Compositions for forming organic films, methods for forming patterns, and compounds and polymers for forming organic films.

Abstract

To provide: a compound and a polymer which allow formation of an organic film that is excellent in heat resistance and properties of filling and planarizing a pattern and also has favorable film formability on and adhesiveness to a substrate; and a composition for forming an organic film containing them.SOLUTION: An organic film forming composition contains: an organic film forming material shown by the general formula (I) and / or (II) in the figure; and an organic solvent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an organic film-forming composition used for fine patterning by a multilayer resist method in the semiconductor device manufacturing process, a pattern-forming method using the composition, and compounds and polymers used in the organic film-forming composition. [Background technology]

[0002] With the increasing integration and speed of LSIs, the miniaturization of pattern dimensions is progressing rapidly. Lithography technology has achieved the formation of fine patterns in line with this miniaturization by shortening the wavelength of the light source and appropriately selecting the resist composition. At the heart of this is the single-layer positive photoresist composition. This single-layer positive photoresist composition has a framework in the resist resin that is resistant to dry etching with chlorine-based or fluorine-based gas plasma, and also has a switching mechanism that causes the exposed area to dissolve, thereby forming a pattern by dissolving the exposed area, and the remaining resist pattern is used as an etching mask to dry etch the workpiece (substrate).

[0003] However, when the thickness of the photoresist film used was kept the same while miniaturization was achieved, i.e., the pattern width was reduced, the resolution performance of the photoresist film decreased. Furthermore, when attempting to develop the photoresist film using a developer, the aspect ratio became too large, resulting in pattern collapse. For this reason, as patterns became smaller, the photoresist film was made thinner.

[0004] On the other hand, the processing of substrates typically involves using a photoresist film with a pattern formed on it as an etching mask and processing the substrate by dry etching. However, in reality, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate. As a result, the resist film is damaged and disintegrates during substrate processing, making it impossible to accurately transfer the resist pattern to the substrate. Therefore, with the miniaturization of patterns, higher dry etching resistance has been required for resist compositions. However, at the same time, in order to improve resolution, resins with low light absorption at the exposure wavelength have been required for the resins used in photoresist compositions. Therefore, as the exposure light has become shorter in wavelength, from i-line to KrF and ArF, the resins have also changed to novolac resins, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons. However, in reality, the etching rate under dry etching conditions during substrate processing has become fast, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] This means that the substrate to be processed must be dry-etched using a thinner photoresist film with weaker etching resistance, making the securing of materials and processes for this processing step crucial.

[0006] One way to solve these problems is through the multilayer resist method. In this method, a photoresist film (i.e., a resist upper layer) and an intermediate film with different etching selectivity are interposed between the resist upper layer and the substrate to be processed. After obtaining a pattern on the resist upper layer, the resist upper layer pattern is used as a dry etching mask to transfer the pattern to the intermediate film by dry etching, and then the intermediate film is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] One multilayer resist method is the three-layer resist method, which can be performed using the same resist compositions as those used in the single-layer resist method. In this three-layer resist method, for example, an organic film made of novolac resin is deposited on the substrate to be processed, a silicon-containing film is deposited on top of it as a resist interlayer, and a normal organic photoresist film is formed on top of that as the resist upper layer. When dry etching is performed using a fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity ratio compared to the silicon-containing resist interlayer, so the resist upper layer pattern can be transferred to the silicon-containing resist interlayer by dry etching with a fluorine-based gas plasma. With this method, even if a resist composition that does not have sufficient thickness to form a pattern for direct processing of the substrate or a resist composition that does not have sufficient dry etching resistance for substrate processing is used, the pattern can be transferred to the silicon-containing film (resist interlayer), and then by performing pattern transfer by dry etching with an oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist lower layer) made of novolac resin or the like with sufficient dry etching resistance for substrate processing can be obtained. As for the organic films described above, many are already known, such as those described in Patent Document 1.

[0008] On the other hand, in recent years, there has been increased activity in the development of new semiconductor devices with structures such as multi-gate structures, and in response to this, there is a growing demand for organic films with superior planarization and filling characteristics compared to conventional films. For example, when the underlying substrate has minute pattern structures such as holes, trenches, and fins, the organic film needs to be able to completely fill the gaps within the patterns with the film. Also, when there are steps in the underlying substrate, or when densely patterned areas and areas without patterns exist on the same wafer, it is necessary to planarize the film surface with the organic film. By planarizing the surface of the organic film, it is possible to suppress variations in the film thickness of the resist interlayer and resist top layer deposited on it, thereby suppressing a decrease in the focus margin in lithography and the margin in subsequent processing steps of the substrate.

[0009] Furthermore, organic film materials with excellent embedding / planarization properties are not limited to underlayer films for multilayer resists, but can also be widely applied as planarization materials for semiconductor device manufacturing, such as substrate planarization prior to patterning by nanoimprinting. In addition, while the CMP process is currently commonly used for global planarization in semiconductor device manufacturing, CMP is a high-cost process, and these materials are expected to serve as an alternative global planarization method.

[0010] Organic film materials containing polymers obtained by the reaction of aromatic compounds with compounds having carbon-oxygen double bonds, such as carbonyl groups, have been proposed for the formation of planarization films to flatten uneven semiconductor substrates (Patent Document 2). However, these materials have insufficient planarization performance in wide trench areas within the substrate to meet the requirements of state-of-the-art devices, and there is a growing need for organic film materials that exhibit superior planarity on a wider range of substrate structures.

[0011] Furthermore, as mentioned above, the structure of the substrates to be processed is becoming more complex, and new materials with high electron mobility, such as strained silicon and gallium arsenide, as well as ultrathin polysilicon films controlled in angstroms, are also being considered for the surface of the substrates to be processed, resulting in a wide variety of possibilities. covered The film is expected to be deposited on the surface shape and material of the processed substrate. Therefore, in order to ensure process margins, not only excellent embedding and planarization characteristics are important, but also the ability to deposit the film regardless of the material and shape of the substrate being processed. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] Japanese Patent Publication No. 2004-205685 [Patent Document 2] International Publication No. 2019 / 225615 [Overview of the project] [Problems that the invention aims to solve]

[0013] The present invention has been made in view of the above circumstances, and aims to provide compounds and polymers that can form organic films that not only have excellent heat resistance and embedding and planarization properties of patterns formed on a substrate, but also have good film-forming properties and adhesion to the substrate, as well as organic film-forming compositions containing said compounds and / or polymers. Furthermore, the present invention aims to provide a pattern-forming method using said composition. [Means for solving the problem]

[0014] To solve the above problems, the present invention provides an organic film-forming composition characterized by containing an organic film-forming material represented by the following general formula (I) and / or general formula (II) and an organic solvent. [ka] (In the above general formula (I), R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyloxy group, a C2-C4 alkenyloxy group, a C1-C6 linear, branched, or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; R3 is a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, it means that a cyclic ether structure is formed between aromatic rings. k represents an integer from 0 to 2. V independently represents a hydrogen atom or a linkage.) [ka] (In the above general formula (II), R4 is a hydrogen atom, an allyl group, or a propargyl group; R5 is a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; R6 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. i represents 0 or 1, q represents an integer of 0 to 2, h and j each independently represent an integer of 0 to 2, satisfying the relationship of 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 1, it means that a cyclic ether structure is formed between aromatic rings. W is either a single bond or a divalent group represented by the following formula (3). V each independently represents a hydrogen atom or a linking portion.)

Chemical formula

[0015] For such a composition for forming an organic film, not only is it excellent in heat resistance, embedding and planarization characteristics of a pattern formed on a substrate, but it can also form an organic film with good film-forming property and adhesion to the substrate.

[0016] In this case, the organic film-forming material can be a compound represented by the following general formula (1) and / or (2).

Chemical formula

Chemical formula

[0017] The compounds of the present invention represented by the above general formulas (1) and / or (2) have excellent heat resistance, making them suitable for use as organic film materials on their own. Furthermore, they exhibit superior thermal fluidity compared to high molecular weight compounds, resulting in excellent embedding / planarization properties when used as organic films on patterned substrates. In addition, because they possess a cyclic amide structure within the molecule, they do not impair heat resistance and can improve adhesion to substrates and film formation properties.

[0018] In addition, it is preferable that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the compound represented by the general formula (1) and / or (2) measured by gel permeation chromatography is 1.00 ≤ Mw / Mn ≤ 1.10.

[0019] By controlling the Mw / Mn ratio of the organic film-forming compound within this range, it is possible to form organic films with excellent embedding properties and flatness.

[0020] Furthermore, in the present invention, the organic film-forming material may be a polymer having repeating units represented by the following general formulas (4) and / or (5). [ka] (In the general formula (4) above, R1, R2, R3, m, n, l, and k are the same as described above. L is a divalent organic group having 1 to 40 carbon atoms.) [ka] (In the above general formula (5), R4, R5, R6, W, L, h, i, j, q, and r are the same as described above.)

[0021] By using polymers having such repeating units, it is possible to form dense organic films without degradation of etching resistance and by improving curability, resulting in an organic film-forming composition that is excellent in film formation regardless of the substrate material or shape.

[0022] In this case, it is preferable that L is a divalent organic group represented by the following general formula (6). [ka] (In the above general formula (6), R7 is an organic group containing a hydrogen atom or an aromatic ring with 1 to 20 carbon atoms, and the dashed line represents a bond.)

[0023] By forming repeating units with such linking groups L, properties such as curability and etching resistance can be improved.

[0024] Furthermore, it is preferable that the weight-average molecular weight of the polymer, calculated on a polystyrene basis by gel permeation chromatography, is between 1,000 and 5,000.

[0025] A composition for forming organic films containing polymers having a weight-average molecular weight within this range can suppress outgassing during baking without impairing solubility in organic solvents.

[0026] Furthermore, in the present invention, the organic film-forming material may contain one or more compounds selected from the following general formulas (1) and / or (2) and polymers having repeating units represented by the following general formulas (4) and / or (5). [ka] (In the above general formula (1), R1, R2, R3, m, n, l, and k are the same as described above.) [ka] (In the above general formula (2), R4, R5, R6, i, q, h, j, r, and W are the same as described above.) [ka] (In the general formula (4) above, R1, R2, R3, m, n, l, and k are the same as described above. L is a divalent organic group having 1 to 40 carbon atoms.) [ka] (In the above general formula (5), R4, R5, R6, W, L, h, i, j, q, and r are the same as described above.)

[0027] With such a mixture, it becomes possible to adjust various physical properties required when used to form organic films, such as embedding / planarization characteristics and sublimation-induced outgassing, within an appropriate range.

[0028] In addition, it is preferable that the organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0029] If the above organic solvent is the above mixture, the addition of the high-boiling-point solvent to the above compound and / or polymer imparts thermal fluidity to the organic film, thereby giving the organic film-forming composition advanced embedding / planarization properties.

[0030] Furthermore, it is preferable that the above-mentioned organic film-forming composition contains one or more of the surfactants and plasticizers.

[0031] A composition for forming organic films containing the above-mentioned additives will have superior coatability and embedding / planarization properties.

[0032] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the above-mentioned organic film forming composition, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition, forming a circuit pattern on the resist upper layer, transferring the pattern to the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern has been formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further forming a pattern on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0033] The pattern formation method using the above three-layer resist process makes it possible to form fine patterns on the workpiece (workpiece substrate) with high precision.

[0034] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the above-mentioned organic film forming composition, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming an organic anti-reflective film (BARC) on the silicon-containing resist interlayer, forming a resist upper layer on the BARC using a photoresist composition to form a four-layer structure, forming a circuit pattern on the resist upper layer, transferring the pattern to the BARC film and the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern has been formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further etching the workpiece using the organic film on which the pattern has been transferred as a mask to form a pattern on the workpiece.

[0035] The pattern formation method using the four-layer resist process described above allows for the formation of fine patterns on the workpiece with even greater precision.

[0036] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the above-mentioned organic film forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition to form a circuit pattern on the resist upper layer film, etching the inorganic hard mask using the resist upper layer film on which the pattern is formed as a mask, etching the organic film using the inorganic hard mask on which the pattern is formed as a mask, and further etching the workpiece using the organic film on which the pattern is formed as a mask to form a pattern on the workpiece.

[0037] This three-layer resist process allows for the formation of fine patterns on a workpiece with high precision.

[0038] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the above-mentioned organic film forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic anti-reflective film (BARC) on the inorganic hard mask, forming a resist upper layer film on the BARC using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist upper layer film, etching the BARC film and the inorganic hard mask using the resist upper layer film on which the pattern is formed as a mask, etching the organic film using the inorganic hard mask on which the pattern is formed as a mask, and further etching the workpiece using the organic film on which the pattern is formed as a mask to form a pattern on the workpiece.

[0039] This four-layer resist process allows for the formation of fine patterns on the workpiece with greater precision.

