｒ⁶）_4-c］₂Ｙ_b

（式（Ａ２）中、Ｒ⁵はアルキル基を表し、Ｒ⁶はアルコキシ基、アシルオキシ基又はハロゲン基を表し、Ｙはアルキレン基又はアリーレン基を表し、ｂは０又は１の整数を表し、ｃは０又は１の整数を表す。）
＜１５＞ ＜１＞〜＜１４＞いずれか１つのレジスト下層膜形成用組成物を用いて形成されたリソグラフィー用下層膜。
＜１６＞ 基板上に、＜１＞〜＜１４＞いずれか１つのレジスト下層膜形成用組成物を用いてレジスト下層膜を形成し、前記レジスト下層膜上に、少なくとも１層のフォトレジスト層を形成した後、該フォトレジスト層の所定の領域に放射線を照射し、現像を行うことを含む、パターン形成方法。
＜１７＞ 基板上に塗布型有機下層膜材料を用いて有機下層膜を形成し、
前記有機下層膜上に、＜１＞〜＜１４＞のいずれか１つのレジスト下層膜形成用組成物を用いてレジスト下層膜を形成し、前記レジスト下層膜上に、上層レジスト膜組成物を用いて上層レジスト膜を形成し、前記上層レジスト膜に上層レジストパターンを形成し、前記上層レジストパターンをマスクにして前記レジスト下層膜にエッチングでパターンを転写し、パターンが転写された前記レジスト下層膜をマスクにして前記有機下層膜にエッチングでパターンを転写し、パターンが転写された前記有機下層膜をマスクにして前記基板にエッチングでパターンを転写することを含むパターン形成方法。
＜１８＞ 基板上に炭素を主成分とする有機ハードマスクをＣＶＤ法で形成し、前記有機ハードマスク上に、＜１＞〜＜１４＞のいずれか１つのレジスト下層膜形成用組成物を用いてレジスト下層膜を形成し、前記レジスト下層膜上に、上層レジスト膜組成物を用いて上層レジスト膜を形成し、前記上層レジスト膜に上層レジストパターンを形成し、前記上層レジストパターンをマスクにして前記レジスト下層膜にエッチングでパターンを転写し、パターンが転写された前記レジスト下層膜をマスクにして前記有機ハードマスクにエッチングでパターンを転写し、パターンが転写された前記有機ハードマスクをマスクにして前記基板にエッチングでパターンを転写することを含むパターン形成方法。 The composition for resist underlayer film formation containing the compound containing <1> tellurium, or resin containing tellurium, and a silicon-containing compound.
<2> The composition for forming a resist underlayer film of <1>, wherein the silicon-containing compound is a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolytic condensate thereof.
<3> A composition for forming a resist underlayer film of <1> or <2>, wherein the compound containing tellurium is represented by the following formula (A).

(In the formula (A), X is a 2m-valent group having 0 to 30 carbon atoms including tellurium, Z is an oxygen atom, a sulfur atom or non-crosslinking, and R ⁰ is each independently oxygen A monovalent group containing an atom, a monovalent group containing a sulfur atom, a monovalent group containing a nitrogen atom, a hydrocarbon group, or a halogen atom, m is an integer of 1 to 4, and p is Each independently is an integer of 0 to 2, and n is each independently an integer of 0 to (5 + 2 × p).
<4> The composition for forming a resist lower layer film of <3>, wherein the compound containing tellurium is represented by the following formula (1).

(In formula (1), X, Z, m and p are as defined in the above formula (A), R ¹ is each independently an alkyl group, an aryl group, an alkenyl group or a halogen atom, R ² Each independently represents a hydrogen atom or an acid-dissociable reactive group, each n ¹ independently represents an integer of 0 to (5 + 2 × p), and each n ² independently represents an integer of 0 to (5 + 2) It is an integer of × p), provided that at least one n ² is an integer of 1 to (5 + 2 × p).
<5> The composition for resist underlayer film formation of <4> by which the compound containing the said tellurium is shown by following formula (2).

(In formula (2), Z, R ¹ , R ² , p, n ¹ and n ² are as defined in the above formula (1), and X ¹ is a halogen atom)
<6> The composition for resist underlayer film formation of <5> by which the compound containing the said tellurium is shown by following formula (3).

(In Formula (3), R ¹ , R ² , X ¹ , n ¹ and n ² have the same meanings as in Formula (2) above).
<7> The composition for resist underlayer film formation of <6> in which the compound containing the said tellurium is shown by following formula (4).

(In Formula (4), R ¹ , R ² , and X ¹ have the same meanings as in Formula (3) above).
<8> The composition for forming a resist underlayer film of <4>, wherein the compound containing tellurium has at least one acid-dissociative reactive group as R ² in the formula (1).
<9> The composition for forming a resist underlayer film of <4>, wherein all the R ² in the formula (1) are hydrogen atoms in the compound containing tellurium.
<10> The composition for forming a resist lower layer film of <1> or <2>, wherein the tellurium-containing resin is a resin containing a constitutional unit derived from a compound represented by the following formula (A).

(In the formula (A), X is a 2m-valent group having 0 to 30 carbon atoms including tellurium, Z is an oxygen atom, a sulfur atom or non-crosslinking, and R ⁰ is each independently oxygen A monovalent group containing an atom, a monovalent group containing a sulfur atom, a monovalent group containing a nitrogen atom, a hydrocarbon group, or a halogen atom, m is an integer of 1 to 4, and p is Each independently is an integer of 0 to 2, and n is each independently an integer of 0 to (5 + 2 × p).
<11> The composition for forming a resist underlayer film according to any one of <1> to <10>, further comprising a solvent.
<12> The composition for forming a lower underlayer film according to any one of <1> to <11>, further containing an acid.
The composition for resist underlayer film formation any one of <1>-<12> which further contains a <13> acid crosslinking agent.
<14> The silicon-containing compound is at least one hydrolyzable organosilane selected from the group consisting of the following formulas (A1) and (A2), a hydrolyzate thereof, or a hydrolytic condensate thereof Composition for resist underlayer film formation any one of <13>.

Formula (A1): (R ³ ) _a Si (R ⁴ ) _4-a

(In formula (A1), R ³ represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an alkoxy An organic group having an aryl group, an acyloxyaryl group, an isocyanurate group, a hydroxy group, a cyclic amino group, or a cyano group; or a combination thereof, which is bonded to a silicon atom by a Si-C bond , R ⁴ represents an alkoxy group, an acyloxy group or a halogen group, and a represents an integer of 0 to 3.)

Formula (A2): [(R ⁵ ) _c Si (R ⁶ ) _4-c ] ₂ Y _b

(In formula (A2), R ⁵ represents an alkyl group, R ⁶ represents an alkoxy group, an acyloxy group or a halogen group, Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, c Represents an integer of 0 or 1.)
The underlayer film for lithography formed using the composition for <15><1>-<14> any one resist underlayer film formation.
A resist underlayer film is formed on a <16> substrate using the composition for forming a resist underlayer film according to any one of <1> to <14>, and at least one photoresist layer is formed on the resist underlayer film. After forming, the pattern formation method including irradiating with radiation to the predetermined area | region of this photoresist layer, and performing development.
<17> An organic underlayer film is formed on a substrate using a coating type organic underlayer film material,
A resist underlayer film is formed on the organic underlayer film using the composition for forming a resist underlayer film of any one of <1> to <14>, and an upper layer resist film composition is used on the resist underlayer film. The upper layer resist film is formed, the upper layer resist pattern is formed on the upper layer resist film, the pattern is transferred to the resist lower layer film by etching using the upper layer resist pattern as a mask, and the resist lower layer film on which the pattern is transferred is formed. A pattern forming method comprising: transferring a pattern to the organic lower layer film by etching as a mask; and transferring a pattern to the substrate by etching the organic lower layer film to which the pattern is transferred as a mask.
An organic hard mask containing carbon as a main component is formed by a CVD method on a <18> substrate, and any one composition for forming a resist underlayer film of <1> to <14> is used on the organic hard mask. A resist underlayer film is formed, an upper layer resist film is formed using the upper layer resist film composition on the resist underlayer film, an upper layer resist pattern is formed on the upper layer resist film, and the upper layer resist pattern is used as a mask The pattern is transferred to the resist underlayer film by etching, and the pattern is transferred to the organic hard mask by using the resist underlayer film to which the pattern is transferred as a mask, and the organic hard mask to which the pattern is transferred is used as a mask A pattern forming method comprising transferring a pattern to the substrate by etching.

  According to the present invention, it is possible to provide a composition for forming a resist underlayer film excellent in rectangularity of a pattern, an underlayer film for lithography, and a pattern forming method.

  The composition for forming a resist underlayer film of the present invention comprises a tellurium-containing compound or a tellurium-containing resin, and a silicon-containing compound (for example, a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolytic condensate thereof) It is a composition for resist lower layer film formation containing the above. The composition for forming a resist underlayer film of the present invention has a relatively high carbon concentration, a relatively low oxygen concentration, high heat resistance, and high solvent solubility. Therefore, the rectangularity of the pattern is excellent.

The composition for forming a resist underlayer film of the present invention can be suitably used, for example, in a multilayer resist method in which a resist underlayer film is further provided between an upper layer resist (photoresist etc.) and a hard mask or an organic underlayer film. . In such a multilayer resist method, for example, a resist underlayer film is formed thereon by a coating method or the like via an organic underlayer film or hard mask on a substrate, and an upper layer resist (for example, photoresist, etc.) is formed on the resist underlayer film. Electron beam resist, EUV resist) is formed. Then, a resist pattern is formed by exposure and development, the resist underlayer film is dry etched using the resist pattern to transfer the pattern, the organic underlayer film is etched to transfer the pattern, and the organic underlayer film is used. Process the substrate.
That is, the resist underlayer film formed using the composition for forming a resist underlayer film of the present invention is less likely to cause intermixing with the upper layer resist, and has heat resistance, and for example, halogen-based (fluorine-based) etching Since the etching rate for the gas is larger than that of the patterned upper resist used as a mask, a rectangular and good pattern can be obtained. Furthermore, since a resist underlayer film formed using the composition for forming a resist underlayer film of the present invention has high resistance to an oxygen-based etching gas, it can be used as a good mask when patterning a layer provided on a substrate such as a hard mask. Can function. The composition for forming a resist underlayer film of the present invention can also be used in an embodiment in which a plurality of resist underlayer films are laminated. In this case, the position of the resist underlayer film formed using the composition for forming a resist underlayer film of the present invention (the layer on which the layer is laminated) is not particularly limited, and may be directly under the upper layer resist. It may be a layer located closest to the substrate side, or may be an embodiment sandwiched by a resist lower layer film.

In forming a fine pattern, the resist film thickness tends to be thin in order to prevent pattern collapse. In dry etching for transferring a pattern to a film existing in the lower layer by thinning the resist, pattern transfer can not be performed unless the etching rate is higher than that of the upper film. In the present invention, the substrate may be coated with the resist lower layer film (containing a silicon compound) of the present invention via the organic lower layer film, and the resist layer (organic resist film) may be further coated thereon. The dry etching rate greatly differs depending on the choice of etching gas between the film of organic type component and the film of inorganic type component, the film of organic type component becomes high in dry etching speed by oxygen type gas, and the film of inorganic type component contains halogen The gas increases the dry etching rate.
For example, using the resist underlayer film on which the pattern is transferred, the organic underlayer film under the layer is dry etched with an oxygen-based gas to perform pattern transfer onto the organic underlayer film, and the organic underlayer film on which the pattern is transferred Can be used to process the substrate.

