TW202119131A - Pattern formation composition and pattern formation method - Google Patents

Abstract

The present invention addresses the problem of providing a pattern formation composition that makes it possible to form a pattern formation film that exhibits excellent etchability. The present invention relates to a pattern formation composition that includes a polymer. When Pr is the free volume radius of the polymer and Mr is the nuclear radius of a metal that is introduced when a pattern is formed from the pattern formation composition, 2 ≤ Pr/Mr ≤ 3.3.

Description

Pattern forming composition and pattern forming method

The present invention relates to a pattern forming composition and a pattern forming method.

Electronic devices such as semiconductors require high-definition due to miniaturization. In addition, the patterns of related semiconductor devices are also reviewed for the diversification of shapes. Known methods for forming such patterns are: double patterning, electron beam lithography, nanoimprinting, and the use of guided self-assembly materials (Directed Self Assembly, hereinafter also referred to as "directed pattern formation Self-assembly composition") pattern formation method of directional self-assembly.

The oriented self-assembly composition for pattern formation is oriented self-assembly by performing phase separation. Because it does not require high-priced electron beam drawing devices, it does not cause the patterning process in the double patterning method to become complicated, so it is cost-effective. Advantage. Known directional self-assembly composition systems for pattern formation include diblock copolymers such as polystyrene-polymethyl methacrylate (PS-PMMA) (for example, Patent Document 1).

The directional self-assembly composition for pattern formation has also been reviewed for the use of materials other than PS-PMMA. For example, the oriented self-assembly composition for pattern formation disclosed in Patent Document 2 has a styrene-based polymer, an acrylic polymer, etc. as the main chain and a group containing a heteroatom at the end. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] US2012/0241411 A1 [Patent Document 2] Japanese Patent Laid-Open No. 2014-5325

(The problem to be solved by the invention)

After the pattern is formed by using the oriented self-assembly composition for pattern formation as described above, an etching step of further performing pattern shape processing on the silicon wafer substrate is provided with the pattern as a protective film. However, in the conventional method, when performing pattern shape processing on a substrate, the etching processability may be poor, which becomes a problem.

The reason is that, in order to solve the problems of the conventional technology, the inventors of the present application conducted a review for the purpose of providing a pattern formation composition capable of forming a pattern formation film exhibiting excellent etching processability. (Technical means to solve the problem)

Specifically, the present invention has the following configuration.

[化2]

一般式(103)及(104)中，R¹ 係各自獨立表示氫原子、氟原子、氯原子、溴原子、碘原子、烷基、醯基、芳基、三甲基矽烷基或磷醯基，複數R¹ 係可為相同、亦可為不同；R⁵ 係表示氫原子或烷基；X¹ 及Y¹ 係各自獨立表示單鍵或連接基；r係表示1以上的整數，⁎標記係當r為2以上的情況，表示與R¹ 中任一者間的鍵結部位，或者表示取代R¹ 而與R¹ 所鍵結氧原子中之任一者間的鍵結部位。 [5]如[4]所記載的圖案形成用組成物，其中，聚合物係更進一步具有下述一般式(105)所示構造； [化3]

一般式(105)中，W¹ 係表示 碳原子或矽原子；W² 係表示-CR₂ -、-O-、-S-或-SiR₂ -(其中，R係表示氫原子或碳數1~5之烷基，複數R係可為相同、亦可為不同)；R¹¹ 係表示氫原子、碳數1以上且3以下之烷基或羥基；R¹² 係表示氫原子、羥基、乙醯基、甲氧基羰基、芳基、烯丙基、環氧丙醚基、環氧丙酯基、異氰酸酯基或吡啶基。 [6]如[1]~[5]中任一項所記載的圖案形成用組成物，其中，聚合物係含有源自糖衍生物的單元，且聚合物中源自糖衍生物的單元含有率係60~90質量%。 [7]如[1]~[6]中任一項所記載的圖案形成用組成物，係圖案形成用遮罩材料。 [8]一種圖案形成方法，係包括有： 將含有聚合物的圖案形成用組成物塗佈於基板上，而形成圖案形成用膜的步驟；以及 將金屬導入於圖案形成用膜至少其中一部分，獲得含金屬之圖案形成用膜的步驟； 其中，將聚合物的自由體積半徑設為Pr、 將金屬的原子核半徑設為Mr時， 滿足2≦Pr/Mr≦3.3的條件。 [9]如[8]所記載的圖案形成方法，其中，含金屬之圖案形成用膜所含金屬的總含量係4.0atom%以上； 將含金屬之圖案形成用膜之厚度方向的最大金屬含有率設為Aatom%，圖案形成用膜之厚度方向中間點的金屬含有率設為Batom%時，A/B值係10.0以下。 [10]如[8]或[9]所記載的圖案形成方法，其中，在形成圖案形成用膜的步驟後，更進一步包括有：在圖案形成用膜上形成圖案的步驟。 [11]如[8]~[10]中任一項所記載的圖案形成方法，其中，在獲得含金屬之圖案形成用膜的步驟後，更進一步包括有蝕刻步驟。 (對照先前技術之功效)[1] A composition for pattern formation, a composition for pattern formation containing a polymer; wherein the free volume radius of the polymer is set to Pr, and the nucleus radius of the metal introduced when the pattern formation composition is patterned When it is set as Mr, the condition of 2≦Pr/Mr≦3.3 is satisfied. [2] The composition for pattern formation as described in [1], wherein the composition for pattern formation is applied on a substrate to form a film for pattern formation with a thickness of 300 nm, and a metal gas is introduced into the pattern under a pressure of 500 Pa When the film is formed for 300 seconds, the total metal content of the film for pattern formation is 4.0 atom% or more; the maximum metal content in the thickness direction of the film for pattern formation is set to Aatom%, the middle point in the thickness direction of the film for pattern formation When the metal content of is set to Batom%, the A/B value is 10.0 or less. [3] The composition for pattern formation as described in [1] or [2], wherein the polymer system contains a unit derived from a sugar derivative. [4] The pattern-forming composition as described in [3], wherein the unit system derived from a sugar derivative contains the structure represented by the following general formula (103) and the structure represented by the following general formula (104) Choose at least one of them; [化1]

[化2]

In general formulas (103) and (104), R ¹ independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, an acyl group, an aryl group, a trimethylsilyl group, or a phosphoryl group. , The plural R ¹ systems may be the same or different; R ⁵ represents a hydrogen atom or an alkyl group; X ¹ and Y ¹ each independently represent a single bond or a linking group; r represents an integer of 1 or more, ⁎ label system the case when r is 2 or more, represents a bond portion between any one of R ^1, or represents ¹ and the substituent bonded portion between any one of R ¹ are bonded to an oxygen atom of R. [5] The pattern forming composition as described in [4], wherein the polymer system further has a structure represented by the following general formula (105); [化3]

In general formula (105), W ¹ represents a carbon atom or a silicon atom; W ² represents -CR ₂ -, -O-, -S- or -SiR _2- (wherein, R represents a hydrogen atom or a carbon number of 1 ~5 alkyl groups, the plural R may be the same or different); R ¹¹ represents a hydrogen atom, an alkyl group with a carbon number of 1 or more and 3 or less or a hydroxyl group; R ¹² represents a hydrogen atom, hydroxyl, acetyl Group, methoxycarbonyl group, aryl group, allyl group, glycidyl ether group, glycidyl group, isocyanate group or pyridyl group. [6] The composition for pattern formation as described in any one of [1] to [5], wherein the polymer contains a unit derived from a sugar derivative, and the polymer contains a unit derived from a sugar derivative The rate is 60~90% by mass. [7] The composition for pattern formation as described in any one of [1] to [6] is a mask material for pattern formation. [8] A pattern forming method comprising: coating a pattern forming composition containing a polymer on a substrate to form a pattern forming film; and introducing a metal into at least a part of the pattern forming film, The step of obtaining a metal-containing pattern formation film; wherein, when the free volume radius of the polymer is set to Pr and the nucleus radius of the metal is set to Mr, the condition of 2≦Pr/Mr≦3.3 is satisfied. [9] The pattern forming method as described in [8], wherein the total content of the metal contained in the metal-containing pattern forming film is 4.0 atom% or more; and the largest metal in the thickness direction of the metal-containing pattern forming film is contained When the ratio is set to Aatom% and the metal content rate at the intermediate point in the thickness direction of the film for pattern formation is set to Batom%, the A/B value is 10.0 or less. [10] The pattern forming method as described in [8] or [9], wherein after the step of forming the pattern forming film, the method further includes a step of forming a pattern on the pattern forming film. [11] The pattern forming method as described in any one of [8] to [10], wherein after the step of obtaining a metal-containing pattern forming film, an etching step is further included. (Compared with the effect of previous technology)

According to the present invention, it is possible to improve the etching processability when the pattern shape processing is performed on the substrate after the pattern forming film is formed from the pattern forming composition.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below is based on representative embodiments and specific examples, but the present invention is not limited to these embodiments. In addition, in this specification, the relevant substituents that do not clearly indicate substitution/unsubstitution means that the group may have any substituents.

(Composition for pattern formation) The present invention relates to a composition for forming a pattern containing a polymer. Metal is introduced into the pattern-forming film formed from the pattern-forming composition of the present invention. At this time, if the nucleus radius of the metal introduced into the pattern-forming film is set to Mr, the polymer contained in the pattern-forming composition of the present invention is free When the volume radius is set to Pr, the condition of 2≦Pr/Mr≦3.3 is satisfied. Accordingly, the present invention relates to a pattern-forming composition containing a polymer having a free volume radius (Mr) that satisfies the above-mentioned conditions with respect to the nucleus radius (Mr) of the metal introduced in the pattern-forming step ( Pr).