[0040] In this case, it is preferable that the inorganic hard mask is formed by CVD or ALD.

[0041] When the above inorganic hard mask is formed by CVD or ALD, fine patterns can be formed on the workpiece with higher precision.

[0042] Furthermore, it is preferable to form the pattern of the resist upper layer film by photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0043] By using the above method to form a circuit pattern on the resist upper layer film, fine patterns can be formed on the workpiece with higher precision.

[0044] Furthermore, in the pattern formation method described above, exposure and development are performed to form a circuit pattern on the resist upper layer film, and it is preferable that the development is alkaline development or development with an organic solvent.

[0045] When using alkaline development or development with organic solvents as the development method, fine patterns can be formed on the workpiece with higher precision.

[0046] Furthermore, it is preferable to use a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film as the workpiece.

[0047] In the present invention, for example, the above-mentioned workpiece can be used.

[0048] In this case, it is preferable that the above metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.

[0049] These can be used as the metals mentioned above. In this way, when pattern formation is performed using the organic film-forming composition of the present invention, it becomes possible to transfer and form the pattern of the upper layer photoresist on the workpiece with high precision.

[0050] Furthermore, the present invention provides a compound represented by the following general formula (1). [ka] (In the formula, R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyloxy group, a C2-C4 alkenyloxy group, a C1-C6 linear, branched, or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; R3 is a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, it means that a cyclic ether structure is formed between aromatic rings. k represents an integer from 0 to 2.)

[0051] Furthermore, the present invention provides a compound represented by the following general formula (2). [ka] (In the formula, R4 is a hydrogen atom, an allyl group, or a propargyl group; R5 is a nitro group, a halogen atom, a hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyloxy group, a C2-C4 alkenyloxy group, a C1-C6 linear, branched, or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; R6 is a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j each independently represent an integer from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 1, it means that a cyclic ether structure is formed between aromatic rings. W is either a single bond or a divalent group represented by formula (3) below.) [ka] (The dashed lines represent connections.)

[0052] Compounds represented by the above general formula (1) or (2) are compounds for organic film-forming compositions that can form organic films with excellent heat resistance, embedding / planarization properties, and film-forming properties.

[0053] Furthermore, the present invention provides a polymer having repeating units represented by the following general formula (4). [ka] (In the above formula, R1, R2, R3, m, n, l, and k are the same as above. L is a divalent organic group with 1 to 40 carbon atoms.)

[0054] The present invention also provides a polymer having repeating units represented by the following general formula (5). [ka] (In the above formula, R4, R5, R6, i, q, h, j, r, W, and L are the same as above.)

[0055] Polymers represented by the above general formulas (4) and (5) are polymers for organic film-forming compositions that can form organic films with excellent curability.

[0056] In this case, it is preferable that L is a divalent organic group represented by the following general formula (6). [ka] (In the above general formula (6), R7 is an organic group containing a hydrogen atom or an aromatic ring with 1 to 20 carbon atoms, and the dashed line represents a bond.)

[0057] By introducing such linking groups L, various properties of the polymer, such as curability and etching resistance, can be improved. [Effects of the Invention]

[0058] As described above, the compounds or polymers of the present invention are excellent in heat resistance and are useful for forming organic films with excellent embedding / planarization performance, film formation properties, and adhesion. Furthermore, organic film-forming compositions containing these compounds and / or polymers are useful materials for forming organic films that possess various properties such as heat resistance and embedding / planarization characteristics, can be formed independently of the processed substrate, and have excellent adhesion. For this reason, they are extremely useful as organic film-forming compositions in multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer, or a four-layer resist process using a silicon-containing resist interlayer and an organic anti-reflective film, or as planarization materials for semiconductor device manufacturing. Moreover, with the pattern formation method of the present invention, fine patterns can be formed on the workpiece with high precision in a multilayer resist process. [Brief explanation of the drawing]

[0059] [Figure 1] This is an explanatory diagram illustrating an example of a pattern formation method using the three-layer resist process of the present invention. [Figure 2] This is an explanatory diagram of the embedding characteristics evaluation method in the examples and comparative examples. [Figure 3] This is an explanatory diagram of the method for evaluating planarization characteristics in the examples and comparative examples. [Figure 4] This is an explanatory diagram showing the adhesion measurement method in the examples and comparative examples. [Modes for carrying out the invention]

[0060] As described above, in the fine patterning process using the multilayer resist method in semiconductor device manufacturing processes, there has been a need for an organic film-forming composition that can form organic films with excellent film-forming properties and flatness even on workpieces (workpiece substrates) that have particularly difficult-to-planar parts such as wide trench structures, a pattern formation method using the same, and compounds and polymers suitable for such organic film-forming compositions.

[0061] As a result of diligent research into the above-mentioned problems, the inventors of the present invention have found that compounds or polymers that form the main skeleton by a specific heterocyclic structure of the present invention are useful for forming organic films with excellent embedding / planarization properties, and have completed the present invention.

[0062] In other words, the present invention is an organic film-forming composition characterized by containing an organic film-forming material and an organic solvent represented by the following general formula (I) and / or general formula (II). [ka] (In the above general formula (I), R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyloxy group, a C2-C4 alkenyloxy group, a C1-C6 linear, branched, or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; R3 is a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, it means that a cyclic ether structure is formed between aromatic rings. k represents an integer from 0 to 2. V independently represents a hydrogen atom or a linkage.) [ka] (In the above general formula (II), R4 is a hydrogen atom, an allyl group, or a propargyl group; R5 is a nitro group, a halogen atom, a hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyloxy group, a C2-C4 alkenyloxy group, a C1-C6 linear, branched, or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; R6 is a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j each independently represent an integer from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 1, it means that a cyclic ether structure is formed between aromatic rings. W is either a single bond or a divalent group represented by formula (3) below. V each independently represents a hydrogen atom or a linkage.) [ka] (The dashed lines represent connections.)

[0063] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0064] [Composition for organic film formation] The organic film-forming composition of the present invention contains an organic film-forming material and an organic solvent, which are represented by a specific general formula described later.

[0065] The above-mentioned organic film-forming composition may contain an organic film-forming material represented by the above general formula and an organic solvent, and may optionally contain additives such as surfactants and plasticizers. The components included in the composition of the present invention will be described below.

[0066] [Organic film forming material] The organic film-forming composition of the present invention is characterized by containing an organic film-forming material represented by the following general formula (I) and / or (II). [ka] (In the above general formula (I), R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyloxy group, a C2-C4 alkenyloxy group, a C1-C6 linear, branched, or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; R3 is a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, it means that a cyclic ether structure is formed between aromatic rings. k represents an integer from 0 to 2. V independently represents a hydrogen atom or a linkage.) [ka] (In the above general formula (II), R4 is a hydrogen atom, an allyl group, or a propargyl group; R5 is a nitro group, a halogen atom, a hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyloxy group, a C2-C4 alkenyloxy group, a C1-C6 linear, branched, or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; R6 is a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j each independently represent an integer from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 1, it means that a cyclic ether structure is formed between aromatic rings. W is either a single bond or a divalent group represented by formula (3) below. V each independently represents a hydrogen atom or a linkage.) [ka] (The dashed lines represent connections.)

[0067] In the above general formula (I), R1 is a hydrogen atom, an allyl group, or a propargyl group. From the viewpoint of thermosetting properties, a hydrogen atom or a propargyl group is preferred, and from the viewpoint of imparting thermal fluidity, a propargyl group is particularly preferred. Furthermore, R1 can be used in any proportion of hydrogen atoms, allyl groups, and propargyl groups. In this case, when the proportion of hydrogen atoms is a% and the proportion of allyl groups and propargyl groups is b%, the composition ratio of R1 satisfies the relationship a+b=100(%). To improve film formation and adhesion of the film to the substrate, the proportion of hydrogen atoms a should be increased, i.e., a>b. To improve curability, heat resistance, and flatness, the proportion of allyl groups or propargyl groups should be increased. of a <bと May it happen You should 。 These can be adjusted to any ratio to suit the required performance.

[0068] In the above general formula, R2 represents a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, an alkynyloxy group having 2 to 4 carbon atoms such as a propargyloxy group, an alkenyloxy group having 2 to 4 carbon atoms such as an allyloxy group, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms such as a methyl group, an isobutyl group, or a cyclohexyl group, a trifluoromethyl group, or a trifluoromethyloxy group.

[0069] In the general formula above, R3 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. Examples include the following. Among these, alkynyl or alkenyl groups are preferred from the viewpoint of ease of raw material availability and imparting thermosetting properties, and allyl or propargyl groups are more preferred from the viewpoint of ease of synthesis. Furthermore, R3 can be used in any proportion of hydrogen atoms combined with alkyl groups, alkynyl groups, and alkenyl groups. In this case, if the proportion of hydrogen atoms is A% and the proportion of allyl and propargyl groups is B%, the composition ratio of R3 satisfies the relationship A+B=100(%). To improve film formation and adhesion of the film to the substrate, the proportion of hydrogen atoms A should be increased, i.e., A>B. To improve curability, heat resistance, and flatness, the proportion of allyl or propargyl groups should be increased. Increase B , in other words A <Bとすればよい 。 These can be adjusted to any ratio to suit the required performance.

[0070] [ka] (The dashed lines represent connections.)

[0071] m represents 0 or 1, n represents an integer of 1 or 2, and l represents 0 or 1, meaning that when l=1, a cyclic ether structure is formed between aromatic rings. Also, n and l can satisfy the relationship 1≦n+l≦3. k represents an integer from 0 to 2. m is preferably 0, l is preferably 0, and k is preferably 0.

[0072] In the above general formula (II), W is either a single bond or the above general formula (3). Among these, an ether bond is preferred from the viewpoint of imparting thermal fluidity. In the case of an ether bond, it is possible to impart thermal fluidity without impairing heat resistance.

[0073] In the above general formula (II), R4 is a hydrogen atom, an allyl group, or a propargyl group. From the viewpoint of thermosetting properties, a hydrogen atom or a propargyl group is preferred, and from the viewpoint of imparting thermal fluidity, a propargyl group is particularly preferred. Similar to R1 in the above general formula (I), in R4, a hydrogen atom, an allyl group, and a propargyl group can be used in any combination in any proportion according to the required performance.

[0074] In the above general formula (II), R5 represents a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, an alkynyloxy group having 2 to 4 carbon atoms such as a propargyloxy group, an alkenyloxy group having 2 to 4 carbon atoms such as an allyloxy group, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms such as a methyl group, an isobutyl group, or a cyclohexyl group, a trifluoromethyl group, or a trifluoromethyloxy group.

[0075] In the above general formula (II), R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. Specific examples include those identical to R3 in the above general formula (I). Allyl and propargyl groups are more preferable due to their thermosetting properties and ease of synthesis. Furthermore, as mentioned above, R6 can also be a combination of a hydrogen atom, alkyl group, alkynyl group, and alkenyl group in any proportion to suit the required performance, similar to R3 in general formula (I).

[0076] In the above general formulas (I) and (II), V independently represents either a hydrogen atom or a linking group. When all V are hydrogen atoms (no linking groups), the organic film-forming material represented by the above general formulas is a monomolecule compound and corresponds to the compounds represented by general formulas (1) and (2) described later. When V is a linking group, the organic film-forming material is a polymer. A linking group is a part that connects the structures represented by the above general formulas, and can be, for example, a single bond or a linking group L described later. In other words, the polymer includes polymers having repeating units represented by general formulas (4) and (5) described later.

[0077] i represents 0 or 1, q represents an integer between 0 and 2, and h and j each independently represent an integer between 0 and 2, satisfying the relationship 1 ≤ h + j ≤ 4. r represents 0 or 1, and when r = 1, it means that a cyclic ether structure is formed between the aromatic rings. Furthermore, h, j, and l can satisfy the relationships 1 ≤ h + l ≤ 3 and 1 ≤ j + l ≤ 3. i is preferably 0, q is preferably 0, and r is preferably 0.

[0078] The above organic film-forming material may be a compound represented by general formula (1) or general formula (2) described later (hereinafter, these compounds will also be referred to as "compounds for organic film-forming compositions"), or a polymer having repeating units represented by general formula (4) or general formula (5) described later (hereinafter, these polymers will also be referred to as "polymers for organic film-forming compositions"). Furthermore, the above organic film-forming material may contain one or more compounds selected from general formula (1) and / or (2) and polymers having repeating units represented by general formula (4) and / or (5). The organic film-forming material (compounds and polymers) will be further explained below.

[0079] <Compound for organic film-forming composition> The compounds for the organic film-forming composition of the present invention may be compounds represented by the following general formulas (1) and / or (2). [ka] (In the above general formula (1), R1, R2, R3, m, n, l, and k are as described above.)

[0080] [ka] (In the general formula (2) above, R4, R5, R6, i, q, h, j, and r are as described above, and W is either a single bond or a divalent group represented by the following formula (3).) [ka] (The dashed lines represent connections.)