  Further, a resist underlayer film comprising the composition for forming a resist underlayer film of the present invention comprises a tellurium-containing compound or a tellurium-containing compound having excellent ability to absorb actinic light, and a silicon-containing compound (for example, hydrolyzable organosilane By including the hydrolyzate or the hydrolytic condensate thereof, the sensitivity of the upper layer resist is improved, and no intermixing occurs with the upper layer resist, and the shape of the pattern of the resist lower film-forming film after exposure and development Becomes a rectangle. This enables substrate processing with a fine pattern.

  Moreover, since the resist underlayer film by the composition for resist underlayer film formation of this invention has high heat resistance, it can be used also under high temperature baking conditions. Furthermore, due to its relatively low molecular weight and low viscosity, even substrates having steps (in particular, fine spaces, hole patterns, etc.) can be easily filled uniformly to every corner, as a result The material for forming an underlayer film for lithography using this tends to relatively advantageously improve the planarizing property and the embedding property.

  Hereinafter, embodiments of the present invention will be described. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

[Composition for forming resist lower layer film]
The composition for forming a resist underlayer film of the present invention is a composition for forming a resist underlayer film, which contains a tellurium-containing compound or a resin containing a tellurium, and a silicon-containing compound. The composition for forming a resist underlayer film of the present invention contains a compound or resin having a specific structure and a silicon-containing compound (for example, hydrolyzable organosilane, its hydrolyzate or its hydrolytic condensate) Thus, the carbon concentration is relatively high, the oxygen concentration is relatively low, the heat resistance is high, and the solvent solubility is also high.
The composition for forming a resist lower layer film is obtained, for example, from a compound represented by the following formula (A) and a resin obtained by using this as a monomer (that is, containing a constitutional unit derived from the compound represented by the formula (A)) It contains one or more selected.

(Compound containing tellurium represented by the formula (A))
The composition for resist lower layer film formation of this embodiment can contain the compound containing the tellurium shown by following formula (A).

（式（Ａ）中、Ｘは、テルルを含む炭素数０〜３０の２ｍ価の基であり、Ｚは、酸素原子、硫黄原子又は無架橋であり、Ｒ⁰は、各々独立して、酸素原子を含む１価の基、硫黄原子を含む１価の基、窒素原子を含む１価の基、炭化水素基、又はハロゲン原子であり、ｍは、１〜４の整数であり、ｐは、各々独立して０〜２の整数であり、ｎは、各々独立して０〜（５＋２×ｐ）の整数である。）

(In the formula (A), X is a 2m-valent group having 0 to 30 carbon atoms including tellurium, Z is an oxygen atom, a sulfur atom or non-crosslinking, and R ⁰ is each independently oxygen A monovalent group containing an atom, a monovalent group containing a sulfur atom, a monovalent group containing a nitrogen atom, a hydrocarbon group, or a halogen atom, m is an integer of 1 to 4, and p is Each independently is an integer of 0 to 2, and n is each independently an integer of 0 to (5 + 2 × p).

  The compound to be contained in the composition for forming a resist lower layer film of the present embodiment contains tellurium as in the above-mentioned formula (A), and therefore, a sensitizing effect can be expected particularly in lithography by EUV. Moreover, since it has a benzene skeleton or a naphthalene skeleton etc., it is excellent in heat resistance.

In said Formula (A), m is an integer of 1-4. When m is an integer of 2 or more, the structural formulas of m repeating units may be the same or different. In the above formula (A), m is preferably 1 to 3 in terms of heat resistance, resolution, and resist properties such as roughness.
In addition, although the compound of this embodiment is not a polymer, for convenience, the structure in [] (brackets) bonded to X in the above-mentioned formula (A) may be referred to as “structural formula of repeating unit” , And the same for the formula).

In the above formula (A), p is each independently an integer of 0 to 2, and an attached ring structure (a ring structure represented by naphthalene in formula (A) (hereinafter, the ring structure is simply referred to as “ring structure A It is a value which determines the structure of "). That is, as shown below, in the formula (A), in the case of p = 0, the ring structure A represents a benzene structure, in the case of p = 1 the ring structure A represents a naphthalene structure, and in the case of p = 2, the ring Structure A shows a tricyclic structure such as anthracene or phenanthrene. The ring structure A is preferably, but not limited to, a benzene structure or a naphthalene structure from the viewpoint of solubility. In formula (A), X, Z and R ⁰ are attached to any bondable site on ring structure A.

  In said Formula (A), X is a C2-C30 2m-valent group containing tellurium. As X, a single bond containing tellurium, or a C1-C30 2m-valent hydrocarbon group containing tellurium can be mentioned. In addition, the single bond containing tellurium may have a substituent such as a halogen group.

The 2m-valent group is, for example, an alkylene group having 1 to 30 carbon atoms when m = 1, an alkanetetrayl group having 1 to 30 carbon atoms when m = 2, and a carbon number when m = 3 When it is 2 to 30 alkanehexayl group and m = 4, it indicates that the C3 to C30 alkane octayl group. Examples of the 2m-valent group include those having a linear, branched or cyclic structure.
The 2m-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 30 carbon atoms. Here, as for the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included.
X preferably has a fused polycyclic aromatic group (in particular, a fused ring structure of 2 to 4 rings) from the viewpoint of heat resistance, and from the viewpoint of solubility in a safe solvent and heat resistance, polyphenyl such as biphenyl group It is preferred to have a group.

  As a specific example of C2-C30 2m-valent group containing tellurium shown by X, the following groups are mentioned, for example.

  In the above formula (A), Z represents an oxygen atom, a sulfur atom or no crosslinking. When m is 2 or more, each Z may be the same or different. In addition, when m is 2 or more, structural formulas of different repeating units may be linked via Z. For example, when m is 2 or more, structural formulas of different repeating units may be linked via Z, and structural formulas of a plurality of repeating units may constitute a cup-shaped structure or the like. Although not particularly limited, Z is preferably an oxygen atom or a sulfur atom from the viewpoint of heat resistance.

In formula (A), each R ⁰ independently represents a monovalent group containing an oxygen atom, a monovalent group containing a sulfur atom, a monovalent group containing a nitrogen atom, a hydrocarbon group, or a halogen atom It is.

  Here, the monovalent group containing an oxygen atom is not limited to the following, and examples thereof include an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a linear group having 1 to 6 carbon atoms Alkyloxy group, branched alkyloxy group having 3 to 20 carbon atoms, cyclic alkyloxy group having 3 to 20 carbon atoms, linear alkenyloxy group having 2 to 6 carbon atoms, branched alkenyloxy group having 3 to 6 carbon atoms Group, cyclic alkenyloxy group having 3 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkoxycarbonyloxy group having 2 to 20 carbon atoms, alkoxy having 2 to 20 carbon atoms A carbonyl alkyl group, a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms, a cyclic ether oxy group having 2 to 20 carbon atoms, an alkoxyalkyloxy group having 2 to 20 carbon atoms, glycidyl Oxy group, allyloxy group, (meth) acrylic groups, glycidyl acrylate group include glycidyl methacrylate groups and hydroxyl groups and the like.

  Examples of the acyl group having 1 to 20 carbon atoms include, but are not limited to, methanoyl group (formyl group), ethanoyl group (acetyl group), propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, octanoyl group, decanoyl group And benzoyl group.

  Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms include, but are not limited to, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group and an octyloxycarbonyl group. And decyloxycarbonyl group.

  Examples of the linear alkyloxy group having 1 to 6 carbon atoms include, but are not limited to, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group Etc.

  Examples of the branched alkyloxy group having 3 to 20 carbon atoms include, but are not limited to, isopropoxy group, isobutoxy group, tert-butoxy group and the like.

  As a C3-C20 cyclic alkyloxy group, although it is not limited to the following, for example, cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclooctyloxy group, cyclodecyloxy group etc. may be mentioned .

  Examples of the linear alkenyloxy group having 2 to 6 carbon atoms include, but are not limited to, vinyloxy group, 1-propenyloxy group, 2-propenyloxy group, 1-butenyloxy group, 2-butenyloxy group, etc. Be

  Examples of the branched alkenyloxy group having 3 to 6 carbon atoms include, but are not limited to, isopropenyloxy group, isobutenyloxy group, isopentenyloxy group, isohexenyloxy group and the like.

  Examples of the cyclic alkenyloxy group having 3 to 10 carbon atoms include, but are not limited to, cyclopropenyloxy group, cyclobutenyloxy group, cyclopentenyloxy group, cyclohexenyloxy group, cyclooctenyloxy group, cyclodecenyl group Nyloxy group etc. are mentioned.

  Examples of the aryloxy group having 6 to 10 carbon atoms include, but are not limited to, phenyloxy group (phenoxy group), 1-naphthyloxy group, 2-naphthyloxy group and the like.

  As a C1-C20 acyloxy group, although it is not limited to the following, For example, formyloxy group, acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, benzoyloxy group etc. are mentioned.

  Examples of the alkoxycarbonyloxy group having 2 to 20 carbon atoms include, but are not limited to, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a propoxycarbonyloxy group, a butoxycarbonyloxy group, an octyloxycarbonyloxy group, and decyloxycarbonyl group. An oxy group etc. are mentioned.

  Examples of the alkoxycarbonylalkyl group having 2 to 20 carbon atoms include, but are not limited to, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylmethyl group, and an n-butoxycarbonylmethyl group. Etc.

  The C2-C20 1-substituted alkoxymethyl group is not limited to, for example, 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group And 1-cyclooctylmethoxymethyl group and 1-adamantylmethoxymethyl group.

  Examples of the cyclic ether oxy group having 2 to 20 carbon atoms include, but are not limited to, for example, tetrahydropyranyloxy group, tetrahydrofuranyloxy group, tetrahydrothiopyranyloxy group, tetrahydrothiofuranyloxy group, 4-methoxytetrahydrofuran The pyranyloxy group and 4-methoxy tetrahydro thiopyranyloxy group etc. are mentioned.

  Examples of the alkoxyalkyloxy group having 2 to 20 carbon atoms include, but are not limited to, methoxymethoxy, ethoxyethoxy, cyclohexyloxymethoxy, cyclohexyloxyethoxy, phenoxymethoxy, phenoxyethoxy and the like. .

  Examples of the (meth) acrylic group include, but are not limited to, an acryloyloxy group and a methacryloyloxy group. Further, the glycidyl acrylate group is not particularly limited as long as it can be obtained by reacting glycidyloxy group with acrylic acid. Furthermore, the glycidyl methacrylate group is not particularly limited as long as it can be obtained by reacting glycidyloxy group with methacrylic acid.

  Examples of monovalent groups containing a sulfur atom include, but are not limited to, thiol groups and the like. The monovalent group containing a sulfur atom is preferably a group in which a sulfur atom is directly bonded to a carbon atom constituting the ring structure (A) in the formula (A).