Here, the nucleus radius (Mr) of the metal introduced into the film for pattern formation refers to the value of E Clementi, DL Raimondi, WP Reinhardt (1963) J Chem Phys. 38: 2686. _{In addition, in the case of metal oxides such as metal-based Al 2} O ₃ introduced into the film for pattern formation, it is only necessary that the nucleus radius of the metal element (Al) satisfies the above-mentioned conditions.

In addition, the free volume radius (Pr) of the polymer is a value measured as follows. First, it was dissolved in PGMEA to obtain 3% by mass of polymer and 0.3% by mass of p-toluenesulfonic acid to obtain a copolymer solution sample. Then, the copolymer solution sample was spin-coated on a 2-inch silicon wafer substrate. After coating and forming a film with a thickness of 500 nm, it was calcined on a hot plate at 230°C for 5 minutes to form a film for pattern formation. Next, the positron annihilation time was measured for the formed film for pattern formation, and the free volume radius (Pr) of the polymer was calculated. Specifically, the film for pattern formation was set in a positron annihilation time measuring device. The positron beam source uses a 22Na base positron beam, and the γ-ray detector uses a BaF ₂ scintillator and a photomultiplier tube. The positron annihilation time is measured under the following conditions. In addition, the positron annihilation time measuring device can use, for example, a small positron beam generator PALS-200A manufactured by Fuji Imvac. Device constant: 263~272ps, 24.55ps/ch Beam intensity: 1.5keV Measuring depth: 0~25μm (estimated) Measuring temperature: Room temperature Measuring environment: Vacuum Total value: Approximately 5,000,000 counts Sample pre-processing: Apply vacuum at room temperature For degassing, the positron annihilation time curve obtained above is analyzed using the nonlinear least squares formula POSITRONFIT, and the average free volume radius is calculated, which is set as the free volume radius (Pr) of the polymer.

The preferred free volume radius (Pr) of the polymer varies according to the nucleus radius of the metal introduced into the patterning film. For example, the free volume radius (Pr) of the polymer is preferably 0.10 nm or more, more preferably 0.20 nm Above, especially preferred is above 0.25nm. In addition, the free volume radius (Pr) of the polymer is preferably 0.50 nm or less, more preferably 0.40 nm or less, and particularly preferably 0.35 nm or less. In order to set the free volume radius (Pr) of the polymer within the above-mentioned range, for example, adjusting the content of the sugar derivative-derived unit constituting the polymer, adjusting the polymerization degree or sugar chain length of the sugar moiety, and adjusting appropriately The content rate of other structural units other than the sugar derivative-derived unit.

The Pr/Mr value should be 2 or more, preferably 2.1 or more, more preferably 2.2 or more, particularly preferably 2.3 or more, and most preferably 2.4 or more. In addition, the value of Pr/Mr may be 3.3 or less, preferably 3.2 or less, more preferably 3.1 or less, and particularly preferably 3.0 or less. By setting the Pr/Mr value within the above range, the permeability of the metal to the pattern forming film can be increased, thereby forming a high-strength pattern forming film. Therefore, it is possible to more effectively improve the etching processability when the pattern shape processing is performed on the substrate after the pattern formation film is formed from the pattern formation composition.

Here, the etching processability can be evaluated by calculating the etching selection ratio, and the etching selection ratio can be calculated as follows, for example. When calculating the etching selection ratio, first, it was dissolved in PGMEA so as to become 3% by mass of polymer and 0.3% by mass of p-toluenesulfonic acid to obtain a copolymer solution sample. Then, the copolymer solution sample was spin-coated on a 2-inch silicon wafer substrate. After coating and forming a film with a thickness of 300 nm, it was calcined on a hot plate at 230°C for 1 minute to form a film for pattern formation. Next, an ArF excimer laser exposure machine was used to mask the lines and spaces (line width 100 nm, space width 100 nm), and exposure was performed using a commercially available ArF photoresist. Then, it was calcined on a hot plate at 105°C for 1 minute, and then immersed in a developer solution to form a pattern of lines and spaces. Next, the pattern sample was subjected to oxygen plasma treatment (100 sccm, 4 Pa, 100 W, 60 seconds) using an ICP plasma etching device (manufactured by Tokyo Electron Corporation) to form a pattern of lines and spaces on the pattern forming film . Then, the patterning film was placed in an ALD (atomic layer deposition apparatus: SUNALE R-100B manufactured by PICUSAN), and TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas was introduced at 95°C for 300 seconds, Introduce water vapor for another 150 seconds. By repeating this operation three times, Al ₂ O _{3 was} introduced into the film for pattern formation. Using this pattern as a mask, using hexafluoroethane (C ₂ F ₆ ) and Ar gas, plasma treatment (100 sccm, 0.4 Pa, 200 W, 120 seconds) using an ICP plasma etching device (manufactured by Tokyo Electron Co., Ltd.) , And the implementation of dry etching of the silicon oxide film. Then, the patterned cross section of the silicon oxide film before and after the plasma treatment was observed using a scanning electron microscope (SEM) JSM7800F (manufactured by JEOL) at an acceleration voltage of 1.5 kV, an emission current of 37.0 μA, and a magnification of 100,000. The thickness of the pattern forming film into which the metal was introduced and the processing depth of the silicon oxide film were measured, and the etching selection ratio was calculated from the following formula. Etching selection ratio = processing depth of the silicon oxide film/(the thickness of the patterning film before plasma treatment-the thickness of the patterning film after plasma treatment) The etching selection is better than 2.0, more preferably 2.5 or more, and features The best system is above 3.0, the best system is above 5.0, and the best system is above 10.0. In this specification, when the etching selection ratio is within the above-mentioned range, the etching processability when the pattern shape processing is performed on the substrate can be judged to be good. In addition, when the etching processability is good, generally the upper substrate can be dug deep.

In this embodiment, the maximum metal content (atom%) when metal is introduced into the pattern forming film is preferably 15 atom% or more, more preferably 20 atom% or more, and particularly preferably 25 atom% or more. In addition, the maximum metal content rate (atom%) when metal is introduced into the film for pattern formation is calculated as follows. First, it was dissolved in PGMEA to obtain 3% by mass of polymer and 0.3% by mass of p-toluenesulfonic acid to obtain a copolymer solution sample. Then, the copolymer solution sample was spin-coated on a 2-inch silicon wafer substrate. After coating and forming a film with a thickness of 300 nm, it was calcined on a hot plate at 230°C for 5 minutes to form a film for pattern formation. Next, the patterning film was placed in an ALD (atomic layer deposition apparatus: SUNALE R-100B manufactured by PICUSAN), and TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas was introduced at 95°C for 300 seconds, and then Introduce water vapor for 150 seconds. By repeating this operation three times, Al ₂ O _{3 was} introduced into the film for pattern formation. The pattern forming film introduced with Al ₂ O ₃ was set in an XPS apparatus (Nexsa XPS System manufactured by Thermo Fisher Scientific), and the Al element concentration distribution in the film thickness direction was obtained by XPS analysis (X-ray photoelectron spectroscopy). In addition, the _{film thickness of the patterning film introduced with Al 2} O _{3 is} formed by scratching the sample surface with tweezers to expose the surface of the silicon substrate to form a gradient, using a palpable gradiometer (model made by Kosaka Manufacturing Co., Ltd.: ET-4000) is obtained by measuring the gradient part. That is, the "maximum metal content (atom%)" is the metal content at the thickness of the film for pattern formation at the thickness containing the most metal.

The metal system introduced in the film for pattern formation includes, for example, Li, Be, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc. Among them, it is preferable to use Al, B, Si, Sn, Te, Zr, and W as the metal introduced into the film for pattern formation.

In one embodiment, when the patterning composition is applied on a substrate to form a patterning film with a thickness of 300 nm, and then a metal gas is introduced into the patterning film under a pressure of 500 Pa for 300 seconds, it is preferably used for patterning When the total content of metals in the film is 4.0 atom% or more, and the maximum metal content in the thickness direction of the patterning film is set to Aatom%, and the metal content at the midpoint in the thickness direction of the patterning film is set to Batom%, The A/B value is preferably 10.0 or less. Accordingly, in the pattern formation step of the pattern formation composition of the present embodiment, the total content of the introduced metal and the metal distribution in the pattern formation film may satisfy the above-mentioned conditions.

When the pattern-forming composition of the present embodiment satisfies the above-mentioned conditions, the etching processability when patterning the substrate after the pattern-forming film is formed from the pattern-forming composition can be more effectively improved.

In this embodiment, when the metal gas is introduced into the patterning film for 300 seconds under a pressure of 500 Pa, the total content (atom%) of the metal contained in the patterning film may be 4.0 atom% or more, preferably 4.5 Atom% or more, more preferably 5.0atom% or more. In addition, the total content of metals contained in the film for pattern formation is preferably 60 atom% or less, more preferably 50 atom% or less. In addition, the total metal content (atom%) is the content of the metal relative to the total atomic weight in the film for pattern formation. The total content of the metal contained in the film for pattern formation can be adjusted by selecting the type of metal or adjusting the structural units constituting the polymer. The total metal content (atom%) in the patterning film is a value calculated from the Al content depth distribution (XPS measurement) of the patterning film, as described later. Specifically, the Al content of each depth in the film for dot pattern formation is traced, an approximate curve is obtained by the nonlinear least square method, and this is set as a depth distribution. This distribution is calculated from the integral value of the film thickness range area obtained by using a stylus-type gradiometer when the maximum metal content (atom%) in the thickness direction of the film for pattern formation described later is measured. In simple terms, you can also cut the outline printed on paper and calculate the total content by weight comparison. At this time, the total content of 0% is set to weight 0g, and the total content of 100% is set to the depth distribution up to 100%, and the weight that is printed and cut is used.

