Organic film forming material, organic film forming method, pattern forming method, and compound

Abstract

The present invention relates to an organic film forming material, an organic film forming method, a pattern forming method, and a compound. The present invention provides an organic film forming material, characterized in that it contains a compound represented by the following general formula (1) and an organic solvent. #imgabs0# In the general formula (1), X is an n-valent organic group with a carbon number of 2 to 50 or an oxygen atom, n is an integer of 1 to 10, and R1 is independently any one of the following general formula (2). #imgabs1# In the general formula (2), the dashed line indicates the bonding site to X, Q1 is a monovalent organic group containing a carbonyl group, and at least a part is a group represented by the following general formula (3). #imgabs2# In the general formula (3), the dashed line indicates the bonding site, X1 represents a single bond, or a divalent organic group with a carbon number of 1 to 20, and the organic group may also have a substituent when it has an aromatic ring. R2 represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ** represents a bonding site.

Description

Technical Field

[0001] The present invention relates to an organic film forming material for forming an organic film that is effective as a resist underlayer film or a flattening material for manufacturing a semiconductor device, wherein the resist underlayer film is used in a multilayer resist step used for microfabrication in the manufacturing steps of a semiconductor device, etc.; and to a film forming method using the organic film forming material, a pattern forming method using the aforementioned organic film forming material that is suitable for exposure to extreme ultraviolet rays, KrF excimer laser (248nm), ArF excimer laser (193nm), F2 laser (157nm), Kr laser (146nm), Ar laser (126nm), soft X-rays (EUV), electron beams (EB), ion beams, X-rays, etc., and a compound that is effective as a component of the aforementioned organic film forming material. Background Art

[0002] With the high integration and high speed of LSI, the miniaturization of pattern size is progressing rapidly. The photolithography technology and the miniaturization have achieved the formation of fine patterns through the shortening of the wavelength of the light source and the appropriate selection of the resist composition corresponding to the shortening of the wavelength of the light source. The core technology is the positive photoresist composition used in a single layer. The single-layer positive photoresist composition has a skeleton in the resist resin that is resistant to dry etching using chlorine-based or fluorine-based gas plasma, and has a resist mechanism in which the exposed part dissolves, so that the exposed part dissolves and forms a pattern, and then the remaining resist pattern is used as an etching mask to perform dry etching on the substrate coated with the resist composition.

[0003] However, if the thickness of the photoresist film used is directly miniaturized, that is, if the pattern width is reduced, the resolution of the photoresist film will decrease, and if the photoresist film is used for pattern development with a developer, the so-called aspect ratio will become too large, resulting in pattern collapse. Therefore, along with miniaturization, the thickness of the photoresist film is reduced.

[0004] On the other hand, the processing of the substrate to be processed usually uses a method of processing the substrate by dry etching using a photoresist film formed with a pattern as an etching mask, but in reality there is no dry etching method that can obtain complete etching selectivity between the photoresist film and the substrate to be processed, so the resist film will also be damaged during the processing of the substrate, and the resist film will collapse during the processing of the substrate, and it will become impossible to correctly transfer the resist pattern to the substrate to be processed. Therefore, with the miniaturization of the pattern, higher dry etching resistance is sought for the resist composition. In addition, due to the shortening of the exposure wavelength, the resin used in the photoresist composition requires a resin with low light absorption at the exposure wavelength, so in response to the change toward i-rays, KrF, and ArF, the resin also changes toward novolac resin, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons, but in reality the etching speed under the above-mentioned dry etching conditions will become faster, and the recent photoresist composition with high resolution has a tendency to weaken etching resistance.

[0005] In view of this situation, it becomes necessary to perform dry etching processing on the substrate to be processed using a thinner photoresist film with weaker etching resistance, and securing the materials and processes in this processing step becomes a top priority.

[0006] One method to solve such a problem is a multilayer resist method. In this method, an intermediate film having an etching selectivity different from that of the photoresist film (i.e., the resist upper film) is inserted between the resist upper film and the substrate to be processed, and after the resist upper film has a pattern, the resist upper film pattern is used as a dry etching mask, and the pattern is transferred to the intermediate film by dry etching, and then the intermediate film is used as a dry etching mask, and the pattern is transferred to the substrate to be processed by dry etching.

[0007] One of the multilayer resist methods is a three-layer resist method that can be implemented using a general resist composition used in the single-layer resist method. The three-layer resist method, for example, forms an organic film formed of a novolac resin or the like as a resist lower film on a substrate to be processed, forms a film containing silicon thereon as a resist intermediate film, and then forms a normal organic photoresist film thereon as a resist upper film. For dry etching using fluorine-based gas plasma, the organic resist upper film can achieve a better etching selectivity ratio with respect to the silicon-containing resist intermediate film, so the resist upper film pattern is transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. Furthermore, for etching using oxygen or hydrogen, the silicon-containing resist intermediate film can achieve a better etching selectivity ratio with respect to the organic lower film, so the silicon-containing intermediate film pattern is transferred to the lower film by etching using oxygen or hydrogen. According to this method, even if a resist composition is used that is difficult to form a pattern having a film thickness sufficient for directly processing a substrate to be processed, or a resist composition whose dry etching resistance is not sufficient for processing a substrate, as long as the pattern can be transferred to a silicon-containing film (resist intermediate film), a pattern of an organic film (resist underlayer film) formed of a novolac resin or the like having dry etching resistance sufficient for processing can still be obtained.

[0008] There are many technologies known for organic lower films as described above (e.g., Patent Document 1), but in recent years, in addition to the need for dry etching resistance, the need for excellent filling characteristics, flattening characteristics, or adhesion to the substrate has gradually increased. For example, when the processed substrate of the base has micro-pattern structures such as holes and grooves, it is necessary to have a filling characteristic that fills the pattern with a film without gaps. In addition, when the processed substrate of the base has a height difference, or when there are pattern-dense parts and pattern-free areas on the same wafer, it is necessary to use an underlayer film to flatten the film surface. By flattening the surface of the underlayer film, the thickness variation of the intermediate layer and photoresist formed thereon can be suppressed, and the focal length tolerance of the lithography or the tolerance of the subsequent processing steps of the processed substrate can be expanded. In addition, when an inorganic hard mask is formed on the organic lower layer film, adhesion to the substrate is required. By improving the adhesion, film peeling can be prevented when an inorganic hard mask is formed on an organic film using a CVD method or an ALD method, and an organic film with excellent process latitude can be formed.

[0009] Some people have proposed adding liquid additives such as polyether polyols as a method for improving the filling / planarization characteristics of the lower film material (Patent Document 2). However, the organic film formed by this method contains a large amount of polyether polyol units with poor etching resistance, so the etching resistance will be greatly reduced, which is not suitable for use as a three-layer resist lower film. In addition, some people have proposed a resist lower film material with a lactone ring structure as a component as a method for improving the adhesion of the lower film material to the substrate (Patent Document 3). However, the adhesion of the resist lower film material to the substrate is not enough to meet the requirements of the most advanced devices. In this way, it is necessary to have both excellent filling / planarization characteristics / adhesion to the substrate and sufficient etching resistance of the resist lower film material, and a pattern forming method using the resist lower film material.

[0010] Furthermore, the use of organic film materials with excellent filling characteristics / flattening characteristics / adhesion to substrates is not limited to the three-layer resist lower film, and can also be widely used as a flattening material for semiconductor device manufacturing such as substrate flattening before patterning by nanoimprinting. In addition, global flattening in the semiconductor device manufacturing step is currently generally performed using a CMP process, but CMP is a high-cost process, and the present invention is also expected to be a material that can replace CMP as a global flattening method.

[0011] [Prior Technical Literature]

[0012] [Patent Document]

[0013] [Patent Document 1] Japanese Patent Application Publication No. 2004-205685

[0014] [Patent Document 2] Japanese Patent No. 4784784

[0015] [Patent Document 3] Japanese Patent No. 3985165 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic film forming material for forming an organic film having dry etching resistance and high filling / planarization properties and adhesion to a substrate.

[0018] Solutions for solving problems

[0019] In order to solve the above-mentioned problems, the present invention provides an organic film-forming material comprising a compound represented by the following general formula (1) and an organic solvent.

[0020] [Chemistry 1]

[0021]

[0022] In the above general formula (1), X is an n-valent organic group having 2 to 50 carbon atoms or an oxygen atom, n is an integer of 1 to 10, and R1 is independently any one of the following general formula (2).

[0023] [Chemistry 2]

[0024]

[0025] In the above general formula (2), the dashed line indicates a bonding site to X, Q1 is a monovalent organic group containing a carbonyl group, and at least a part of the group is a group represented by the following general formula (3).

[0026] [Chemistry 3]

[0027]

[0028] In the above general formula (3), the dashed line indicates a bonding site, X1 indicates a single bond or a divalent organic group having 1 to 20 carbon atoms, and when the organic group has an aromatic ring, it may have a substituent. R2 indicates a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ** indicates a bonding site.

[0029] Such an organic film forming material can form an organic film having high dry etching resistance and high filling / planarization properties. In addition, since it has two carbonyl groups, it has high adhesion to the substrate, and when it also has an amide group, it can form an organic film with higher adhesion.

[0030] In this case, the compound represented by the general formula (1) is preferably an organic film forming material represented by the following general formulas (4), (6), (7), (8), (9), (10), (11), (12), (13) and (14).

[0031] [Chemistry 4]

[0032]

[0033] In the above general formula (4), n7 and n8 each independently represent 0 or 1, W is a single bond or any of the structures represented by the following general formula (5). R1 ​​is the same as above, m1 and m2 each independently represent an integer from 0 to 4, and m1+m2 is 1 or more and 8 or less.

[0034] [Chemistry 5]

[0035]

[0036] In the above general formula (5), n9 represents an integer from 0 to 3, R a ~R fare independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, or a phenyl group, and R a With R b They can also be bonded to form a ring.

[0037] [Chemistry 6]

[0038]

[0039] In the above general formula (6), R1 is the same as above, R g represents a hydrogen atom, a methyl group, or a phenyl group.

[0040] [Chemistry 7]

[0041]

[0042] In the above general formulae (7) to (11), R1 is the same as above, and R h , R i , R j , R k , R l , R m , R n Each of them represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group or a phenyl group which may have a substituent on the aromatic ring. Y represents R1 or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in the general formula (11) are R1.

[0043] [Chemistry 8]

[0044]

[0045] In the above general formulae (12) to (14), R1 is the same as above. o represents a linear, branched or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms, wherein R in the above general formula (13) p It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0046] Such an organic film forming material can provide an organic film having good dry etching resistance and high filling properties, planarization properties, and adhesion to a substrate.

[0047] Furthermore, the present invention provides an organic film forming material, characterized in that: Q1 in the aforementioned general formula (2) is composed of any one or more of the aforementioned general formula (3) and any one or more of the following general formulas (15) and (16).

[0048] [Chemistry 9]

[0049]

[0050] In the above general formula (15), R q represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and R q The methylene group may also be substituted with an oxygen atom or a carbonyl group. s represents a hydrogen atom or a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, and R t represents a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, n12 and n13 represent integers of 0 to 7, and n12+n13 is in the range of 0 to 7.

[0051] If the organic film forming material contains such a compound, by combining the aromatic ring structure and the structure of the hydrocarbon terminal group, many physical properties such as heat resistance, etching resistance, high degree of filling / planarization characteristics, adhesion to the substrate, control of optical constants, etc. can be appropriately adjusted and improved according to the required performance.

[0052] Furthermore, the organic solvent is preferably 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.

[0053] In such an organic film forming material, by adding a high boiling point solvent to the above-described polymer to impart thermal fluidity to the film, an organic film forming material having both high filling and planarizing properties can be obtained.