  Examples of the monovalent group containing a nitrogen atom include, but are not limited to, a nitro group, an amino group and a diazo group. The monovalent group containing a nitrogen atom is preferably a group in which a nitrogen atom is directly bonded to a carbon atom constituting the ring structure (A) in the formula (A).

  The hydrocarbon group is not limited to the following, for example, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and 2 carbon atoms A linear alkenyl group of -6, a branched alkenyl group of 3 to 6 carbon atoms, a cyclic alkenyl group of 3 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, and the like can be mentioned.

  Examples of the linear alkyl group having 1 to 6 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like. Be

  Examples of the branched alkyl group having 3 to 6 carbon atoms include, but not limited to, isopropyl group, isobutyl group, tert-butyl group, neopentyl group and 2-hexyl group.

  Although it does not limit to the following as a C3-C10 cyclic alkyl group, For example, cyclopropyl group, cyclobutyl group, a cyclopentyl group, a cyclohexyl group, cyclooctyl group, cyclodecyl group etc. are mentioned.

  Examples of the linear alkenyl group having 2 to 6 carbon atoms include, but are not limited to, vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, and the like. -A pentenyl group, 2-hexenyl group, etc. are mentioned.

  Examples of the branched alkenyl group having 3 to 6 carbon atoms include, but not limited to, isopropenyl group, isobutenyl group, isopentenyl group, isohexenyl group and the like.

  Examples of the cyclic alkenyl group having 3 to 10 carbon atoms include, but are not limited to, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclohexenyl group, cyclooctenyl group, cyclodecynyl group and the like.

  As a C6-C10 aryl group, although it is not limited to the following, For example, a phenyl group, a naphthyl group, etc. are mentioned.

  Examples of the halogen atom include, but are not limited to, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  In Formula (1) above, n is independently an integer of 0 to (5 + 2 x p). In the present embodiment, it is preferable that at least one of n in the formula (A) is an integer of 1 to 4 from the viewpoint of solubility in a solvent.

In the present embodiment, from the viewpoint of solubility in a solvent and introduction of crosslinkability, it is preferable that at least one of R ⁰ in the formula (A) is a monovalent group containing an oxygen atom.

-Tellurium-containing compound represented by the formula (1)-
It is preferable that the compound containing tellurium shown by said Formula (A) is a tellurium containing compound shown by following formula (1).

（式（１）中、Ｘ、Ｚ、ｍ、ｐは前記式（Ａ）と同義であり、Ｒ¹は、各々独立して、アルキル基、アリール基、アルケニル基又はハロゲン原子であり、Ｒ²は、各々独立して、水素原子又は酸解離性反応基であり、ｎ¹は各々独立して、０〜（５＋２×ｐ）の整数であり、ｎ²は各々独立して、０〜（５＋２×ｐ）の整数である。但し、少なくとも一つのｎ²は１〜（５＋２×ｐ）の整数である。）

(In formula (1), X, Z, m and p are as defined in the above formula (A), R ¹ is each independently an alkyl group, an aryl group, an alkenyl group or a halogen atom, R ² Each independently represents a hydrogen atom or an acid-dissociable reactive group, each n ¹ independently represents an integer of 0 to (5 + 2 × p), and each n ² independently represents an integer of 0 to (5 + 2) It is an integer of × p), provided that at least one n ² is an integer of 1 to (5 + 2 × p).

In Formula (1), n ¹ is each independently an integer of 0 to (5 + 2 × p), and n ² is each independently an integer of 0 to (5 + 2 × p). In addition, at least one n ² is an integer of 1 to (5 + 2 × p). That is, the tellurium-containing compound of the general formula (1) has at least one “—OR ² ” for one ring structure A. In formula (1), X, Z, R ¹ and -OR ² are bonded to any bondable site on ring structure A. Therefore, the upper limit of n ¹ + n ² in one ring structure A coincides with the upper limit of the number of bondable sites of the ring structure A after taking into consideration X and Z and the bonding site.

Each of the alkyl group, aryl group, alkenyl group and halogen atom represented by R ¹ is independently a substituted or unsubstituted linear, substituted or unsubstituted branched or substituted or unsubstituted cyclic alkyl group; It may be a substituted or unsubstituted aryl group; a substituted or unsubstituted alkenyl group; or a halogen atom.

As described above, the alkyl group represented by R ¹ includes a substituted or unsubstituted linear, substituted or unsubstituted branched or substituted or unsubstituted cyclic alkyl group.

  The linear, branched or cyclic alkyl group is not limited to the following, for example, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and 3 to 10 carbon atoms And a cyclic alkyl group of

  Examples of the linear alkyl group having 1 to 6 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like. Be

  Examples of the branched alkyl group having 3 to 6 carbon atoms include, but not limited to, isopropyl group, isobutyl group, tert-butyl group, neopentyl group and 2-hexyl group.

  Although it does not limit to the following as a C3-C10 cyclic alkyl group, For example, cyclopropyl group, cyclobutyl group, a cyclopentyl group, a cyclohexyl group, cyclooctyl group, cyclodecyl group etc. are mentioned.

As described above, examples of the aryl group represented by R ¹ include, but are not limited to, aryl groups having 6 to 10 carbon atoms, such as phenyl group and naphthyl group.

As described above, the alkenyl group represented by R ¹ includes, but is not limited to, a substituted or unsubstituted alkenyl group, and examples thereof include a linear alkenyl group having 2 to 6 carbon atoms, and 3 to 3 carbon atoms 6 branched alkenyl groups and C3-C10 cyclic alkenyl groups may be mentioned.

  Examples of the linear alkenyl group having 2 to 6 carbon atoms include, but are not limited to, vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, and the like. -A pentenyl group, 2-hexenyl group, etc. are mentioned.

  Examples of the branched alkenyl group having 3 to 6 carbon atoms include, but not limited to, isopropenyl group, isobutenyl group, isopentenyl group, isohexenyl group and the like.

  Examples of the cyclic alkenyl group having 3 to 10 carbon atoms include, but are not limited to, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclohexenyl group, cyclooctenyl group, cyclodecynyl group and the like.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom is mentioned, for example.

  In the present specification, “substituted” means, unless otherwise defined, one or more hydrogen atoms in the functional group are a halogen atom, a hydroxyl group, a cyano group, a nitro group, a heterocyclic group, one carbon atom. To 20 linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, 7-30 aralkyl group, alkoxy group having 1 to 20 carbon atoms, amino group having 0 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, alkoxy having 2 to 20 carbon atoms It means that it is substituted by a carbonyl group, a C1-C20 alkylloyloxy group, a C7-C30 aryloyloxy group, or a C1-C20 alkylsilyl group.

The unsubstituted C1-C20 linear aliphatic hydrocarbon group is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl And octadecyl groups.
As a substituted C1-C20 linear aliphatic hydrocarbon group, a fluoromethyl group, 2-hydroxyethyl group, 3-cyanopropyl group, 20-nitro octadecyl group etc. are mentioned, for example.

The unsubstituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms is, for example, isopropyl group, isobutyl group, tertiary butyl group, neopentyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2 -Dodecyl group, 2-hexadecyl group, 2-octadecyl group etc. are mentioned.
Examples of the substituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms include 1-fluoroisopropyl group and 1-hydroxy-2-octadecyl group.

The unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms is, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group, cyclo An octadecyl group etc. are mentioned.
Examples of the substituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms include a 2-fluorocyclopropyl group and a 4-cyanocyclohexyl group.

As a C6-C20 unsubstituted aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example.
Examples of the substituted aryl group having 6 to 20 carbon atoms include 4-isopropylphenyl group, 4-cyclohexylphenyl group, 4-methylphenyl group, 6-fluoronaphthyl group and the like.

Examples of the unsubstituted alkenyl group having 2 to 20 carbon atoms include a vinyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, octynyl group, octynyl group, decynyl group, dodecynyl group, hexadecynyl group and octadecynyl group.
As a substituted C2-C20 alkenyl group, a chloropropynyl group etc. are mentioned, for example.

  The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In formula (1), each R ² is independently a hydrogen atom or an acid dissociable reactive group. In formula (1), each R ² independently represents a hydrogen atom or an acid dissociable reactive group. In the present embodiment, when a positive pattern is formed by alkali development or a negative pattern is formed by organic development, the compound represented by the formula (1) is at least one acid dissociable reaction as R ^2. It is preferred to have a group. In the embodiment, when a negative pattern is formed by alkali development, a compound containing tellurium in which all R ^{2 s} are hydrogen atoms can be used as the compound represented by the formula (1).

  As used herein, the term "acid-dissociable reactive group" refers to a characteristic group that is cleaved in the presence of an acid to produce a change such as an alkali soluble group. The alkali-soluble group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group and the like, a phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable. The acid dissociable reactive group is not particularly limited, but, for example, among those proposed in hydroxystyrene resins, (meth) acrylic acid resins and the like used in chemically amplified resist compositions for KrF and ArF. It can select suitably from and use.

  In the present embodiment, the compound represented by the formula (1) is preferably a compound represented by the following formula (2) from the viewpoint of solubility in a safe solvent and heat resistance.

（式（２）中、Ｚ、Ｒ¹、Ｒ²、ｐ、ｎ¹、ｎ²は前記式（１）と同義であり、Ｘ¹はハロゲン原子である。）

(In formula (2), Z, R ¹ , R ² , p, n ¹ and n ² are as defined in the above formula (1), and X ¹ is a halogen atom)

  In the present embodiment, the compound represented by the formula (2) is preferably a compound represented by the following formula (3) from the viewpoint of heat resistance.

（式（３）中、Ｒ¹、Ｒ²、Ｘ¹、ｎ¹、ｎ²は前記式（２）と同義である。）

(In Formula (3), R ¹ , R ² , X ¹ , n ¹ and n ² have the same meanings as in Formula (2) above).

  In the present embodiment, the compound represented by the formula (3) is preferably a compound represented by the following general formula (4) from the viewpoint of ease of production.

（式（４）中、Ｒ¹、Ｒ²、Ｘ¹は前記と同様である。）

(In formula (4), R ¹ , R ² and X ¹ are as defined above.)

In the present embodiment, the method for producing the compound represented by the formula (A) is not particularly limited. For example, a polyalkoxybenzene compound is obtained by reacting an alkoxybenzene with a corresponding halogenated tellurium, and subsequently There is a method of obtaining a polyphenol compound by reduction with a reducing agent such as boron tribromide.
Also, a method of obtaining polyphenol compounds by reacting phenols or thiophenols with corresponding tellurium halides, and further, phenols or thiophenols with corresponding tellurium aldehydes or tellurium-containing ketones And the method of obtaining a polyphenol compound by making it react under an acid or a base catalyst, etc. can be mentioned.

  The halogenated tellurium is not particularly limited, and examples thereof include tellurium (IV) tetrafluoride, tellurium (IV) tetrachloride, tellurium (IV) tetrabromide, tellurium (IV) tetraiodide and the like.