In this embodiment, when the metal gas is introduced into the patterning film for 300 seconds under a pressure of 500 Pa, the maximum metal content in the thickness direction of the patterning film is set to Aatom%, and the metal at the midpoint in the thickness direction of the patterning film is contained When the ratio is set to Batom%, the A/B value is preferably 10.0 or less, more preferably 9.0 or less, and particularly preferably 8.5 or less. In addition, the A/B value is preferably 2 or less, more preferably 1.5 or less. The A/B value can be adjusted by selecting the type of metal or adjusting the constituent units of the polymer.

In this embodiment, the value of A/B in the above-mentioned range means that in the film for pattern formation, the metal also wets in the depth direction. Generally, when a metal gas is introduced into the film for pattern formation, the surface of the film for pattern formation contains the most metal. However, in this embodiment, by appropriately controlling the structure of the polymer, the ratio of sugar derivatives, the length of sugar chains, the ratio of crosslinking groups, etc., the metal is not only distributed on the surface of the pattern forming film, but also distributed on the pattern forming film. In the depth direction of the film. Thereby, the strength in the thickness direction of the film for pattern formation can be improved, and a strong film for pattern formation can be formed as a whole. As a result, it is possible to improve the etching processability when the pattern shape processing is performed on the substrate after the pattern formation film is formed on the substrate.

The maximum metal content (atom%) in the thickness direction of the film for pattern formation is calculated as follows. First, it was dissolved in PGMEA to obtain 3% by mass of polymer and 0.3% by mass of p-toluenesulfonic acid to obtain a copolymer solution sample. Then, the copolymer solution sample was spin-coated on a 2-inch silicon wafer substrate. After coating and forming a film with a thickness of 300 nm, it was fired on a hot plate at 230°C for 5 minutes to form a film for pattern formation. Next, the patterning film was placed in an ALD (atomic layer deposition apparatus: SUNALE R-100B manufactured by PICUSAN), and TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas was introduced at 95°C for 300 seconds, and then Introduce water vapor for 150 seconds. By repeating this operation three times, Al ₂ O _{3 was} introduced into the film for pattern formation. The film for pattern formation after the introduction of Al ₂ O ₃ was set in an XPS device (Nexsa XPS System manufactured by Thermo Fisher Scientific), and sputtering using Ar ions was repeatedly performed by XPS analysis (X-ray photoelectron spectroscopy) , Surface element concentration measurement, and film thickness measurement to obtain the Al element concentration distribution in the film thickness direction. The concentration distribution of Al element is, for example, the distribution shown in FIG. In addition, the _{film thickness of the pattern forming film after the introduction of Al 2} O ₃ was measured using a palpable gradiometer (Model: ET-4000 manufactured by Kosaka Manufacturing Co., Ltd.) according to the sputtering time. Part, and the gradient generated by the unsputtered part can be obtained. Then, the maximum Al element concentration system in the obtained Al element concentration distribution becomes the maximum metal content rate (atom%).

The maximum metal content (atom%) in the thickness direction of the film for pattern formation is preferably 15 atom% or more, more preferably 17 atom% or more, particularly preferably 20 atom% or more, and most preferably 25 atom% or more. In addition, the maximum metal content (atom%) in the thickness direction of the film for pattern formation is preferably 50 atom% or less. By setting the maximum metal content in the thickness direction of the film for pattern formation within the above-mentioned range, the etching processability when the pattern shape is processed on the substrate can be more effectively improved.

The metal content (atom%) at the middle point in the thickness direction of the patterning film is calculated from the Al element concentration distribution in the film thickness direction obtained when the maximum metal content (atom%) of the thickness direction of the patterning film is calculated. Can be calculated. From the Al element concentration distribution in the film thickness direction, it can be calculated by reading the metal content rate at the midpoint in the thickness direction of the patterning film.

The metal content (atom%) at the intermediate point in the thickness direction of the film for pattern formation is preferably 1.5 atom% or more, more preferably 5 atom% or more, particularly preferably 15 atom% or more, and most preferably 25 atom% or more. In addition, the metal content (atom%) at the midpoint in the thickness direction of the film for pattern formation is preferably 50 atom% or less. By setting the metal content at the intermediate point in the thickness direction of the pattern forming film within the above range, it is possible to more effectively improve the etching processability when performing pattern shape processing on the substrate.

The pattern formation composition of this embodiment is preferably a pattern formation mask material. That is, the pattern formation film formed from the pattern formation composition of the present embodiment is preferably used as a protective film when etching the substrate. The pattern-forming film formed from the pattern-forming composition of this embodiment can expect an effect even with respect to the gas permeability necessary for the nanoimprint method. Such a film for pattern formation can also be peeled and removed after the etching step.

In addition, the composition for pattern formation of this embodiment may be an oriented self-assembly composition for pattern formation. The so-called "Directed Self-Assembly" in this manual refers to the phenomenon of autonomously constructing organization and structure not only caused by the control of external factors. For example, the oriented self-assembly composition for pattern formation is coated on a substrate, and annealing is performed to form a film having a phase-separated structure caused by oriented self-assembly (oriented self-assembly film), and by removing the oriented self-assembly Part of the phase of the film can be patterned on the substrate. Such a pattern shape becomes a protective film, and the required etching treatment can be performed on the substrate.

(polymer) The composition for pattern formation of the present invention contains a polymer, and the polymer preferably contains a unit derived from a sugar derivative. The sugar derivative system may be a sugar derivative derived from a monosaccharide, or may have a structure in which a sugar derivative derived from a monosaccharide is multiple-bonded. In addition, in a polymer containing a unit derived from a sugar derivative, the unit system derived from a sugar derivative may be a structural unit having a structure derived from a sugar derivative in the side chain, or may have a main chain derived from a sugar derivative. The constituent unit of the structure.

The unit derived from a sugar derivative is preferably at least one selected from a unit derived from a pentose derivative and a unit derived from a six-carbon sugar derivative. The pentose derivatives are prepared before the hydroxyl groups of the pentose sugars of known monosaccharides or polysaccharides are modified by at least substituents and are derived from the pentose structure, and the rest is not particularly limited. The pentose derivative is preferably at least one selected from hemicellulose derivatives, xylose derivatives and xylo-oligosaccharide derivatives, and more preferably at least one selected from hemicellulose derivatives and xylo-oligosaccharide derivatives. The six-carbon sugar derivatives are prepared before the hydroxyl groups of the six-carbon sugars of known monosaccharides or polysaccharides are modified by at least substituents and are derived from the structure of six-carbon sugars, and the rest is not particularly limited. The six-carbon sugar derivative is preferably at least one selected from glucose derivatives and cellulose derivatives, more preferably cellulose derivatives. Among them, the unit derived from a sugar derivative is preferably at least one selected from a unit derived from a cellulose derivative, a unit derived from a hemicellulose derivative, and a unit derived from a xylo-oligosaccharide derivative.

Among them, the unit derived from a sugar derivative preferably contains at least one selected from the structure represented by the following general formula (103) and the structure represented by the following general formula (104).

[化5]

[化4]

[化5]

In general formulas (103) and (104), R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, an acyl group, an aryl group, a trimethylsilyl group or a phosphoryl group independently of each other, The plural R ¹ systems may be the same or different. R ⁵ represents a hydrogen atom or an alkyl group. X ¹ and Y ¹ represent independent single bonds or linking groups. r represents an integer of 1 or more, and the ⁎ symbol represents the bonding site to any one of ^{R 1 when r is 2 or more, or replace R 1} with any one of the oxygen atoms bonded to R ¹ Bonding site.

In general formulas (103) and (104), R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, an acyl group, an aryl group, a trimethylsilyl group or a phosphoryl group independently of each other, The plural R ¹ systems may be the same or different. Among them, R ^{1 is} preferably an independent hydrogen atom or an acyl group having 1 or more and 3 or less carbon atoms. In addition, the above-mentioned alkyl group also includes sugar chains. That is, the sugar chain parts of general formulas (103) and (104) may further have branched chains.

When R ¹ is an alkyl group or an acyl group, the carbon number system can be appropriately selected according to the purpose. For example, the carbon number is preferably 2 or more, preferably 200 or less, more preferably 100 or less, particularly preferably 20 or less, and most preferably 4 or less.

Specific examples of R ¹ include, for example, acetyl, propyl, butyryl, isobutyryl, pentyl, isopentyl, pivaloyl, hexyl, octyl, and chloroacetyl. , Trifluoroacetyl, cyclopentanecarbonyl, cyclohexanecarbonyl, benzyl, methoxybenzyl, chlorobenzyl and other acyl groups; methyl, ethyl, propyl, butyl , Tertiary butyl and other alkyl groups. Among these, preferred are acetyl, propyl, butyryl, and isobutyryl, and more preferably acetyl.

