Composition for forming resist underlayer film and patterning process
The present invention provides a composition for forming a resist underlayer film, containing an organic solvent and either or both of a compound shown by the following general formula (1) and a condensate of the compound. There can be provided a composition for forming a resist underlayer film that is capable of forming an underlayer film, especially for use in a three-layer resist process, that can reduce reflectance, has high pattern-bend resistance, and prevents line fall and wiggling after etching of a high aspect line especially thinner than 60 nm, and a patterning process using the same.
1. A composition for forming a resist underlayer film, comprising an organic solvent and either or both of a compound shown by the following general formula (1) and a condensate of the compound,
wherein R 1 , R 3 , R 5 , and R 7 represent Z 1 , a diglycidylamino group, or a dipropargylamino group; R 2 , R 4 , R 6 , and R 8 represent Z 2 , a glycidyl group, a diglycidylamino group, or a dipropargylamino group; X represents a group shown by the following formula (1-1); n1 to n8 are each a number satisfying 0≦n1≦4, 0≦n2≦4, 0≦n3≦4, 0≦n4≦4, 0≦n5≦4, 0≦n6≦4, 0≦n7≦4, 0≦n8≦4, 0≦n1+n2≦4, 0≦n3+n4≦4, 0≦n5+n6≦4, 0≦n7+n8≦4, and 1≦n1+n2+n3+n4+n5+n6+n7+n8≦16, where Z 1 represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and Z 2 represents Z 1 , a hydrogen atom, or a hydroxyaryl group having 6 to 14 carbon atoms,
wherein * represents a binding site with R p where p represents 2, 4, 6, or 8.
2. The composition for forming a resist underlayer film according to claim 1 , wherein the condensate is obtained by a reaction of one or more compounds shown by the general formula (1) with one or more compounds selected from a compound shown by the following general formula (2-1), a compound shown by the following general formula (2-2), trioxane, paraformaldehyde, and fluorenone,
Y 1 —CHO (2-1)
wherein Y 1 represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms and optionally containing a substituent,
R 9 —CH 2 —Y 2 —CH 2 —R 9 (2-2)
wherein Y 2 represents an aromatic group having 6 or more carbon atoms and optionally containing a substituent; R 9 represents an alkoxy group or alkanoyloxy group having 1 to 6 carbon atoms, or a halogen atom.
3. The composition for forming a resist underlayer film according to claim 1 , wherein the condensate is obtained by a reaction with one or more compounds selected from compounds shown by the following general formulae (3-1), (3-2), (3-3), (3-4), and (3-5),
wherein R 11 and R 13 represent Z 1 , where Z 1 is as defined above, an amino group, a diglycidylamino group, or a dipropargylamino group; R 12 and R 14 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 11 to R 14 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 11 to R 14 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; two substituents selected from R 11 , R 12 , R 13 , and R 14 may be bonded intramolecularly to form a cyclic substituent; X 1 represents a group shown by the following formula (3-6); and n11 to n14 are each a number satisfying 0≦n11≦4, 0≦n12≦4, 0≦n13≦4, 0≦n14≦4, 0≦n11+n12≦4, 0≦n13+n14≦4, and 1≦n11+n12+n13+n14≦8,
wherein R 15 represents a fluorine atom, a chlorine atom, Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 16 represents Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 15 and R 16 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 15 and R 16 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; two substituents selected from R 15 and R 16 may be bonded intramolecularly to form a cyclic substituent; X 1 represents a group shown by the following formula (3-6); and n15 and n16 are each a number satisfying 0≦n15≦6, 0≦n16≦6, and 1≦n15+n16≦6,
wherein R 17 , R 19 , R 21 , and R 23 represent Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 18 and R 22 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a glycidyloxyethyl group, a diglycidylamino group, or a dipropargylamino group; R 20 and R 24 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 17 to R 24 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 17 to R 24 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; X 1 represents a group shown by the following formula (3-6); and n17 to n24 are each a number satisfying 0≦n17≦4, 0≦n18≦4, 0≦n19≦3, 0≦n20≦3, 0≦n21≦4, 0≦n22≦4, 0≦n23≦3, 0≦n24≦3, 0≦n17+n18≦4, 0≦n19+n20≦3, 0≦n21+n22≦4, 0≦n23+n24≦3, 1≦n17+n18+n19+n20≦7, and 1≦n21+n22+n23+n24≦7,
wherein R 25 and R 27 represent Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 26 and R 28 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a glycidyloxyethyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 25 to R 28 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 25 to R 28 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; X 1 represents a group shown by the following formula (3-6); and n25 to n28 are each a number satisfying 0≦n25≦5, 0≦n26≦5, 0≦n27≦5, 0≦n28≦5, 1≦n25+n26≦5, and 1≦n27+n28≦5,
wherein R 29 and R 31 represent Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 30 , R 32 , and R 33 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 29 to R 33 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 29 to R 33 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; X 1 represents a group shown by the following formula (3-6); and n29 to n32 are each a number satisfying 0≦n29≦4, 0≦n30≦4, 0≦n31≦4, 0≦n32≦4, 0≦n29+n30≦4, and 0≦n31+n32≦4,
wherein * represents a binding site with R q where q represents 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, or 32.