[0054] Thus, by using the organic film forming material of the present invention in the formation of a multilayer resist film suitable for microfabrication in the manufacturing steps of semiconductor devices, etc., an organic film (resist underlayer film) having high dry etching resistance and high filling / planarization characteristics and adhesion to the substrate can be provided. In addition, a planarizing material for semiconductor device manufacturing having high filling / planarization characteristics and adhesion to the substrate that can be applied to planarization in the manufacturing steps of semiconductor devices other than the multilayer resist process can also be provided.

[0055] The present invention also provides an organic film forming method, which is a method for forming an organic film that functions as an organic flat film suitable for a manufacturing step of a semiconductor device, characterized in that the organic film forming material is spin-coated on a substrate to be processed, and the substrate to be processed is heat-treated at a temperature of 100° C. to 600° C. for a period of 10 seconds to 600 seconds to form a cured film.

[0056] Thus, by applying the organic film forming material and heat treating the organic film forming material at a temperature of 100° C. to 600° C. for 10 to 600 seconds, the crosslinking reaction can be promoted and intermixing with the upper film can be prevented.

[0057] The present invention also provides an organic film forming method, which is a method for forming an organic film that functions as an organic flat film suitable for a manufacturing step of a semiconductor device, wherein the organic film forming material is spin-coated on a substrate to be processed, and the substrate to be processed is heat-treated in an environment with an oxygen concentration of 0.1% to 21% to form a cured film.

[0058] By heat-treating (calcining) the organic film-forming material of the present invention in such an oxygen atmosphere, a sufficiently hardened organic film can be obtained.

[0059] In the above, the substrate to be processed preferably has a structure or a height difference of 30 nm or more.

[0060] The organic film forming material of the present invention is particularly effective in forming a flat organic film on a structure having a height of 30 nm or more or on a substrate having a height difference, because of its high filling / flattening properties and excellent adhesion to the substrate.

[0061] Furthermore, the present invention provides a pattern forming method, characterized in that: an organic film forming material is used on a workpiece to form an anti-etching lower layer film, an anti-etching intermediate layer film material containing silicon atoms is used on the anti-etching lower layer film to form an anti-etching intermediate layer film, an anti-etching upper layer film material of a photoresist composition is used on the anti-etching intermediate layer film to form an anti-etching upper layer film, a circuit pattern is formed on the anti-etching upper layer film, the anti-etching upper layer film on which the circuit pattern is formed is used as an etching mask and the pattern of the anti-etching intermediate layer film is transferred by etching, the anti-etching intermediate layer film on which the circuit pattern is transferred is used as an etching mask and the pattern of the anti-etching lower layer film is transferred by etching, and then the anti-etching lower layer film on which the circuit pattern is transferred is used as an etching mask and the circuit pattern is formed on the workpiece by etching.

[0062] In such a multilayer resist process, if the pattern forming method using the organic film forming material of the present invention is used, a fine pattern can be formed on the substrate to be processed with high precision.

[0063] In addition, the present invention provides a pattern forming method, which is characterized by: using the above-mentioned organic film forming material to form a resist lower layer film on the workpiece, using a resist intermediate layer film material containing silicon atoms to form a resist intermediate layer film on the above-mentioned resist lower layer film, forming a BARC film (organic anti-reflective film) on the above-mentioned resist intermediate layer film, using a resist upper layer film material of a photoresist composition on the above-mentioned BARC film to form a resist upper layer film and make a 4-layer film structure, forming a circuit pattern on the above-mentioned resist upper layer film, using the above-mentioned resist upper layer film with the circuit pattern formed as an etching mask and using etching to transfer the pattern of the above-mentioned BARC film and the above-mentioned resist intermediate layer film, using the above-mentioned resist intermediate layer film with the circuit pattern transferred as an etching mask and using etching to transfer the pattern of the above-mentioned resist lower layer film, and then using the above-mentioned resist lower layer film with the circuit pattern transferred as an etching mask and using etching to form the above-mentioned circuit pattern on the above-mentioned workpiece.

[0064] In this way, a BARC film (organic antireflective film) can be formed on the resist intermediate layer film by spin coating or the like, and a resist upper layer film can be formed thereon, instead of directly forming a photoresist film in the form of a resist upper layer film on the resist intermediate layer film.

[0065] In addition, the present invention provides a pattern forming method, which is characterized by: using the above-mentioned organic film forming material to form an anti-etching lower layer film on the workpiece, forming an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film on the above-mentioned anti-etching lower layer film, using the anti-etching upper layer film material of the photoresist composition on the above-mentioned inorganic hard mask intermediate film to form a resist upper layer film, forming a circuit pattern on the above-mentioned resist upper layer film, using the above-mentioned resist upper layer film with the circuit pattern formed as an etching mask and transferring the pattern of the above-mentioned inorganic hard mask intermediate film by etching, using the above-mentioned inorganic hard mask intermediate film with the circuit pattern transferred as an etching mask and transferring the pattern of the above-mentioned resist lower layer film by etching, and then using the above-mentioned resist lower layer film with the circuit pattern transferred as an etching mask and forming the above-mentioned circuit pattern on the above-mentioned workpiece by etching.

[0066] In addition, the present invention provides a pattern forming method, which is characterized by: using the above-mentioned organic film forming material to form a resist lower layer film on a workpiece, forming an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film on the above-mentioned resist lower layer film, forming a BARC film (organic anti-reflective film) on the above-mentioned inorganic hard mask intermediate film, using a resist upper layer film material of a photoresist composition on the above-mentioned BARC film to form a resist upper layer film and make a 4-layer film structure, forming a circuit pattern on the above-mentioned resist upper layer film, using the above-mentioned resist upper layer film with the circuit pattern formed as an etching mask and using etching to transfer the pattern of the above-mentioned BARC film and the above-mentioned inorganic hard mask intermediate film, using the above-mentioned inorganic hard mask intermediate film with the circuit pattern transferred as an etching mask and using etching to transfer the pattern of the above-mentioned resist lower layer film, and then using the above-mentioned resist lower layer film with the circuit pattern transferred as an etching mask and using etching to form the above-mentioned circuit pattern on the above-mentioned workpiece.

[0067] In this way, a resist intermediate film can be formed on the resist lower film, and it can also be replaced by forming any inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film on the resist lower film. In addition, a photoresist film can be directly formed on the inorganic hard mask intermediate film in the form of a resist upper film, and a BARC film (organic anti-reflective film) can be formed on the inorganic hard mask intermediate film by spin coating, etc., and a resist upper film can be formed thereon. When a SiON film (silicon oxide nitride film) is used as an inorganic hard mask intermediate film, the two-layer anti-reflective film of the SiON film and the BARC film can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another benefit of forming a BARC film is that it has the effect of reducing the tailing of the photoresist pattern above the SiON film.

[0068] Furthermore, in the pattern forming method of the present invention, the inorganic hard mask intermediate film may be formed by a CVD method or an ALD method.

[0069] As described above, in the pattern forming method of the present invention, a combination of an inorganic hard mask intermediate film formed by a CVD method or an ALD method and a resist underlayer film formed by a spin coating method or the like may be used.

[0070] When forming the pattern of the resist upper layer film, it is preferable to form the pattern by optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

[0071] In addition, the development method in the above-mentioned pattern forming method is preferably development using an alkali or an organic solvent.

[0072] The present invention can preferably use such a pattern forming method and a developing method.

[0073] Furthermore, the aforementioned processed body is preferably a semiconductor device substrate, or a semiconductor device substrate on which 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 formed.

[0074] Furthermore, the aforementioned workpiece preferably uses metal silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[0075] According to the pattern forming method of the present invention, the above-mentioned object to be processed can be used and processed to form a pattern.

[0076] Furthermore, the present invention provides a compound represented by the following general formula (1).

[0077] [Chemistry 10]

[0078]

[0079] In the above general formula (1), X is an n-valent organic group having 2 to 50 carbon atoms or an oxygen atom, n is an integer of 1 to 10, and R1 is independently any one of the following general formula (2).

[0080] [Chemistry 11]

[0081]

[0082] In the above general formula (2), the dashed line indicates a bonding site to X, Q1 is a monovalent organic group containing a carbonyl group, and at least a part of the group is a group represented by the following general formula (3).

[0083] [Chemistry 12]

[0084]

[0085] In the above general formula (3), the dashed line indicates a bonding site, X1 indicates a single bond or a divalent organic group having 1 to 20 carbon atoms, and the organic group may have a substituent when it has an aromatic ring. R2 indicates a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ** indicates a bonding site.

[0086] If it is the compound of the present invention, when it is used as a component of an organic film forming material, the obtained organic film forming material can form an organic film with high dry etching resistance and a high degree of filling / planarization characteristics. By appropriately selecting the terminal substituent containing a triple bond, high heat curing can be imparted, and the film shrinkage during calcination can be reduced. By reducing film shrinkage, an organic film with excellent planarization characteristics can be formed, and the internal stress of the coating film is reduced, so the adhesion to the substrate will also be improved. In addition, the terminal substituent has 2 carbonyl groups, so the adhesion to the substrate is high, and when having an amide group at the same time, an organic film with higher adhesion can be formed. Again, by having a terminal substituent containing a triple bond, sublimates will not be produced even in an inert gas environment, and sufficient heat curing is shown, so film formation can be performed without causing damage to carbonyl and amide groups, not only in the atmosphere, but also in an inert gas, and high adhesion to the substrate is shown. Therefore, the compound of the present invention is extremely effective as an organic film forming material for forming an organic film having high filling characteristics and high planarization characteristics and excellent adhesion to a substrate.

[0087] In this case, the compound represented by the general formula (1) is preferably any one of the compounds represented by the following general formulas (4), (6), (7), (8), (9), (10), (11), (12), (13) and (14).

[0088] [Chemistry 13]

[0089]

[0090] In the above general formula (4), n7 and n8 each independently represent 0 or 1, W is a single bond or any of the structures represented by the following general formula (5). R1 ​​is the same as above, m1 and m2 each independently represent an integer from 0 to 4, and m1+m2 is 1 or more and 8 or less.

[0091] [Chemistry 14]

[0092]

[0093] In the above general formula (5), n9 represents an integer from 0 to 3, R a ~R f are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, or a phenyl group, and R a With R b They can also be bonded to form a ring.

[0094] [Chemistry 15]

[0095]

[0096] In the above general formula (6), R1 is the same as above, R grepresents a hydrogen atom, a methyl group, or a phenyl group.

[0097] [Chemistry 16]

[0098]

[0099] In the above general formulae (7) to (11), R1 is the same as above, and R h , R i , R j , R k , R l , R m , R n Each of them represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group or a phenyl group which may have a substituent on the aromatic ring. Y represents R1 or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in the general formula (11) are R1.

[0100] [Chemistry 17]

[0101]

[0102] In the above general formulae (12) to (14), R1 is the same as above. o represents a linear, branched or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms, wherein R in the above general formula (13) p It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0103] If it is such a compound, it will have high-degree filling characteristics, flattening characteristics, and excellent adhesion, and the etching resistance and optical characteristics can be appropriately adjusted in accordance with the required performance. When used as a component of an organic film forming material, it will become a component of an organic film forming material that can form an organic film that has both dry etching resistance and adhesion to a substrate in accordance with the required performance.

[0104] In this case, a compound characterized in that Q1 in the above general formula (2) is composed of one or more of any one of the above general formula (3) and one or more of any one of the following general formulas (15) and (16) can be prepared.

[0105] [Chemistry 18]

[0106]

[0107] In the above general formula (15), R q represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and R qThe methylene group may also be substituted with an oxygen atom or a carbonyl group. s represents a hydrogen atom or a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, and R t represents a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, n12 and n13 represent integers of 0 to 7, and n12+n13 is in the range of 0 to 7.

[0108] If it is such a compound, by being blended into an organic film forming material and by using a combination of an aromatic ring structure and a hydrocarbon terminal group structure, when used as a component of an organic film forming material, many physical properties such as heat resistance, etching resistance, high degree of filling / planarization characteristics, adhesion to the substrate, control of optical constants, etc. can be appropriately adjusted and improved according to the required performance.