In general formulas (103) and (104), R ⁵ represents a hydrogen atom or an alkyl group. Among them, R ^{5 is} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

In general formulas (103) and (104), X ¹ and Y ¹ represent independent single bonds or linking groups. When X ¹ is a linking group, X ¹ may include, for example, a group containing alkylene, -O-, -NH ₂ -, carbonyl, etc. X ^{1 is} preferably a single bond, or a carbon number of 1 to 6 The alkylene group is more preferably an alkylene group having a carbon number of 1 or more and 3 or less. When Y ¹ is a linking group, Y ¹ may include, for example, groups containing alkylene, phenylene, -O-, -C(=O)O-, and the like. The Y ¹ system may be a linking group composed of these groups. Among them, Y ^{1 is} preferably a linking group shown in the following structural formula.

[化6]

In the above structural formula, the ※ mark indicates the bonding site with the main chain side; the ⁎ mark indicates the bonding site with the sugar unit of the side chain.

In general formulas (103) and (104), r represents an integer of 1 or more, and may be 2 or more, or may be 3 or more. In addition, r is preferably 1500 or less, more preferably 1200 or less, particularly preferably 500 or less, most preferably 100 or less, most preferably 50 or less, and more preferably 10 or less.

The average degree of polymerization of the sugar unit is the same as the above-mentioned preferable range of r. In addition, the average degree of polymerization of sugar units is the number of sugar units forming one sugar moiety. When the sugar moiety has a side chain structure, the number of sugar units constituting the side chain is also included in the average degree of polymerization. The average degree of polymerization of the above-mentioned sugar units can be calculated according to the following measurement method. First, the solution containing the sugar derivative was kept at 50°C, and centrifuged at 15000 rpm for 15 minutes to remove insoluble matter. Then, the total sugar content and the reducing sugar content of the supernatant liquid (both in xylose conversion) were measured. Then, the total sugar amount is divided by the reducing sugar amount to calculate the average degree of polymerization. In addition, when the above measurement methods are not used, for example: gel permeation chromatography, particle size sieve chromatography, light scattering method, viscosity method, terminal group quantification method, precipitation rate method, MULDI-TOF-MS Method, structural analysis method using NMR, etc. When the average degree of polymerization of the sugar units is measured after the copolymer is synthesized, ^{the integrated value of the peak derived from the sugar chain (near 3.3-5.5ppm) is calculated by 1} H-NMR, and the integration value of other components derived from the sugar derivative is calculated. Peak integral value, and then calculate the average degree of polymerization from the ratio of each integral value. ^{In addition, when R 1 in the} general formulas (103) and (104) is not a hydrogen atom, it is also possible to replace the peak derived from the sugar chain, and instead use ^{the peak integral value derived from the -OR 1} group (wherein this case ^{R 1} of the -OR ¹ group is not a sugar chain).

The symbol ⁎ in general formulas (103) and (104) indicates the bonding site to any one of ^{R 1 when r is 2 or more, or indicates that R 1 is} replaced with the oxygen atom bonded ^{to R 1} The bonding site of either one. I.e., polymerized saccharide units of general formula (103) and (104) may be based at saccharide units R ^1, R ¹ are bonded, or of any one of an oxygen atom, a preferred system according to any of the polymerization. In addition, when R ¹ is an alkyl group with substituents, because R ¹ can also be a sugar chain, the ⁎-marked bonding site in general formulas (103) and (104) is actually one, but in fact the sugar chain There are also cases where it has side chains composed of sugar chains.

The unit derived from a sugar derivative contains at least one of the structure shown in the above general formula (103) and the structure shown in the above general formula (104), and preferably mainly contains the structure shown in the above general formula (103) . The reason is that the structure shown in the above general formula (103) is smaller than the structure shown in the above general formula (104), and it is easier to control the free volume radius of the polymer.

The polymer contained in the pattern forming composition is preferably a copolymer. The copolymer may also be a block copolymer, but is preferably a random copolymer. By using a random copolymer, a more homogeneous pattern formation film can be formed.

In the case of the polymer-based copolymer contained in the pattern-forming composition, the polymer preferably further has a structure represented by the following general formula (105).

[化7]

In general formula (105), W ¹ represents a carbon atom or a silicon atom. Among them, W ^{1 is} preferably a carbon atom. In addition, in general formula (105), W ² represents -CR ₂ -, -O-, -S- or -SiR _2- (However, R represents a hydrogen atom or an alkyl group with 1 to 5 carbons, and the plural R The lines can be the same or different). Among them, W ^{2 is} preferably -CR ₂ -, more preferably -CH ₂ -.

In general formula (105), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyl group. The alkyl group having 1 to 3 carbon atoms is preferably a methyl group, and R ^{11 is more} preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.

In general formula (105), R ¹² represents a hydrogen atom, a hydroxyl group, an acetoxy group, a methoxycarbonyl group, an aryl group, an allyl group, a glycidyl ether group, a glycidyl group, an isocyanate group, or a pyridyl group. The allyl group is preferably the group represented by -R ₃ -CH=CH ₂ , the glycidyl ether group is preferably the group represented by -CH ₂ OR ₃ -epoxy, and the glycidyl ester group is preferably the group represented by -COO-R _{The group represented by 3} -epoxy, and the isocyanate group is preferably a group represented by -COO-R 3 -NCO. Here, R ₃ may be an alkylene group having a substituent. Examples of alkylene systems that may have substituents include: -CH ₂ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) _5- , -CH ₂ OCH ₂ -, -(CH ₂ ) ₂ OCH ₂ -, -(CH ₂ ) ₃ OCH ₂ -, -(CH ₂ ) ₄ OCH ₂ -, -(CH ₂ ) ₅ OCH ₂ -, etc. In addition, the alkylene group which may have a substituent may be a cycloalkylene group, or a cyclic cycloalkylene group may be cross-linked.

Among them, R ^{12 is} preferably a methoxycarbonyl group, an aryl group, a glycidyl ether group, a glycidyl ester group or a pyridyl group, more preferably a glycidyl ester group or an aryl group, and particularly preferably a glycidyl ester group Or phenyl. In addition, the phenyl group is preferably a phenyl group having a substituent. Examples of substituted phenyl groups include 4-tert-butylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, trimethylsilylphenyl, tetramethyldisilanephenyl, etc. . In addition, R ^{12 is} preferably a naphthyl group.

As described above, R ^{12 is} preferably a phenyl group. In this case, the unit derived from the structure represented by the general formula (105) is a unit derived from a styrene compound. Examples of styrene compounds include: styrene, o-methyl styrene, p-methyl styrene, ethyl styrene, p-methoxy styrene, p-phenyl styrene, 2,4-dimethyl styrene , P-n-octyl styrene, p-n-decyl styrene, p-n-dodecyl styrene, chlorinated styrene, brominated styrene, trimethylsilyl styrene, hydroxystyrene, 3,4, 5-Methoxystyrene, Pentamethyldisilylstyrene, etc. Among them, the styrene compound is preferably at least one selected from styrene and trimethylsilyl styrene, more preferably styrene.

Furthermore, R ^{12 is} preferably a glycidyl ester group. In this case, the unit derived from the structure represented by general formula (105) is a unit derived from a glycidyl acrylate compound. Examples of the glycidyl acrylate compound series include: glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate-glycidyl ether, and ethylene oxide-2-ylmethyl-2 ‐Ethylene pentaether, etc. Among them, the glycidyl acrylate compound is preferably at least one selected from glycidyl methacrylate and 4-hydroxybutyl acrylate-glycidyl ether.

The weight average molecular weight (Mw) of the polymer is preferably 500 or more, more preferably 1,000 or more, and particularly preferably 1,500 or more. In addition, the weight average molecular weight (Mw) of the polymer is preferably 1 million or less, more preferably 500,000 or less, particularly preferably 300,000 or less, and most preferably 250,000 or less. In addition, the weight average molecular weight (Mw) of the polymer is a value measured by GPC in terms of polystyrene.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) of the polymer to the number average molecular weight (Mn) is preferably 1 or more. In addition, Mw/Mn is preferably 2 or less, more preferably 1.5 or less, particularly preferably 1.3 or less. By setting Mw/Mn within the above-mentioned range, the pattern forming composition of the present embodiment can form a good pattern structure with higher precision and fineness.

As mentioned above, the polymer contains units derived from sugar derivatives, and the content of units derived from sugar derivatives in the polymer is preferably 60% by mass or more, more preferably 65% by mass or more, and particularly preferably 70% by mass or more . In addition, the content of the sugar derivative-derived unit in the polymer is preferably 90% by mass or less, and more preferably 85% by mass or less. By setting the content of the sugar derivative-derived unit in the polymer within the above range, the solubility in organic solvents can be improved.

Furthermore, the content of the unit represented by the general formula (105) in the polymer relative to the total mass of the polymer may be 5% by mass or more, or 10% by mass or more. In addition, the content of the unit represented by the general formula (105) in the polymer is preferably 40% by mass or less, and more preferably 30% by mass or less. In addition, the content rate of the unit represented by the general formula (105) in the polymer can be ^{calculated by 1} H-NMR.

In addition, the polymer system may have other structural units in addition to the above-mentioned structural units. Examples of other structural unit systems include lactic acid-derived units, siloxane bond-containing units, amide bond-containing units, and urea bond-containing units.

(Synthesis method of polymer) The synthesis of the polymer can be carried out using known polymerization methods such as living radical polymerization, living anionic polymerization, and atom transfer radical polymerization. For example, in the case of living radical polymerization, a polymerization initiator like AIBN (α,α'-azobisisobutyronitrile) is used, and the polymer can be obtained by reacting with the monomer. In the case of living anionic polymerization, a polymer can be obtained by reacting butyl lithium with a monomer in the presence of lithium chloride.