[0081] In the above general formulas (1) and (2), R1 to R6, k, l, m, n, h, i, j, q, and r are as explained for the above general formulas (I) and (II).

[0082] Examples of monomolecule compounds represented by the above general formula (1) include the following: R1, R 2、 R3 and k are the same as described above. Among the following, structures that satisfy k=0, l=0, and m=0 in general formula (1) are preferred from the viewpoint of embedding / flatness improvement.

[0083] [ka]

[0084] Examples of monomolecule compounds represented by the above general formula (2) include R4, R4, and R4. 5、 R6 and q are the same as described above. Among the following, structures that satisfy i=0, q=0, and r=0 in general formula (2) are preferred from the viewpoint of embedding / flatness improvement. [ka]

[0085] In addition, it is preferable that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn, calculated on a polystyrene basis by gel permeation chromatography (GPC) of the compound represented by the general formula (1) or / and (2) described above, is 1.00 ≤ Mw / Mn ≤ 1.10. By definition, a monomolecule compound has an Mw / Mn of 1.00, but due to the separation capabilities of GPC, the measured value may exceed 1.00. Generally, polymers with repeating units are extremely difficult to approach Mw / Mn = 1.00 unless a special polymerization method is used, and they have a distribution of Mw, resulting in an Mw / Mn value greater than 1. In this invention, in order to distinguish between monomolecule compounds and polymers, 1.00 ≤ Mw / Mn ≤ 1.10 is defined as an indicator of monomolecule nature.

[0086] By controlling the Mw / Mn ratio of the compound for the organic film-forming composition within this range, it is possible to form an organic film with excellent embedding properties and flatness.

[0087] The compounds of the present invention have a structure containing numerous aromatic rings, resulting in excellent heat resistance and etching resistance. Furthermore, substituents that impart fluidity and curability, as well as film-forming properties and adhesion, are also present. ru Because various heterocyclic structures can be combined, it is useful as a compound for organic film-forming compositions.

[0088] [Method for producing compounds] As an example of a method for producing the compounds represented by general formulas (1) and (2) of the present invention, one example is a method obtained by an acid-catalyzed dehydration condensation reaction between indole-2,3-diones and aromatic compounds having OR1 or OR4 as substituents. However, when a cyclic ether structure is formed between aromatic rings in general formulas (1) and (2), when l=1 or r=1, the ether bond is formed when the aromatic compound has a hydroxyl group at a specific substitution position.

[0089] (In the case of general formula (1)) [ka]

[0090] (In the case of general formula (2)) [ka]

[0091] As acid catalysts used in the above dehydration condensation reaction, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide can be used. The amount of these catalysts used is in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the number of moles of the indole-2,3-dione intermediate.

[0092] There are no particular restrictions on the solvents used, but examples include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These can be used individually or in combination of two or more types. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to around the boiling point of the solvent, and more preferably from room temperature to 150°C. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0093] The reaction methods include charging indole-2,3-diones, aromatic compounds, and an acid catalyst all at once; dispersing or dissolving indole-2,3-diones and aromatic compounds, then adding the catalyst all at once or in portions, or diluting with a solvent and adding it dropwise; and dispersing or dissolving the catalyst, then adding indole-2,3-diones and aromatic compounds separately all at once or in portions, or diluting with a solvent and adding them dropwise. In this case, depending on the reactivity of the aromatic compounds, when indole-2,3-diones are considered as 1 mole, aromatic compounds It is preferable to use 2 moles or more of the compound. After the reaction is complete, the catalyst used in the reaction can be removed by diluting with an organic solvent and then performing liquid-liquid washing to recover the target product.

[0094] The organic solvent used at this time is not particularly limited as long as it can dissolve the target substance and separates into two layers when mixed with water, but examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, and ethylcyclopentyl methyl ether; chlorine-based solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used at this time can usually be what is called deionized water or ultrapure water. One or more washes are sufficient, but washing more than 10 times does not necessarily mean that the washing effect will be obtained, so preferably it is about 1 to 5 times.

[0095] To remove acidic components or residual aromatic compounds from the system during liquid-liquid washing, washing with a basic aqueous solution may be performed. Examples of basics include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium compounds.

[0096] Furthermore, in order to remove metal impurities or basic components from the system during liquid-liquid washing, washing with an acidic aqueous solution may be performed. Examples of suitable acids include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids, and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0097] The above-mentioned separation and washing with basic aqueous solutions and acidic aqueous solutions may be performed individually or in combination. From the viewpoint of removing metal impurities, it is preferable to perform the separation and washing in the order of basic aqueous solution followed by acidic aqueous solution.

[0098] After the liquid-liquid washing with the above-mentioned basic and acidic aqueous solutions, further washing with neutral water may be performed. One or more washes are sufficient, but preferably 1 to 5 washes. As neutral water, deionized water or ultrapure water as described above can be used. One or more washes are sufficient, but if the number of washes is insufficient, basic and acidic components may not be removed. Washing more than 10 times does not necessarily guarantee the desired effect, so preferably 1 to 5 washes are sufficient.

[0099] Furthermore, the reaction product after the liquid-liquid separation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced pressure or atmospheric pressure. However, to improve the handling when preparing the organic film-forming composition, it is also possible to keep it in a solution of an appropriate concentration. The concentration at this time is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by weight. At such a concentration, the viscosity does not tend to become high, thus preventing impairment of handling, and it is also economical because the amount of solvent does not become excessive.

[0100] The solvent used in this case is not particularly limited as long as it can dissolve the compound, but specific examples include ketones such as cyclohexanone and methyl-2-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate. These can be used individually or in combination of two or more types.

[0101] <Polymer for organic film-forming composition> The polymer for the organic film-forming composition of the present invention may be a polymer having repeating units represented by the following general formula (4) or / and (5). [ka] (In the above general formula (4), R1, R2, R3, n, m, l, and k are the same as described above, and L is a divalent organic group having 1 to 40 carbon atoms.) [ka] (In the above general formula (4), R4, R5, R6, W, L, h, i, j, q, and r are the same as described above.)

[0102] These polymers are obtained using compounds represented by the above general formulas (1) and (2), and because they use the aforementioned compounds, they exhibit excellent heat resistance, flatness, and thermosetting properties. Furthermore, because they are polymers with repeating units rather than monomers, they have fewer outgassing components, and because they are polymers with a molecular weight distribution, their crystallinity is relaxed, and improved film-forming properties can be expected.

[0103] The L linking group that constitutes the repeating units of the above general formulas (4) and (5) is a group with 1 to 40 carbon atoms. value It is an organic group, and specific examples include the following. [ka]

[0104] Furthermore, it is preferable that the linking group L of the polymer described above is of the following general formula (6). [ka] (The general formula R7 above represents an organic group containing a hydrogen atom or an aromatic ring with 1 to 20 carbon atoms; the dashed lines represent bonding bonds.)

[0105] The following are some specific examples of the general formula (6) mentioned above, and among these, a methylene group, i.e., R7 being a hydrogen atom, is preferred due to the ease of obtaining the raw materials. [ka]

[0106] Furthermore, the weight-average molecular weight (Mw) of the polymer described above is preferably 1000 to 5000, and more preferably 1000 to 4000. The molecular weight can be determined as the weight-average molecular weight (Mw) on a polystyrene basis by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent.

[0107] Within this molecular weight range, solubility in organic solvents can be ensured, and sublimation during baking can be suppressed. Furthermore, because the polymer for organic film-forming compositions has good thermal fluidity, when incorporated into a material, it not only allows for good embedding of the microstructure formed on the substrate, but also enables the formation of an organic film where the entire substrate is flat.

[0108] [Method for producing polymers] A polymer used in the organic film-forming composition of the present invention can be obtained by an acid-catalyzed polycondensation reaction of a compound represented by general formula (1) or (2) with aldehydes, ketones, or benzyl alcohols. In the following formula, R1, R2, R 3、 R 4、 R 5、 R 6、 h, i, j, n, m, l, k, q, r, W, and L are the same as described above, and R8 and R9 are hydrogen atoms or monovalent organic groups. If either or both of R8 and R9 are hydrogen atoms, it represents an aldehyde; otherwise, it represents a ketone, and it represents polycondensation with a compound represented by general formula (1) or (2). Preferably, R8 is a hydrogen atom and R9 is a hydrogen atom or an organic group containing an aromatic ring with 1 to 20 carbon atoms. Also, AR represents an aromatic compound such as benzene or naphthalene, and the substituent represented by -CH2-OH is a substituent on the aromatic ring.

[0109] (In the case of general formula (4)) [ka]

[0110] (In the case of general formula (5)) [ka]

[0111] The polycondensation reactions described above can usually be obtained in an organic solvent in the presence of an acid catalyst at room temperature or under cooling or heating as necessary. As acid catalysts, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide can be used.

[0112] Examples of solvents that can be used include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These can be used individually or in combination of two or more types.

[0113] The reaction method and the method for recovering the polymer can be carried out by the method described in the above-mentioned method for producing the compound represented by general formulas (1) and (2).

[0114] [Alternative Method for Producing Compounds and Polymers] In addition, for the compounds represented by the general formulas (1) and (2) or the polymers represented by the general formulas (4) and (5) used in the composition for forming an organic film of the present invention, when R 1、 R 4、 is other than a hydrogen atom, as an alternative production method, a step (STEP1) of obtaining an intermediate by a dehydration condensation reaction using an acid catalyst with indole-2,3-diones and aromatic compounds having a hydroxyl group, so-called phenols or naphthols, as raw materials, and a step (STEP2-1) of performing a substitution reaction using a base catalyst with the raw material represented by R1-X or R4-X having a hydroxyl group of the obtained aromatic compounds and a leaving group X. There is also a method for obtaining a polymer by performing a polycondensation reaction (STEP2-2) using the compound obtained in (STEP1) and then performing a substitution reaction (STEP3) using a base catalyst with the compound represented by R1-X or R4-X having a leaving group X as a raw material to convert the hydroxyl group to OR1. In this case, it is also possible to use one or more of R1-X or R4-X alone, and furthermore, by controlling the reaction rate, it is possible to control the ratio of the hydroxyl group to OR1 or OR4. By partially introducing a polar structure such as a hydroxyl group, it is also possible to control the film-forming property and the adhesion of the film to the substrate substrate. Further, when R1 and R3 in the compound represented by the general formula (1) and the polymer represented by the general formula (4), and R4 and R6 in the compound represented by the general formula (2) and the polymer represented by the general formula (5) are the same, although only an example of the general formula (1) is shown, using a raw material in which R1 of indole-2,3-diones is a hydrogen atom, it is possible to introduce R1 and at the same time introduce R3 by converting the hydroxyl group of the aromatic compounds by the method shown in (STEP2-1). The same method can also be applied to the compound of the general formula (2) and the polymers of the general formulas (4) and (5). R1, R2, R 3、 R 4、 R 5、 R 6、 R8, R 9、 h, i, j, n, m, l, k, q, r, W, L, A R are the same as described above.

[0115] In the case of general formula (1) and general formula (4) [ka]

[0116] In the case of general formula (2) and general formula (5) [ka]

[0117] In general formula (1), when R1 = R3 [ka]

[0118] The dehydration condensation reaction in (STEP 1) and the polycondensation reaction in (STEP 2-2) can be carried out by the methods for producing the compounds of general formulas (1) and (2) and the polymers of general formulas (4) and (5), respectively. The reaction method and the method for recovering the compounds or polymers can be carried out by the methods for producing the compounds shown in general formulas (1) and (2) above.

[0119] The base catalysts used in the substitution reactions of (STEP2-1) and (STEP3) include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine. thing These are some examples, and they may be used individually or in combination of two or more.

[0120] The solvent used in this process is not particularly limited as long as it is inert to the above reaction. For example, ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water can be used individually or in combination.

[0121] The above substitution reaction method and the method for recovering the compound or polymer can be carried out by the method for producing the compound shown in the above general formulas (1) and (2).

[0122] In preparing the compounds or polymers used in the organic film-forming compositions obtained by this method, various halides, tosylates, and mesylates can be used individually or in combination according to the required performance. For example, those with side chain structures that contribute to improved planarization properties, and rigid aromatic ring structures that contribute to etching resistance and heat resistance can be combined in any proportion. compound or Polymer-based organic film formation compositions can achieve a high level of both embedding / planarization properties and etching resistance.

[0123] As described above, the compound or polymer for organic film-forming compositions of the present invention provides an organic film-forming composition with good film-forming properties and excellent embedding / planarization characteristics.

[0124] <Composition for organic film formation> Furthermore, the present invention provides an organic film-forming composition that contains the above-described organic film-forming composition compound and / or polymer and organic solvent of the present invention.

[0125] [Compounds and / or polymers for organic film-forming compositions] In the organic film-forming composition of the present invention, which contains the above-mentioned organic film-forming compound and / or polymer and an organic solvent as an organic film-forming material, the above-mentioned organic film-forming compound or polymer can be used alone or in combination of multiple others.