[0109] Effects of the Invention

[0110] As described above, the present invention can provide a compound that is effective as a component of an organic film forming material for forming an organic film having both high embedding / planarization characteristics and adhesion to a substrate, and an organic film forming material containing the compound. In addition, since the organic film forming material has high embedding / planarization characteristics and adhesion to a substrate, and has other characteristics such as heat resistance and etching resistance, it is very effective as a resist lower film material in a multi-layer resist process such as a two-layer resist process, a three-layer resist process using an intermediate film containing silicon atoms, or a four-layer resist process using an intermediate film containing silicon atoms and an organic anti-reflection film, or as a planarizing material for semiconductor device manufacturing.

[0111] Furthermore, if the organic film forming method of the present invention is used, a flat organic film can be formed by sufficiently hardening on the processed substrate. Furthermore, if the pattern forming method of the present invention is used, a fine pattern can be formed on the processed substrate with high precision in a multilayer resist process. BRIEF DESCRIPTION OF THE DRAWINGS

[0112] [ Figure 1 ](A) to (F) are explanatory diagrams of an example of a pattern forming method by the three-layer resist process of the present invention.

[0113] [ Figure 2 ](G) to (I) are explanatory diagrams of the landfill characteristic evaluation method of the embodiment and the comparative example.

[0114] [ Figure 3](J) to (K) are explanatory diagrams of the planarization characteristic evaluation method of the embodiment and the comparative example.

[0115] [ Figure 4 ] is an explanatory diagram showing the adhesion measurement method of an embodiment. DETAILED DESCRIPTION

[0116] As described above, an organic film forming material for forming an organic film having both high filling / planarization characteristics and adhesion to a substrate is required.

[0117] As a result of repeated and in-depth studies on the above-mentioned issues, the inventors have discovered that an organic film forming material comprising a compound represented by the following general formula (1) can form an organic film having both high filling / planarization properties and excellent adhesion to a substrate, thereby completing the present invention.

[0118] That is, the present invention is an organic film-forming material comprising a compound represented by the following general formula (1) and an organic solvent.

[0119] [Chemistry 19]

[0120]

[0121] In the above general formula (1), X is an n-valent organic group having 2 to 50 carbon atoms or an oxygen atom, n is an integer of 1 to 10, and R1 is independently any one of the following general formula (2).

[0122] [Chemistry 20]

[0123]

[0124] In the above general formula (2), the dashed line indicates a bonding site to X, Q1 is a monovalent organic group containing a carbonyl group, and at least a part of the group is a group represented by the following general formula (3).

[0125] [Chemistry 21]

[0126]

[0127] In the above general formula (3), the dashed line indicates a bonding site, X1 indicates a single bond or a divalent organic group having 1 to 20 carbon atoms, and the organic group may have a substituent when it has an aromatic ring. R2 indicates a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ** indicates a bonding site.

[0128] Hereinafter, the embodiment of the present invention will be described, but the present invention is not limited thereto. In addition, the organic film-forming material of the present invention may be referred to as an organic film material or an organic film-forming composition.

[0129] [Organic film-forming compound]

[0130] The compound of the present invention is represented by the following general formula (1).

[0131] [Chemistry 22]

[0132]

[0133] In the above general formula (1), X is an n-valent organic group having 2 to 50 carbon atoms or an oxygen atom, n is an integer of 1 to 10, and R1 is independently any one of the following general formula (2).

[0134] [Chemistry 23]

[0135]

[0136] In the above general formula (2), the dashed line indicates a bonding site to X, Q1 is a monovalent organic group containing a carbonyl group, and at least a part of the group is a group represented by the following general formula (3).

[0137] [Chemistry 24]

[0138]

[0139] In the above general formula (3), the dashed line indicates a bonding site, X1 indicates a single bond or a divalent organic group having 1 to 20 carbon atoms, and the organic group may have a substituent when it has an aromatic ring. R2 indicates a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ** indicates a bonding site.

[0140] The compound represented by the general formula (1) can be specifically exemplified by the following (the part not including R1 is X). R1 ​​in the following formula is the same as that described above. m1 and m2 each independently represent an integer from 0 to 4, and m1+m2 is greater than 1 and less than 8. n9 represents an integer from 0 to 3. Here, R1 each independently represents any one of the general formula (2), or all of them may be the same.

[0141] [Chemistry 25]

[0142]

[0143] [Chemistry 26]

[0144]

[0145] [Chemistry 27]

[0146]

[0147] [Chemistry 28]

[0148]

[0149] [Chemistry 29]

[0150]

[0151] In addition, specific examples of X1 in the general formula (3) include the following.

[0152] [Chemistry 30]

[0153]

[0154] Dashed lines indicate bonding sites.

[0155] In this case, the compound of the general formula (1) is preferably a compound represented by the following general formula (4), (6), (7), (8), (9), (10), (11), (12), (13) or (14).

[0156] [Chemistry 31]

[0157]

[0158] In the above general formula (4), n7 and n8 each independently represent 0 or 1, W is a single bond or any of the structures shown in the following (5). R1 ​​is the same as above, m1 and m2 each independently represent an integer from 0 to 4, and m1+m2 is 1 or more and 8 or less.

[0159] [Chemistry 32]

[0160]

[0161] In the above general formula (5), n9 represents an integer from 0 to 3, R a ~R f are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, or a phenyl group, and R a With R b They can also be bonded to form a ring.

[0162] [Chemistry 33]

[0163]

[0164] In the above general formula (6), R1 is the same as above, R g represents a hydrogen atom, a methyl group, or a phenyl group.

[0165] [Chemistry 34]

[0166]

[0167] In the above general formulae (7) to (11), R1 is the same as above, and R h , R i , R j , Rk , R l , R m , R n Each of them represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group or a phenyl group which may have a substituent on the aromatic ring. Y represents R1 or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in the general formula (11) are R1.

[0168] [Chemistry 35]

[0169]

[0170] In the above general formulae (12) to (14), R1 is the same as above. o represents a linear, branched or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms, and R in the general formula (13) is p It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0171] The compound represented by the general formula (4) is particularly preferably the following one from the viewpoint of heat resistance and etching resistance.

[0172] [Chemistry 36]

[0173]

[0174] The compound represented by the general formula (6) is particularly preferably the following one from the viewpoint of heat resistance, etching resistance and curability.

[0175] [Chemistry 37]

[0176]

[0177] In the present invention, among the compounds represented by the general formulae (7) to (11), the following are particularly preferred from the viewpoints of etching resistance, optical properties, and adhesion.

[0178] [Chemistry 38]

[0179]

[0180] In the present invention, among the compounds represented by the general formulae (12) to (14), the following are particularly preferred from the viewpoint of high filling characteristics, planarization, and adhesion.

[0181] [Chemistry 39]

[0182]

[0183] Furthermore, Q1 in the above general formula (2) may be composed of one or more of the above general formula (3) and one or more of the following general formulas (15) and (16).

[0184] [Chemistry 40]

[0185]

[0186] In the above general formula (15), R q represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and R q The methylene group may also be substituted with an oxygen atom or a carbonyl group. s represents a hydrogen atom or a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, and R t represents a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, n12 and n13 represent integers of 0 to 7, and n12+n13 is in the range of 0 to 7.

[0187] Examples of the terminal group structure represented by the general formula (15) are as follows. In the following formula, n14 represents an integer of 0 to 30, and n15 represents an integer of 0 to 20.

[0188] [Chemistry 41]

[0189]

[0190] [Chemistry 42]

[0191]

[0192] [Chemistry 43]

[0193]

[0194] Examples of the terminal group structure represented by the general formula (16) are as follows. n16 in the following formula represents an integer of 0-9.

[0195] [Chemistry 44]

[0196]

[0197] If it is an organic film forming material containing these compounds, by combining the terminal group structure, many physical properties such as heat resistance and etching resistance, high-level filling / planarization characteristics, and substrate adhesion can be adjusted according to the required performance. In addition, the optical constants can also be controlled, so especially during the exposure of multi-layer ArF lithography, appropriate optical constants can be given and reflected light can be suppressed, and the resolution can be excellent.

[0198] Furthermore, by using an organic film forming material containing such a compound in a resist underlayer film material used in forming a multilayer resist film suitable for microfabrication in a manufacturing step of a semiconductor device, etc., a resist underlayer film material, a resist underlayer film forming method, and a pattern forming method for forming a resist underlayer film having both high filling / planarizing characteristics and adhesion to a substrate can be provided. Furthermore, the present invention can also provide a planarizing material for semiconductor device manufacturing having high filling / planarizing characteristics and adhesion to a substrate that can be applied to planarization in a semiconductor device manufacturing step other than a multilayer resist process.

[0199] [Method for producing compound]

[0200] The compound used in the organic film forming material of the present invention (compound for organic film material) can be produced by selecting the most suitable method according to the structure. Hereinafter, an example of a method for synthesizing the organic film material compound represented by the above general formula (1) will be described in detail. In addition, the method for producing the compound for organic film material is not limited to this.

[0201] For example, specifically, the following manufacturing method can be cited, including:

[0202] In the first step, a carboxylic acid compound represented by any one of the following general formulas (17) is obtained by an addition reaction of a carboxylic acid anhydride represented by (X1CO)2O with an alcohol or an amine.

[0203] [Chemistry 45]

[0204]

[0205] In the above general formula (17), X1 and R2 are the same as above;

[0206] In the second step, the compound for organic film material represented by the general formula (1) is obtained by an addition reaction of an epoxy compound represented by the following general formula (18) and a carboxylic acid compound (monocarboxylic acid) represented by the general formula (17).

[0207] [Chemistry 46]

[0208]

[0209] In the above general formula (18), X and n are the same as above, and R3 is any one of the following general formula (19).

[0210] [Chemistry 47]

[0211]

[0212] In the above general formula (19), the dashed line indicates the bonding site to X.

[0213] In the reaction of the carboxylic anhydride and the alcohol or amine in the first step, the feed amount of the alcohol or amine is preferably 0.5 to 1.5 mol, more preferably 0.7 to 1.3 mol, and even more preferably 0.8 to 1.2 mol, relative to 1 mol of the carboxylic anhydride.

[0214] In the first step, the raw materials may be mixed in a solvent or without a solvent, and the mixture may be cooled or heated. When a solvent is used in the reaction, the solvent specifically includes: alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 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; chlorine-based solvents such as dichloromethane, 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; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric acid triamide, and these can be used alone or in combination of two or more. These solvents can be used in an amount within a range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw materials.

[0215] These syntheses may also use a base catalyst as needed, and the base catalyst may include: inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium phosphate, etc.; organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, etc., and they may be used alone or in combination of two or more. The amount of the catalyst used is preferably 0.001 to 100% by weight relative to the reaction raw materials, and more preferably in the range of 0.005 to 50% by weight.

[0216] The reaction temperature is preferably -20°C to 200°C, more preferably 0°C to 150°C. When a solvent is used, the upper limit is preferably about the boiling point of the solvent. If the reaction temperature is above -20°C, there is no concern that the reaction will be slowed down, and if it is below 200°C, it is not easy to cause side reactions such as decomposition reactions of the product. The reaction time of the above reaction is preferably determined by monitoring the progress of the reaction by thin layer chromatography, liquid chromatography, gel filtration chromatography, etc. in order to improve the yield, and is usually about 0.5 to 200 hours. After the reaction is completed, a conventional aqueous work-up can be performed as needed to obtain the compound represented by formula (17). If necessary, the compound represented by formula (17) can also be purified by conventional methods such as crystallization, liquid separation, chromatography, adsorption treatment, etc. according to its properties. Depending on different situations, no additional treatment can be performed after the reaction and the second step can be continued.

[0217] The reaction method may be, for example, a method of feeding the raw materials, the reaction catalyst, and the solvent as required at once, or a method of dropping the raw materials or raw material solutions alone or in a mixed state in the presence of the reaction catalyst.