The sugar moiety of the above-mentioned sugar derivative can be obtained synthetically, but it can also be combined with a step of extracting lignocellulose derived from woody plants or herbaceous plants. In the case of obtaining sugar moieties, when a method of extracting lignocellulose derived from woody plants or herbaceous plants is used, the extraction method described in Japanese Patent Laid-Open No. 2012-100546 and the like can be used. The related wood glue is extracted by the method disclosed in, for example, Japanese Patent Laid-Open No. 2012-180424. In addition, the related cellulose system can be extracted in accordance with, for example, the method disclosed in Japanese Patent Application Laid-Open No. 2014-148629.

When obtaining a sugar derivative, it is preferable to use the OH group of the sugar moiety obtained by the above extraction method after modification such as acetylation and halogenation. For example, in the case of introducing an acetyl group, by reacting with acetic anhydride, an acetylated sugar derivative can be obtained.

The compound system having the structure represented by the general formula (105) can be formed by synthesis, or commercially available products can also be used. When synthesizing a compound having a structure represented by general formula (105), a known synthesis method can be used. In addition, when commercially available products are used, for example, amino-terminated PS (Mw=12300Da, Mw/Mn=1.02, manufactured by Polymer Source), allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), Glycidyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-hydroxybutyl acrylate-glycidyl ether (manufactured by Mitsubishi Chemical Corporation), ethylene oxide Alk-2-ylmethyl-2-ethylene pentaether (manufactured by Achemica), 3-,4-epoxycyclohexyl methacrylate (manufactured by Daicel), and the like.

The copolymer system can be synthesized with reference to Macromolecules Vol. 36, No. 6, 2003. Specifically, in a solvent containing DMF, water, acetonitrile, etc., a sugar derivative and a compound having a structure represented by general formula (105) are placed, and a reducing agent is added. Examples of the reducing agent system include NaCNBH ₃ and the like. Then, stirring is performed at 30°C or higher and 100°C or lower for 1 day or longer and 20 days or shorter, and a reducing agent is appropriately added as necessary. The precipitate is obtained by adding water, and then the solid content is vacuum dried to obtain the copolymer.

In addition to the above-mentioned methods, the method of synthesizing the copolymer may also include, for example, a synthesis method using radical polymerization, RAFT polymerization, ATRP polymerization, click reaction, and NMP polymerization. Radical polymerization is a polymerization reaction initiated by adding an initiator and generating two free radicals by thermal reaction and photoreaction. The monomer (such as styrene monomer and the sugar methacrylate compound of methacrylic acid added to the β-1 position of the end of the xylo-oligosaccharide), and the initiator (such as azobisbutyronitrile (AIBN)) The azo compound) can be heated at 150°C to synthesize polystyrene-glycan methacrylate random copolymer. RAFT polymerization uses free radicals to initiate the polymerization reaction accompanied by the exchange chain reaction of the thiocarbonylthio group. For example, the OH group at the 1-position of the xylo-oligosaccharide terminal is converted to a thiocarbonylthio group, and then a styrene monomer is reacted at 30°C or higher and 100°C or lower to synthesize a copolymer (Material Matters vol. 5, No. .1 The latest polymer synthesis (Sigma-Aldrich Japan Co., Ltd.). ATRP polymerization system halogenated the OH group of the sugar terminal, and then combined with the metal complex [(CuCl, CuCl ₂ , CuBr, CuBr ₂ , or CuI, etc.)+TPMA(tris(2-pyridylmethyl)amine, refer to (2-pyridylmethyl)amine基)amine)], MeTREN (tris[2-(dimethylamino)ethyl]amine, reference [2-(dimethylamino)hexyl]amine), etc.), monomers (such as styrene monomer), and polymerization The starting agent (2,2,5-trimethyl-3-(1-phenylethoxy)-4-phenyl-3-azahexane) can be reacted to synthesize sugar copolymers (such as sugar- Styrene block copolymer). The NMP polymerization system uses the alkoxyamine derivative as the initiator to heat, which initiates the reaction between the monomer molecules and the coupling agent and generates nitrogen oxides. Then, the polymerization reaction proceeds by generating radicals by thermal dissociation. This kind of NMP polymerization is a kind of living radical polymerization. After mixing with monomers (such as styrene monomer and sugar methacrylate compound with methacrylic acid added to the β-1 position at the end of the xylo-oligosaccharide), and using 2,2,6,6-tetramethylpiperidine 1- oxyl (TEMPO, 2,2,6,6-tetramethylpiperidine-1-oxyl) as the starting agent, heating at 140℃, can synthesize polystyrene-glycan methacrylate random copolymer Things. The click reaction system uses a 1,3-bipolar azide/alkyne cyclization addition reaction with a propargyl sugar and a Cu catalyst.

(Method for manufacturing pattern forming composition) It is preferable to mix the above-mentioned polymer and a solvent in the manufacturing method of the composition for pattern formation. The solvent is preferably an organic solvent, and examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, sulfur-containing solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents. These solvent systems can be used individually by 1 type or in combination of 2 or more types.

Examples of alcoholic solvents include: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, tertiary butanol, n-pentanol, isoamyl alcohol, 2-methyl Butanol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, 3- Heptanol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonane Alcohol, sec-tetradecanol, sec-heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc.; Glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1H,1H-trifluoroethanol, 1H,1H-pentafluoropropanol, 6-(perfluoroethyl)hexanol and the like.

Furthermore, the polyol partial ether solvent system may include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and ethylene glycol monoethyl ether. Alcohol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethyl Glycol monohexyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc.

Examples of the ether-based solvent system include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, and tetrahydrofuran (THF).

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl n-acetone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentanone, ethyl n-butyl ketone, methyl n-hexanone, Diisobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, furfural Wait.

Examples of the sulfur-containing solvent system include dimethyl sulfoxide.

Examples of amide-based solvents include: N,N'-dimethylimidazolindione, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide Amine, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, N-methylpyrrolidone, etc.

Examples of ester-based solvents include: diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-acetate Butyl acetate, isobutyl acetate, second butyl acetate, n-pentyl acetate, second pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-Ethylhexyl Acetate, Benzyl Acetate, Cyclohexyl Acetate, Methyl Cyclohexyl Acetate, N-Nonyl Acetate, Methyl Acetate, Ethyl Acetate, Ethylene Glycol Acetate Monomethyl Ether , Glycol acetate monoethyl ether, diethylene glycol acetate monomethyl ether, diethylene glycol acetate monoethyl ether, diethylene glycol acetate mono-n-butyl ether, propylene glycol acetate monomethyl ether (PGMEA), acetic acid Propylene glycol monoethyl ether, propylene glycol acetate monopropyl ether, propylene glycol acetate monobutyl ether, dipropylene glycol acetate monomethyl ether, dipropylene glycol acetate monoethyl ether, ethylene glycol diacetate, methoxytriethylene glycol acetate , Ethyl propionate, n-butyl propionate, isoamyl propionate, methyl 3-methoxypropionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate Esters, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc.

Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, N-octane, isooctane, cyclohexane, methylcyclohexane, etc.; aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methyl Ethylbenzene, n-propylbenzene, cumene, diethylbenzene, isobutylbenzene, triethylbenzene, dicumylbenzene, n-pentanaphthalene, anisole, etc.

Among these, more preferred are propylene glycol acetate monomethyl ether (PGMEA), N,N-dimethylformamide (DMF), propylene glycol monomethyl ether (PGME), anisole, ethanol, methanol, acetone, methyl ethyl ketone , Hexane, tetrahydrofuran (THF), dimethyl sulfide (DMSO), 1H,1H-trifluoroethanol, 1H,1H-pentafluoropropanol, 6-(perfluoroethyl)hexanol, ethyl acetate, acetic acid Propyl ester, butyl acetate, cyclohexanone, furfural, especially PGMEA or DMF, the best PGMEA. These solvent systems can be used individually by 1 type or in combination of 2 or more types.

The polymer content in the pattern-forming composition is preferably 0.1% by mass or more, and more preferably 1% by mass or more with respect to the total mass of the pattern-forming composition. In addition, the polymer content is preferably 30% by mass or less with respect to the total mass of the composition for pattern formation.

＜Optional ingredients＞ When manufacturing the composition for pattern formation, an ionic liquid of any component may be blended. The so-called "ionic liquid" refers to a solvent that is in a liquid state below 100°C and consists only of ions. At least one of the ion-based cation part or the anion part constituting the ionic liquid is composed of organic ions.

When the composition for pattern formation contains an ionic liquid, the compatibility between the polymer and the organic solvent can be improved. In addition, the ionic liquid also has the effect of promoting the phase separation of the block copolymer.

The ionic liquid system is formed of a cation part and an anion part. The cation part of the ionic liquid is not particularly limited, and the cation part of general ionic liquids can be used. The cation part of the ionic liquid preferably includes, for example, nitrogen-containing aromatic ions, ammonium ions, and phosphonium ions.

鎓離子、嘧啶鎓離子、吡

鎓離子、咪唑鎓離子、吡唑鎓離子、㗁唑啉鎓離子、1,2,3-三唑嗡離子、1,2,4-三唑嗡離子、噻唑鎓離子、哌啶鎓離子、吡咯啶鎓離子等。Examples of nitrogen-containing aromatic cations include: pyridinium ion, pyridine

Onium ion, pyrimidinium ion, pyridine

Onium ion, imidazolium ion, pyrazolium ion, azolinium ion, 1,2,3-triazolium ion, 1,2,4-triazolium ion, thiazolium ion, piperidinium ion, pyrrole Pyridium ions and so on.