[0126] Furthermore, in the present invention, it is preferable that the organic film-forming composition contains one or more compounds and polymers selected from the above-mentioned compounds and polymers, more specifically, that the organic film-forming material contains one or more compounds selected from the compounds represented by the above general formula (1) and / or (2) and polymers having repeating units represented by the above general formula (4) and / or (5).

[0127] With the above-mentioned mixtures, it becomes possible to adjust various physical properties required when using organic films, such as embedding / planarization characteristics and outgassing due to sublimation, within an appropriate range. In other words, the organic film-forming material may consist of (i) one or more compounds for organic film-forming compositions, (ii) one or more polymers for organic film-forming compositions, or (iii) a mixture consisting of one or more compounds and polymers selected from those for organic film-forming compositions, and can be freely combined to provide an organic film with desired properties. If a compound or polymer is used alone, preparation is easy, and if a mixture of compounds and polymers is used, the workability of the composition and the degree of freedom in controlling the physical properties of the organic film are increased.

[0128] [Organic solvents] The organic solvent that can be used in the organic film-forming composition of the present invention is not particularly limited as long as it dissolves the above-mentioned compound and / or polymer (base polymer), and, if included, the surfactant, plasticizer, acid generator, crosslinking agent, and other additives described later. Specifically, solvents with a boiling point of less than 180°C, such as the solvents described in paragraphs

[0091] to

[0092] of Japanese Patent Application Publication No. 2007-199653, can be used. Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more of these are preferably used. The amount of organic solvent blended is preferably 200 to 10,000 parts, more preferably 300 to 5,000 parts, per 100 parts of (A) the compound and / or polymer.

[0129] Such an organic film-forming composition can be applied by rotary coating, and because it contains the organic film-forming compound and / or polymer of the present invention as described above, it becomes an organic film-forming composition that combines heat resistance and high embedding / planarization properties.

[0130] Furthermore, the organic film-forming composition of the present invention may also contain, as an organic solvent, a high-boiling-point solvent with a boiling point of 180°C or higher added to the above-mentioned solvent with a boiling point of less than 180°C (a mixture of a solvent with a boiling point of less than 180°C and a solvent with a boiling point of 180°C or higher). As for the high-boiling-point organic solvent, there are no particular restrictions on hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., as long as it can dissolve the compounds and / or polymers for the organic film-forming composition. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 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, glycerin, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, triethylene Glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, which may be used individually or in combination.

[0131] The boiling point of the high-boiling point solvent mentioned above can be appropriately selected according to the temperature at which the organic film-forming composition is heat-treated. Preferably, the boiling point of the added high-boiling point solvent is 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no risk of excessive volatilization during baking (heat treatment) due to a boiling point that is too low, thus ensuring sufficient thermal fluidity. Furthermore, with such a boiling point, there is no risk of residual solvent remaining in the film after baking without volatilizing, thus avoiding adverse effects on film properties such as etching resistance.

[0132] Furthermore, when using the high-boiling point solvent described above, the amount of the high-boiling point solvent added is preferably 1 to 30 parts by mass per 100 parts by mass of solvent with a boiling point of less than 180°C. With such an amount, sufficient thermal fluidity can be provided, no residue remains in the film, and film properties such as etching resistance are also good.

[0133] With such an organic film-forming composition, the addition of a high-boiling-point solvent imparts thermal fluidity to the above-mentioned organic film-forming composition, resulting in an organic film-forming composition that also possesses advanced embedding / planarization properties.

[0134] [Acid Generator] In the organic film-forming composition of the present invention, an acid generator can be added to further accelerate the curing reaction. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and either type can be added. Specifically, materials described in paragraphs

[0061] to

[0085] of Japanese Patent Application Publication No. 2007-199653 can be added, but are not limited to these.

[0135] The above acid generating agents can be used individually or in combination of two or more. When adding an acid generating agent, the amount to be added is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, per 100 parts of the compound and / or polymer.

[0136] [Surfactants] The organic film-forming composition of the present invention may contain a surfactant to improve its applicability in spin coating. For example, the surfactant described in sections

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953 can be used. When a surfactant is added, the amount is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, per 100 parts of the compound and / or polymer.

[0137] In the present invention, it is preferable that the above-mentioned organic film-forming composition further contains one or more of surfactants and plasticizers.

[0138] [Crosslinking agent] Furthermore, the organic film-forming composition of the present invention may also contain a crosslinking agent to enhance curability and further suppress intermixing with the upper film. The crosslinking agent is not particularly limited, and various known types of crosslinking agents can be widely used. Examples include methylol or alkoxymethyl type crosslinking agents for polynuclear phenols, melamine-based crosslinking agents, glycoluryl-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and epoxy-based crosslinking agents. When a crosslinking agent is added, the amount added is preferably 1 to 100 parts, more preferably 5 to 50 parts, per 100 parts of the compound and / or polymer.

[0139] Examples of melamine-based crosslinking agents include hexamethoxymethylated melamine, hexasubtoxicmethylated melamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of glycoluryl-based crosslinking agents include tetramethoxymethylated glycoluryl, tetrabutoxymethylated glycoluryl, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of β-hydroxyalkylamide-based crosslinking agents include N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate. Examples of aziridine-based crosslinking agents include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Examples of oxazoline-based crosslinking agents include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymers.Examples of epoxy crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0140] Examples of polynuclear phenolic crosslinking agents include the compounds represented by the following general formula (7). [ka] (In the formula, Q is a single bond or a bond with 1 to 20 carbon atoms) s It is a valence hydrocarbon group. 10 (where is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; s is an integer from 1 to 5.)

[0141] Q is a single bond or an s-valent hydrocarbon group having 1 to 20 carbon atoms. s is an integer from 1 to 5, more preferably 2 or 3. Specifically, Q can be derived from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. s An example of a group with a hydrogen atom removed is R. 10 The C1-C20 alkyl group is either a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosanyl groups, with hydrogen atoms or methyl groups being preferred.

[0142] As examples of compounds represented by the above general formula (7), the following compounds can be specifically exemplified. Among these, triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylated tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and uniformity of the organic film. 10 This is the same as above. [ka]

[0143] [ka]

[0144] [Plasticizer] Furthermore, a plasticizer may be added to the organic film-forming composition of the present invention to further improve the planarization / embedding properties. The plasticizer is not particularly limited, and various known types of plasticizers can be widely used. Examples include low molecular weight compounds such as phthalates, adipicates, phosphates, trimelliticates, and citrates, as well as polymers such as polyethers, polyesters, and polyacetal polymers described in Japanese Patent Application Publication No. 2013-253227. When a plasticizer is added, the amount added is preferably 1 to 100 parts, more preferably 5 to 30 parts, per 100 parts of the compound and / or polymer.

[0145] Furthermore, the organic film-forming composition of the present invention preferably uses, as an additive to impart embedding / planarization properties in the same way as a plasticizer, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a pyrolytic polymer having a weight loss rate of 40% by mass or more between 30°C and 250°C and a weight-average molecular weight of 300 to 200,000. This pyrolytic polymer preferably contains repeating units having an acetal structure represented by the following general formulas (DP1) and (DP1a).

[0146] [ka] (In the formula, R 11 (where Y is a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, which may be substituted. Y is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.)

[0147] [ka] (In the formula, R 12 (where is an alkyl group having 1 to 4 carbon atoms; Z is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may have an ether bond; t represents the average number of repeating units, which is 3 to 500.)

[0148] [Other ingredients] The organic film-forming composition of the present invention may also be blended with other compounds or polymers. The blending compounds or polymers, when mixed with the organic film-forming composition of the present invention, play a role in improving the film-forming properties of spin coating and the embedding properties on substrates with steps.

[0149] Such materials include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5- Diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'dimethyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'diallyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'difluoro-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'diphenyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'dimethoxy-4,4'-(9H- Fluorene-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spirovidene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirovidene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirovidene-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirovidene-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-Tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl Examples include novolac resins such as bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, and limonene, as well as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthalene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricycline, poly(meth)acrylate, and copolymers thereof. Furthermore, it is also possible to blend naphthol dicyclopentadiene copolymer described in Japanese Patent Publication No. 2004-205685, fluorene bisphenol novolac resin described in Japanese Patent Publication No. 2005-128509, acenaphthylene copolymer described in Japanese Patent Publication No. 2005-250434, fullerene having a phenol group described in Japanese Patent Publication No. 2006-227391, bisphenol compound and novolac resin described in Japanese Patent Publication No. 2006-293298, novolac resin of adamantanephenol compound described in Japanese Patent Publication No. 2006-285095, bisnaphthol compound and novolac resin described in Japanese Patent Publication No. 2010-122656, fullerene resin compound described in Japanese Patent Publication No. 2008-158002, etc.

[0150] The amount of the above-mentioned blending compound or blending polymer is preferably 0 to 1,000 parts by mass, and more preferably 0 to 500 parts by mass, per 100 parts by mass of the organic film-forming composition of the present invention.

[0151] The organic film-forming materials of the present invention can be used individually or in combination of two or more types. The above organic film-forming composition can be used as an organic film material or a planarization material for semiconductor device manufacturing.

[0152] Furthermore, the organic film-forming composition of the present invention is extremely useful as an organic film material for multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing interlayer, and a four-layer resist process using a silicon-containing inorganic hard mask and an organic anti-reflective film.

[0153] (Organic film formation method) The present invention provides a method for forming an organic film that functions as an organic film for multilayer resist films used in lithography or as a planarization film for semiconductor manufacturing, using the above-described organic film forming composition.

[0154] In the organic film formation method using the organic film formation composition of the present invention, the above-mentioned organic film formation composition is coated onto a substrate to be processed by a spin coating method or the like. By using a spin coating method or the like, good embedding characteristics can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction in order to prevent mixing with the resist upper layer film and resist interlayer film. Baking is preferably performed in the range of 100°C to 600°C for 10 to 600 seconds, and more preferably in the range of 200°C to 500°C for 10 to 300 seconds. Considering the impact on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 600°C or less, and more preferably 500°C or less.

[0155] Furthermore, in the method for forming an organic film using the organic film-forming composition of the present invention, the organic film-forming composition of the present invention is coated onto a substrate to be processed by a spin coating method or the like, as described above, and the organic film-forming composition is cured by firing in an atmosphere with an oxygen concentration of 0.1% by volume or more and 21% by volume or less to form an organic film.

[0156] By firing the organic film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently hardened film can be obtained. While air may be used as the atmosphere during baking, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce oxygen levels and prevent oxidation of the organic film. To prevent oxidation, it is necessary to control the oxygen concentration, preferably 1000 ppm or less, more preferably 100 ppm or less (by volume). Preventing oxidation of the organic film during baking is preferable because it prevents increased absorption and reduced etching resistance.

[0157] (Pattern formation method) The present invention provides a pattern formation method for a three-layer resist process using such an organic film forming composition, which involves forming a pattern on a workpiece, comprising at least the following steps: forming an organic film on the workpiece using the organic film forming composition of the present invention; forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material; forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition; forming a circuit pattern on the resist upper layer; transferring the pattern to the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask; and further forming a pattern on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0158] Since the silicon-containing resist interlayer in the above three-layer resist process exhibits etching resistance to oxygen gas or hydrogen gas, it is preferable to perform the dry etching of the organic film using the silicon-containing resist interlayer as a mask in the above three-layer resist process using an etching gas mainly composed of oxygen gas or hydrogen gas.

[0159] As the silicon-containing resist interlayer in the above three-layer resist process, a polysiloxane-based interlayer is also preferably used. By giving the silicon-containing resist interlayer an anti-reflective effect, reflection can be suppressed. In particular, for 193nm exposure, if a material containing many aromatic groups as an organic film and having high etching selectivity with the substrate is used, the k value will be high and substrate reflection will be high. However, by giving the silicon-containing resist interlayer an absorption that results in an appropriate k value, it is possible to suppress reflection, and substrate reflection can be reduced to 0.5% or less. As silicon-containing resist interlayers with an anti-reflective effect, anthracene is preferably used for 248nm and 157nm exposure, and polysiloxane is preferably used for 193nm exposure, with phenyl groups or absorbent groups having silicon-silicon bonds pendanted and crosslinked by acid or heat.

[0160] Furthermore, it is also suitable as a four-layer resist process using an organic anti-reflective film. In this case, at least an organic film is formed on a workpiece using the organic film forming composition of the present invention, a silicon-containing resist interlayer is formed on the organic film using a silicon-containing resist interlayer material, an organic anti-reflective film (BARC) is formed on the silicon-containing resist interlayer, a resist upper layer is formed on the BARC using a photoresist composition to form a four-layer structure, a circuit pattern is formed on the resist upper layer, the pattern is transferred to the BARC film and the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask, the pattern is transferred to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further, the workpiece is etched using the organic film on which the pattern has been transferred as a mask to form a pattern on the workpiece, thereby forming a semiconductor device circuit pattern on the substrate.