[0218] In the reaction of the epoxy compound and the carboxylic acid compound in the second step, the feed amount of the carboxylic acid is preferably 0.3 to 2.0 moles, more preferably 0.5 to 1.5 moles, and even more preferably 0.75 to 1.25 moles, when the molar amount of the epoxide in the epoxy compound is 1 mole. In this way, if the feed amount of the carboxylic acid is an appropriate amount relative to the epoxide unit, there is no concern that the unreacted epoxy group will remain and damage the storage stability of the organic film material, and the unreacted carboxylic acid can be prevented from remaining and becoming the cause of the escaped gas.

[0219] In addition, in the reaction between the epoxy compound and the carboxylic acid compound, in order to improve the required performance, such as optical constant (n / k), thermal fluidity, etching resistance, heat resistance, solvent solubility, and adhesion of the substrate, multiple carboxylic acid compounds can also be used simultaneously within the feed amount range of the above-mentioned carboxylic acid. As for the combination of such carboxylic acid compounds, the carboxylic acid compound represented by any one of the general formula (17) can be combined, and it is particularly preferable to simultaneously combine the carboxylic acid compound represented by the following general formula (20) (carboxylic acid compound (20)) and the carboxylic acid compound represented by the following general formula (21) (carboxylic acid compound (21)), or it is also possible to simultaneously combine multiple carboxylic acid compounds (20) and carboxylic acid compounds (21). As for the feed amount when the carboxylic acid compound (20) and the carboxylic acid compound (21) are used simultaneously, when the overall carboxylic acid feed amount is 100 mol%, it can be adjusted in the range of 1 to 99 mol%, respectively. Considering the viewpoints of etching resistance and heat resistance, it is preferable to use more than 20 mol% of the carboxylic acid compound (21), and it is more preferable to use more than 30 mol%.

[0220] [Chemistry 48]

[0221]

[0222] In the formula, R q Same as above.

[0223] [Chemistry 49]

[0224]

[0225] In the formula, R s , R t , n11, n12 and n13 are the same as above.

[0226] The above-mentioned compound can be generally obtained by reacting an epoxy compound with a carboxylic acid compound in the absence of a solvent or in a solvent in the presence of a reaction catalyst at room temperature or under cooling or heating as required. When a solvent is used in the reaction, the solvent used specifically includes: alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 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; chlorine-based solvents such as dichloromethane, 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; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric acid triamide, and these can be used alone or in combination of two or more. These solvents can be used in an amount within a range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw materials.

[0227] Specific examples of the reaction catalyst include benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, trimethylbenzyl hydroxide Quaternary ammonium salts such as ammonium, N-lauryl pyridinium chloride, N-lauryl 4-picoline chloride, N-lauryl picoline chloride, trimethylphenyl ammonium bromide, N-benzyl picoline chloride; quaternary phosphonium salts such as tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, tetraphenyl phosphonium chloride; tertiary amines such as tri[2-(2-methoxyethoxy)ethyl]amine, tri(3,6-dioxaheptyl)amine, tri(3,6-dioxaoctyl)amine, etc. The amount of the catalyst used is preferably 0.001 to 100% by weight, more preferably 0.005 to 50% by weight, relative to the reaction raw materials.

[0228] The reaction temperature is preferably -50°C to about the boiling point of the solvent, more preferably room temperature to 150°C. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0229] The reaction method includes: a method in which the epoxy compound, the carboxylic acid compound, and the catalyst are fed at once; a method in which the epoxy compound and the carboxylic acid compound are dispersed or dissolved, and the catalyst is added at once or diluted with a solvent and added dropwise; or a method in which the epoxy compound and the carboxylic acid compound are dispersed or dissolved, and the epoxy compound and the carboxylic acid compound are added at once or diluted with a solvent and added dropwise.

[0230] After the reaction in each step is completed, the product may be used directly as an organic film material, or may be diluted with an organic solvent and then separated and washed for recovery in order to remove unreacted raw materials, catalysts, etc. in the reaction system.

[0231] The organic solvent used at this time is not particularly limited if it is a soluble compound and can separate into two layers after mixing with water. 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 tert-butyl ether, and ethyl cyclopentyl methyl ether; chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used at this time can be what is generally called deionized water or ultrapure water. The number of washing times can be more than one. Even if washing is performed more than 10 times, the corresponding washing effect may not be obtained, so it is preferably about 1 to 5 times.

[0232] In order to remove unreacted carboxylic acid or acidic components in the reaction system during liquid separation and washing, washing with an alkaline aqueous solution can also be performed. Specific examples of the alkali include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0233] In addition, in order to remove metal impurities or alkaline components in the reaction system during liquid separation and cleaning, cleaning can also be carried out with an acidic aqueous solution. Specific examples of the acid 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, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0234] The above-mentioned liquid separation cleaning using alkaline aqueous solution and acidic aqueous solution may be performed alone or in combination. From the viewpoint of removing metal impurities, liquid separation cleaning is preferably performed in the order of alkaline aqueous solution and acidic aqueous solution.

[0235] After the above-mentioned liquid separation cleaning using alkaline aqueous solution and acidic aqueous solution, it is also possible to continue cleaning with neutral water. The cleaning frequency can be implemented more than once, preferably about 1 to 5 times. Neutral water can be used as the deionized water, ultrapure water, etc. mentioned above. If the cleaning frequency is more than once, it can be sufficient. If the frequency is less, sometimes the alkaline components and acidic components cannot be removed. Even if the cleaning is performed more than 10 times, the corresponding cleaning effect may not be obtained, so it is preferably about 1 to 5 times.

[0236] In addition, the reaction product after the liquid separation operation can be concentrated and dried or crystallized under reduced pressure or normal pressure, and recovered in the form of powder, but in order to improve the operability when preparing the organic film material, it can also be made into a solution state of appropriate concentration in advance. The concentration at this time is preferably 0.1 to 50% by weight, and more preferably 0.5 to 30% by weight. If it is such a concentration, the viscosity is not easy to increase, so it can prevent damage to the operability, and the amount of solvent will not be too much, so it is more economical.

[0237] The solvent in this case is not particularly limited as long as it is a solvent in which the compound can be dissolved. Specific examples include: ketones such as cyclohexanone and methyl-2-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; 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 mono-tert-butyl ether acetate, and these may be used alone or in combination of two or more.

[0238] As described above, the compound for an organic film material of the present invention can be easily produced and can be preferably used in the organic film-forming material of the present invention as described above.

[0239] [Organic film forming material]

[0240] The present invention provides an organic film-forming material comprising (A) the above-mentioned compound and (B) an organic solvent. In the organic film-forming material of the present invention, the above-mentioned (A) compound may be used alone or in combination of two or more.

[0241] The organic solvent (component (B)) used in the organic film forming material of the present invention is not particularly limited, but is preferably one that dissolves the aforementioned base polymer, acid generator, crosslinking agent, other additives, etc. Specifically, a solvent having a boiling point of less than 180° C., such as the solvents described in paragraphs (0091) to (0092) of Japanese Patent Publication No. 2007-199653, can be used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and a mixture of two or more thereof can be preferably used. In addition, the solvent can be the same as or different from the solvent used in the manufacture of the aforementioned component (A).

[0242] Such a composition can be applied by spin coating, and because it contains the organic film-forming compound of the present invention as described above, it becomes an organic film-forming material (organic film-forming composition) having good dry etching resistance and heat resistance and high filling / planarization properties.

[0243] In addition, in the organic film forming material of the present invention, as for the organic solvent, one or more high boiling point solvents having a boiling point of 180°C or higher (a mixture of a solvent having a boiling point of less than 180°C and a solvent having a boiling point of 180°C or higher) may be added to the above-mentioned solvent having a boiling point of less than 180°C. The high boiling point organic solvent is not particularly limited as long as it can dissolve the (A) compound, and is a hydrocarbon, alcohol, ketone, ester, ether, chlorine-based solvent, etc. Specific examples include: 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, diol Propylene glycol, triethylene glycol, tripropylene glycol, glycerol, 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 methyl 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 ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, n-nonyl acetate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., which can be used alone or in combination.

[0244] The boiling point of the high boiling point solvent can be appropriately selected in accordance with the temperature of the heat treatment of the organic film forming material. The boiling point of the added high boiling point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. If it is such a boiling point, there is no concern that the solvent will volatilize too quickly during baking (heat treatment) due to a too low boiling point, and sufficient thermal fluidity can be obtained. In addition, if it is such a boiling point, there will be no situation where the solvent remains in the film after baking due to the high boiling point and does not volatilize, so there is no concern that it will have an adverse effect on the film properties such as etching resistance.

[0245] When the high boiling point solvent is used, the amount of the high boiling point solvent blended is preferably 1 to 30 parts by mass relative to 100 parts by mass of the solvent having a boiling point of less than 180° C. If the blended amount is such, there is no concern that the blended amount is too small and sufficient thermal fluidity cannot be imparted during baking, or that the blended amount is too large and remains in the film, thereby deteriorating the film properties such as etching resistance.

[0246] Such an organic film composition can be an organic film forming composition having high filling / planarizing properties by adding a high boiling point solvent to the organic film forming compound to impart thermal fluidity.

[0247] The organic film-forming material of the present invention may contain other components as necessary in addition to the above-mentioned components (A) and (B).

[0248] [Compounds for blending, etc.]

[0249] The organic film forming material of the present invention may be further blended with other compounds or polymers. The blending compound or the blending polymer is mixed with the organic film forming material of the present invention to improve the film forming property of spin coating or the filling property of the substrate having a height difference.Examples of 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, and 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, gallol, 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')-spirobiindene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2' ,3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirobiindene-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- Novolac resins such as naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 3-hydroxynaphthalene-2-carboxylic acid methyl ester, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornene, 5-vinylnorbornene-2-ene, α-pinene, β-pinene, limonene, etc., polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricycloene, poly(meth)acrylate, and copolymers thereof.Furthermore, naphthol dicyclopentadiene copolymers described in Japanese Patent Application Laid-Open No. 2004-205685, bisphenol fluorene novolac resins described in Japanese Patent Application Laid-Open No. 2005-128509, acenaphthene copolymers described in Japanese Patent Application Laid-Open No. 2005-250434, fullerenes having a phenolic group described in Japanese Patent Application Laid-Open No. 2006-227391, bisphenol compounds and novolac resins thereof described in Japanese Patent Application Laid-Open No. 2006-293298, novolac resins of adamantane ol compounds described in Japanese Patent Application Laid-Open No. 2006-285095, bisnaphthol compounds and novolac resins thereof described in Japanese Patent Application Laid-Open No. 2010-122656, fullerene resin compounds described in Japanese Patent Application Laid-Open No. 2008-158002, and the like may be blended. The blending amount of the above-mentioned compound for blending or the polymer for blending is preferably 0 to 1,000 parts by mass, more preferably 0 to 500 parts by mass, based on 100 parts by mass of the organic film material of the present invention.

[0250] [Acid generator]

[0251] In the organic film material of the present invention, an acid generator may be added to further promote the curing reaction. The acid generator may generate acid by thermal decomposition or by light exposure, and either may be added. Specifically, the materials described in paragraphs (0061) to (0085) of Japanese Patent Publication No. 2007-199653 may be added, but the present invention is not limited thereto.

[0252] The acid generator may be used alone or in combination of two or more. The amount of the acid generator added is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts of the compound.

[0253] [Surfactant]

[0254] The organic film material of the present invention may contain a surfactant in order to improve coating properties during spin coating. For example, the surfactant described in (0142) to (0147) of JP-A-2009-269953 may be used.

[0255] [Crosslinking agent]

[0256] In addition, in the composition for forming an organic film of the present invention, a crosslinking agent may be added in order to improve the hardening property and further suppress the mutual mixing with the upper film of the resist. The crosslinking agent is not particularly limited, and crosslinking agents of various known systems can be widely used. Examples thereof include: melamine-based crosslinking agents, hydroxymethyl or methoxymethyl-type crosslinking agents of polynuclear phenols, glycoluril-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.