  The alkoxybenzenes are not particularly limited. For example, methoxybenzene, dimethoxybenzene, methylmethoxybenzene, methyldimethoxybenzene, phenylmethoxybenzene, phenyldimethoxybenzene, methoxynaphthalene, dimethoxynaphthalene, ethoxybenzene, diethoxybenzene, methyl Examples include ethoxybenzene, methyldiethoxybenzene, phenylethoxybenzene, phenyldiethoxybenzene, ethoxynaphthalene, diethoxynaphthalene and the like.

A reaction solvent may be used when producing the polyalkoxybenzene compound. The reaction solvent is not particularly limited as long as the reaction between the alkoxybenzenes used and the corresponding tellurium halide proceeds, but, for example, water, methylene chloride, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, dimethylacetamide, N -Methyl pyrrolidone or a mixed solvent of these can be used.
The amount of the solvent is not particularly limited, and can be, for example, in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material.

When producing the tellurium-containing polyphenol compound, the reaction temperature is not particularly limited and can be appropriately selected according to the reactivity of the reaction raw material, but is preferably in the range of 10 to 200 ° C.
The method for producing the polyalkoxybenzene is not particularly limited, and examples thereof include a method in which alkoxybenzenes and the corresponding tellurium halide are charged at once, and a method in which the alkoxybenzenes and the corresponding corresponding tellurium halide are dropped . After completion of the reaction, the temperature of the reaction kettle may be raised to 130 to 230 ° C. to remove the volatile components at about 1 to 50 mmHg in order to remove unreacted raw materials and the like present in the system.

  The amount of the raw material at the time of producing the polyalkoxybenzene compound is not particularly limited. For example, 1 mole to excess of alkoxybenzenes is used with respect to 1 mole of tellurium halide under normal pressure at 20 to 150 ° C. The reaction can be carried out by reacting for about 20 minutes to about 100 hours.

  When the polyalkoxybenzene compound is produced, after completion of the reaction, the desired product can be isolated by a known method. The method for isolating the desired product is not particularly limited. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, and after cooling to room temperature, filtration is performed to separate the obtained solid The reaction product is filtered and dried, followed by column chromatography to separate and purify the by-product, solvent evaporation, filtration and drying to obtain the target compound.

  The polyphenol compound can be obtained by reducing a polyalkoxybenzene compound. The reduction reaction can be carried out using a reducing agent such as boron tribromide. When manufacturing the said polyphenol compound, you may use the reaction solvent. The reaction time, reaction temperature, amount of raw materials and method of isolation are not particularly limited as long as the polyphenol compound can be obtained.

  Specific examples of the tellurium-containing compound represented by the formula (A) include, for example, the following.

(A resin containing a structural unit derived from formula (A))
The composition for forming a resist underlayer film of the present embodiment may contain a resin containing a structural unit derived from Formula (A) instead of or in addition to the tellurium-containing compound represented by Formula (A) Good. In other words, the composition for forming a resist lower layer film of the present embodiment can contain a resin obtained by using the compound represented by the formula (A) as a monomer.
In addition, the resin of the present embodiment can be obtained, for example, by reacting a compound represented by Formula (A) with a compound having crosslinking reactivity.
As the compound having crosslinking reactivity, known compounds can be used without particular limitation as long as they can oligomerize or polymerize the compound represented by the formula (A). Specific examples thereof include, but not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

  Specific examples of the structural unit derived from the formula (A) include the following.

  Here, the resin in the present embodiment may be a homopolymer of the compound represented by the formula (A), but may be a copolymer with another phenol. Examples of phenols that can be copolymerized here include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include propylphenol, pyrogallol, thymol and the like, but are not particularly limited thereto.

  In addition to the above-described other phenols, the resin in this embodiment may be copolymerized with a polymerizable monomer. Such copolymerization monomers include, for example, naphthol, methyl naphthol, methoxy naphthol, dihydroxy naphthalene, indene, hydroxy indene, benzofuran, hydroxy anthracene, acenaphthylene, biphenyl, bisphenol, tris phenol, dicyclopentadiene, tetrahydro indene, 4-vinylcyclohexene And norbornadiene, vinyl norbornaene, pinene, limonene and the like, but not limited thereto. In addition, even if the resin in the present embodiment is a binary or more (for example, a two- to four-way copolymer) copolymer of the compound represented by the formula (A) and the phenol described above, the resin Even if it is a binary or more (for example, 2 to 4 binary system) copolymer of the compound represented by A) and the copolymerizable monomer described above, the compound represented by the formula (A) and the phenol described above And three or more (for example, three- to four-component) copolymers of the above-mentioned copolymer monomers.

  In addition, the molecular weight of the resin in the present embodiment is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, and more preferably 750 to 20,000. In addition, from the viewpoint of enhancing the crosslinking efficiency and suppressing the volatile component during baking, the resin in the present embodiment has a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) in the range of 1.2 to 7 preferable. In addition, said Mn can be calculated | required by the method as described in the Example mentioned later.

  The compound represented by the above-mentioned formula (A) and / or the resin obtained by using the compound as a constituent unit has high solubility in a solvent from the viewpoint of easier application of a wet process, etc. preferable. More specifically, when using these compounds and / or resins as solvents, 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA), the solubility in the solvent is 10% by mass or more. Is preferred. Here, the solubility in PGME and / or PGMEA is defined as “mass of resin × (mass of resin + mass of solvent) × 100 (mass%)”. For example, the compound of the formula (A) and / or the compound of the formula (A) are evaluated as dissolving 10 g of the compound represented by the formula (A) and / or the compound as a monomer in 90 g of PGMEA. The solubility of the resin obtained using the compound as a monomer in PGMEA is "3% by mass or more", and it is evaluated as not dissolving when the solubility is "less than 3% by mass".

(Other ingredients)
The composition for forming a resist lower layer film includes a tellurium-containing compound or a tellurium-containing resin, a solvent, an acid, an acid crosslinking agent, a hydrolyzable organosilane, a hydrolyzate thereof, a hydrolytic condensate thereof, and the like. It can further include. Furthermore, as optional components, an organic polymer compound, an acid generator and a surfactant, others, water, an alcohol, a curing catalyst and the like can be included.
In the resist underlayer film forming material, the compound represented by the above-mentioned formula (A) and the monomer are 0.1 to 70 in the composition for forming the resist underlayer film from the viewpoint of coating properties and quality stability. It is preferable that it is mass%, It is more preferable that it is 0.5-50 mass%, It is especially preferable that it is 3.0-40 mass%.

-Solvent-
As the solvent used in the present embodiment, known solvents can be appropriately used as long as the compound represented by the above-mentioned formula (A) and / or the resin obtained by using the compound as a constitutional unit is at least dissolved. .

  Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cellosolv solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, Ester solvents such as isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol and 1-ethoxy-2-propanol; aromatic solvents such as toluene, xylene and anisole Although a hydrocarbon etc. are mentioned, it is not specifically limited to these. These organic solvents can be used alone or in combination of two or more.

  Among the above solvents, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate and anisole are particularly preferable in terms of safety.

  The content of the solvent is not particularly limited, but from the viewpoint of solubility and film formation, it is 100 to 10,000 parts by mass with respect to 100 parts by mass of the total solid content of the composition for forming a resist lower layer film. Is preferable, 200 to 8,000 parts by mass is more preferable, and 200 to 5,000 parts by mass is more preferable.

-Acid-
The composition for forming a resist lower layer film can contain an acid from the viewpoint of curing promotion. Examples of the acid include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfone and the like.

  The content of the acid is not particularly limited, but from the viewpoint of solubility and shape stability of the coating, 0.001 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the composition for forming a resist lower layer film. Is preferable, 0.005 to 10 parts by mass is more preferable, and 0.01 to 5 parts by mass is more preferable.

-Acid crosslinker-
The composition for forming a resist underlayer film may contain one or more acid crosslinking agents when used as a negative resist material or as an additive for increasing the strength of a pattern even in a positive resist material. The acid crosslinking agent is a compound capable of intramolecular or intermolecular crosslinking of the compound represented by the formula (A) in the presence of the above-mentioned acid. Although such an acid crosslinking agent is not particularly limited, for example, mention is made of a compound having one or more groups capable of crosslinking the compound represented by the formula (A) (hereinafter referred to as "crosslinkable group"). Can.

  Although it does not specifically limit as a specific example of such a crosslinkable group, For example, (i) Hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group) Hydroxyalkyl group such as acetoxy (C1-C6 alkyl group) or a group derived therefrom; (ii) carbonyl group such as formyl group, carboxy (C1-C6 alkyl group) or the like (Iii) nitrogen-containing group-containing groups such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group and the like; (iv) glycidyl ether group, glycidyl ester group, Glycidyl group-containing groups such as glycidyl amino group; (v) Carbon number such as benzyloxymethyl group, benzoyloxymethyl group A group derived from an aromatic group such as allyloxy of 6 to 6 (alkyl group of 1 to 6 carbon atoms), aralkyloxy of 1 to 6 carbon atoms (alkyl group of 1 to 6 carbon atoms); (vi) vinyl group, Examples thereof include polymerizable multiple bond-containing groups such as isopropenyl group. As the crosslinkable group of the acid crosslinking agent (G), a hydroxyalkyl group, an alkoxyalkyl group and the like are preferable, and an alkoxymethyl group is particularly preferable.

The acid crosslinking agent is not particularly limited, and examples thereof include methylol groups such as (i) methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing glycoluril compounds and methylol group-containing phenol compounds. (Ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds; iii) Carboxymethyl group-containing melamine compound, Carboxymethyl group-containing benzoguanamine compound, Carboxymethyl group-containing urea compound, Carboxymethyl group-containing Carboxymethyl group-containing compounds such as recalluril compounds and carboxymethyl group-containing phenol compounds; (iv) bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy compounds And epoxy compounds such as poly (hydroxystyrene) epoxy compounds.
In addition, for example, those described in International Publication WO 2013/024779 can be mentioned as a specific example of the acid crosslinking agent.

  As the acid crosslinking agent, compounds having a phenolic hydroxyl group, and compounds and resins obtained by introducing the above-mentioned crosslinkable group into an acidic functional group in an alkali-soluble resin to impart crosslinkability can be used. The introduction rate of the crosslinkable group in that case is not particularly limited, and is, for example, 5 to 100% by mole, preferably 10 to 60 based on all the acidic functional groups in the compound having a phenolic hydroxyl group and the alkali-soluble resin. It is preferably adjusted to mol%, more preferably 15 to 40 mol%. It is preferable that the content is in the above range, since the crosslinking reaction occurs sufficiently to reduce the residual film rate, the swelling phenomenon of the pattern, the meandering, and the like.

  The content of the acid crosslinking agent is not particularly limited, but from the viewpoint of solubility and shape stability of the coating, it is 0.01 to 30 based on 100 parts by mass of the total solids of the composition for forming a resist underlayer film. It is preferable that it is a mass part, It is more preferable that it is 0.05-20 mass parts, It is further more preferable that it is 0.1-10 mass parts.