[0161] Also, silicon-containing resists middleAn inorganic hard mask may be formed instead of a film. In this case, at a minimum, an organic film is formed on the workpiece using the organic film-forming composition of the present invention, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, a resist upper layer film is formed on the inorganic hard mask using a photoresist composition to form a circuit pattern on the resist upper layer film, the inorganic hard mask is etched using the resist upper layer film on which the pattern is formed as a mask, the organic film is etched using the inorganic hard mask on which the pattern is formed as a mask, and further, the workpiece is etched using the organic film on which the pattern is formed as a mask to form a pattern on the workpiece, thereby forming a semiconductor device circuit pattern on the substrate.

[0162] As described above, when forming an inorganic hard mask on an organic film, silicon oxide films, silicon nitride films, and silicon oxynitride films (SiON films) can be formed by CVD or ALD methods. For example, a method for forming a silicon nitride film is described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, and more preferably 10 to 100 nm. Furthermore, as the inorganic hard mask, a SiON film, which has a high effect as an anti-reflective film, is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the organic film needs to be able to withstand temperatures of 300 to 500°C. The organic film forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C, so it is possible to combine an inorganic hard mask formed by CVD or ALD with an organic film formed by rotary coating.

[0163] Furthermore, it is also suitable as a four-layer resist process using an organic anti-reflective film. In this case, at least an organic film is formed on a workpiece using the organic film-forming composition of the present invention, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, an organic anti-reflective film (BARC) is formed on the inorganic hard mask, a resist upper layer film is formed on the BARC using a photoresist composition to form a four-layer film structure, a circuit pattern is formed on the resist upper layer film, the BARC film and the inorganic hard mask are etched using the resist upper layer film on which the pattern is formed as a mask, the organic film is etched using the inorganic hard mask on which the pattern is formed as a mask, and further, the workpiece is etched using the organic film on which the pattern is formed as a mask to form a pattern on the workpiece, thereby forming a semiconductor device circuit pattern on the substrate.

[0164] As described above, a photoresist film may be formed as a resist top layer on an inorganic hard mask, or an organic anti-reflective coating (BARC) may be formed on the inorganic hard mask by spin coating, and then a photoresist film may be formed on top of that. In particular, when a SiON film is used as the inorganic hard mask, the two layers of anti-reflective coatings, the SiON film and BARC, make it possible to suppress reflection even in immersion lithography with high NA values ​​exceeding 1.0. Another advantage of forming BARC is that it has the effect of reducing the trailing of the photoresist pattern directly on top of the SiON film.

[0165] In the above multilayer resist process, the resist upper layer can be either positive or negative, and the same photoresist composition as commonly used can be used. After spin-coating the photoresist composition, pre-baking is performed, preferably at 60-180°C for 10-300 seconds. Thereafter, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain the resist pattern. The thickness of the resist upper layer is not particularly limited, but is preferably 30-500 nm, and especially preferably 50-400 nm.

[0166] Furthermore, examples of exposure light include high-energy rays with wavelengths of 300 nm or less, specifically excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays, electron beams, and X-rays with wavelengths of 3 to 20 nm.

[0167] As a method for forming the pattern of the resist upper layer film described above, it is preferable to use photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof to form the pattern.

[0168] Furthermore, it is preferable that the development method in the pattern formation method be alkaline development or development with an organic solvent.

[0169] Next, etching is performed using the obtained resist pattern as a mask. In the three-layer resist process, etching of the silicon-containing resist interlayer and inorganic hard mask is performed using a fluorocarbon-based gas with the upper resist pattern as a mask. This forms the silicon-containing resist interlayer pattern and the inorganic hard mask pattern.

[0170] Next, the obtained silicon-containing resist interlayer pattern and inorganic hard mask pattern are used as masks to perform etching of the organic film.

[0171] The etching of the next workpiece can also be performed by conventional methods. For example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching is performed mainly with a fluorocarbon gas. For p-Si, Al, or W, etching is performed mainly with a chlorine-based or bromine-based gas. When the substrate is etched with a fluorocarbon gas, the silicon-containing resist interlayer pattern in the three-layer resist process is removed simultaneously with the substrate processing. When the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist interlayer pattern must be removed separately by dry etching with a fluorocarbon gas after the substrate processing.

[0172] The organic films obtained using the organic film-forming composition of the present invention have excellent etching resistance when these workpieces are etched.

[0173] The workpiece (workpiece substrate) is not particularly limited and can be any substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, or a substrate on which the workpiece layer has been deposited. Various low-k films and their stopper films can be used as the workpiece layer, typically with a thickness of 50 to 10,000 nm, and especially 100 to 5,000 nm. When depositing the workpiece layer, the substrate and the workpiece layer are made of different materials.

[0174] Preferably, the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films are deposited: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or a substrate on which the above-mentioned metal films, etc., are deposited as the workpiece layer, can be used.

[0175] Various low-k films and their stopper films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, can be used as the workpiece layer, and can typically be formed to a thickness of 50 to 10,000 nm, and especially 100 to 5,000 nm. When forming the workpiece layer, the substrate and the workpiece layer are made of different materials.

[0176] Furthermore, the metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, ruthenium, or an alloy thereof.

[0177] Furthermore, it is preferable to use a workpiece that has a structure or step with a height of 30 nm or more as the workpiece.

[0178] An example of a three-layer resist process is shown below using Figure 1. In the three-layer resist process, as shown in Figure 1(A), an organic film 3 is formed on a workpiece layer 2 stacked on a substrate 1 using the organic film-forming composition of the present invention, then a silicon-containing resist interlayer 4 is formed, and finally a resist upper layer 5 is formed on top of it.

[0179] Next, as shown in Figure 1(B), the required portion 6 of the resist upper layer 5 is exposed, and PEB and development are performed to form a resist pattern 5a (Figure 1(C)). Using this obtained resist pattern 5a as a mask, the silicon-containing resist interlayer 4 is etched using a CF-based gas to form a silicon-containing resist interlayer pattern 4a (Figure 1(D)). After removing the resist pattern 5a, the organic film 3 is etched with oxygen plasma using this obtained silicon-containing resist interlayer pattern 4a as a mask to form an organic film pattern 3a (Figure 1(E)). Furthermore, after removing the silicon-containing resist interlayer pattern 4a, the layer to be processed 2 is etched using the organic film pattern 3a as a mask to form pattern 2a (Figure 1(F)).

[0180] When using an inorganic hard mask, the silicon-containing resist interlayer 4 is the inorganic hard mask, and when laying a BARC, a BARC layer is provided between the silicon-containing resist interlayer 4 and the resist upper layer 5. Etching of the BARC may be performed consecutively prior to etching of the silicon-containing resist interlayer 4, or etching of only the BARC may be performed first, and then the etching equipment may be changed to etch the silicon-containing resist interlayer 4.

[0181] Thus, with the pattern formation method of the present invention, fine patterns can be formed on a workpiece substrate with high precision in a multilayer resist process.

[0182] In particular, the present invention uses an organic film-forming composition containing an organic solvent and an organic film-forming material comprising (i) a compound represented by the above general formula (1) and / or (2), and (ii) a polymer having repeating units represented by the above general formula (4) and / or (5). Therefore, in a multilayer resist process, fine patterns can be formed on the workpiece with even greater precision. [Examples]

[0183] The present invention will be further described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. The molecular weight and dispersion were determined by calculating the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in polystyrene terms using gel permeation chromatography (GPC) with tetrahydrofuran as the eluent, and then determining the dispersion (Mw / Mn).

[0184] Synthesis Examples: Synthesis of Compounds and Polymers for Organic Film-Forming Compositions For the synthesis of compounds or polymers (A1) to (A13) for organic film-forming compositions and polymers (R1) to (R3) for comparative examples, compounds (B1) to (B10) were used as aromatic compounds, compounds (C1) to (C4) as indole-2,3-diones, and compounds (D1) to (D3) as aldehydes or ketones. A 37% aqueous solution of (D1) was used.

[0185] Aromatic compounds: [ka]

[0186] Indor-2,3-Zeon types: [ka]

[0187] Aldehydes or ketones: [ka]

[0188] (Synthesis Example 1) (Synthesis of Compound (A1)) [Chemical Formula] Under a nitrogen atmosphere, 81.7 g of compound (B1), 30.0 g of compound (C1), and 450 g of methylene chloride were added to form a homogeneous dispersion at room temperature. Then, 91.8 g of trifluoromethanesulfonic acid was slowly added dropwise, and the reaction was carried out at room temperature for 8 hours. After the reaction was completed, 1000 ml of MIBK (methyl isobutyl ketone) was added, and the mixture was washed 6 times with 300 ml of pure water. The organic layer was dried under reduced pressure. After adding 240 g of MIBK to the residue to form a homogeneous solution, it was crystallized in 1200 g of IPE (diisopropyl ether). The precipitated crystals were separated by filtration and washed 2 times with 400 g of IPE and recovered. The recovered crystals were dried under vacuum at 70 °C to obtain compound (A1). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A1): Mw = 520, Mw / Mn = 1.02

[0189] (Synthesis Example 2) (Synthesis of Compound (A2)) [Chemical Formula] Under a nitrogen atmosphere, 49.1 g of compound (B2), 30.0 g of compound (C2), and 240 g of methylene chloride were added to form a homogeneous dispersion at room temperature. Then, 69.6 g of trifluoromethanesulfonic acid was slowly added dropwise, and the reaction was carried out at room temperature for 8 hours. antiAfter the reaction was complete, 1000 ml of MIBK (methyl isobutyl ketone) was added, and the mixture was washed six times with 300 ml of pure water. The organic layer was then dried under reduced pressure. 240 g of DMF (dimethylformamide) and 84.8 g of potassium carbonate were added to the recovered residue, and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 64.9 g of allyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 600 ml of MIBK was added, and the mixture was washed six times with 600 ml of pure water. The organic layer was then dried under reduced pressure. 250 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 1000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 200 g of hexane, and recovered. Compound (A2) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A2): Mw=630, Mw / Mn=1.04

[0190] (Synthesis Example 3) Synthesis of compound (A3) [ka] Under a nitrogen atmosphere, 33.5 g of compound (B3), 30.0 g of compound (C3), 250 g of methylene chloride, and 46.7 g of methanesulfonic acid were added to a homogeneous dispersion at room temperature. Then, 1.7 g of 3-mercaptopropionic acid was added, and the reaction was carried out at room temperature for 8 hours. After the reaction was complete, 600 ml of MIBK (methyl isobutyl ketone) was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 180 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were crystallized in 800 g of hexane. The precipitated crystals were separated by filtration, washed twice with 200 g of hexane, and recovered. Compound (A3) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A3): Mw=340, Mw / Mn=1.01

[0191] (Synthesis Example 4) Synthesis of compound (A4) [ka] Under a nitrogen atmosphere, 65.7 g of compound (B4), 30.0 g of compound (C4), 400 g of methylene chloride, and 46.2 g of methanesulfonic acid were added to a homogeneous dispersion at room temperature. Then, 1.7 g of 3-mercaptopropionic acid was added, and the reaction was carried out at room temperature for 8 hours. After the reaction was complete, 800 ml of MIBK (methyl isobutyl ketone) was added, and the mixture was washed six times with 300 ml of pure water. The organic layer was dried under reduced pressure. 250 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were crystallized in 1000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 300 g of hexane, and recovered. Compound (A4) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A4): Mw=590, Mw / Mn=1.03

[0192] (Synthesis Example 5) Synthesis of compound (A5) [ka] Under a nitrogen atmosphere, 67.5 g of compound (B5), 30.0 g of compound (C3), 400 g of methylene chloride, and 46.7 g of methanesulfonic acid were added to a homogeneous dispersion at room temperature. Then, 1.7 g of 3-mercaptopropionic acid was added, and the reaction was carried out at room temperature for 8 hours. After the reaction was complete, 800 ml of MIBK (methyl isobutyl ketone) was added, and the mixture was washed six times with 300 ml of pure water. The organic layer was dried under reduced pressure. 250 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were crystallized in 1000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 300 g of hexane, and recovered. Compound (A5) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A5): Mw=590, Mw / Mn=1.02

[0193] (Synthesis Example 6) Synthesis of compound (A6) [ka] Under a nitrogen atmosphere, 226.5 g of compound (B6), 30.0 g of compound (C1), 1000 g of methylene chloride, and 58.8 g of methanesulfonic acid were added to a homogeneous dispersion at room temperature. Then, 2.2 g of 3-mercaptopropionic acid was added, and the reaction was carried out at room temperature for 8 hours. After the reaction was complete, 300 g of pure water and 1000 ml of toluene were added, and the methylene chloride used in the reaction was removed by distillation at atmospheric pressure. The aqueous layer was removed, and the mixture was washed five times with 600 g of 3% sodium hydroxide aqueous solution, twice with 300 g of pure water, twice with 300 g of 1% nitric acid aqueous solution, and five times with 300 g of pure water. The organic layer was dried under reduced pressure. 250 g of MIBK was added to the residue to make a homogeneous solution, and the mixture was crystallized in 1000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 300 g of hexane, and recovered. Compound (A6) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A6): Mw=520, Mw / Mn=1.04