[0257] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy and / or hydroxyl-substituted melamines thereof, and partial self-condensates thereof.

[0258] Examples of the methoxymethyl crosslinking agent of polynuclear phenols include tetramethylolates and tetramethoxymethylates of bisphenols such as bisphenol A and bisphenol F, hexamethoxymethylates of trisphenols such as trisphenolmethane, trisphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and partial condensates thereof.

[0259] Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0260] Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0261] Specific examples of the urea crosslinking agent include dimethoxymethylated dimethoxyethylene urea, alkoxy and / or hydroxyl substitution products thereof, and partial self-condensates thereof.

[0262] Specific examples of the β-hydroxyalkylamide crosslinking agent include N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide.

[0263] Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0264] Specific examples of the aziridine crosslinking agent include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0265] Specific examples of the oxazoline crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-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-tert-butyl-2-oxazoline), 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymers.

[0266] Specific examples of the epoxy crosslinking agent 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.

[0267] [Plasticizer]

[0268] In addition, in order to further improve the high degree of landfill / planarization characteristics, a plasticizer may be added to the organic film material of the present invention. The plasticizer is not particularly limited, and various known plasticizers can be widely used. Examples thereof include low molecular weight compounds such as phthalates, adipic acid esters, phosphates, trimellitic acid esters, and citrates; and polymers such as polyethers, polyesters, and polyacetal polymers described in Japanese Patent Application Laid-Open No. 2013-253227.

[0269] [Other additives]

[0270] In addition, in the composition for forming an organic film of the present invention, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a pyrolyzable 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 is preferably used as an additive for imparting filling / planarization properties similar to a plasticizer. The pyrolyzable polymer is preferably one containing a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP1a).

[0271] [Chemistry 50]

[0272]

[0273] In the formula, R4 is a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms which may be substituted. Y1 is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.

[0274] [Chemistry 51]

[0275]

[0276] In the formula, R 4a Y is an alkyl group having 1 to 4 carbon atoms. a It is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms and may have an ether bond. n represents the average number of repeating units and is 3 to 500.

[0277] The organic film-forming material of the present invention may be used alone or in combination of two or more thereof. The organic film-forming material can be used particularly as a resist underlayer film material or a planarizing material for semiconductor device manufacturing.

[0278] In addition, the organic film forming material of the present invention is extremely effective as a resist underlayer film material for multi-layer resist processes such as a two-layer resist process, a three-layer resist process using an intermediate film containing silicon atoms, and a four-layer resist process using an inorganic hard mask intermediate film containing silicon atoms and an organic anti-reflective film.

[0279] [Substrates for semiconductor device manufacturing]

[0280] The present invention also provides a substrate for manufacturing a semiconductor device, on which an organic film formed by curing the above-mentioned organic film forming material is formed.

[0281] If the resist underlayer film formed by curing the organic film forming material of the present invention has both high filling / planarization characteristics and substrate adhesion, it becomes a resist underlayer film without micro voids caused by poor filling, without unevenness on the resist underlayer film surface caused by insufficient planarity, and without film peeling when an inorganic hard mask intermediate film is formed on the resist underlayer film. The substrate for semiconductor device manufacturing formed by planarizing the resist underlayer film in this way has a wider process latitude during patterning, and semiconductor devices can be manufactured with good yield.

[0282] [Organic film formation method]

[0283] The present invention provides a method for forming an organic film that functions as a resist underlayer film of a multilayer resist film used for photolithography or a planarizing film for semiconductor manufacturing, using the above-mentioned organic film material.

[0284] The organic film forming method of the present invention applies the above-mentioned organic film material to the processed substrate by spin coating or the like. By using the spin coating method or the like, good filling characteristics can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to prevent mixing with the resist upper film and the resist intermediate film and to promote the cross-linking reaction. The baking is preferably performed at a temperature of 100°C to 600°C for 10 to 600 seconds, and is more preferably performed at a temperature of 200°C to 500°C for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer process of photolithography is preferably below 600°C, and is more preferably below 500°C.

[0285] Furthermore, the organic film forming method of the present invention can also form an organic film by coating the organic film material of the present invention on the processed substrate by spin coating or the like in the same manner as described above, and calcining (heat treating) the organic film material in an environment with an oxygen concentration of 0.1% to 21% to harden it.

[0286] By calcining the organic film material of the present invention in such an oxygen atmosphere, a sufficiently hardened film can be obtained.

[0287] The heat treatment environment may be air or filled with an inert gas such as N2, Ar, or He. The heat treatment temperature and the like may be the same as those described above.

[0288] The substrate to be processed may have a structure with a height of 30 nm or more or a height difference.

[0289] The organic film forming method of the present invention can obtain a flat cured film regardless of the unevenness of the processed substrate by utilizing its high degree of filling / flattening characteristics. Therefore, it is particularly effective when forming a flat cured film on a processed substrate having a structure with a height of 30 nm or more or a height difference.

[0290] [Pattern Formation Method]

[0291] The present invention provides a pattern forming method for a three-layer resist process using such an organic film forming material, which is a method for forming a pattern on a workpiece, wherein at least on the workpiece, a resist lower layer film is formed using the organic film forming material of the present invention, a resist middle layer film material containing silicon atoms is used on the resist lower layer film to form a resist middle layer film (resist middle layer film containing silicon atoms), and a resist upper layer film material composed of a photoresist composition is used on the resist middle layer film to form a resist upper layer film and form a multilayer resist film, After the pattern circuit area of ​​the aforementioned resist upper film is exposed, it is developed with a developer to form a resist pattern (circuit pattern) on the aforementioned resist upper film, the aforementioned resist upper film formed with the resist pattern is used as an etching mask to etch the aforementioned resist intermediate film to transfer the pattern to the resist intermediate film, the aforementioned resist lower film is etched using the obtained resist intermediate film pattern as an etching mask to transfer the pattern to the resist lower film, and the aforementioned processed substrate is etched using the resist lower film pattern as an etching mask to form a pattern on the aforementioned processed substrate.

[0292] The resist intermediate layer film containing silicon atoms in the above-mentioned three-layer resist process is resistant to etching using oxygen or hydrogen. Therefore, in the above-mentioned three-layer resist process, it is advisable to use an etching gas mainly composed of oxygen or hydrogen to implement the etching of the resist lower layer film using the resist intermediate layer film as a mask.

[0293] The resist intermediate layer film containing silicon atoms in the above three-layer resist process can also be preferably used as an intermediate layer film based on polysilsesquioxane. By making the resist intermediate layer film have an anti-reflection effect, reflection can be suppressed. In particular, for 193nm exposure, if a material containing a large amount of aromatic groups and having high substrate etching resistance is used as the resist lower layer film, the k value becomes higher and the substrate reflection becomes higher. By suppressing the reflection with the resist intermediate layer film, the substrate reflection can be controlled to less than 0.5%. For the resist intermediate layer film with anti-reflection effect, it is preferable to use anthracene pendant for 248nm and 157nm exposure, and polysilsesquioxane pendant with a light-absorbing group having a phenyl group or a silicon-silicon bond for 193nm exposure, and cross-linked with acid or heat.

[0294] In this case, the formation of the resist interlayer film containing silicon by the spin coating method is simpler than the CVD method and has a cost advantage.

[0295] Furthermore, a four-layer resist process using an organic anti-reflection film is also ideal. In this case, at least the organic film forming material of the present invention can be used on the workpiece to form a resist lower layer film, a resist middle layer film material containing silicon atoms can be used on the resist lower layer film to form a resist middle layer film (resist middle layer film containing silicon atoms), a BARC film (organic anti-reflection film) is formed on the resist middle layer film, and a resist upper layer film material of a photoresist composition is used on the BARC film to form a resist upper layer film and form a multilayer resist film. After the pattern circuit area of ​​the resist upper layer film is exposed, it is developed with a developer to form a resist pattern (circuit pattern) on the resist upper layer film, the BARC film and the resist intermediate layer film are etched using the resist pattern as an etching mask to transfer the pattern to the resist intermediate layer film, the resist intermediate layer film pattern is used as an etching mask to etch the resist lower layer film to transfer the pattern to the resist lower layer film, and the resist lower layer film pattern is then used as an etching mask to etch the processed object to form the pattern on the processed object.

[0296] Furthermore, an inorganic hard mask intermediate film may be formed as an intermediate film. In this case, at least the organic film forming material of the present invention may be used on the workpiece to form a resist lower film, an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film may be formed on the resist lower film, a resist upper film material composed of a photoresist composition may be used on the inorganic hard mask intermediate film to form a resist upper film, and a pattern circuit area of ​​the resist upper film may be exposed. , developing with a developer to form a resist pattern (circuit pattern) on the aforementioned resist upper film, using the resist pattern as an etching mask to etch the aforementioned inorganic hard mask intermediate film to transfer the pattern to the inorganic hard mask intermediate film, using the inorganic hard mask intermediate film pattern as an etching mask to etch the aforementioned resist lower film to transfer the pattern to the resist lower film, and then using the resist lower film pattern as an etching mask to etch the aforementioned workpiece to form the pattern on the aforementioned workpiece.

[0297] As described above, when an inorganic hard mask intermediate film is formed on the resist lower film, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film (SiON film) can be formed by using a CVD method, an ALD method, or the like. The method for forming a silicon nitride film is described in, for example, Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, and more preferably 10 to 100 nm. In addition, as for the inorganic hard mask intermediate film, it is best to use a SiON film that has a high effect as an anti-reflection film. Since the substrate temperature when forming the SiON film reaches 300 to 500°C, the lower film needs to withstand a temperature of 300 to 500°C. The organic film forming material used in the present invention has high heat resistance and can withstand high temperatures of 300°C to 500°C, so it can be a combination of an inorganic hard mask intermediate film formed by CVD or ALD and a resist underlayer film formed by spin coating.

[0298] Furthermore, the formation of an inorganic hard mask intermediate film is also ideal for a four-layer resist process using an organic anti-reflection film. In this case, at least the organic film forming material of the present invention can be used on the workpiece to form a resist lower layer film, an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the resist lower layer film, a BARC film (organic anti-reflection film) is formed on the inorganic hard mask intermediate film, and a resist upper layer film material of a photoresist composition is used on the BARC film to form a resist upper layer film and form a multilayer resist film. After the pattern circuit area of ​​the resist upper film is exposed, it is developed with a developer to form a resist pattern (circuit pattern) on the resist upper film, and the BARC film and the inorganic hard mask intermediate film are etched using the resist pattern as an etching mask to transfer the pattern to the inorganic hard mask intermediate film, and the inorganic hard mask intermediate film pattern is used as an etching mask to etch the resist lower film to transfer the pattern to the resist lower film, and then the resist lower film pattern is used as an etching mask to etch the aforementioned workpiece to form a pattern on the aforementioned workpiece.

[0299] As described above, a photoresist film can be directly formed on the inorganic hard mask intermediate film in the form of a resist upper film, or a BARC film (organic anti-reflective film) can be formed on the inorganic hard mask intermediate film by spin coating, and then a photoresist film can be formed thereon. In particular, when a SiON film is used as an inorganic hard mask intermediate film, the two-layer anti-reflective film of the SiON film and the BARC film can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another benefit of forming a BARC film is that it has the effect of reducing the tailing of the photoresist pattern above the SiON film.

[0300] The resist upper film in the aforementioned three-layer or four-layer resist process can be either positive or negative, and can usually be the same as the photoresist composition used. After spin coating the photoresist composition, pre-baking will be carried out, preferably in the range of 60 to 180° C. and 10 to 300 seconds. Thereafter, exposure is carried out according to the usual method, and then PEB (post-exposure baking) and development are carried out to obtain a resist pattern. In addition, the thickness of the resist upper film is not particularly limited, and is preferably 30 to 500 nm, and 50 to 400 nm is particularly preferred.