-Silicon-containing compound-
The composition for forming a resist underlayer film contains a silicon-containing compound as well as a compound containing tellurium. The silicon-containing compound may be either an organic silicon-containing compound or an inorganic silicon-containing compound, but is preferably an organic silicon-containing compound. Examples of the inorganic silicon-containing compound include silicon oxides, silicon nitrides, and polysilazane compounds made of silicon oxynitride which can be formed into a film by a coating method at a low temperature. Moreover, as said organosilicon containing compound, a polysilsesquioxane based compound, hydrolysable organosilane, its hydrolyzate, or its hydrolysis-condensation product is mentioned, for example. The specific material of the polysilsesquioxane base is not limited to the following, but, for example, those described in JP-A-2007-226170 and JP-A-2007-226204 can be used. In addition, as the hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolytic condensate thereof, at least one selected from the group consisting of a hydrolyzable organosilane of the following formula (A1) and the following formula (A2) Hydrolysable organosilanes, their hydrolysates, or their hydrolytic condensates (hereinafter referred to simply as “at least one organosilicon compound selected from the group consisting of formula (A1) and formula (A2) (Which may be referred to as When the composition for forming a resist underlayer film contains at least one organosilicon compound selected from the group consisting of Formula (A1) and Formula (A2), control of Si-O bond is controlled by adjustment of curing conditions. It is easy, cost-effective and suitable for the introduction of organic components. Therefore, the composition for forming a resist underlayer film is formed using the composition for forming a resist underlayer film, which includes at least one organosilicon compound selected from the group consisting of Formula (A1) and Formula (A2). The layer is useful as an intermediate layer of the resist layer (a layer between the upper resist layer and the organic underlayer provided on the substrate).

Formula (A1): (R ³ ) _a Si (R ⁴ ) _4-a
(In formula (A1), R ³ represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, "Organic group" having an alkoxyaryl group, an acyloxyaryl group, an isocyanurate group, a hydroxy group, a cyclic amino group, or a cyano group; or a combination thereof and is bonded to a silicon atom by a Si-C bond R ⁴ represents an alkoxy group, an acyloxy group or a halogen group, and a represents an integer of 0 to 3.)

Formula (A2): [(R ⁵ ) _c Si (R ⁶ ) _4-c ] ₂ Y _b
(In formula (A2), R ⁵ represents an alkyl group, R ⁶ represents an alkoxy group, an acyloxy group or a halogen group, Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, c Represents an integer of 0 or 1.)

  In the composition for forming a resist underlayer film, a compound containing tellurium represented by the formula (A) or a resin containing tellurium, and a silicon-containing compound (for example, selected from the group consisting of the formula (A1) and the formula (A2) The molar ratio of at least one organosilicon compound) can be used in the range of 1: 2 to 1: 200 in molar ratio. In order to obtain a good resist shape, for example, the molar ratio can be used in the range of 1: 2 to 1: 100. It is preferable to use at least one organosilicon compound selected from the group consisting of Formula (A1) and Formula (A2) as a hydrolysis condensate (polymer of polyorganosiloxane).

R ³ in the hydrolyzable organosilane represented by the formula (A1) is an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, an epoxy group, an acryloyl group An “organic group” having a group, methacryloyl group, mercapto group, alkoxyaryl group, acyloxyaryl group, isocyanurate group, hydroxy group, cyclic amino group, or cyano group, or a combination thereof, and a Si—C bond R ⁴ is an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 0 to 3.

  The hydrolyzable organosilane represented by the formula (A1) is, for example, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, methyltrimethoxy Silane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltriaryloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriethoxysilane Triphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxye Titrilyethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxy Propyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxy Propyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxy Butyltrimethoxysilane, -Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) Methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,3, 4-epoxycyclohexyl) Propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxy Silane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyl Dimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glyci Xypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyl diphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyl diethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane , Vinyltriacetoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, γ-chloropropyltrimetho Sisilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3, 3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethylsilane Dimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxyp Ropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, phenylsulfonylaminopropyltriethoxysilane, methylsulfonylaminopropyltriethoxysilane, And phenylsulfonylaminopropyltrimethoxysilane, methylsulfonylaminopropyltrimethoxysilane and the like.

  As the hydrolyzable organosilane represented by the formula (A1), a combination of tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane with phenyltrialkoxysilane such as phenyltrimethoxysilane and phenyltriethoxysilane is particularly preferable. . Furthermore, it is preferable to combine an alkyltrialkoxysilane such as methyltrimethoxysilane or methyltriethoxysilane with these combinations.

R ^{5 in} the hydrolyzable organosilane of formula (A2) represents an alkyl group, R ⁶ represents an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group or an arylene group, and b is 0 or 1 Represents an integer, c represents an integer of 0 or 1;

  Hydrolyzable organosilanes of the formula (A2) are, for example, methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane , Phenylene bis trimethoxysilane, phenylene bis triethoxysilane, phenylene bis methyldiethoxy silane, phenylene bis methyl dimethoxysilane, naphthalene bis trimethoxysilane, bis trimethoxy disilane, bis triethoxy disilane, bis ethyl diethoxy disilane, bis methyl dimethoxy disilane, etc. It can be mentioned.

In the present invention, the film may be formed as a mixture without reacting the tellurium compound and the hydrolyzable organosilane or the like, but a compound containing tellurium in the composition for forming a resist underlayer film, Synthesis of tellurium-containing silicon compounds by hydrolysis and condensation using the above-mentioned hydrolyzable organosilane or the like with one or more compounds selected from inorganic acids, aliphatic sulfonic acids and aromatic sulfonic acids as an acid catalyst You may
Examples of the acid catalyst used at this time include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid and the like. The amount of the catalyst used is preferably 10 ^-6 to 10 moles, more preferably 10 ^{-5 to} 5 moles, still more preferably, per mole of the monomer (the total amount of the compound containing tellurium and the hydrolyzable organosilane etc.) Is 10 ^-4 to 1 mole.

  The amount of water when obtaining a tellurium-containing silicon compound by hydrolysis condensation from these monomers is 0 per mol of hydrolyzable substituent bonded to the monomer (the compound containing tellurium and the hydrolyzable organosilane etc.) It is preferable to add .01 to 100 mol, more preferably 0.05 to 50 mol, and still more preferably 0.1 to 30 mol. Addition of 100 moles or less is economical because the apparatus used for the reaction is not excessive.

  As an operation method at the time of synthesizing the tellurium-containing silicon compound, for example, a monomer is added to a catalyst aqueous solution to start a hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, a monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100 ° C, more preferably 40 to 100 ° C. It is preferable to keep the temperature at 5 to 80 ° C. at the time of dropping the monomer and then to age at 40 to 100 ° C.

  Organic solvents which can be added to the aqueous catalyst solution or which can be added to dilute the monomers include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone Acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether , Propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate Propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ -Butyrolactone and mixtures thereof are preferred.

  Among these solvents, more preferred are water-soluble ones. For example, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, Polyhydric alcohol condensate derivatives such as propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran and the like can be mentioned. Particularly preferred among these is one having a boiling point of 100 ° C. or less.

  The amount of the organic solvent used is preferably 0 to 1,000 ml, particularly preferably 0 to 500 ml, per 1 mol of the monomer (the total amount of the compound containing tellurium and the hydrolyzable organosilane etc.). If the amount of use of the organic solvent is 1,000 ml or less, it is economical because the reaction container will not be excessive.

  Thereafter, neutralization reaction of the catalyst is carried out if necessary, and the alcohol produced by the hydrolysis condensation reaction is removed under reduced pressure to obtain an aqueous reaction mixture solution. At this time, the amount of the alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. The alkaline substance may be any substance as long as it exhibits alkalinity in water.

  Subsequently, it is preferable to remove by-products such as alcohol generated by the hydrolysis condensation reaction from the reaction mixture. At this time, the temperature at which the reaction mixture is heated depends on the type of organic solvent added and the alcohol generated in the reaction, preferably 0 to 100 ° C., more preferably 10 to 90 ° C., still more preferably 15 to 80 ° C. . At this time, the degree of pressure reduction varies depending on the kind of organic solvent and alcohol to be removed, the exhaust device, the condenser and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less in absolute pressure, still more preferably absolute The pressure is 50 kPa or less. At this time, although it is difficult to know exactly the amount of alcohol to be removed, it is desirable to remove about 80% by mass or more of the produced alcohol and the like.

  Next, the acid catalyst used for hydrolytic condensation may be removed from the reaction mixture. As a method of removing an acid catalyst, a method of mixing water and a tellurium-containing silicon compound and extracting the tellurium-containing silicon compound with an organic solvent can be exemplified. As an organic solvent to be used at this time, a solvent capable of dissolving a tellurium-containing silicon compound and capable of being separated into two layers when mixed with water is preferable. For example, 1-butanol, 2-butanol, 2-methyl-1-propanol, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, butanediol monoethyl ether, ethylene glycol diethyl ether, butanediol monopropyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono Mention may be made of t-butyl ether acetate, methyl isobutyl ketone, cyclopentyl methyl ether etc. and mixtures thereof.

  Furthermore, when removing the acid catalyst used for hydrolysis condensation from the reaction mixture, it is also possible to use a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent. For example, methanol + ethyl acetate, ethanol + ethyl acetate, 1-propanol + ethyl acetate, 2-propanol + ethyl acetate, butanediol monomethyl ether + ethyl acetate, propylene glycol monomethyl ether + ethyl acetate, ethylene glycol monomethyl ether + ethyl acetate, butane Diol monoethyl ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate, ethylene glycol monoethyl ether + ethyl acetate, butanediol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl ether + Ethyl acetate, methanol + methyl isobutyl ketone, ethanol + methyl isobutyl ketone, 1-propanol + methyl isobu Ketone, 2-propanol + methyl isobutyl ketone, propylene glycol monomethyl ether + methyl isobutyl ketone, ethylene glycol monomethyl ether + methyl isobutyl ketone, propylene glycol monoethyl ether + methyl isobutyl ketone, ethylene glycol monoethyl ether + methyl isobutyl ketone, propylene glycol Monopropyl ether + methyl isobutyl ketone, ethylene glycol monopropyl ether + methyl isobutyl ketone, methanol + cyclopentyl methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + cyclopentyl methyl ether, 2-propanol + cyclopentyl methyl ether, propylene glycol monomethyl ether + Cyclopen Methyl ether, ethylene glycol monomethyl ether + cyclopentyl methyl ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentyl methyl ether, ethylene glycol monopropyl ether + cyclopentyl Methyl ether, methanol + propylene glycol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, 1-propanol + propylene glycol methyl ether acetate, 2-propanol + propylene glycol methyl ether acetate, propylene glycol monomethyl ether + propylene glycol Methyl ether acetate, ethylene glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate, ethylene glycol monoethyl ether + propylene glycol methyl ether acetate, propylene glycol monopropyl ether + propylene glycol methyl A combination of ether acetate, ethylene glycol monopropyl ether + propylene glycol methyl ether acetate, etc. is preferred, but the combination is not limited thereto.

  The mixing ratio of the water-soluble organic solvent and the poorly water-soluble organic solvent is appropriately selected, but 0.1 to 1,000 parts by mass of the water-soluble organic solvent is preferable with respect to 100 parts by mass of the poorly water-soluble organic solvent, More preferably, it is 1-500 mass parts, More preferably, it is 2-100 mass parts.