Examples of the anion system of the ionic liquid include halide ions, carboxylate ions, phosphonite ions, phosphate ions, phosphonate ions, bis(trifluoromethylsulfonyl) iminium ions, etc. The best system is bis(trifluoromethylsulfonyl) iminium ion. Examples of the halide ion system include chloride ion, bromide ion, and iodide ion, preferably chloride ion. The carboxylate ion system may include, for example, formate ion, acetate ion, propionate ion, butyrate ion, caproate ion, maleate ion, fumarate ion, ethyl acetate Diacid ion, lactate ion, pyruvate ion, etc., preferably formate ion, acetate ion, propionate ion.

The composition for pattern formation may contain optional components such as surfactants. When the composition for pattern formation contains a surfactant, the coatability of the substrate to be patterned can be improved. Preferable surfactants include, for example, nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants. These systems can be used individually by 1 type or in combination of 2 or more types.

In addition, the composition for pattern formation may further contain a catalyst as an optional component. Examples of catalyst systems include: p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, ammonium dodecylbenzenesulfonate , Hydroxybenzoic acid and other acid compounds; and hardeners such as: ethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, dimethylaminopropylamine, meta-xylene diamine, and Phenylenediamine, triethylamine, benzyldimethylamine, etc.

The pattern formation composition of this embodiment may contain monomer components constituting the polymer. For example, in order to improve the desired characteristics, various monomers constituting the polymer may be appropriately added.

(Pattern formation method) The pattern forming method related to the present invention includes: coating a pattern forming composition containing the above-mentioned polymer on a substrate to form a pattern forming film; and introducing a metal into at least a part of the pattern forming film , And the step of obtaining a metal-containing pattern forming film. Here, if the free volume radius of the polymer is Pr and the nucleus radius of the metal is Mr, the condition of 2≦Pr/Mr≦3.3 is satisfied. According to the pattern forming method of the present invention, after the pattern forming film is formed from the pattern forming composition, the etching processability when the pattern shape is processed on the substrate can be improved.

Furthermore, the total metal content of the metal-containing pattern forming film is 4.0 atom% or more, and the maximum metal content in the thickness direction of the metal-containing pattern forming film is Aatom%, and the pattern forming film thickness direction When the metal content of the intermediate point is Batom%, the A/B value is preferably 10.0 or less. That is, the step of obtaining the metal-containing pattern forming film is preferably a step of introducing the metal in such a way that the total content of the metal contained in the metal-containing pattern forming film and the A/B value satisfy the above conditions. By setting the step of obtaining the metal-containing pattern-forming film under the above-mentioned conditions, after the pattern-forming film is formed from the pattern-forming composition, it is possible to more effectively improve the etching processability when patterning the substrate.

Examples of substrates used in the pattern forming method of this embodiment include glass, silicon, SiN, GaN, and AlN substrates. In addition, a substrate made of organic materials such as PET, PE, PEO, PS, cycloolefin polymer, polylactic acid, and cellulose nanofiber can also be used. In addition, between the substrate and the guiding pattern formation layer, a plurality of layers of layers made of different materials may be sandwiched. The material is not specific, and examples include _{inorganic materials such as SiO 2} , SiN, Al ₂ O ₃ , AlN, GaN, GaAs, W, SOC, and SOG; and organic materials such as commercially available adhesives.

There is no particular limitation on the method of coating the pattern-forming composition on the substrate to form the pattern-forming film. For example, it can be applied to the pattern-forming composition to be used by spin coating. The method and so on.

The pattern forming method of this embodiment preferably further includes a step of forming a pattern on the pattern forming film after the step of forming the pattern forming film. In the step of forming a pattern, first, as shown in FIG. 2(a), a pattern forming film 20 is formed by applying a pattern forming composition on a substrate 10. Then, as shown in FIG. 2( b ), with respect to a part of the pattern forming film 20, at least a part of it is removed so as to become the shape of the pattern to be formed on the substrate 10. For example, by laminating a photoresist film on the pattern forming film 20, and performing exposure and development treatments, a pattern shape as shown in FIG. 2(b) can be formed.

The method of removing a part of the patterning film includes, for example, reactive ion etching (RIE) such as chemical dry etching, chemical wet etching (wet development), and physical etching such as sputter etching and ion beam etching. method. When the patterning film is removed, it is preferable to use, for example, tetrafluoromethane, perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), perfluoroethane (C ₂ F ₆ ), boron trichloride, methane trifluoride, trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, chlorine, helium, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride and other gases dry Etching is implemented.

Furthermore, the step of removing a part of the film for pattern formation may also be a chemical wet etching step. The method of wet etching includes, for example, a method of reacting with acetic acid to perform treatment; a method of reacting with a mixed solution of alcohol such as ethanol and isopropanol and water to perform treatment; irradiating UV light or After EB light, acetic acid or alcohol is used for treatment.

As described above, a pattern can be formed on the film for pattern formation. The formed pattern is preferably a line and space pattern, a hole arrangement pattern, or a pillar pattern.

The pattern forming method of this embodiment includes a step of introducing metal into at least a part of the pattern forming film to obtain a metal-containing pattern forming film. The step of obtaining a metal-containing pattern formation film (metal introduction step) is preferably provided after the pattern shape is formed on the pattern formation film, but the metal introduction step may be provided before the pattern formation is formed on the pattern formation film. The metal system introduced in the film for pattern formation includes, for example, Li, Be, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc. The step of introducing metal into the film for pattern formation can be implemented by a method described in, for example, Journal of Photopolymer Science and Technology Volume 29, Number 5 (2016) 653-657. In addition, when introducing a metal into the film for pattern formation, for example, a method of using a metal complex gas, a method of applying a metal-containing solution, or a method of introducing a metal into a photoresist by an ion implantation method can be used. Among them, the step of obtaining a metal-containing pattern formation film (metal introduction step) is preferably a method of spraying a metal complex gas onto the pattern formation film.

The step of obtaining a metal-containing pattern forming film is preferably to introduce metal so that the total metal content of the metal-containing pattern forming film becomes 4.0 atom% or more, more preferably 4.5 atom% or more, and particularly preferably 5.0 Introduce metal with atom% or more. In addition, the upper limit of the total metal content of the film for forming a metal-containing pattern is preferably 60 atom% or less, more preferably 50 atom% or less. Furthermore, in the step of obtaining a metal-containing pattern-forming film, it is preferable to introduce the metal of the pattern-forming film so that the A/B value becomes 10.0 or less. Here, A is the maximum metal content (atom%) in the thickness direction of the metal-containing patterning film, and B is the metal content (atom%) at the midpoint in the thickness direction of the film for patterning.

The step of obtaining a metal-containing pattern forming film is to spray a metal gas on the pattern forming film. The spray pressure of the metal gas at this time is preferably 10 Pa or more, more preferably 50 Pa or more, and particularly preferably 100 Pa or more. The spray pressure of the metal gas is preferably 700 Pa or less, more preferably 650 Pa or less, and particularly preferably 600 Pa or less. In addition, the spray time of the metal gas is preferably 5 seconds or more, more preferably 15 seconds or more, and particularly preferably 30 seconds or more. The spray time of the metal gas is preferably 1800 seconds or less, more preferably 1200 seconds or less, particularly preferably 900 seconds or less. In addition, in the step of obtaining a metal-containing pattern formation film, it is preferable that the total content of the metal contained in the metal-containing pattern formation film when a metal gas is sprayed on the pattern formation film under a pressure of 500 Pa for 300 seconds It becomes 4.0 atom% or more, and the A/B value is 10.0 or less.

After the metal is introduced into at least a part of the pattern forming film to obtain the metal-containing pattern forming film, it is preferable to further provide an etching step. This etching step is a step of etching the substrate by using the patterned film for pattern formation as a protective film (mask) as shown in FIG. 2(c).

Examples of methods for processing the substrate in the etching step include: reactive ion etching (RIE) such as chemical dry etching and chemical wet etching (wet development); well-known methods such as physical etching such as sputter etching and ion beam etching . Substrate processing preferably uses such as: tetrafluoromethane, perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, chlorine, Dry etching of gases such as sulfur hexafluoride, difluoromethane, nitrogen trifluoride, and chlorine trifluoride is carried out.

Furthermore, the etching step can also be a chemical wet etching step. The method of wet etching can include, for example, a method of reacting with acetic acid to perform treatment; a method of reacting with a mixed solution of alcohol such as ethanol and isopropanol and water to perform treatment; irradiating UV light Or after EB light, acetic acid or alcohol is used for treatment. [Example]

Examples and comparative examples are listed below to describe the features of the present invention in more detail. The materials, usage amount, ratio, processing content, processing sequence, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited to the specific examples shown below.

(Example 1) [Synthesis of Copolymer 1] (Synthesis of Acetyl Methacrylate 1) 20 g of xylose was added to a mixed solution of 250 g of acetic anhydride and 320 g of acetic acid, and stirred at 30°C for 2 hours. While stirring, slowly add about 5 times the amount of cold water to the solution, and after stirring for 2 hours, let it stand for 1 night. In 400 mL of THF, 1.2 g of ethylenediamine and 01.4 g of acetic acid were added to a flask to obtain a solution of 0°C, 10 g of precipitated crystals were added, and the mixture was stirred for 4 hours. This was poured into 1 L of cold water, and extraction was performed twice with dichloromethane. 20 g of the extract, 300 mL of dichloromethane, and 4.8 g of triethylamine were put in a flask and cooled to -30°C. 2.8 g of chlorinated methacryloyl groups were added and stirred for 2 hours. This was poured into 300 mL of cold water, extracted twice with dichloromethane, and the solvent was concentrated to obtain 1:16.1 g of acetylxylose methacrylate. The structure of the obtained acetylxylose methacrylate 1 is as follows.