[0301] A circuit pattern is formed on the resist upper film (resist upper film pattern). When forming the circuit pattern, it is preferable to use optical lithography with a wavelength of 10 nm to 300 nm, direct drawing using an electron beam, nanoimprinting, or a combination thereof to form the circuit pattern.

[0302] In addition, the exposure light may include high-energy rays with a wavelength of less than 300nm, specifically, far ultraviolet rays, KrF excimer laser (248nm), ArF excimer laser (193nm), F2 laser (157nm), Kr laser (146nm), Ar laser (126nm), 3 to 20nm soft X-rays (EUV), electron beams (EB), ion beams, X-rays, etc.

[0303] Furthermore, when forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0304] Then, etching is performed using the obtained resist upper film pattern as an etching mask. The etching of the resist intermediate film and the inorganic hard mask intermediate film in the three-layer resist process is performed using a fluorine-based gas using the resist upper film pattern as an etching mask. In this way, the resist intermediate film pattern and the inorganic hard mask intermediate film pattern are formed.

[0305] Then, the resist underlayer film is etched using the obtained resist intermediate layer film pattern and inorganic hard mask intermediate layer film pattern as etching masks.

[0306] The subsequent etching of the processed substrate can also be carried out using conventional methods. For example, if the processed substrate is a SiO2, SiN, or silicon dioxide-based low dielectric constant insulating film, etching is mainly carried out using a fluorine-based gas. If it is p-Si, or Al, or W, etching is mainly carried out using a chlorine-based or bromine-based gas. When etching is performed using a fluorine-based gas during substrate processing, the intermediate film pattern containing silicon atoms in the three-layer resist process will be stripped off at the same time as the substrate processing. When etching the substrate with a chlorine-based or bromine-based gas, the stripping of the intermediate film pattern containing silicon atoms requires additional dry etching stripping using a fluorine-based gas after substrate processing.

[0307] Furthermore, the object to be processed may be a semiconductor device substrate, or a semiconductor device substrate on which 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 formed.

[0308] Furthermore, the aforementioned processed object may be metal silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or an alloy thereof.

[0309] The resist underlayer film obtained by using the organic film forming material of the present invention has a characteristic of being excellent in etching resistance when etching these objects to be processed.

[0310] In addition, there is no particular limitation on the object to be processed. The semiconductor device substrate may be a substrate of Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or a substrate on which a processed layer is formed. The processed layer may be various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and barrier films thereof, and may generally be formed to a thickness of 50 to 10,000 nm, and particularly to a thickness of 100 to 5,000 nm. In addition, when forming the processed layer, the object to be processed and the processed layer may be made of different materials.

[0311] For an example of a 3-layer resist process, use Figure 1 The specific representation is as follows.

[0312] In the case of a 3-layer resist process, Figure 1 As shown in (A), after forming a resist lower layer film 3 using the organic film forming material of the present invention on the processed layer 2 stacked on the processed substrate 1, a resist intermediate film 4 containing silicon atoms is formed, and a resist upper layer film 5 is formed thereon.

[0313] Then, if Figure 1 As shown in (B), the used portion (exposed portion 6) of the resist upper film 5 is exposed, and PEB and development are performed to form a resist upper film pattern 5a ( Figure 1 (C)). The obtained resist upper film pattern 5a is used as an etching mask, and the resist intermediate layer film 4 containing silicon atoms is etched using CF-based gas to form a resist intermediate layer film pattern 4a containing silicon atoms ( Figure 1 After removing the resist upper film pattern 5a, the obtained resist intermediate film pattern 4a containing silicon atoms is used as an etching mask to perform oxygen plasma etching on the resist lower film 3 to form a resist lower film pattern 3a ( Figure 1 After removing the resist intermediate film pattern 4a containing silicon atoms, the resist lower film pattern 3a is used as an etching mask to etch the processed layer 2 to form a pattern 2a ( Figure 1 (F)).

[0314] When an inorganic hard mask interlayer film is used, the resist interlayer film 4 containing silicon atoms is the inorganic hard mask interlayer film, and when a BARC film is applied, the BARC film is provided between the resist interlayer film 4 containing silicon atoms and the resist upper film 5. The etching of the BARC film may be performed continuously before the etching of the resist interlayer film 4 containing silicon atoms, or the etching of the resist interlayer film 4 containing silicon atoms may be performed after only the etching of the BARC film is performed, and then the etching device is changed or the like is used to perform the etching.

[0315] As described above, according to the pattern forming method of the present invention, a fine pattern can be formed with high precision on a substrate to be processed in a multilayer resist process.

[0316] [Example]

[0317] The present invention will be described in more detail below with reference to synthesis examples, comparative synthesis examples, embodiments, and comparative examples, but the present invention is not limited thereto. The molecular weight was specifically measured by the following method.

[0318] [Molecular weight determination]

[0319] The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase, and the dispersion degree (Mw / Mn) was determined.

[0320] [Synthesis Example: Synthesis of Compounds for Organic Film Materials]

[0321] The following epoxy compounds (compound group B: (B1) to (B14)) and carboxylic acid compounds (compound group C: (C1) to (C8)) are used to synthesize the polymers (A1) to (A28) for organic film materials.

[0322] Compound Group B:

[0323] [Chemistry 52]

[0324]

[0325] The following reagents were used as they were purchased.

[0326] (B1) EXA-850CRP (manufactured by DIC Corporation) Epoxy equivalent: 172

[0327] (B2) HP-4700 (manufactured by DIC Corporation) Epoxy equivalent: 165

[0328] (B3) HP-4770 (manufactured by DIC Corporation) Epoxy equivalent: 205

[0329] (B5) 1032H60 (Mitsubishi Chemical Co., Ltd.) Epoxy equivalent: 167

[0330] (B10) DAG-G (manufactured by Shikoku Chemical Industry Co., Ltd.) Epoxy equivalent: 168

[0331] (B11) TG-G (manufactured by Shikoku Chemical Industry Co., Ltd.) Epoxy equivalent: 92

[0332] (B13) EPOLIGHT MF (manufactured by Kyoei Chemical Industry Co., Ltd.) Epoxy equivalent: 140

[0333] (B14) PETG (Showa Denko Co., Ltd.) Epoxy equivalent: 90

[0334] Compound Group C:

[0335] [Chemistry 53]

[0336]

[0337] [Synthesis of Carboxylic Acid Compound (C1)]

[0338] Slowly drop 6.16 g of propargyl alcohol into a mixture of 10.0 g of succinic anhydride and 50 g of N,N-dimethylformamide. After stirring at room temperature for 30 minutes under a nitrogen atmosphere, raise the internal temperature to 40°C and stir for 24 hours. After cooling, add 50 mL of a 20% aqueous hydrochloric acid solution to stop the reaction. Add 100 g of ethyl acetate, wash three times with 100 g of pure water, and then reduce the pressure to dry the organic layer. After adding 100 g of toluene to the residue to make a uniform solution, crystallize with 200 g of hexane. Separate the precipitated crystals by filtration, wash twice with 100 g of hexane and recover them. By vacuum drying the recovered crystals at 70°C, a carboxylic acid compound (C1) is obtained with a yield of 32%.

[0339] [Synthesis of Carboxylic Acid Compound (C2)]

[0340] The carboxylic acid compound (C2) is obtained under the same reaction conditions as the carboxylic acid compound (C1) except for the carboxylic anhydride used.

[0341] [Synthesis of Carboxylic Acid Compound (C3)]

[0342] Slowly drop a solution prepared by dissolving 12.06 g of 3-ethynylaniline in 10 g of N,N-dimethylformamide into a mixture of 10.0 g of succinic anhydride and 40 g of N,N-dimethylformamide, and stir at room temperature for 24 hours under a nitrogen atmosphere. After cooling, add 100 g of ethyl acetate, wash three times with 100 g of pure water, and then dry the organic layer under reduced pressure. Add 100 g of toluene to the residue to make a uniform solution, and then crystallize it in an ice bath. Separate the precipitated crystals by filtration, wash twice with 100 g of toluene, and recover them. By vacuum drying the recovered crystals at 70°C, a carboxylic acid compound (C3) is obtained with a yield of 47%.

[0343] [Synthesis of Carboxylic Acid Compounds (C4) to (C8)]

[0344] Carboxylic acid compounds (C4) to (C8) are obtained under the same reaction conditions as those for carboxylic acid compound (C3) except for the carboxylic acid anhydride and amine compound used.

[0345] [Synthesis Example 1] Synthesis of Compound (A1)

[0346] [Chemistry 54]

[0347]

[0348] 10.0 g of epoxy compound (B1), 9.08 g of carboxylic acid compound (C1), and 100 g of 2-methoxy-1-propanol were prepared into a uniform solution at an internal temperature of 100°C under a nitrogen atmosphere, and then 0.69 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of 2% NaHCO3 aqueous solution and 100 g of 3% nitric acid aqueous solution, and then washed 5 times with 100 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (A1). When the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, Mw=1030 and Mw / Mn=1.04.

[0349] [Synthesis Examples 2 to 28] Synthesis of Compounds (A2) to (A28)

[0350] Compounds (A2) to (A28) shown in Tables 1 to 4 were obtained as products under the same reaction conditions as in Synthesis Example 1 except that the epoxy compounds and carboxylic acid compounds shown in Tables 1 to 4 were used. The Mw (weight average molecular weight) and the dispersity (Mw / Mn) of these compounds were determined and are shown in Table 5.

[0351] [Table 1]

[0352]

[0353] [Table 2]

[0354]

[0355]

[0356] [Table 3]

[0357]

[0358]

[0359] [Table 4]

[0360]

[0361]

[0362] [Table 5]

[0363]

[0364]

[0365] [Comparative Synthesis Example 1] Synthesis of Compound (R1)

[0366] 20.0 g of epoxy compound (B2), 17.7 g of 4-ethynylbenzoic acid, and 200 g of 2-methoxy-1-propanol were prepared into a uniform solution at an internal temperature of 100°C under a nitrogen atmosphere, and then 1.00 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of 2% NaHCO3 aqueous solution and 100 g of 3% nitric acid aqueous solution, and then washed 5 times with 100 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (R1). When the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, Mw=1740 and Mw / Mn=1.33.

[0367] [Chemistry 55]

[0368]

[0369] [Comparative Synthesis Example 2] Synthesis of Compound (R2)

[0370] 20.0 g of epoxy compound (B2), 23.3 g of 4-butoxybenzoic acid, and 200 g of 2-methoxy-1-propanol were prepared into a uniform solution at an internal temperature of 100°C under a nitrogen atmosphere, and then 1.00 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of 2% NaHCO3 aqueous solution and 100 g of 3% nitric acid aqueous solution, and then washed 5 times with 100 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (R2). When the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, Mw=1930 and Mw / Mn=1.32.

[0371] [Chemistry 56]

[0372]

[0373] [Comparative Synthesis Example 3] Synthesis of Compound (R3)

[0374] 20.0 g of epoxy compound (B2), 16.7 g of 4-hydroxybenzoic acid, and 200 g of 2-methoxy-1-propanol were prepared into a uniform solution at an internal temperature of 100°C under a nitrogen atmosphere, and then 1.00 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of 2% NaHCO3 aqueous solution and 100 g of 3% nitric acid aqueous solution, and then washed 5 times with 100 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (R3). When the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, Mw=1610 and Mw / Mn=1.35.

[0375] [Chemistry 57]

[0376]

[0377] [Comparative Synthesis Example 4] Synthesis of Compound (R4)

[0378] 17.4 g of 9,9-bis-(4-aminophenyl)fluorene, 16.5 g of 4-ethylbenzoyl chloride, 5.1 g of triethylamine and 150 g of N,N-dimethylacetamide were stirred at a liquid temperature of 0°C for 1 hour under a nitrogen atmosphere, and then the mixture was heated to room temperature and stirred for 3 hours. After the reaction was completed, 500 g of methyl isobutyl ketone was added, and the organic layer was washed 5 times with 200 g of pure water, and then the organic layer was dried under reduced pressure. 300 mL of THF was added to the residue, and the polymer was reprecipitated with 1,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain compound (R4). When the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, Mw=1,150 and Mw / Mn=1.03.