  A tellurium-containing silicon compound having an acid catalyst remaining and a tellurium-containing silicon compound from which an acid catalyst has been removed. In any case, a final solvent is added and solvent exchange is performed under reduced pressure to obtain a tellurium-containing silicon compound solution. be able to. The temperature of the solvent exchange at this time depends on the type of reaction solvent and extraction solvent to be removed, but is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 15 to 80 ° C. The degree of pressure reduction at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less in absolute pressure, still more preferably 50 kPa in absolute pressure It is below.

-Other optional components-
The composition for forming a resist lower layer film may contain an organic polymer compound, a crosslinking agent, a photoacid generator, a surfactant and the like as needed in addition to the above components.

Adjusting the dry etching rate (reduction amount of film thickness per unit time), attenuation coefficient, refractive index and the like of the resist underlayer film formed from the composition for forming a resist underlayer film, by using an organic polymer compound Can.
There is no restriction | limiting in particular as an organic polymer compound, Various organic polymers can be used. Condensation polymerization polymers and addition polymerization polymers can be used. Addition polymerization polymers and condensation polymers such as polyesters, polystyrenes, polyimides, acrylic polymers, methacrylic polymers, polyvinyl ethers, phenol novolaks, naphthol novolaks, polyethers, polyamides, polycarbonates and the like can be used. An organic polymer having an aromatic ring structure such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, and a quinoxaline ring that functions as an absorption site is preferably used.

By using a crosslinking agent, it is possible to adjust the dry etching rate (the amount of reduction of the film thickness per unit time) and the like of the resist underlayer film formed from the composition for forming a resist underlayer film.
There is no restriction | limiting in particular as a crosslinking agent, Various crosslinking agents can be used. Specific examples of the crosslinking agent that can be used in the present embodiment include, for example, double bonds such as melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and alkenyl ether groups. And compounds having at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group as a substituent (crosslinkable group), and the like, but not limited thereto. In addition, these crosslinking agents can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use these as an additive. In addition, the crosslinkable group may be introduced as a pendant group to a polymer side chain in a resin obtained by using the compound represented by the formula (1) and / or the compound as a monomer. In addition, compounds containing a hydroxy group can also be used as the crosslinking agent. Among these, in particular, melamine compounds, glycoluril compounds and the like are preferably used.

  Specific examples of the melamine compound include, for example, hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine And compounds in which 1 to 6 of methylol groups of hexamethylolmelamine are acyloxymethylated or a mixture thereof. Specific examples of the epoxy compound include, for example, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylol ethane triglycidyl ether and the like.

  Specific examples of the guanamine compound include, for example, tetramethylol guanamine, tetramethoxymethyl guanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxy guanamine, The compound etc. in which the acyloxymethylation of 1-4 methylol group of tetramethylol guanamine was carried out, etc. are mentioned. Specific examples of the glycoluril compound include, for example, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, tetramer The compound etc. which the acyloxymethylation of 1 to 4 of methylol group of methylol glycol uryl carried out, or its mixture etc. are mentioned. Specific examples of the urea compound include, for example, tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 methylol groups of tetramethylolurea are methoxymethylated or a mixture thereof, and tetramethoxyethylurea.

  Specific examples of the compound containing an alkenyl ether group include, for example, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neo Pentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc. It can be mentioned.

  The content of the crosslinking agent in the composition for forming a resist lower layer film is not particularly limited, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the compound containing tellurium or the resin containing tellurium. And more preferably 1 to 5 parts by mass. By setting the above-mentioned preferable range, the occurrence of mixing phenomenon with the resist layer tends to be suppressed, and the antireflective effect tends to be enhanced, and the film formation after crosslinking tends to be enhanced.

  The composition for forming a resist lower layer film can contain an acid generator. As an acid generator, although what generate | occur | produces an acid by thermal decomposition, the thing which generate | occur | produces an acid by light irradiation, etc. are known, any thing can be used. As the acid generator, for example, those described in International Publication WO 2013/024779 can be used.

  When an acid generator is used, the proportion thereof is 0.01 parts by mass to 5 parts by mass, or 0.1 parts by mass to 3 parts by mass with respect to 100 parts by mass of the compound containing tellurium or the resin containing tellurium It is a mass part, or 0.5 mass part-1 mass part.

The surfactant is effective in suppressing the occurrence of surface defects and the like when the composition for forming a resist underlayer film is applied to a substrate.
Examples of the surfactant contained in the composition for forming a resist lower layer film include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. Polyoxyethylene alkyl aryl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan mono Sorbitan fatty acid esters such as oleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sol Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate And the like. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is, for example, 0.0001 parts by mass to 5 parts by mass, or 0.001 parts by mass with respect to 100 parts by mass of the compound containing tellurium or the resin containing tellurium It is 1 mass part, or 0.01 mass part-0.5 mass part.

[Underlayer film for lithography and pattern formation method]
The underlayer film for lithography of the present invention can be formed using the composition for forming a resist underlayer film of the present invention. The underlayer film for lithography of the present invention can be suitably used as a lower layer (resist underlayer film) of a photoresist (upper layer) used in a multilayer resist method.
In the present invention, for example, a resist underlayer film is formed using a composition for forming a resist underlayer film, and at least one photoresist layer is formed on the resist underlayer film, and then a predetermined photoresist layer is formed. A pattern can be formed by irradiating the region with radiation and performing development.
Moreover, as an aspect of the pattern formation method of the present invention using the composition for forming a resist underlayer film prepared as described above, an organic underlayer film is formed on a substrate using a coating type organic underlayer film material A resist underlayer film is formed on the organic underlayer film using the composition for forming a resist underlayer film of the present invention, and an upper layer resist film is formed on the resist underlayer film using an upper layer resist film composition, An upper layer resist pattern is formed on the upper layer resist film, the pattern is transferred to the resist lower layer film by etching using the upper layer resist pattern as a mask, and the organic lower layer film is etched using the resist lower layer film to which the pattern is transferred as a mask. And transfer the pattern to the substrate (object to be processed) by etching using the organic lower layer film to which the pattern is transferred as a mask. It can be mentioned pattern forming method.

  As another embodiment of the pattern forming method of the present invention, an organic hard mask mainly composed of carbon is formed on a substrate by a CVD method, and the composition for forming a resist underlayer film of the present invention is used on the organic hard mask. A resist underlayer film is formed, an upper layer resist film is formed on the resist underlayer film using the upper layer resist film composition, an upper layer resist pattern is formed on the upper layer resist film, and the upper layer resist pattern is used as a mask The pattern is transferred to the lower layer film by etching, and the pattern is transferred to the organic hard mask by using the resist lower layer film to which the pattern is transferred as a mask, and the pattern is transferred by etching. The pattern formation method which transcribes | transfers a pattern to a base material (processed object) by an etching can be mentioned.

For example, a semiconductor substrate can be used as the base material. Although a silicon substrate can be generally used as the semiconductor substrate, it is not particularly limited, and Si, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN , Al, etc., which are different in material from the processing layer.
Moreover, as a metal which comprises the said base material (processed object; containing the said semiconductor substrate), silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, an indium, a gallium, an arsenic, palladium, iron Tantalum, iridium, or molybdenum, or an alloy thereof can be used.

In addition, any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxynitride film is formed as a process layer (process portion) on a semiconductor substrate Etc. can be used. As a process layer containing such a metal, for example, Si, SiO ₂ , SiN, SiON, SiON, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, W W-Si, Al, Cu, Al-Si, etc., as well as various low dielectric films and their etching stopper films can be used to form a thickness of usually 50 to 10,000 nm, especially 100 to 5,000 nm.

  In the pattern formation method of the present invention, an organic lower layer film or an organic hard mask can be formed on a substrate. Among them, the organic lower layer film can be formed from a coating type organic lower layer film material by using a spin coating method or the like, and the organic hard mask is formed from a material of an organic hard mask containing carbon as a main component by using a CVD method. be able to. The types and the like of the organic lower layer film and the organic hard mask are not particularly limited. However, in the case where the upper layer resist film forms a pattern by exposure to light, those which exhibit a sufficient antireflective film function are preferable. By forming such an organic lower layer film or an organic hard mask, the pattern formed by the upper layer resist film can be transferred onto the base (workpiece) without causing a size conversion difference. In addition, a hard mask “based on carbon as a main component” is made of a carbon-based material such as amorphous hydrogenated carbon in which 50% by mass or more of solid content is also called amorphous carbon and is displayed as aC: H. Mean a hard mask. Although a-C: H films can be deposited by various techniques, plasma enhanced chemical vapor deposition (PECVD) is widely used for cost efficiency and film quality tunability. As an example of the hard mask, for example, those described in JP-A-2013-526783 can be referred to.

  The resist underlayer film using the composition for forming a resist lower layer film of the present invention used in the method for forming a pattern of the present invention was provided with an organic underlayer film etc. from the composition for forming a resist underlayer film by spin coating etc. It is possible to produce on a processing object. In the case where the lower resist film is formed by spin coating, it is desirable that the solvent is evaporated after spin coating, and baking is performed to accelerate the crosslinking reaction for the purpose of preventing mixing with the upper resist film. The baking temperature is preferably in the range of 50 to 500 ° C. At this time, although depending on the structure of the device to be manufactured, in order to reduce heat damage to the device, the baking temperature is particularly preferably 400 ° C. or less. The baking time is preferably in the range of 10 seconds to 300 seconds.

  Further, in the pattern formation method of the present invention, as a method of forming a pattern on the upper layer resist film, any of lithography method using light having a wavelength of 300 nm or less or EUV light; electron beam direct writing method or induced self-assembly method. Either method can be used suitably. By using such a method, a fine pattern can be formed on the resist upper layer film.

  The upper layer resist film composition can be appropriately selected according to the method for forming a pattern on the above upper layer resist film. For example, when lithography using light of 300 nm or less or EUV light is performed, a chemically amplified photoresist film material can be used as the upper layer resist film composition. As such a photoresist film material, after forming a photoresist film and performing exposure, a positive type pattern is formed by dissolving an exposed portion using an alkaline developer, or development comprising an organic solvent It can be exemplified that the negative pattern is formed by dissolving the unexposed area using a liquid.

  The resist underlayer film formed from the composition for forming a resist underlayer film of the present invention may absorb the light depending on the wavelength of the light used in the lithography process. And in such a case, it can function as an anti-reflective film which has the effect of preventing the reflected light from a board | substrate.

  In addition to the function as a hard mask, the lower layer film of the EUV resist can also be used for the following purposes. Without intermixing with the EUV resist, it is possible to prevent the reflection of unwanted exposure light during EUV exposure (wavelength 13.5 nm), for example UV or DUV (ArF light, KrF light) mentioned above, from the substrate or interface The composition for forming the tellurium-containing resist lower layer film can be used as a lower layer anti-reflection film of a resist. Reflection can be efficiently prevented in the lower layer of the EUV resist. Further, since the composition for forming the lower layer film is excellent in EUV absorbability, it is possible to express the sensitizing effect of the upper layer resist composition, which contributes to the improvement of sensitivity. When used as an EUV resist underlayer film, the process can be performed in the same manner as the photoresist underlayer film.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited thereto.