[0194] (Synthesis Example 7) Synthesis of compound (A7) [ka] Under a nitrogen atmosphere, 245.0 g of compound (B7), 30.0 g of compound (C1), 1000 g of methylene chloride, and 58.8 g of methanesulfonic acid were added to a homogeneous dispersion at room temperature. Then, 2.2 g of 3-mercaptopropionic acid was added, and the reaction was carried out at room temperature for 8 hours. After the reaction was complete, 300 g of pure water and 1000 ml of toluene were added, and the methylene chloride used in the reaction was removed by distillation at atmospheric pressure. The separated aqueous layer was removed, and the mixture was washed five times with 600 g of 3% sodium hydroxide aqueous solution, twice with 300 g of pure water, twice with 300 g of 1% nitric acid aqueous solution, and five times with 300 g of pure water. The organic layer was dried under reduced pressure. 250 g of MIBK was added to the residue to make a homogeneous solution, and the mixture was crystallized in 1000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 300 g of hexane, and recovered. Compound (A7) was obtained by vacuum drying the recovered crystals at 70°C. When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A7): Mw = 550, Mw / Mn = 1.05

[0195] (Synthesis Example 8) Synthesis of Compound (A8) [Chemical formula] Under a nitrogen atmosphere, 20.0 g of compound (A6), 33.0 g of potassium carbonate, and 120 g of DMF were added, and a homogeneous dispersion was obtained at an internal temperature of 50°C. 23.8 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After completion of the reaction, 200 ml of MIBK was added, and washing was performed 6 times with 100 ml of pure water. The organic layer was dried under reduced pressure. After adding 80 g of MIBK to the residue to form a homogeneous solution, crystallization was carried out in 400 g of MeOH (methanol). The precipitated crystals were separated by filtration and washed twice with 200 g of MeOH and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A8). When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A8): Mw = 650, Mw / Mn = 1.04

[0196] (Synthesis Example 9) Synthesis of Compound (A9) [Chemical formula] Under a nitrogen atmosphere, 10.0 g of compound (A7), 10.4 g of potassium carbonate, and 60 g of DMF were added, and a homogeneous dispersion was obtained at an internal temperature of 50°C. 4.7 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After completion of the reaction, 100 ml of MIBK was added, and washing was performed 6 times with 50 ml of pure water. The organic layer was dried under reduced pressure. After adding 40 g of MIBK to the residue to form a homogeneous solution, crystallization was carried out in 200 g of hexane. The precipitated crystals were separated by filtration and washed twice with 100 g of hexane and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A9). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A9): Mw=670, Mw / Mn=1.07

[0197] (Synthesis Example 10) Synthesis of the process (A10) [ka] Under a nitrogen atmosphere, 20.0 g of compound (A3), 2.7 g of compound (D1), and 50 g of 1,2-dichloroethane were added, and a homogeneous solution was obtained at an internal temperature of 50°C. 2.0 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was complete, the mixture was cooled to room temperature, 200 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was dried under reduced pressure. 60 g of THF was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 300 g of hexane. The precipitated crystals were separated by filtration, washed twice with 100 g of hexane, and recovered. Polymer (A10) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A10): Mw=3300, Mw / Mn=1.82

[0198] (Synthesis Example 11) Synthesis of the process (A11) [ka] Under a nitrogen atmosphere, 20.0 g of compound (A1), 4.2 g of compound (D2), and 100 g of 1,2-dichloroethane were added, and a homogeneous solution was obtained at an internal temperature of 50°C. 2.0 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was complete, the mixture was cooled to room temperature, 200 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was dried under reduced pressure. 70 g of THF was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 350 g of hexane. The precipitated crystals were separated by filtration, washed twice with 100 g of hexane, and recovered. Polymer (A11) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A11): Mw=2900, Mw / Mn=2.12

[0199] (Synthesis Example 12) Synthesis of polymer (A12) [ka] Under a nitrogen atmosphere, 10.0 g of compound (A8), 0.7 g of compound (D1), and 50 g of 1,2-dichloroethane were added, and a homogeneous solution was obtained at an internal temperature of 50°C. 1.0 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was complete, the mixture was cooled to room temperature, 100 ml of MIBK was added, and the mixture was washed six times with 30 ml of pure water. The organic layer was dried under reduced pressure. 30 g of THF was added to the residue to make a homogeneous solution, and then crystallized in 100 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 50 g of MeOH, and recovered. Polymer (A12) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A12): Mw=2800, Mw / Mn=1.65

[0200] (Synthesis Example 13) Synthesis of the process (A13) [ka] Under a nitrogen atmosphere, 20.0 g of compound (A7), 3.4 g of compound (D3), and 100 g of 1,2-dichloroethane were added, and a homogeneous solution was prepared at an internal temperature of 50°C. 7.2 g of pre-mixed methanesulfonic acid and 0.8 g of 3-mercaptopropionic acid were slowly added, and the reaction was carried out at an internal temperature of 50°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, 300 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was dried under reduced pressure. 100 g of DMF and 36.5 g of potassium carbonate were added to the recovered residue, and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 27.0 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 300 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 80g of MIBK was added to the residue to form a homogeneous solution, which was then crystallized in 400g of MeOH. The precipitated crystals were separated by filtration and recovered after being washed twice with 100g of MeOH. Polymer (A13) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A13): Mw=3000, Mw / Mn=1.56

[0201] (Synthesis Example 14) Synthesis of polymer (R1) [ka] Under a nitrogen atmosphere, add 31.8g of compound (B8), 4.9g of compound (D1), 5.0g of oxalic acid, and 50g of dioxane, and heat to an internal temperature of 10°C. 0℃ The reaction was carried out for 24 hours. After the reaction was complete, it was cooled to room temperature, 500 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. tt The organic layer was collected, and the internal temperature was reduced to 150°C and the pressure to 2 mmHg to remove water and solvents, thereby obtaining polymer (R1). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (R1): Mw=3200, Mw / Mn=4.88

[0202] (Synthesis Example 15) Synthesis of polymer (R2) [ka] Under a nitrogen atmosphere, add 42.3g of compound (B9), 5.7g of compound (D1), 5.0g of oxalic acid, and 60g of dioxane, and heat to an internal temperature of 10°C. 0℃ The reaction was carried out for 24 hours. After the reaction was complete, it was cooled to room temperature, 500 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. tt The organic layer was collected, and the internal temperature was reduced to 150°C and the pressure to 2 mmHg to remove water and solvents, thereby obtaining polymer (R2). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (R2): Mw=2600, Mw / Mn=3.55

[0203] (Synthesis Example 16) Synthesis of polymer (R3) [ka] Under a nitrogen atmosphere, 3.1g of indole-2,3-dione (C1), 10.0g of compound (B10), and methanesulfone were mixed. acid 3.0 g of propylene glycol monomethyl ether and 3.4 g of 3-mercaptopropionic acid were added, and the mixture was heated to 140°C and reacted under reflux for 4 hours. After the reaction was complete, the reaction solution was added dropwise to 200 g of methanol / pure water = 1 / 1 (mass ratio) and crystallized. The settled crystals were separated by filtration and recovered after washing twice with 100 g of pure water. The recovered crystals were vacuum-dried at 60°C to obtain polymer (R3). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (R3): Mw=8500, Mw / Mn=2.30

[0204] Tables 1-3 show a list of Mw and Mw / Mn results for the compounds and polymers (A1)-(A13) used in the examples and the polymers (R1)-(R3) used in the comparative examples.

[0205] [Table 1]

[0206] [Table 2]

[0207] [Table 3]

[0208] Preparation of organic film-forming compositions (UDL-1 to 18, comparative UDL-1 to 9) The above compounds and / or polymers (A1) to (A13) and (R1) to (R3), the compounds (B8) and (B9) described in the above synthesis example, a crosslinking agent (XL), a thermoacid generator (TAG), and as high-boiling point solvents, (S1) 1,6-diacetoxyhexane (boiling point 260°C) and (S2) tripropylene glycol monomethyl ether (boiling point 242°C) were used to dissolve the compounds in the proportions shown in Table 4 using propylene glycol monomethyl ether acetate (PGMEA) containing 0.1% by mass of PF-6320 (manufactured by Omnova), and the mixture was filtered through a 0.1 μm fluororesin filter to prepare organic film-forming compositions (UDL-1 to 18, comparative UDL-1 to 9).

[0209] The structural formulas of the compounds, crosslinking agents, and thermoacid generators used in the preparation of the organic film-forming composition are shown below. (compound) [ka] (Crosslinking agent) [ka] (Thermal acid generator) [ka]

[0210] [Table 4]

[0211] Example 1 Solvent resistance test (Examples 1-1 to 1-18, Comparative Examples 1-1 to 1-9) UDL-1 to 18 and comparative UDL-1 to 9, prepared as described above, were coated onto a silicon substrate. After baking in air at the temperatures shown in Table 5 for 60 seconds, the film thickness was measured. PGMEA solvent was then dispensed onto the film, left for 30 seconds, and spin-dried. The PGMEA was then evaporated by baking at 100°C for 60 seconds, and the film thickness before and after PGMEA treatment was measured. The residual film percentage (b / a × 100) was calculated using the film thickness after deposition and the film thickness after PGMEA treatment. The results are shown in Table 5.

[0212] In the following, the organic film-forming compositions UDL-1, 3, 5, 6, 7, 10, 11, 14, and 17 were used in Examples 1-1, 1-3, 1-5, 1-6, 1-7, 1-10, 1-11, 1-14, and 1-17 in Table 5, Examples 2-1, 2-3, 2-5, 2-6, 2-7, 2-10, 2-11, 2-14, and 2-17 in Table 6, and Examples 3-1, 3-3, 3-5, 3-6, 3-7, 3-10, 3-11, 3-14, and 3-17 in Table 7. Tables 8-8, 4-3, 4-5, 4-6, 4-7, 4-10, 4-11, 4-14, 4-17; Tables 9-9, 5-1, 5-3, 5-5, 5-6, 5-7, 5-10, 5-11, 5-14, 5-17; Tables 10-10, 6-3, 6-5, 6-6, 6-7, 6-10, 6-11, 6-14, 6-17; and Tables 14-14, 7-3, 7-5, 7-6, 7-7, 7-10, 7-11, 7-14, 7-17 are for reference only. [ka]

[0213] As shown in Table 5, the organic films using the compounds and / or polymers of the present invention (Examples 1-1 to 1-18) showed a residual film rate of 98% or more after PGMEA treatment in Examples 1-3 and 1-6, and 99% or more in the other examples, indicating that crosslinking reactions occurred due to heat treatment, resulting in sufficient solvent resistance. In Examples 1-3 and 1-6, since they were monomolecular compounds with few sites contributing to curing, the residual film rate was only about 98% even after treatment at 400°C. However, by combining them with polymers, as in Examples 1-14 and 1-15, solvent resistance of 99.0% or more was obtained, demonstrating that solvent resistance can be improved by combining the compounds of the present invention with polymers. Furthermore, comparing Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-4 and 1-7 to 1-9, it was found that the compounds of the present invention exhibited sufficient curability despite being monomolecular compounds. In contrast, Comparative Examples 1-7 and 1-8, which used only monomolecular compounds, lacked solvent resistance due to factors such as insufficient curability, insufficient heat resistance, or sublimation due to their small molecular weight. To ensure solvent resistance, it was necessary to add a crosslinking agent, as in Comparative Example 1-9. Also, as shown in the results of Comparative Examples 1-1 and 1-3, curability was ensured with the polymer alone, but in Comparative Examples 1-2 and 1-4, which were mixed with the polymer, solvent resistance was not ensured due to factors such as insufficient curability, insufficient heat resistance, and sublimation, as described above. In addition, in Comparative Example 1-5, despite using a polymer, the polymer alone did not exhibit curability, and to ensure solvent resistance, it was necessary to add a crosslinking agent and a thermal acid generator, as in Comparative Example 1-6.

[0214] Example 2: Evaluation of heat resistance properties (Examples 2-1 to 2-18, Comparative Examples 2-1 to 2-9) The above organic film-forming compositions (UDL-1 to 18, comparative UDL-1 to 9) were each applied to a silicon substrate and baked in air at the temperatures listed in Table 6 for 60 seconds. about A 200 nm coated film was formed, and the film thickness A was measured. This substrate was then fired at 400°C for another 20 minutes under a nitrogen atmosphere with an oxygen concentration controlled to 0.2 volume% or less, and the film thickness B was measured. These results are shown in Table 6.