[0379] [Chemistry 58]

[0380]

[0381] [Comparative Synthesis Example 5] Synthesis of Compound (R5)

[0382] 10.0 g of epoxy compound (B9), 9.9 g of succinic anhydride, and 50 g of 2-methoxy-1-propanol were mixed under nitrogen atmosphere at an internal temperature of 100°C to form a uniform solution, and then 0.50 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 50 g of 2% NaHCO3 aqueous solution and 50 g of 3% nitric acid aqueous solution, and then washed 5 times with 50 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (R5). When the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, Mw=1320 and Mw / Mn=1.17.

[0383] [Chemistry 59]

[0384]

[0385] None of the above compounds (R1) to (R5) has a group represented by the general formula (3) of the present invention.

[0386] [Preparation of (UDL-1 to 30, Comparative UDL-1 to 5)]

[0387] The above compounds (A1) to (A28) and comparative compounds (R1) to (R5) were used, as well as (S1) 1,6-diacetoxyhexane: boiling point 260°C, (S2) tripropylene glycol monomethyl ether: boiling point 242°C as a high boiling point solvent, XL1 as a crosslinking agent, and AG1 as a thermal acid generator. Propylene glycol monomethyl ether acetate (PGMEA) containing 0.1% by mass of PF636 (manufactured by OMNOVA) as a surfactant was dissolved in the ratio shown in Table 6, and filtered with a 0.1 μm fluororesin filter to prepare organic film-forming compositions (UDL-1 to 30, comparative UDL-1 to 5).

[0388] In addition, PGME and CyHO were solvents.

[0389] The structural formulas of the crosslinking agent (XL1) and the acid generator (AG1) used in the comparative example UDL are shown below.

[0390] [Chemistry 60]

[0391]

[0392] [Table 6]

[0393]

[0394]

[0395]

[0396] [Evaluation of landfill characteristics (Examples 1-1 to 1-30, Comparative Examples 1-1 to 1-5)]

[0397] The organic film forming compositions (UDL-1 to 30, comparative UDL-1 to 5) were coated on SiO2 wafer substrates having a dense hole pattern (hole diameter 0.16 μm, hole depth 0.50 μm, center distance between two adjacent holes 0.32 μm), and calcined in the atmosphere using a hot plate under the conditions shown in Table 7, as shown in Table 7. Figure 2 The resist lower layer film 8 is formed as shown in (I). The substrate used is as follows Figure 2 (G) (top view) and Figure 2 The cross-sectional shape of each wafer substrate obtained by observing the cross-sectional shape of each wafer substrate was used to confirm whether the holes were filled with organic film without voids. The results are shown in Table 7. When an organic film material with poor filling characteristics was used, voids were generated inside the holes in this evaluation. When an organic film material with good filling characteristics was used, voids were generated inside the holes in this evaluation. Figure 2 As shown in (I), the pores are filled with an organic film without any gaps inside.

[0398] [Table 7]

[0399]

[0400]

[0401] As shown in Table 7, Examples 1-1 to 1-30 using the organic film-forming composition (UDL-1 to 30) of the present invention can fill the hole pattern without generating voids, and it can be confirmed that they have a high degree of filling property. In addition, the structure having two carbonyl groups has a high degree of adhesion to the substrate, so no peeling is observed. On the other hand, Comparative Examples 1-1 and 1-2 have insufficient adhesion, and peeling on the pattern substrate is observed. In addition, in Comparative Examples 1-3, 1-4, and 1-5, peeling due to insufficient adhesion is not observed, but the generation of voids due to insufficient filling properties is observed.

[0402] [Evaluation of Flattening Characteristics (Examples 2-1 to 2-30, Comparative Examples 2-1 to 2-5)]

[0403] The organic film-forming compositions (UDL-1 to 30, comparative UDL-1 to 5) were applied to the surfaces having the giant isolated groove pattern ( Figure 3 The substrate 9 (SiO2 wafer substrate) having a groove width of 10 μm and a groove depth of 0.10 μm was calcined in the atmosphere using a heating plate under the conditions shown in Table 8, and then the height difference ( Figure 3 The results are shown in Table 8. In this evaluation, the smaller the height difference, the better the planarization characteristics. In addition, in this evaluation, the groove pattern with a depth of 0.10μm is usually planarized using an organic film material with a film thickness of about 0.2μm, which becomes a strict evaluation condition in order to evaluate the quality of the planarization characteristics.

[0404] [Table 8]

[0405]

[0406]

[0407] As shown in Table 8, Examples 2-1 to 2-30 using the organic film-forming composition (UDL-1 to 30) of the present invention have a smaller height difference between the groove portion and the non-groove portion of the resist underlayer film than Comparative Examples 2-1 to 2-5 using the comparative organic film-forming composition (Comparative UDL-1 to 5), and are confirmed to have excellent planarization characteristics. In addition, by comparing Examples 2-29 to 2-30 using the compound (A9) and adding a high boiling point solvent with Example 2-9 not adding the compound (A9), it can be confirmed that the addition of the high boiling point solvent further improves the planarization. On the other hand, Comparative Examples 2-2, 2-3, and 2-5 requiring a crosslinking agent have large film shrinkage during baking, and thus it can be confirmed that the height difference between the groove portion and the non-groove portion of the resist underlayer film becomes larger.

[0408] [Adhesion Test (Examples 3-1 to 3-30, Comparative Examples 3-1 to 3-5)]

[0409] The above-mentioned organic film forming composition (UDL-1~30, comparative UDL-1~5) is coated on a SiO2 wafer substrate, and calcined in the atmosphere under the conditions shown in Table 9 using a hot plate to form an organic film with a thickness of 200nm. The wafer with the organic film is cut into 1×1cm squares, and an aluminum pin with epoxy adhesive is installed on the wafer cut using a special jig. Thereafter, the aluminum pin is bonded to the substrate by heating at 150°C for 1 hour using an oven. After cooling to room temperature, the initial adhesion is evaluated by resistance using a thin film adhesion strength measuring device (Sebastian Five-A).

[0410] Figure 4 An explanatory diagram showing a method for measuring adhesion is shown. Figure 4 11 represents a silicon wafer (substrate), 12 represents a hardened film, 13 represents an aluminum pin provided with an adhesive, 14 represents a support seat, 15 represents a clamping portion, and 16 represents a stretching direction. The adhesion force is the average value of 12 measurements, and the higher the value, the higher the adhesion of the organic film to the substrate. The adhesion is evaluated by comparing the obtained values. The results are shown in Table 9.

[0411] [Table 9]

[0412]

[0413]

[0414] As shown in Table 9, Examples 3-1 to 3-30 using the organic film-forming composition of the present invention (UDL-1 to 30) have better adhesion than Comparative Examples 3-1 to 3-5 using the comparative organic film-forming composition (Comparative UDL-1 to 5). It can be seen that Examples 3-1 to 3-30 using the organic film-forming composition of the present invention have about twice the adhesion compared to Comparative UDL-1 and 2 which peeled off during the evaluation of the embedding characteristics. In addition, Example 3-13 having both two carbonyl groups and an amide group has about 1.4 times the adhesion of Comparative Example 3-4 having only an amide group, indicating that a structure having two carbonyl groups and an amide group at the same time contributes to the development of high adhesion. In addition, Examples 3-21 to 3-23 having triple bond terminal groups have about 1.2 to 1.3 times greater adhesion than Comparative Example 3-5 not containing triple bond terminal groups, indicating that the reduction in film shrinkage due to triple bond terminal groups contributes to adhesion.

[0415] [Film shrinkage test (Examples 4-1 to 4-30, Comparative Examples 4-1 to 4-5)]

[0416] The UDL-1 to 30 and comparative UDL-1 to 5 prepared above were coated on a BareSi substrate, and baked at 100°C for 60 seconds in the air using a hot plate, and the film thickness was measured. Then, additional baking was performed in the air under the calcination conditions described in Table 10, and the film thickness was measured again. The film thickness ratio before and after the additional baking was calculated to evaluate the film shrinkage. That is, the film shrinkage (%) = 100 × [(film thickness before additional baking) - (film thickness after additional baking)] / (film thickness before additional baking), and the results are shown in Table 10.

[0417] [Table 10]

[0418]

[0419]

[0420] As shown in Table 10, Examples 4-1 to 4-28 using the organic film-forming composition (UDL-1 to 28) of the present invention have small shrinkage after additional baking. On the other hand, Comparative Examples 4-2, 4-3, and 4-5 using the organic film-forming composition for comparative examples (Comparative UDL-2, 3, and 5) have large shrinkage after additional baking due to the presence of a crosslinking agent, and the film thickness variation is larger than that of Examples 4-1 to 4-28. Moreover, Examples 4-29 and 4-30 using the organic film-forming composition (UDL-29 and 30) of the present invention have large shrinkage after additional baking compared to Example 4-9 using the same compound, but are less than half of those of Comparative Examples 4-2, 4-3, and 4-5. In addition, since Comparative Examples 4-1 and 4-4 using comparative organic film-forming compositions (Comparative UDL-1 and 4) contain terminal groups containing triple bonds, the shrinkage amount becomes small.

[0421] [Pattern etching test (Examples 5-1 to 5-30, Comparative Examples 5-1 to 5-5)]

[0422] The UDL-1 to 30 and comparative UDL-1 to 5 prepared above were applied to a SiO2 substrate having a groove pattern (groove width 10 μm, groove depth 0.10 μm) formed with a SiO2 film having a thickness of 200 nm treated with HMDS, and calcined under the conditions shown in Table 14 in the atmosphere so as to have a film thickness of 200 nm on a BareSi substrate, thereby forming a resist lower layer film. A resist intermediate layer material (SOG-1) containing silicon atoms was applied thereon, and baked at 220°C for 60 seconds to form a resist intermediate layer film having a film thickness of 35 nm, and a resist upper layer film material (SL resist for ArF) was applied thereon, and baked at 105°C for 60 seconds to form a resist upper layer film having a film thickness of 100 nm. An immersion protective film (TC-1) was applied to the resist upper layer film, and baked at 90°C for 60 seconds to form a protective film having a film thickness of 50 nm.

[0423] The resist upper film material (single-layer resist for ArF) is prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 11, and filtering with a 0.1 μm fluororesin filter.

[0424] [Table 11]

[0425]

[0426] The structural formulas of the polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) used are shown below.

[0427] [Chemistry 61]

[0428]

[0429] The wet protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent at the ratio shown in Table 12, and filtering the solution with a 0.1 μm fluororesin filter.

[0430] [Table 12]

[0431]

[0432] The structural formula of the polymer (PP1) used is shown below.

[0433] [Chemistry 62]

[0434]

[0435] The anti-etching intermediate layer material (SOG-1) containing silicon atoms is prepared by dissolving a polymer represented by an ArF silicon-containing intermediate film polymer (SiP1) and a cross-linking catalyst (CAT1) in an organic solvent containing 0.1% by mass of FC-4430 (produced by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 13, and filtering with a fluororesin filter having a pore size of 0.1 μm to obtain the anti-etching intermediate layer material (SOG-1) containing silicon atoms.

[0436] [Table 13]

[0437]

[0438] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and the crosslinking catalyst (CAT1) used are shown below.

[0439] [Chemistry 63]

[0440]

[0441] Then, the film was exposed using an ArF immersion exposure device (manufactured by Nikon Co., Ltd.; NSR-S610C, NA1.30, σ0.98 / 0.65, 35 degree dipole s-polarized illumination, 6% half-step phase shift mask), 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 a 55nm 1:1 positive line and space pattern.