[Measuring method]
(1) Structure of Compound The structure of the compound was confirmed by ¹ H-NMR measurement under the following conditions using “Advance 600 II spectrometer” manufactured by Bruker.
Frequency: 400 MHz
Solvent: d6-DMSO
Internal standard: TMS
Measurement temperature: 23 ° C

(2) Molecular Weight of Compound The molecular weight of the compound was measured by LC-MS analysis using “Acquity UPLC / MALDI-Synapt HDMS” manufactured by Waters.

Production Example 1 Synthesis of Compound (BHPT) Tellurium tetrachloride (5.39 g, 20 mmol) is charged in a 50 mL container in a glove box, 10.8 g (100 mmol) of anisole is added, and the mixture is refluxed at 160 ° C. for 6 hours under reflux conditions. The reaction was done. The obtained product was dried under reduced pressure, recrystallized twice with acetonitrile, and filtered to obtain orange crystals. The obtained crystals were dried under reduced pressure for 24 hours to obtain 5.95 g of BMPT (bis (4-methoxyphenyl) tellurium dichloride).
The molecular weight of the obtained compound (BMPT) was 414 as a result of measurement by the above-mentioned measurement method (LC-MS).

About the obtained compound (BMPT), when NMR measurement was performed on the above-mentioned measurement conditions, the following peaks were found and it confirmed that it had a chemical structure of a compound (BMPT) shown below.
δ (ppm) 7.0 to 7.9 (8 H, Ph-H), 3.8 (6 H, -CH ₃ )

Subsequently, 1.1 g (2.8 mmol) of bis (4-methoxyphenyl) tellurium dichloride and 18 ml of methylene dichloride were added to a container with an internal volume of 100 mL equipped with a stirrer, a condenser and a burette, and 3.9 g of boron tribromide (15.75 mmol) was added dropwise, and the reaction was allowed to proceed at -20.degree. C. for 48 hours. The solution after reaction was added dropwise to a 0.5 N hydrochloric acid solution in an ice bath, and after filtration, a yellow solid was recovered. Dissolve with ethyl acetate, add magnesium sulfate, dehydrate and concentrate, and separate and purify by column chromatography to obtain 0.1 g of BHPT (bis (4-hydroxyphenyl) tellurium dichloride).
As a result of measuring the obtained compound (BHPT) by the above-mentioned measuring method (LC-MS), the molecular weight was 386.
About the obtained compound (BHPT), when NMR measurement was performed on the above-mentioned measurement conditions, the following peaks were discovered and it confirmed having a chemical structure of the compound (BHPT) shown below.
δ (ppm) 10.2 (2H, -OH), 6.8 to 7.8 (8H, Ph-H)

Synthesis Example 1
3.86 g (10 mol%) of the compound (BHPT), 14.56 g (70 mol%) of tetraethoxysilane, 5.56 g (20 mol%) of β-glycidoxyethyltriethoxysilane, and 60 g of acetone are placed in a 300 ml flask, While stirring the mixed solution with a magnetic stirrer, 0.1 g of methanesulfonic acid was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and reacted under heating and reflux for 240 minutes. Thereafter, the reaction solution is cooled to room temperature, 72.00 g of propylene glycol monomethyl ether acetate is added to the reaction solution, ethanol, water and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to give propylene glycol as a hydrolysis condensation product. A monomethyl ether acetate solution was obtained. Propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether were added, and the solvent ratio of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether 20/80 was adjusted to 15% by mass in terms of solid residue at 140 ° C. The weight average molecular weight by GPC of the obtained polymer (tellurium containing silicon compound) was Mw 1420 in polystyrene conversion.

(Composition example 2)
3.86 g (10 mol%) of the compound (BHPT), 4.94 g (20 mol%) of 3- (isocyanatopropyl) triethoxysilane, 12.48 g (60 mol%) of tetraethoxysilane, 4.15 g of ethylene bistriethoxysilane ( 10 mol%) and 60 g of acetone were placed in a 300 ml flask, and 0.1 g of methanesulfonic acid was dropped into the mixed solution while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and reacted under heating and reflux for 240 minutes. Thereafter, the reaction solution is cooled to room temperature, 72.00 g of propylene glycol monomethyl ether acetate is added to the reaction solution, ethanol, water and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to give propylene glycol as a hydrolysis condensation product. A monomethyl ether acetate solution was obtained. Propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether were added, and the solvent ratio of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether 20/80 was adjusted to 15% by mass in terms of solid residue at 140 ° C. The weight average molecular weight by GPC of the obtained polymer (tellurium containing silicon compound) was Mw 1830 in polystyrene conversion.

(Comparative Example 1)
A 300 ml flask was charged with 8.34 g (30 mol%) of β-glycidoxyethyltriethoxysilane, 14.56 g (70 mol%) of tetraethoxysilane, and 60 g of acetone, and the mixed solution was stirred with a magnetic stirrer to give a methanesulfone 0.1 g of acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and reacted under heating and reflux for 240 minutes. Thereafter, the reaction solution is cooled to room temperature, 72.00 g of propylene glycol monomethyl ether acetate is added to the reaction solution, ethanol, water and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to give propylene glycol as a hydrolysis condensation product. A monomethyl ether acetate solution was obtained. Propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether were added, and the solvent ratio of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether 20/80 was adjusted to 15% by mass in terms of solid residue at 140 ° C. The weight average molecular weight by GPC of the obtained polymer was Mw 1610 in polystyrene conversion.

(Comparative Synthesis Example 2)
3.15 g (30 mol%) of 3- (isocyanatopropyl) triethoxysilane, 23.49 g (60 mol%) of tetraethoxysilane, ethylene bistriethoxysilane (10 mol%), and 60 g of acetone are placed in a 300 ml flask, and the mixed solution is added. While stirring with a magnetic stirrer, 0.1 g of methanesulfonic acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and reacted under heating and reflux for 240 minutes. Thereafter, the reaction solution is cooled to room temperature, 72.00 g of propylene glycol monomethyl ether acetate is added to the reaction solution, ethanol, water and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to give propylene glycol as a hydrolysis condensation product. A monomethyl ether acetate solution was obtained. Propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether were added, and the solvent ratio of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether 20/80 was adjusted to 15% by mass in terms of solid residue at 140 ° C. The weight average molecular weight by GPC of the obtained polymer was Mw 2030 in terms of polystyrene.

Example 1
(Preparation of composition for forming tellurium-containing resist underlayer film)
After adding 160 g of a 15% by mass solution of the tellurium-containing silicon compound obtained in Synthesis Example 1, 640 g of propylene glycol monomethyl ether, and 80 g of deionized water and stirring and homogenizing, a polyethylene filter with an aperture of 5 nm is used every minute The mixture was subjected to circulation filtration at a flow rate of 10 ml for 1 hour to prepare a composition for forming a tellurium-containing resist underlayer film.

(Measurement of optical constant)
Next, the composition for forming the tellurium-containing resist lower layer film is filled in a clean container, followed by spin coating on a silicon wafer at 1500 rpm using a spin coater, and heating at 240 ° C. for 60 seconds, 35 nm thick A coated film was produced. Then, using these resist underlayer films as a spectroscopic ellipsometer (VUV-VASE VU-302 manufactured by JA Woollam Co., Ltd.), the refractive index (n value) at a wavelength of 193 nm and the optical absorption coefficient (k value, attenuation coefficient) Also called). The results are shown in Table 1 below.

(Preparation of composition for forming organic lower layer film)
1.60 g (10 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich) and 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1 in a container with an inner volume of 100 ml equipped with a stirrer, a condenser and a burette 1 .82 g (10 mmol) and 30 ml of methyl isobutyl ketone were charged, 5 ml of 95% sulfuric acid was added, and the reaction solution was stirred at 100 ° C. for 6 hours for reaction. Next, the reaction solution was concentrated, and 50 g of pure water was added to precipitate a reaction product, which was cooled to room temperature and then separated by filtration. The obtained solid was filtered and dried, and then separated and purified by column chromatography to obtain 3.05 g of a target compound (BisN-1) represented by the following formula.
The following peaks found by 400 MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula. In addition, it was confirmed that the substitution position of 2,6-dihydroxynaphthol is at the 1-position because the signals of protons at the 3- and 4-positions are doublets.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.7 (2 H, O-H), 7.2 to 8.5 (19 H, Ph-H), 6.6 (1 H, C-H)

  To 2.0 g of the compound (BisN-1) obtained above, 18.0 g of ethyl lactate is added to form a uniform solution, and the solution is filtered with a polyethylene filter having an opening of 5 nm to obtain a composition for forming an organic lower layer film. Prepared.

(Preparation of photoresist solution)
74.3 g (3.71 mol) of anhydrous HF and 50.5 g (0.744 mol) of BF ₃ are charged into an autoclave (made of SUS 316 L) with an internal volume of 500 mL capable of controlling the temperature, and the contents are stirred. The pressure was increased to 2 MPa with carbon monoxide while maintaining the liquid temperature at -30 ° C. Thereafter, while maintaining the pressure at 2 MPa and the liquid temperature at -30 ° C., a raw material in which 57.0 g (0.248 mol) of 4-cyclohexylbenzene and 50.0 g of n-heptane were mixed was supplied and maintained for 1 hour After that, the contents were collected, placed in ice, diluted with benzene and neutralized, and the oil layer obtained was analyzed by gas chromatography. When the reaction result was calculated | required, it was 100% of 4-cyclohexylbenzene conversion and 97.3% of 4-cyclohexyl benzaldehyde selectivity.
The objective component was isolated by simple distillation, and analyzed by GC-MS. As a result, it showed a molecular weight 188 of 4-cyclohexylbenzaldehyde (hereinafter referred to as "CHBAL") of interest. That is, the molecular weight was measured using GC-MS QP2010 Ultra manufactured by Shimadzu Iron Works. Further, the chemical shift value (δ ppm, reference to TMS) of ¹ H-NMR in heavy chloroform solvent is 1.0 to 1.6 (m, 10 H), 2.6 (m, 1 H), 7.4 (d , 2H), 7.8 (d, 2 H), 10.0 (s, 1 H).

A well-dried four-necked flask (1000 mL) equipped with a dropping funnel, a Jim Rohto condenser, a thermometer, and a stirring blade, which had been sufficiently dried and purged with nitrogen, under a nitrogen stream, resorcinol (22 g, 0. 2 mol), the said 4-cyclohexyl benzaldehyde (46.0 g, 0.2 mol), and dehydrated ethanol (200 mL) were thrown in, and the ethanol solution was prepared. The solution was heated to 85 ° C. with a mantle heater while stirring. Next, 75 mL of concentrated hydrochloric acid (35%) was added dropwise over 30 minutes using a dropping funnel, and the mixture was subsequently stirred at 85 ° C. for 3 hours. After completion of the reaction, the reaction solution was allowed to cool, allowed to reach room temperature, and cooled in an ice bath. After standing for 1 hour, pale yellow objective crude crystals were formed, which were separated by filtration. The crude crystals were washed twice with 500 mL of methanol, separated by filtration, and dried under vacuum to obtain 50 g of a product (hereinafter referred to as "CR-1A").
The structure of this product showed a molecular weight of 1121 as a result of analysis by LC-MS. The chemical shift values (δ ppm, TMS reference) of ¹ H-NMR in heavy chloroform solvent are 0.8 to 1.9 (m, 44 H), 5.5, 5.6 (d, 4 H), It was 0 to 6.8 (m, 24H) and 8.4, 8.5 (m, 8H).
From these results, the obtained product was identified as the target compound (CR-1A) (yield 91%).