[化8]

(Synthesis of Acetyl Xylose Methacrylate-Styrene-Glycidyl Methacrylate Random Copolymer) 12.0 g of acetyl methacrylate, 2.6 g of styrene (manufactured by Tokyo Chemical Co., Ltd.), 2.6 g of glycidyl methacrylate (manufactured by Tokyo Chemical Co., Ltd.), 100 g of THF as a solvent, and azo as a polymerization initiator After putting 0.8 g of bisisobutyronitrile into the flask, the glass container was sealed, and the temperature was raised to 78° C. and stirred for 6.0 hours in a nitrogen-substituted nitrogen environment. Then, it returned to room temperature, the inside of the glass container was made into the atmosphere, and the obtained solution was dropped in 300 g of methanol to deposit the polymer. Then, the solution containing the precipitated polymer was subjected to suction filtration to obtain 1:12 g of a white copolymer. The obtained copolymer 1 contains the following structural units.

[化9]

[Preparation of solution samples] The copolymer solution was obtained by dissolving it in PGMEA by dissolving the copolymer in a method of 1:3% by mass and 0.3% by mass of p-toluenesulfonic acid as a polymerization catalyst.

(Example 2) [Synthesis of Copolymer 2] (Synthesis of Acetyl Xylose Methacrylate-Styrene-Glycidyl Methacrylate Random Copolymer) Except that during the synthesis of copolymer 1, the addition amount of styrene was changed from 2.6 g to 2.3 g, and the addition amount of glycidyl methacrylate was changed from 2.6 g to 0.8 g, the rest were in accordance with Example 1. The same method is used to obtain copolymer 2: 12.0 g. In addition, in the same manner as in Example 1, a copolymer solution sample was obtained.

(Example 3) [Synthesis of copolymer 3] (Synthesis of Acetyl Xylose Methacrylate-Styrene Random Copolymer) Except that during the synthesis of copolymer 1, the amount of styrene added was changed from 2.6 g to 2.1 g, and glycidyl methacrylate was not added, the rest were followed by the same method as in Example 1 to obtain copolymer 3: 12.0g. In addition, in the same manner as in Example 1, a copolymer solution sample was obtained.

(Example 4) [Synthesis of copolymer 4] (Synthesis of acetylxylotriose methacrylate-styrene random copolymer) Except for the synthesis of copolymer 1, xylose was changed to xylotriose Other than that, the same method as in Example 1 was followed to obtain copolymer 4: 12.1 g. In addition, in the same manner as in Example 1, a copolymer solution sample was obtained. The obtained copolymer 4 contains the following structural units. [化10]

[Copolymer Analysis] (Unit (l): Unit (m): Unit (n) Ratio) Using ¹ H-NMR to determine the ratio of unit (l) and unit (m): unit (n) constituting the copolymer (Mass ratio), the results are shown in Table 1. Specifically, 10 mg of copolymers obtained in Examples and Comparative Examples were weighed and dissolved in 1 mL of heavy chloroform to prepare an NMR solution. The obtained solution was transferred to an NMR sample tube (Kanto Chemical Co., Ltd.) and used FT-NMR ( JNM-ECZ600R: JEOL company) performs ¹ H-NMR measurement.

[Evaluation of free volume radius] The copolymer solution samples obtained in the examples and comparative examples were spin-coated on a 2-inch silicon wafer substrate. After the coating is applied so that the film thickness becomes 500 nm, it is calcined on a hot plate at 230°C for 5 minutes to form a film for pattern formation. The pattern-forming film thus formed was further cut into 15mm×15mm squares, and set in a small positron beam generator PALS-200A (a positron annihilation time measuring device corresponding to thin films) manufactured by Fuji Imvac. The positron beam source uses a 22Na base positron beam, and the γ-ray detector uses a BaF ₂ scintillator and a photomultiplier tube. The positron annihilation time is measured according to the following conditions. Device constant: 263~272ps, 24.55ps/ch Beam intensity: 1.5keV Measuring depth: 0~25μm (estimated) Measuring temperature: Room temperature Measuring environment: Vacuum Total value: Approximately 5,000,000 counts Sample pre-processing: Apply vacuum at room temperature The degassing is based on the analysis of the positron annihilation time curve obtained above by using the nonlinear least square formula POSITRONFIT to calculate the average free volume radius. The results are shown in Table 1.

[Al content measurement] The copolymer solution samples obtained in the Examples and Comparative Examples were spin-coated on a 2-inch silicon wafer substrate. After the coating was applied so that the film thickness became 300 nm, it was calcined on a hot plate at 230°C for 5 minutes to form a film for pattern formation. The film for pattern formation thus formed is placed in ALD (Atomic Layer Deposition Equipment: SUNALE R-100B manufactured by PICUSAN), and TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas is introduced at 95°C for 300 seconds , And then introduce water vapor for 150 seconds. By repeating this operation three times, Al ₂ O ₃ is introduced into the pattern forming film. The copolymer film-forming sample introduced by Al ₂ O ₃ was set in an XPS device (Nexsa XPS System manufactured by Thermo Fisher Scientific), and the sputtering of Ar ions and the analysis by XPS (X-ray photoelectron energy) were repeatedly used in sequence. Spectral analysis) performed surface element concentration measurement and film thickness measurement to obtain the Al element (nucleus radius: 0.118 nm) concentration distribution in the film thickness direction. The film thickness of the pattern forming film introduced with Al ₂ O _{3 was} measured by using a palpation gradiometer (Model: ET-4000, manufactured by Kosaka Manufacturing Co., Ltd.) according to each sputtering time. Obtained from the gradient part generated by the sputtered part. The "Al content in the film" shown in Table 2 is calculated from the obtained depth distribution, which is equivalent to the total amount of Al element content in the film. The "maximum Al content rate" shown in Table 2 is the Al element content rate at which the Al element concentration in the film of each distribution becomes the maximum point. The "Al content rate at 1/2 of the total film thickness" shown in Table 2 refers to the content rate of Al elements distributed at the midpoint of the film thickness. The "A/B ratio" shown in Table 2 is the ratio of the Al element content obtained by the following formula. A/B ratio = maximum Al element content rate / Al content rate at 1/2 of the total film thickness

[Production of Samples for Etching Selection Ratio Measurement] The copolymer solution samples obtained in the Examples and Comparative Examples were spin-coated on a 2-inch silicon wafer substrate with a silicon oxide film (film thickness 2um). After coating and forming a film with a thickness of 300 nm, it is calcined on a hot plate at 230°C for 1 minute to form a film for pattern formation. Using an ArF excimer laser exposure machine, masks were applied in a manner of forming lines and spaces (line width 100nm, space width 100nm), and exposure was performed using a commercially available ArF photoresist. Then, it was calcined at 105°C for 1 minute on a hot plate, and then immersed in a developing solution to make a pattern of lines and spaces. Next, the pattern sample was subjected to oxygen plasma treatment (100 sccm, 4 Pa, 100 W, 60 seconds) on the substrate using an ICP plasma etching device (manufactured by Tokyo Electron Co., Ltd.) to remove the photoresist and form it on the pattern forming film Line and space pattern. Then, in accordance with the evaluation of the metal introduction rate of the copolymer, metal introduction was performed on the film for pattern formation. Using this pattern as a mask, using hexafluoroethane (C ₂ F ₆ ) and Ar gas, plasma treatment (100 sccm, 0.4 Pa, 200 W, 120 seconds) using an ICP plasma etching device (manufactured by Tokyo Electron Co., Ltd.) , And the implementation of dry etching of the silicon oxide film.

[Evaluation of etching] using a scanning electron microscope (SEM) JSM7800F (manufactured by JEOL), in accordance with an acceleration voltage of 1.5 kV, the emission current is 37.0μA, magnification of 100,000 times, was observed by the use of hexafluoroethane (C ₂ F ₆₎ and Before and after Ar gas plasma treatment, the silicon oxide film has been patterned, and the thickness of the patterning film introduced by the metal was measured (the thickness c in Fig. 2(b) and the thickness c'in Fig. 2(c)) ), and the depth of the silicon oxide film portion (depth d in Figure 2(c)). Then, the etching selection ratio was calculated from the following equation. Etching selection ratio=processing depth of the silicon oxide film/(film thickness for pattern formation before plasma treatment-thickness of pattern formation film after plasma treatment) Then, the etching processability was evaluated according to the following criteria. A: Etching selection ratio is more than 10 B: Etching selection ratio is more than 2 and less than 10 C: Etching selection ratio is less than 2

(Example 5) Except when metal was introduced into the pattern forming film in Example 1, instead of TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas, trimethyl borate (B(OCH ₃₎ ) ₃ ) Except for gas, various evaluations were performed in the same manner as in Example 1.

(Comparative Example 1) Except when metal was introduced into the film for pattern formation in Example 1, instead of TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas, trimethyl borate (B(OCH ₃₎ ) ₃ ) Except for the gas, various evaluations were performed in the same manner as in Example 3.