[0442] Then, using an etching apparatus Telius manufactured by Tokyo Electron, the SOG-1 film was processed using the resist upper film pattern produced by dry etching as an etching mask, the SOG-1 film pattern was used as an etching mask to process the resist lower film, and the SiO2 film was processed using the resist lower film pattern as an etching mask. The etching conditions were as follows.

[0443] Transfer conditions of the resist upper layer film pattern to the SOG-1 film.

[0444]

[0445] Transfer conditions of the SOG-1 film pattern to the resist underlayer film.

[0446]

[0447] Transfer conditions of the resist underlayer film pattern to the SiO2 film.

[0448]

[0449] Table 14 shows the results of observing the pattern cross section using an electron microscope (S-4700) manufactured by Hitachi, Ltd.

[0450] [Table 14]

[0451]

[0452]

[0453] As shown in Table 14, the results of the organic film forming material of the present invention (Examples 5-1 to 5-30) confirm that in any case, the resist upper film pattern is finally well transferred to the substrate, and the organic film forming material of the present invention can be ideally used in micro-processing using a multilayer resist method. On the other hand, in Comparative Examples 5-1 to 5-5, as shown in the evaluation of the embedding characteristics and the adhesion test, the embedding characteristics and adhesion are insufficient, so pattern collapse occurs during pattern processing, and a pattern cannot be formed.

[0454] [Pattern Formation Test (Examples 6-1 to 6-30, Comparative Examples 6-1 to 6-5)]

[0455] The UDL-1 to 30 and comparison UDL-1 to 5 prepared as described above were coated on a SiO2 substrate having a groove pattern (groove width 10 μm, groove depth 0.10 μm) formed with a SiO2 film with a film thickness of 200 nm treated with HMDS, and calcined under the conditions shown in Table 15 in a nitrogen flow with an oxygen concentration managed below 0.2%. In addition, the coated film was formed by the same method as the pattern etching test, patterning and dry etching were performed, and the completed pattern shape was observed.

[0456] [Table 15]

[0457]

[0458]

[0459]

[0460] As shown in Table 15, the results of the organic film forming material of the present invention (Examples 6-1 to 6-30) confirm that in any case, the resist upper film pattern is finally well transferred to the substrate, and the organic film forming material of the present invention can be ideally used for micro-processing using the multilayer resist method even when the film is formed under an inert gas. On the other hand, in Comparative Examples 6-1 to 6-5, pattern collapse occurs as when the film is formed in the atmosphere, and a pattern cannot be formed.

[0461] From the above results, it can be seen that if it is the organic film forming material of the present invention, it is extremely effective as an organic film forming material used in the multilayer resist method because it has a high degree of filling / flattening characteristics and adhesion to the substrate. Furthermore, if it is the pattern forming method of the present invention using the organic film forming material, even if the processed body is a substrate with height differences, a fine pattern can be formed with high precision.

[0462] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and those having substantially the same configuration as the technical concept described in the claims of the present invention and having the same functions and effects are intended to be included in the technical scope of the present invention.

[0463] [Description of Reference Numerals]

[0464] 1: Processed substrate

[0465] 2: Processing layer

[0466] 2a: Pattern (pattern formed on the processed layer)

[0467] 3: Resist lower layer film

[0468] 3a: Resist lower film pattern

[0469] 4: Resist interlayer containing silicon atoms

[0470] 4a: Resist interlayer pattern containing silicon atoms

[0471] 5: Resist upper film

[0472] 5a: Resist upper film pattern

[0473] 6: Exposure part

[0474] 7: Base substrate with dense hole pattern

[0475] 8: Resist lower layer film

[0476] 9: Base substrate with giant isolated groove pattern

[0477] 10: Resist lower layer film

[0478] delta10: height difference of the resist underlayer film 10 between the groove part and the non-groove part

[0479] 11: Silicon Wafer

[0480] 12: Hardened film

[0481] 13: Aluminum pin with adhesive

[0482] 14: Support seat

[0483] 15: Clamping part

[0484] 16: stretching direction

Claims

1. An organic film-forming material comprising a compound represented by any one of the following general formulas (4), (6), (7), (8), (9), (10), (11), (12), (13), and (14) and an organic solvent; In the general formula (4), n7 and n8 each independently represent 0 or 1, W is a single bond or any one of the structures represented by the following general formula (5); m1 and m2 each independently represent an integer from 0 to 4, m1+m2 is greater than 1 and less than 8, and R1 is independently any one of the structures represented by the following general formula (2); In the general formula (2), the dashed line represents a bonding site, and Q1 is a group represented by the following general formula (3); In the general formula (3), the dashed line represents the bonding site, and X1 represents the following group; R2 represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group; ** represents a bonding site, In the general formula (5), n9 represents an integer from 0 to 3, R a ~R f are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or a phenyl group which may be substituted with fluorine, and R a With R b Optional bonds to form a ring; In the general formula (6), R1 is the same as above, R g represents a hydrogen atom, a methyl group, or a phenyl group; In the general formulae (7) to (11), R1 is the same as above, and R h , R i , R j , R k , R l , R m , R n R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, R1-R o -R1 (12) In the general formulae (12) to (14), R1 is the same as described above. o represents a linear, branched or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms, and R in the general formula (13) p It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

2. The organic film-forming material according to claim 1, wherein Q1 in the general formula (2) is composed of any one or more of the general formula (3) and any one or more of the following general formulas (15) and (16); In the general formula (15), R q represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and R q The methylene group of s represents a hydrogen atom or a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, and R t It represents a straight-chain hydrocarbon group having 1 to 10 carbon atoms, or a branched hydrocarbon group having 3 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms; n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, n12 and n13 represent integers of 0 to 7, and n12+n13 is greater than 0 and less than 7.

3. The organic film-forming material according to claim 1 or 2, wherein 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.

4. A method for forming an organic film, which is a method for forming an organic film that functions as an organic flat film suitable for a manufacturing step of a semiconductor device, characterized in that: The organic film forming material according to any one of claims 1 to 3 is spin-coated on a substrate to be processed, and the substrate to be processed is heat-treated at a temperature of 100° C. to 600° C. for 10 to 600 seconds to form a cured film.

5. A method for forming an organic film, which is a method for forming an organic film that functions as an organic flat film suitable for a manufacturing step of a semiconductor device, characterized in that: The organic film forming material according to any one of claims 1 to 3 is spin-coated on a substrate to be processed, and the substrate to be processed is heat-treated in an environment with an oxygen concentration of 0.1% to 21% to form a cured film.

6. The method for forming an organic film according to claim 4 or 5, wherein: The substrate to be processed uses a substrate to be processed having a structure with a height of 30 nm or more or a height difference.

7. A pattern forming method, characterized in that: An organic film forming material according to any one of claims 1 to 3 is used to form a resist lower layer film on a workpiece, a resist middle layer film material containing silicon atoms is used to form a resist middle layer film on the resist lower layer film, a resist upper layer film material of a photoresist composition is used to form a resist upper layer film on the resist middle layer film, a circuit pattern is formed on the resist upper layer film, the resist upper layer film with the circuit pattern formed is used as an etching mask and the pattern is transferred to the resist middle layer film by etching, the resist middle layer film with the circuit pattern transferred is used as an etching mask and the pattern is transferred to the resist lower layer film by etching, and the resist lower layer film with the circuit pattern transferred is used as an etching mask and the circuit pattern is formed on the workpiece by etching.

8. A method for forming a pattern, characterized in that: An organic film forming material according to any one of claims 1 to 3 is used to form a resist lower layer film on a workpiece, a resist middle layer film material containing silicon atoms is used to form a resist middle layer film on the resist lower layer film, a BARC film is formed on the resist middle layer film, a resist upper layer film material of a photoresist composition is used on the BARC film to form a resist upper layer film and a four-layer film structure is formed, a circuit pattern is formed on the resist upper layer film, the resist upper layer film with the circuit pattern formed is used as an etching mask and the pattern of the BARC film and the resist middle layer film is transferred by etching, the resist middle layer film with the circuit pattern transferred is used as an etching mask and the pattern of the resist lower layer film is transferred by etching, and the resist lower layer film with the circuit pattern transferred is used as an etching mask and the circuit pattern is formed on the workpiece by etching.

9. A pattern forming method, characterized in that: An organic film forming material according to any one of claims 1 to 3 is used to form a resist lower layer film on a workpiece, an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the resist lower layer film, a resist upper layer film material of a photoresist composition is used to form a resist upper layer film on the inorganic hard mask intermediate film, a circuit pattern is formed on the resist upper layer film, the resist upper layer film with the circuit pattern formed is used as an etching mask and the pattern is transferred to the inorganic hard mask intermediate film by etching, the inorganic hard mask intermediate film with the circuit pattern transferred is used as an etching mask and the pattern is transferred to the resist lower layer film by etching, and the resist lower layer film with the circuit pattern transferred is used as an etching mask and the circuit pattern is formed on the workpiece by etching.

10. A method for forming a pattern, characterized in that: An organic film forming material according to any one of claims 1 to 3 is used to form a resist lower layer film on a workpiece, an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the resist lower layer film, a BARC film is formed on the inorganic hard mask intermediate film, a resist upper layer film material of a photoresist composition is used on the BARC film to form a resist upper layer film and a four-layer film structure is formed, a circuit pattern is formed on the resist upper layer film, the resist upper layer film with the circuit pattern formed is used as an etching mask to transfer the pattern of the BARC film and the inorganic hard mask intermediate film by etching, the inorganic hard mask intermediate film with the circuit pattern transferred is used as an etching mask to transfer the pattern of the resist lower layer film by etching, and the resist lower layer film with the circuit pattern transferred is used as an etching mask to form the circuit pattern on the workpiece by etching.

11. The pattern forming method according to claim 9 or 10, wherein: The inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

12. The pattern forming method according to any one of claims 7 to 10, wherein: The patterning method of the resist upper layer film is patterning by optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

13. The pattern forming method according to any one of claims 7 to 10, wherein: The development method in the pattern forming method is development using an alkali or an organic solvent.

14. The pattern forming method according to any one of claims 7 to 10, wherein: The object to be processed is a semiconductor device substrate, or a semiconductor device substrate on which 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 formed.

15. The pattern forming method according to any one of claims 7 to 10, wherein: The workpiece is metal silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or an alloy thereof.

16. A compound characterized by being represented by any one of the following general formulas (4), (6), (7), (8), (9), (10), (11), (12), (13), and (14); In the general formula (4), n7 and n8 each independently represent 0 or 1, W is a single bond or any one of the structures represented by the following general formula (5); m1 and m2 each independently represent an integer from 0 to 4, m1+m2 is greater than 1 and less than 8, and R1 is independently any one of the structures represented by the following general formula (2); In the general formula (2), the dashed line represents a bonding site, and Q1 is a group represented by the following general formula (3); In the general formula (3), the dashed line represents the bonding site, and X1 represents the following group; R2 represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group; ** represents a bonding site, In the general formula (5), n9 represents an integer from 0 to 3, R a ~R f are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or a phenyl group which may be substituted with fluorine, and R a With R b Optional bonds to form a ring; In the general formula (6), R1 is the same as above, R g represents a hydrogen atom, a methyl group, or a phenyl group; In the general formulae (7) to (11), R1 is the same as above, and R h , R i , R j , R k , R l , R m , R n R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, R1-R o -R1 (12) In the general formulae (12) to (14), R1 is the same as described above. o represents a linear, branched or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms, and R in the general formula (13) p It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

17. The compound according to claim 16, wherein Q1 in the general formula (2) is composed of any one or more of the general formula (3) and any one or more of the following general formulas (15) and (16); In the general formula (15), R q represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and R q The methylene group of s represents a hydrogen atom or a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, and R t It represents a straight-chain hydrocarbon group having 1 to 10 carbon atoms, or a branched hydrocarbon group having 3 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms; n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, n12 and n13 represent integers of 0 to 7, and n12+n13 is greater than 0 and less than 7.

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