[0215] [Table 6]

[0216] As shown in Table 6, the organic films formed by the organic film-forming compositions of the present invention (Examples 2-1 to 2-18) exhibit excellent heat resistance, with a film thickness reduction of less than 3% even after long-term baking at 400°C. In particular, compounds and polymers with propargyloxy groups introduced as substituents maintain a residual film rate of 99% or more, demonstrating exceptional heat resistance. Furthermore, similar to the solvent resistance test in Example 1, Examples 2-3, 2-6, and 2-7 show improvements not only in solvent resistance but also in heat resistance when combined with polymers (Examples 2-14 to 2-16). On the other hand, in Comparative Examples 2-2, 2-4, 2-5, 2-7, and 2-8, the residual film percentage was low for those that did not achieve solvent resistance in Example 1. In Comparative Examples 2-7 and 2-8, which used monomolecule compounds, almost no organic film remained after being held at 400°C. Even in Comparative Examples 2-1, 2-3, and 2-6, where solvent resistance was ensured by adding a crosslinking agent or using a polymer, the residual film percentage was lower compared to the examples of the present invention. This indicates that the organic films formed using the compounds and polymers of the present invention have excellent heat resistance due to the contribution of the cyclic amide structure.

[0217] Example 3: Evaluation of film formation properties (Examples 3-1 to 3-18, Comparative Examples 3-1 to 3-9) The organic film-forming compositions prepared above (UDL-1 to 18, comparative UDL-1 to 9) were coated onto Bare-Si substrates, hexamethyldisilazane (HMDS)-treated substrates, and SiON-treated substrates, respectively, as shown in Table 7. These were then baked in air at the temperatures listed in Table 7 for 60 seconds to form organic films with a thickness of 100 nm. The formed organic films were then observed using an optical microscope (Nikon ECLIPSE L200) to check for any coating abnormalities. Note that in this evaluation, the film thickness was kept thin to assess the quality of coating, resulting in strict evaluation conditions that are prone to film formation abnormalities.

[0218] [Table 7]

[0219] As shown in Table 7, the organic film-forming compositions of the present invention (Examples 3-1 to 3-2, 3-4 to 3-18) demonstrate that film formation is independent of the substrate. In Example 3-3, slight pinholes were observed on the SiON substrate due to the use of a monomolecule compound. However, compared to Comparative Examples 3-7 and 3-8, which used monomolecule compounds (B8, B9) with similar structures (cyclic esters), where film formation could not be ensured on any substrate due to insufficient curability and heat resistance, the film formation performance has been improved, confirming the effectiveness of the present invention. Furthermore, as can be seen from the comparison between Example 3-3 and Example 3-14, film formation can also be improved by using a combination of polymers. In addition, as shown in Comparative Examples 3-1 to 3-5 and 3-9, film formation could not be ensured on some substrates even with the addition of crosslinking agents and polymers (Comparative Examples 3-2, 3-4, 3-9) or polymers alone (Comparative Examples 3-1, 3-3, 3-5). A comparison of these results suggests that in the compounds and polymers of the present invention, the cyclic amide structure functions as an adhesion group, contributing to improved film formation. A similar trend can be seen in Comparative Examples 3-5 and 3-6, which used polymers having a cyclic amide structure (R3). In Comparative Example 3-5, the polymer alone, lacking curability and poor heat resistance, could not secure film formation, but in Comparative Example 3-6, where a crosslinking agent was added to form a cured film, film formation improved.

[0220] Thus, the organic film-forming composition of the present invention, by containing an organic film-forming material represented by a specific formula, can form an organic film with excellent curability and heat resistance without the addition of crosslinking agents or thermal acid generators, regardless of whether the material contains one or more monomolecular compounds or polymers, and exhibits good film-forming properties on various substrates.

[0221] Example 4: Evaluation of Embedding Characteristics (Examples 4-1 to 4-18, Comparative Examples 4-1 to 4-9) The organic film-forming compositions prepared above (UDL-1 to 18, comparative UDL-1 to 9) were each applied to an SiO2 wafer substrate having a dense hole pattern (hole diameter 0.16 μm, hole depth 0.50 μm, distance between the centers of two adjacent holes 0.32 μm), and fired in air at the temperature listed in Table 8 for 60 seconds to form an organic film. The substrate used was a base substrate 7 (SiO2 wafer substrate) having a dense hole pattern as shown in Figure 2(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with organic film 8 without any voids (gaps). The results are shown in Table 8. When an organic film-forming composition with inferior filling characteristics was used, voids were generated inside the holes in this evaluation. When an organic film-forming composition with good embedding properties is used, the organic film fills the inside of the holes without voids, as shown in Figure 2(I) in this evaluation.

[0222] [Table 8]

[0223] As shown in Examples 4-1 to 4-18 of Table 8, when using the compounds and / or polymers of the present invention, all organic film-forming materials were found to be capable of filling hole patterns without voids and exhibiting excellent embedding properties. On the other hand, in Comparative Examples 4-1 to 4-5, 4-7, and 4-8, as shown in the results of Examples 1 and 2, it is thought that embedding failures occurred due to insufficient solvent resistance and heat resistance. In Comparative Example 4-6, although solvent resistance was ensured, the use of a polymer resulted in inferior thermal fluidity compared to a monomolecule compound, and a rapid curing reaction occurred due to the action of a thermal acid generator, which is thought to have resulted in insufficient thermal fluidity and voids due to embedding failures. On the other hand, in Comparative Example 4-9, since it is a single compound, it can be seen that embedding properties were ensured due to the contribution of thermal fluidity.

[0224] Example 5: Evaluation of Planarization Characteristics (Examples 5-1 to 5-18, Comparative Examples 5-1 to 5-9) The organic film-forming compositions prepared above (UDL-1 to 18, comparative UDL-1 to 9) were each coated onto a substrate 9 (SiO2 wafer substrate) having a large isolated trench pattern (Figure 3(J), trench width 10 μm, trench depth 0.1 μm), baked in air at the temperatures listed in Table 9 for 60 seconds, and the step difference between the trenched and non-trenched organic films 10 (delta 10 in Figure 3(K)) was observed using a Park Systems NX10 atomic force microscope (AFM). The results are shown in Table 9. In this evaluation, a smaller step difference indicates better planarization characteristics. Note that in this evaluation, a trench pattern with a depth of 0.10 μm was planarized using an organic film with a typical thickness of approximately 0.2 μm, making it a strict evaluation condition for assessing the superiority of planarization characteristics.

[0225] [Table 9]

[0226] As shown in Examples 5-1 to 5-18 of Table 9, when the compounds and / or polymers of the present invention are used, all organic film-forming materials exhibit smaller step differences between the trenched and non-trenched portions of the organic film and superior planarization characteristics compared to Comparative Examples 5-1 to 5-9. In particular, Examples 5-4, 5-5, and 5-8, which are dehydrated condensates of phenol or catechol and indole-2,3-diones and have propargyl groups as substituents, show good results. This is because the results of the heat resistance test in Example 2 show excellent heat resistance, and it is thought that this is due to the encapsulation of hydroxyl groups by etherification, which reduces the viscosity of the compound. In Comparative Examples 5-2, 5-4, 5-5, 5-7, and 5-8, as shown in the results of the heat resistance test in Example 2, the heat resistance is insufficient, resulting in large film shrinkage during baking and thus a step difference. Difference from film thicknessIt is believed that this occurs and the planarization characteristics deteriorate. In addition, in Comparative Examples 5-6 and 5-9, it is believed that the planarization characteristics deteriorated because the rapid curing reaction caused by the use of a crosslinking agent to ensure solvent resistance prevented the benefit of thermal fluidity from being realized. Comparing Examples 5-17 and 5-18 with Examples 5-1 and 5-8, which did not contain the additive, it can be seen that the planarity was further improved by the addition of a high-boiling point solvent. Furthermore, comparing Examples 5-14 to 5-16, which mixed the compound of the present invention with the polymer, with Examples 5-10, 5-12, and 5-13, which contained only the polymer, the planarization characteristics were improved, and by adjusting the blending ratio, it is possible to improve the planarity without impairing the various physical properties required of organic films, such as heat resistance, twist resistance, and etching resistance.

[0227] Example 6: Adhesion Test (Examples 6-1 to 6-18, Comparative Examples 6-1 to 6-4) The above-mentioned organic film-forming compositions (UDL-1 to 16, comparative UDL1, 3, 6, and 9) were applied to an SiO2 wafer substrate, and an organic film with a thickness of 200 nm was formed by baking it in air using a hot plate at the temperatures listed in Table 10 for 60 seconds. The wafer with the organic film was cut into 1 x 1 cm squares, and aluminum pins with epoxy adhesive were attached to the cut wafers using a special jig. Then, the wafers were heated in an oven at 150°C for 1 hour to bond the aluminum pins to the substrate. After cooling to room temperature, the initial adhesion was evaluated by resistance using a thin film adhesion strength measuring device (Sebastian Five-A). Note that adhesion tests could not be performed on comparative UDL2, 4, 5, 7, and 8, for which solvent resistance could not be ensured in Example 1.

[0228] Figure 4 shows an explanatory diagram illustrating the adhesion measurement method. In Figure 4, 11 is the silicon wafer (substrate), 12 is the cured film, 14 is the aluminum pin with adhesive, 13 is the support base, 15 is the grip, and 16 indicates the tensile direction. The adhesion force is the average value of 12 measurements, and a higher value indicates better adhesion of the adhesive film to the substrate. The adhesion was evaluated by comparing the obtained values. The results are shown in Table 10.

[0229] [Table 10]

[0230] As shown in Examples 6-1 to 6-18 in Table 10, when using the compounds and / or polymers of the present invention, the organic films exhibited higher adhesion compared to Comparative Examples 6-1, 6-2, and 6-4. Furthermore, Comparative Example 6-3 also showed high adhesion due to its similar cyclic amide structure. These results suggest that the adhesion was improved by the action of the specific heterocyclic structures introduced into the compounds and polymers of the present invention, resulting in the excellent film-forming properties observed in Example 3.

[0231] Example 7: Pattern formation test (Examples 7-1 to 7-18, Comparative Examples 7-1 to 7-4) The above organic film-forming compositions (UDL-1 to 18, comparative UDL1, 3, 6, 9) have been treated with HMDS to form a trench pattern (trench width 10 μm, trench depth 0.10 μm) with a 200 nm thick SiO2 film. Bare Si An organic film (resist underlayer) was formed by coating it onto a substrate and firing it in air on a bare Si substrate under the conditions shown in Table 14 to a film thickness of 200 nm. A silicon-containing resist interlayer material (SOG1) was then applied on top of this and baked at 220°C for 60 seconds to form a resist interlayer with a thickness of 35 nm. A resist toplayer material (ArF SL resist) was then applied and baked at 105°C for 60 seconds to form a resist toplayer with a thickness of 100 nm. An immersion protective film (TC-1) was applied to the resist toplayer and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm. Note that for comparative UDL2, 4, 5, 7, and 8, where solvent resistance could not be ensured in Example 1, pattern formation tests could not be performed because the silicon-containing resist interlayer material could not be applied.

[0232] The resist upper layer material (SL resist for ArF) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in the proportions shown in Table 11 in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter.

[0233] [Table 11]

[0234] The structural formulas of the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used are shown below. [ka]

[0235] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent in the proportions shown in Table 12 and filtering it through a 0.1 μm fluororesin filter.

[0236] [Table 12]

[0237] The structural formula of the polymer used (PP1) is shown below. [ka]

[0238] As a silicon-containing resist interlayer material (SOG1), a polymer represented by ArF silicon-containing interlayer polymer (SiP1) and a crosslinking catalyst (CAT1) were dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 13, and the mixture was filtered through a fluororesin filter with a pore size of 0.1 μm to prepare the silicon-containing resist interlayer material (SOG1).

[0239] [Table 13]

[0240] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and crosslinking catalyst (CAT1) used are shown below. [ka]

[0241] Next, the samples were exposed using an ArF immersion lithography system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s polarized illumination, 6% halftone phase shift mask) while varying the exposure dose, baked (PEB) at 100°C for 60 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain positive line-and-space patterns with a pitch of 100 nm and resist line widths ranging from 50 nm to 30 nm.

[0242] Next, using the Telius etching system manufactured by Tokyo Electron, a silicon-containing interlayer was processed using a resist pattern obtained by dry etching as a mask, an organic film was processed using the silicon-containing interlayer as a mask, and an SiO2 film was processed using the organic film as a mask.