  As a photoactive compound, 0.5 g of the naphthoquinone diazide photosensitive agent (4NT-300, Toyo Gosei Kogyo Co., Ltd.) of the following structural formula (G) as a photoactive compound is obtained in the above compound (CR-1A) 0.5 g and a solvent Then, 30 g of propylene glycol monomethyl ether was added thereto to make a uniform solution, and then the solution was filtered through a polyethylene filter having an aperture of 5 nm to prepare a photoresist solution.

(Measurement of dry etching rate)
A solution of the composition for forming the tellurium-containing resist underlayer film was applied onto a silicon wafer using a spin coater. C. for 1 minute on a hot plate to form a tellurium-containing resist underlayer film (film thickness 100 nm). Similarly, the composition for forming an organic lower layer film (10% by mass ethyl lactate solution of BisN-1) was coated on a silicon wafer while holding the spin coater to form an organic lower layer film with a thickness of 200 nm. The dry etching rate was measured using O ₂ gas as the etching gas, the dry etching rates of the tellurium-containing resist underlayer film were compared, and the resistance to oxygen-based etching gas (oxygen-based gas resistance) was evaluated.
The etcher and the etching gas used for measuring the dry etching rate were RIE-10 NR (manufactured by Samco): O ₂ . The resistance to oxygen-based gas (O ₂ gas) (etch rate ratio of [the resist underlayer film of the present invention] / [organic underlayer film]) is shown in Table 1 below.

(Resist patterning test)
The composition for forming an organic lower layer film was coated on a silicon wafer using a spin coater to form an organic lower layer film with a thickness of 200 nm. The composition for forming the tellurium-containing resist underlayer film was applied thereon and heated at 240 ° C. for 60 seconds to prepare a tellurium-containing resist underlayer film having a film thickness of 35 nm. Subsequently, the photoresist solution was applied by a spinner, and baked on a hot plate at 110 ° C. for 60 seconds to form a photoresist film having a film thickness of 120 nm.
Then, they are exposed with an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35 ° dipole polarized illumination, 6% halftone phase shift mask), It was baked (PEB) at 100 ° C. for 60 seconds and developed for 30 seconds with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) to obtain a 50 nm 1: 1 positive-working line and space pattern. The resist pattern after the lithography was performed was observed, and in the pattern bottom shape, a rectangular shape of the line was regarded as “rectangular”, and the fatness of the line bottom was evaluated as “defect”. The results are shown in Table 1 below.

Example 2
A coated film is prepared in the same manner as in Example 1 except that 160 g of a 15% by mass solution of the tellurium-containing silicon compound obtained in Synthesis Example 2 is used instead of the tellurium-containing silicon compound obtained in Synthesis Example 1. Various evaluations were made.

[Example 3]
160 g of a 15% by mass solution of the tellurium-containing silicon compound obtained in Synthesis Example 1, 640 g of propylene glycol monomethyl ether, tetramethylol glycoluril as a crosslinking agent, and 80 g of deionized water are added and homogenized after stirring. The mixture was subjected to circulation filtration with a 5 nm polyethylene filter at a flow rate of 10 ml / min for 1 hour to prepare a tellurium-containing resist underlayer film forming composition.

Comparative Example 1
The coated film was obtained in exactly the same manner as in Example 1 except that 160 g of a 15% by mass solution of the hydrolytic condensate of the silicon compound obtained in Comparative Synthesis Example 1 was used instead of the tellurium-containing silicon compound obtained in Synthesis Example 1. It produced and performed various evaluations.

Comparative Example 2
The coated film was obtained in exactly the same manner as in Example 1 except that 160 g of a 15% by mass solution of the hydrolytic condensate of the silicon compound obtained in Comparative Synthesis Example 2 was used instead of the tellurium-containing silicon compound obtained in Synthesis Example 1. It produced and performed various evaluations.

  As can be seen from Table 1, Examples 1 to 3 using the composition for forming a lower layer film of the present invention containing a tellurium compound have refractive index, optical absorption coefficient, resistance to oxygen-based etching gas (oxygen-based gas resistance) (implementation It can be seen that the pattern rectangularity is excellent (except for Example 3). From this, it is understood that the lower layer film using the composition for forming the lower layer film of the present invention has a larger dry etching rate with respect to the fluorine-based etching gas than the upper layer resist (photoresist) and is excellent in heat resistance. The

  Furthermore, by using the tellurium-containing composition for forming a resist underlayer film of the present invention, no intermixing with the resist occurs, and a fluorine-based etching gas has a larger dry etching rate than the resist, and a resist pattern Can be transferred to the resist underlayer film of the present invention, and can exhibit etching resistance to an oxygen-based etching gas, and the resist pattern can be transferred to the organic underlayer film. In addition, it was shown that a pattern having good rectangularity could be obtained as compared with the comparative example.

Claims (18)

  A composition for forming a resist underlayer film, comprising a tellurium-containing compound or a tellurium-containing resin, and a silicon-containing compound.   The composition for forming a resist underlayer film according to claim 1, wherein the silicon-containing compound is a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolytic condensate thereof. The composition for resist underlayer film formation according to claim 1 or 2, wherein the compound containing tellurium is represented by the following formula (A).

(In the formula (A), X is a 2m-valent group having 0 to 30 carbon atoms including tellurium, Z is an oxygen atom, a sulfur atom or non-crosslinking, and R ⁰ is each independently oxygen A monovalent group containing an atom, a monovalent group containing a sulfur atom, a monovalent group containing a nitrogen atom, a hydrocarbon group, or a halogen atom, m is an integer of 1 to 4, and p is Each independently is an integer of 0 to 2, and n is each independently an integer of 0 to (5 + 2 × p). The composition for resist underlayer film formation of Claim 3 in which the compound containing the said tellurium is shown by following formula (1).

(In formula (1), X, Z, m and p are as defined in the above formula (A), R ¹ is each independently an alkyl group, an aryl group, an alkenyl group or a halogen atom, R ² Each independently represents a hydrogen atom or an acid-dissociable reactive group, each n ¹ independently represents an integer of 0 to (5 + 2 × p), and each n ² independently represents an integer of 0 to (5 + 2) It is an integer of × p), provided that at least one n ² is an integer of 1 to (5 + 2 × p). 5. The composition for forming a resist underlayer film according to claim 4, wherein the compound containing tellurium is represented by the following formula (2).

(In formula (2), Z, R ¹ , R ² , p, n ¹ and n ² are as defined in the above formula (1), and X ¹ is a halogen atom) The composition for forming a resist underlayer film according to claim 5, wherein the compound containing tellurium is represented by the following formula (3).

(In Formula (3), R ¹ , R ² , X ¹ , n ¹ and n ² have the same meanings as in Formula (2) above). The composition for forming a resist underlayer film according to claim 6, wherein the compound containing tellurium is represented by the following formula (4).

(In Formula (4), R ¹ , R ² , and X ¹ have the same meanings as in Formula (3) above). The composition for forming a resist underlayer film according to claim 4, wherein the compound containing tellurium has at least one acid dissociable reactive group as R ² in the formula (1). The composition for forming a resist underlayer film according to claim 4, wherein in the compound containing tellurium, all of R ² in the formula (1) are hydrogen atoms. The composition for forming a resist lower layer film according to claim 1 or 2, wherein the tellurium-containing resin is a resin containing a constitutional unit derived from a compound represented by the following formula (A).

(In the formula (A), X is a 2m-valent group having 0 to 30 carbon atoms including tellurium, Z is an oxygen atom, a sulfur atom or non-crosslinking, and R ⁰ is each independently oxygen A monovalent group containing an atom, a monovalent group containing a sulfur atom, a monovalent group containing a nitrogen atom, a hydrocarbon group, or a halogen atom, m is an integer of 1 to 4, and p is Each independently is an integer of 0 to 2, and n is each independently an integer of 0 to (5 + 2 × p).   The composition for forming a resist underlayer film according to any one of claims 1 to 10, further comprising a solvent.   The composition for resist underlayer film formation of any one of Claims 1-11 which further contain an acid.   The composition for resist underlayer film formation of any one of Claims 1-12 which further contain an acid crosslinking agent. The silicon-containing compound is at least one hydrolysable organosilane selected from the group consisting of the following formulas (A1) and (A2), their hydrolysates, or their hydrolytic condensates. The composition for resist underlayer film formation of any one of Claims 13.

Formula (A1): (R ³ ) _a Si (R ⁴ ) _4-a

(In formula (A1), R ³ represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an alkoxy An organic group having an aryl group, an acyloxyaryl group, an isocyanurate group, a hydroxy group, a cyclic amino group, or a cyano group; or a combination thereof, which is bonded to a silicon atom by a Si-C bond , R ⁴ represents an alkoxy group, an acyloxy group or a halogen group, and a represents an integer of 0 to 3.)

Formula (A2): [(R ⁵ ) _c Si (R ⁶ ) _4-c ] ₂ Y _b

(In formula (A2), R ⁵ represents an alkyl group, R ⁶ represents an alkoxy group, an acyloxy group or a halogen group, Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, c Represents an integer of 0 or 1.)   The underlayer film for lithography formed using the composition for resist underlayer film formation of any one of Claims 1-14.   A resist underlayer film is formed on a substrate using the composition for forming a resist underlayer film according to any one of claims 1 to 14, and at least one photoresist layer is formed on the resist underlayer film. And forming a predetermined area of the photoresist layer for development. An organic underlayer film is formed on a substrate using a coating type organic underlayer film material,
A resist underlayer film is formed on the organic underlayer film using the composition for forming a resist underlayer film according to any one of claims 1 to 14,
An upper resist film is formed on the resist lower layer film using an upper resist film composition,
Forming an upper layer resist pattern on the upper layer resist film;
The pattern is transferred to the resist lower layer film by etching using the upper layer resist pattern as a mask;
The pattern is transferred to the organic lower layer film by etching using the resist lower layer film to which the pattern is transferred as a mask,
A pattern forming method comprising transferring a pattern to the substrate by etching using the organic lower layer film to which the pattern has been transferred as a mask. An organic hard mask consisting mainly of carbon is formed on a substrate by a CVD method,
A resist underlayer film is formed on the organic hard mask using the composition for forming a resist underlayer film according to any one of claims 1 to 14,
An upper resist film is formed on the resist lower layer film using an upper resist film composition,
Forming an upper layer resist pattern on the upper layer resist film;
The pattern is transferred to the resist lower layer film by etching using the upper layer resist pattern as a mask;
The pattern is transferred to the organic hard mask by etching using the resist underlayer film to which the pattern is transferred as a mask;
A pattern forming method comprising transferring a pattern to the substrate by etching using the organic hard mask to which the pattern is transferred as a mask.