[B content determination] According to the same method as the above-mentioned [Al content measurement], the concentration distribution of B element (nucleus radius 0.087 nm) in the film thickness direction was obtained. The "B content in the film" shown in Table 3 is calculated from the obtained depth distribution, which is equivalent to the total amount of the B element content in the film. The "maximum B content rate" shown in Table 3 refers to the B element content rate at which the B element concentration in the film of each distribution becomes the maximum point. The "B content at 1/2 of the total film thickness" shown in Table 3 refers to the content of the B element distributed at the midpoint of the film thickness. The "A/B ratio" shown in Table 3 is the ratio of the B element content obtained according to the following formula. A/B ratio = maximum B element content rate / B content rate at 1/2 of the total film thickness

(Example 6) Except when metal was introduced into the patterning film in Example 1, instead of TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas, trimethyl antimony (Sb(CH ₃₎ ) ₃ ) Except for gas, various evaluations were performed in the same manner as in Example 1.

[Sb content determination] According to the same method as the above-mentioned [Al content measurement], the Sb element (nucleus radius: 0.133 nm) concentration distribution in the film thickness direction was obtained. The "Sb content in the film" shown in Table 4 is calculated from the obtained depth distribution, which is equivalent to the total amount of the Sb element content in the film. The "maximum Sb content rate" shown in Table 4 refers to the Sb element content rate at which the Sb element concentration in the film of each distribution becomes the maximum point. The "Sb content at 1/2 of the total film thickness" shown in Table 4 refers to the Sb element content distributed at the midpoint of the film thickness. The "A/B ratio" shown in Table 4 is the ratio of the Sb element content obtained by the following formula. A/B ratio = maximum Sb element content rate / Sb content rate at 1/2 of the total film thickness

(Comparative Example 2) Except when metal was introduced into the pattern forming film in Example 1, instead of TMA (trimethylaluminum, Al(CH ₃ ) ₃ ) gas, trimethyl indium (In(CH ₃₎ ) ₃ ) Except for gas, various evaluations were performed in the same manner as in Example 1.

[In content determination] According to the same method as the above-mentioned [Al content measurement], the concentration distribution of In element (nucleus radius: 0.156 nm) in the film thickness direction was obtained. The "In content in the film" shown in Table 5 is calculated from the obtained depth distribution, which is equivalent to the total amount of the In element content in the film. The "maximum In content rate" shown in Table 5 refers to the In element content rate at which the In element concentration in the film of each distribution becomes the maximum point. The "In content rate at 1/2 of the total film thickness" shown in Table 5 refers to the content rate of In elements distributed at the midpoint of the film thickness. The "A/B ratio" shown in Table 5 is the ratio of the In element content obtained by the following formula. A/B ratio = maximum In element content rate / In content rate at 1/2 of the total film thickness

[Table 1] Copolymer structure (mass%) Doped metal Free volume radius (Pr) (nm) Nuclear radius (Mr) (nm) Pr/Mr Acetyl Xylose Methacrylate Acetyl xylotriose methacrylate Styrene GMA Example 1 70 - 15 15 Al (aluminum) 0.283 0.118 2.398 Example 2 80 - 15 5 Al (aluminum) 0.290 0.118 2.458 Example 3 85 - 15 - Al (aluminum) 0.300 0.118 2.542 Example 4 - 70 15 15 Al (aluminum) 0.265 0.118 2.245 Example 5 70 - 15 15 B (boron) 0.283 0.087 3.253 Example 6 70 - 15 15 Sb (antimony) 0.283 0.133 2.128 Comparative example 1 70 - 15 15 In (Indium) 0.283 0.156 1.814 Comparative example 2 85 - 15 - B (boron) 0.300 0.087 3.448

[Table 2] Copolymer structure (mass%) Doped metal Al content in film (atom%) Maximum Al content (A) (atom%) Al content at 1/2 of the total film thickness (B) (atom%) Al ratio (A/B) Etching processability Acetyl Xylose Methacrylate Acetyl xylotriose methacrylate Styrene GMA Example 1 70 - 15 15 Al (aluminum) 5.4 15.6 1.9 8.21 B Example 2 80 - 15 5 Al (aluminum) 25.6 29.9 27.0 1.11 A Example 3 85 - 15 - Al (aluminum) 15.4 30.5 17.5 1.74 A Example 4 - 70 15 15 Al (aluminum) 5.6 17.5 2.0 8.75 B

[table 3] Copolymer structure (mass%) Doped metal B content in film (atom%) Maximum B content rate (A) (atom%) B content at 1/2 of the total film thickness (B) (atom%) B ratio (A/B) Etching processability Acetyl Xylose Methacrylate Acetyl xylotriose methacrylate Styrene GMA Example 5 70 - 15 15 B (boron) 4.2 15.2 2.5 6.08 B Comparative example 1 85 - 15 - B (boron) 3.7 13.4 1.0 13.40 C

[Table 4] Copolymer structure (mass%) Doped metal Sb content in film (atom%) Maximum Sb content rate (A) (atom%) Sb content at 1/2 of the total film thickness (B) (atom%) Sb ratio (A/B) Etching processability Acetyl Xylose Methacrylate Acetyl xylotriose methacrylate Styrene GMA Example 6 70 - 15 15 Sb (antimony) 5.8 26.3 2.8 9.39 B

[table 5] Copolymer structure (mass%) Doped metal In content in film (atom%) Maximum In content rate (A) (atom%) In content rate at 1/2 of the total film thickness (B) (atom%) In ratio (A/B) Etching processability Acetyl Xylose Methacrylate Acetyl xylotriose methacrylate Styrene GMA Comparative example 2 70 - 15 15 In (Indium) 5.5 28.5 2.6 10.96 C

In Table 1, the nucleus radius is based on the value recorded in E Clementi, DL Raimondi, WP Reinhardt (1963) J Chem Phys. 38: 2686.

Since the example satisfies the condition of 2≦Pr/Mr≦3.3, the etching processability is good. On the other hand, the comparative examples that did not satisfy the condition of 2≦Pr/Mr≦3.3 showed poor etching processability.

10: substrate 20: Film for pattern formation

Fig. 1 is a graph showing the depth distribution (XPS measurement) of Al content in the film for pattern formation obtained in Examples and Comparative Examples; and 2(a) to (c) are schematic diagrams illustrating the steps of forming a pattern on a substrate.

10: substrate

20: Film for pattern formation

Claims (11)

A composition for pattern formation, a composition for pattern formation containing a polymer; wherein, Set the free volume radius of the above polymer as Pr, When the nucleus radius of the metal introduced when the patterning composition is patterned as described above is set to Mr, Satisfy the condition of 2≦Pr/Mr≦3.3. The pattern formation composition of claim 1, wherein the pattern formation composition is coated on a substrate to form a pattern formation film with a thickness of 300 nm, and a metal gas is introduced into the pattern formation under a pressure of 500 Pa When filming for 300 seconds, The total metal content of the film for pattern formation is 4.0 atom% or more; When the maximum metal content in the thickness direction of the film for pattern formation is Aatom%, and the metal content at the middle point in the thickness direction of the film for pattern formation is Batom%, the value of A/B is 10.0 or less. The composition for pattern formation according to claim 1 or 2, wherein the polymer system contains a unit derived from a sugar derivative. The composition for pattern formation of claim 3, wherein the unit derived from the sugar derivative contains at least one selected from the structure shown in the following general formula (103) and the structure shown in the following general formula (104) One; [化1]

[化2]

In general formulas (103) and (104), R ¹ independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, an acyl group, an aryl group, a trimethylsilyl group, or a phosphoryl group. , The plural R ¹ systems may be the same or different; R ⁵ represents a hydrogen atom or an alkyl group; X ¹ and Y ¹ each independently represent a single bond or a linking group; r represents an integer of 1 or more, ⁎ label system When r is 2 or more, it represents ^{a bonding site with any one of R 1} , or represents a bonding site that replaces R ¹ with any one of the oxygen atoms to which R ^{1 is bonded.} The composition for pattern formation according to claim 4, wherein the polymer system further has a structure represented by the following general formula (105); [化3]

In general formula (105), W ¹ represents a carbon atom or a silicon atom; W ² represents -CR ₂ -, -O-, -S- or -SiR _2- (wherein, R represents a hydrogen atom or a carbon number of 1 ~5 alkyl groups, the plural R may be the same or different); R ¹¹ represents a hydrogen atom, an alkyl group with a carbon number of 1 or more and 3 or less or a hydroxyl group; R ¹² represents a hydrogen atom, hydroxyl, acetyl Group, methoxycarbonyl group, aryl group, allyl group, glycidyl ether group, glycidyl group, isocyanate group or pyridyl group. The composition for pattern formation of claim 1 or 2, wherein the polymer contains a unit derived from a sugar derivative, and the content of the unit derived from a sugar derivative in the polymer is 60 to 90 mass %. For example, the pattern formation composition of claim 1 or 2 is a mask material for pattern formation. A pattern forming method includes: The step of coating a patterning composition containing a polymer on a substrate to form a patterning film; and The step of introducing metal into at least a part of the above-mentioned pattern forming film to obtain a metal-containing pattern forming film; Among them, the free volume radius of the above polymer is set to Pr, When the nucleus radius of the above metal is set to Mr, Satisfy the condition of 2≦Pr/Mr≦3.3. The pattern forming method of claim 8, wherein the total content of the metal contained in the metal-containing pattern forming film is 4.0 atom% or more; When the maximum metal content in the thickness direction of the metal-containing patterning film is set to Aatom%, and the metal content at the middle point in the thickness direction of the above-mentioned patterning film is set to Batom%, the value of A/B is 10.0 or less . The pattern forming method according to claim 8 or 9, wherein after the step of forming the pattern forming film, the method further includes a step of forming a pattern on the pattern forming film. The pattern forming method of claim 8 or 9, wherein after the step of obtaining the metal-containing pattern forming film, an etching step is further included.

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