[0243] The etching conditions are as follows: (Conditions for transferring resist patterns to SOG films) Chamber pressure 10.0 Pa RF Power 1,500W CF4 gas flow rate: 15 sccm O2 gas flow rate: 75 sccm Time 15sec

[0244] (Conditions for transferring SOG film to organic film) Chamber pressure 2.0 Pa RF Power 500W Ar gas flow rate: 75 sccm O2 gas flow rate: 45 sccm Time 120sec

[0245] (Conditions for transfer to SiO2 film) Chamber pressure 2.0 Pa RF Power 2,200W C5F 12 Gas flow rate: 20 sccm C2F6 gas flow rate: 10 sccm Ar gas flow rate: 300 sccm O2 gas flow rate: 60 sccm Time 90sec

[0246] The cross-sections of the patterns were observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and their shapes were compared and summarized in Table 14.

[0247] [Table 14]

[0248] As shown in Table 14, the results for the organic film-forming compositions of the present invention (Examples 7-1 to 7-18) show that in all cases the resist upper layer film pattern was successfully transferred to the substrate, confirming that the organic film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method. On the other hand, in Comparative Examples 7-1 to 7-4, the film formation was the same as in Example 3. Sexual evaluation As the results show, During membrane The pinholes that occurred caused the pattern to collapse during pattern processing, making it impossible to form the pattern.

[0249] From the above, it has become clear that the organic film-forming composition of the present invention is extremely useful as an organic film material for use in the multilayer resist method because it has good film-forming properties and excellent embedding / planarization characteristics, and that the pattern-forming method of the present invention using this composition can form fine patterns with high precision even on substrates that have steps.

[0250] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0251] 1...Substrate, 2...Layer to be processed, 2a...Pattern formed on the layer to be processed, 3...Organic film, 3a...Organic film pattern, 4...Silicon-containing resist interlayer, 4a...Silicon-containing resist interlayer pattern, 5...Resist top layer, 5a...Resist pattern, 6...Required area (exposed area), 7...Underlayment substrate with dense hole pattern, 8...Organic film, 9...Underlayment substrate with large isolated trench pattern, 10...Organic film, delta 10...Difference in organic film thickness between trench and non-trench areas. 11...Silicon wafer, 12...Cured film, 13...Support stand, 14...Adhesive-attached aluminum pin, 15...Gripping, 16...Tensile direction.

Claims

1. A composition for forming an organic film, comprising an organic film-forming material and an organic solvent, The organic film-forming material is a compound represented by the following general formula (1) and / or (2), and the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the compound, measured by gel permeation chromatography, is 1.00 ≤ Mw / Mn ≤ 1.10, characterized in that the organic film-forming material is a compound represented by the following general formula (1) and / or (2), and the ratio is 1.00 ≤ Mw / Mn ≤ 1.

10. 【Chemistry 1】 (In the above general formula (1), R １ R is an allyl group or a propargyl group, ２ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ３ The '-' represents an alkyl group with 1 to 4 carbon atoms, an alkynyl group with 2 to 4 carbon atoms, or an alkenyl group with 2 to 4 carbon atoms. 'm' represents 0 or 1, 'n' represents an integer of 1 or 2, and 'l' represents 0 or 1. When l = 0, it means that the aromatic rings at both ends of the '-(O)l-' group are not substituted with '-(O)l-' groups. When l = 1, it means that the aromatic rings form a cyclic ether structure. 'k' represents an integer from 0 to 2. 【Chemistry 2】 (In the above general formula (2), R ４ R is an allyl group or a propargyl group, ５ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ６ represents a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j independently represent integers from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 0, it means that the aromatic rings at both ends of the "-(O)r-" group are not substituted with "-(O)r-" groups. When r = 1, it means that the aromatic rings form a cyclic ether structure. W is one of the divalent groups represented by the following formula (3). 【Transformation 3】 (The dashed lines represent connecting points.)

2. A composition for forming an organic film, comprising an organic film-forming material and an organic solvent, The organic film-forming material is a polymer having repeating units represented by the following general formula (4) and / or (5), An organic film-forming composition characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the polymer, as determined by gel permeation chromatography, is greater than 1.

10. 【Chemistry 4】 (In the above general formula (4), R １ is an allyl group or a propargyl group, and R ２ represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group, and R ３ represents an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l = 0, it means that the aromatic rings at both ends of the "-(O)l-" group are not substituted with the "-(O)l-" group. When l = 1, it means that a cyclic ether structure is formed between the aromatic rings. k represents an integer of 0 to 2. L is a divalent organic group having 1 to 40 carbon atoms and is any one of the following (L1) formulas.) 【Transformation 5】 (R in the above general formula (5) ４ R is an allyl group or a propargyl group, ５ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ６ represents a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j independently represent integers from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 0, it means that the aromatic rings at both ends of the "-(O)r-" group are not substituted with "-(O)r-" groups. When r = 1, it means that the aromatic rings form a cyclic ether structure. W is one of the divalent groups represented by the following formula (3). L is a divalent organic group with 1 to 40 carbon atoms, and is one of the following formulas (L1). 【Transformation 6】 (The dashed lines represent connecting points.) 【Transformation 7】 (The dashed lines represent connecting points.)

3. The organic film-forming composition according to claim 2, characterized in that L is a divalent organic group which is one of the following formulas (L2). 【Transformation 8】 (The dashed lines represent connecting points.)

4. The organic film-forming composition according to claim 2 or 3, characterized in that the weight-average molecular weight of the polymer, measured by gel permeation chromatography on a polystyrene basis, is 1,000 to 5,000.

5. A composition for forming an organic film, comprising an organic film-forming material and an organic solvent, The organic film-forming material contains one or more compounds selected from the following general formulas (1) and / or (2) and polymers having repeating units represented by the following general formulas (4) and / or (5). The ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the compound, measured by gel permeation chromatography, is 1.00 ≤ Mw / Mn ≤ 1.

10. An organic film-forming composition characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the polymer, as determined by gel permeation chromatography, is greater than 1.

10. 【Chemistry 9】 (In the above general formula (1), R １ R is an allyl group or a propargyl group, ２ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ３ The '-' represents an alkyl group with 1 to 4 carbon atoms, an alkynyl group with 2 to 4 carbon atoms, or an alkenyl group with 2 to 4 carbon atoms. 'm' represents 0 or 1, 'n' represents an integer of 1 or 2, and 'l' represents 0 or 1. When l = 0, it means that the aromatic rings at both ends of the '-(O)l-' group are not substituted with '-(O)l-' groups. When l = 1, it means that the aromatic rings form a cyclic ether structure. 'k' represents an integer from 0 to 2. 【Chemistry 10】 (In the above general formula (2), R ４ R is an allyl group or a propargyl group, ５ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ６ represents a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j independently represent integers from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 0, it means that the aromatic rings at both ends of the "-(O)r-" group are not substituted with "-(O)r-" groups. When r = 1, it means that the aromatic rings form a cyclic ether structure. W is one of the divalent groups represented by the following formula (3). 【Chemistry 11】 (The dashed lines represent connecting points.) 【Chemistry 12】 (R in the above general formula (4)) １ , R ２ , R ３ m, n, l, and k are the same as described above. L is a divalent organic group having 1 to 40 carbon atoms, and is one of the following (L1) formulas. 【Chemistry 13】 (R in the above general formula (5) ４ , R ５ , R ６ (W, L, h, i, j, q, and r are the same as above.) 【Chemistry 14】 (The dashed lines represent connecting points.)

6. The organic film-forming composition according to any one of claims 1 to 5, characterized in that the organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

7. The organic film-forming composition according to any one of claims 1 to 6, further characterized in that it contains one or more surfactants and plasticizers.

8. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 7; forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material; forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition; forming a circuit pattern on the resist upper layer; transferring the pattern to the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask; and further forming a pattern on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

9. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 7; forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material; forming an organic anti-reflective film (BARC) on the silicon-containing resist interlayer; forming a resist upper layer on the BARC using a photoresist composition to form a four-layer film structure; forming a circuit pattern on the resist upper layer; transferring the pattern to the BARC film and the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask; and further etching the workpiece using the organic film on which the pattern has been transferred as a mask to form a pattern on the workpiece.

10. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 7; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a photoresist composition to form a circuit pattern on the resist upper layer film; etching the inorganic hard mask using the resist upper layer film on which the pattern is formed as a mask; etching the organic film using the inorganic hard mask on which the pattern is formed as a mask; and further etching the workpiece using the organic film on which the pattern is formed as a mask to form a pattern on the workpiece.

11. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 7; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic anti-reflective film (BARC) on the inorganic hard mask; forming a resist upper layer film on the BARC using a photoresist composition to form a four-layer film structure; forming a circuit pattern on the resist upper layer film; etching the BARC film and the inorganic hard mask using the resist upper layer film on which the pattern is formed as a mask; etching the organic film using the inorganic hard mask on which the pattern is formed as a mask; and further etching the workpiece using the organic film on which the pattern is formed as a mask to form a pattern on the workpiece.

12. The pattern forming method according to claim 10 or 11, characterized in that the inorganic hard mask is formed by a CVD method or an ALD method.

13. The pattern formation method according to any one of claims 8 to 12, characterized in that the pattern formation of the resist upper layer film is performed by photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

14. The pattern forming method according to any one of claims 8 to 13, characterized in that exposure and development are performed to form a circuit pattern on the resist upper layer film, and the development is alkaline development or development with an organic solvent.

15. The pattern forming method according to any one of claims 8 to 14, characterized in that a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film is used as the workpiece.

16. The pattern forming method according to claim 15, characterized in that the metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.

17. A compound represented by the following general formula (1), characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the compound, measured by gel permeation chromatography on a polystyrene basis, is 1.00 ≤ Mw / Mn ≤ 1.

10. 【Chemistry 15】 (In the formula, R １ R is an allyl group or a propargyl group, ２ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ３ The '-' represents an alkyl group with 1 to 4 carbon atoms, an alkynyl group with 2 to 4 carbon atoms, or an alkenyl group with 2 to 4 carbon atoms. 'm' represents 0 or 1, 'n' represents an integer of 1 or 2, and 'l' represents 0 or 1. When l = 0, it means that the aromatic rings at both ends of the '-(O)l-' group are not substituted with '-(O)l-' groups. When l = 1, it means that the aromatic rings form a cyclic ether structure. 'k' represents an integer from 0 to 2.

18. A compound represented by the following general formula (2), characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the compound, measured by gel permeation chromatography on a polystyrene basis, is 1.00 ≤ Mw / Mn ≤ 1.

10. 【Chemistry 16】 (In the formula, R ４ R is an allyl group or a propargyl group, ５ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ６ represents a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j independently represent integers from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 0, it means that the aromatic rings at both ends of the "-(O)r-" group are not substituted with "-(O)r-" groups. When r = 1, it means that the aromatic rings form a cyclic ether structure. W is one of the divalent groups represented by the following formula (3). 【Chemistry 17】 (The dashed lines represent connecting points.)

19. A polymer having repeating units represented by the following general formula (4), characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the polymer, measured by gel permeation chromatography on a polystyrene basis, is greater than 1.

10. [Chemistry 18] (In the formula, R １ R is an allyl group or a propargyl group, ２ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ３ represents an alkyl group with 1 to 4 carbon atoms, an alkynyl group with 2 to 4 carbon atoms, or an alkenyl group with 2 to 4 carbon atoms. m represents 0 or 1, n represents an integer of 1 or 2, and l represents 0 or 1. When l = 0, it means that the aromatic rings at both ends of the "-(O)l-" group are not substituted with "-(O)l-" groups. When l = 1, it means that the aromatic rings form a cyclic ether structure. k represents an integer from 0 to 2. L is a divalent organic group with 1 to 40 carbon atoms, and is one of the following (L1) formulas. 【Chemistry 19】 (The dashed lines represent connecting points.)

20. A polymer having repeating units represented by the following general formula (5), characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the polymer, measured by gel permeation chromatography on a polystyrene basis, is greater than 1.

10. 【Chemistry 20】 (In the formula, R ４ R is an allyl group or a propargyl group, ５ R represents a nitro group, halogen atom, hydroxyl group, C1-C4 alkyloxy group, C2-C4 alkynyloxy group, C2-C4 alkenyloxy group, C1-C6 linear, branched or cyclic alkyl group, trifluoromethyl group, or trifluoromethyloxy group. ６ represents a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group. i represents 0 or 1, q represents an integer from 0 to 2, h and j independently represent integers from 0 to 2, satisfying the relationship 1 ≤ h + j ≤ 4, r represents 0 or 1, and when r = 0, it means that the aromatic rings at both ends of the "-(O)r-" group are not substituted with "-(O)r-" groups. When r = 1, it means that the aromatic rings form a cyclic ether structure. W is one of the divalent groups represented by the following formula (3). L is a divalent organic group with 1 to 40 carbon atoms, and is one of the following formulas (L1). 【Chemistry 21】 (The dashed lines represent connecting points.) 【Chemistry 22】 (The dashed lines represent connecting points.)

21. The polymer according to claim 19 or 20, characterized in that L is a divalent organic group which is one of the following formulas (L2). 【Chemistry 23】 (The dashed lines represent connecting points.)

Images