4. The composition for forming a resist underlayer film according to claim 2 , wherein the condensate is obtained by a reaction with one or more compounds selected from compounds shown by the following general formulae (3-1), (3-2), (3-3), (3-4), and (3-5),
wherein R 11 and R 13 represent Z 1 , where Z 1 is as defined above, an amino group, a diglycidylamino group, or a dipropargylamino group; R 12 and R 14 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 11 to R 14 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 1 to R 14 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; two substituents selected from R 11 , R 12 , R 13 , and R 14 may be bonded intramolecularly to form a cyclic substituent; X 1 represents a group shown by the following formula (3-6); and n11 to n14 are each a number satisfying 0≦n1≦4, 0≦n12≦4, 0≦n13≦4, 0≦n14≦4, 0≦n11+n12≦4, 0≦n13+n14≦4, and 1≦n11+n12+n13+n14≦8,
wherein R 15 represents a fluorine atom, a chlorine atom, Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 16 represents Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 15 and R 16 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 15 and R 16 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; two substituents selected from R 15 and R 16 may be bonded intramolecularly to form a cyclic substituent; X 1 represents a group shown by the following formula (3-6); and n15 and n16 are each a number satisfying 0≦n15≦6, 0≦n16≦6, and 1≦n15+n16≦6,
wherein R 17 , R 19 , R 21 , and R 23 represent Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 18 and R 22 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a glycidyloxyethyl group, a diglycidylamino group, or a dipropargylamino group; R 20 and R 24 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 17 to R 24 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 17 to R 24 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; X 1 represents a group shown by the following formula (3-6); and n17 to n24 are each a number satisfying 0≦n17≦4, 0≦n18≦4, 0≦n19≦3, 0≦n20≦3, 0≦n21≦4, 0≦n22≦4, 0≦n23≦3, 0≦n24≦3, 0≦n17+n18≦4, 0≦n19+n20≦3, 0≦n21+n22≦4, 0≦n23+n24≦3, 1≦n17+n18+n19+n20≦7, and 1≦n21+n22+n23+n24≦7,
wherein R 25 and R 27 represent Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 26 and R 28 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a glycidyloxyethyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 25 to R 28 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 25 to R 28 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; X 1 represents a group shown by the following formula (3-6); and n25 to n28 are each a number satisfying 0≦n25≦5, 0≦n26≦5, 0≦n27≦5, 0≦n28≦5, 1≦n25+n26≦5, and 1≦n27+n28≦5,
wherein R 29 and R 31 represent Z 1 , where Z 1 is as defined above, a diglycidylamino group, or a dipropargylamino group; R 39 , R 32 , and R 33 represent Z 2 , where Z 2 is as defined above, a glycidyl group, a diglycidylamino group, or a dipropargylamino group; a single bond contained in R 29 to R 33 may be substituted by a double bond, a triple bond, an ether group, a carbonyl group, or a carbonyloxy group; a hydrogen atom contained in R 29 to R 33 may be substituted by a fluorine atom, a chlorine atom, or a hydroxyl group; X 1 represents a group shown by the following formula (3-6); and n29 to n32 are each a number satisfying 0≦n29≦4, 0≦n30≦4, 0≦n31≦4, 0≦n32≦4, 0≦n29+n30≦4, and 0≦n31+n32≦4,
wherein * represents a binding site with R 4 where q represents 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, or 32.
5. The composition for forming a resist underlayer film according to claim 1 , further comprising a substituted condensate obtained by substituting a part of hydrogen atoms contained in the condensate by a glycidyl group.
6. The composition for forming a resist underlayer film according to claim 2 , further comprising a substituted condensate obtained by substituting a part of hydrogen atoms contained in the condensate by a glycidyl group.
7. The composition for forming a resist underlayer film according to claim 3 , further comprising a substituted condensate obtained by substituting a part of hydrogen atoms contained in the condensate by a glycidyl group.
8. The composition for forming a resist underlayer film according to claim 4 , further comprising a substituted condensate obtained by substituting a part of hydrogen atoms contained in the condensate by a glycidyl group.
9. The composition for forming a resist underlayer film according to claim 1 , wherein the composition for forming a resist underlayer film comprises two or more of the compound shown by the general formula (1), the condensate of the compound, and a substituted condensate obtained by substituting a part of hydrogen atoms of the condensate by a glycidyl group.
10. The composition for forming a resist underlayer film according to claim 2 , wherein the composition for forming a resist underlayer film comprises two or more of the compound shown by the general formula (1), the condensate of the compound, and a substituted condensate obtained by substituting a part of hydrogen atoms of the condensate by a glycidyl group.
11. The composition for forming a resist underlayer film according to claim 1 , further comprising either or both of a crosslinking agent and an acid generator.
12. A patterning process comprising: forming a resist underlayer film on a body to be processed by using the composition for forming a resist underlayer film according to claim 1 ; forming a resist middle layer film on the resist underlayer film by using a silicon-containing resist middle layer film composition; forming a resist upper layer film on the resist middle layer film by using a resist upper layer film composition which is a photoresist composition; forming a circuit pattern on the resist upper layer film; etching the resist middle layer film by using the resist upper layer film having the formed pattern as a mask; etching the resist underlayer film by using the resist middle layer film having the formed pattern as a mask; further etching the body to be processed by using the resist underlayer film having the formed pattern as a mask, whereby the pattern is formed in the body to be processed.
13. A patterning process comprising: forming a resist underlayer film on a body to be processed by using the composition for forming a resist underlayer film according to claim 1 ; forming a resist middle layer film on the resist underlayer film by using a silicon-containing resist middle layer film composition; forming an organic antireflective film (BARC) on the resist middle layer film; forming a resist upper layer film on the BARC by using a resist upper layer film composition which is a photoresist composition and thereby forming a 4-layered resist film; forming a circuit pattern on the resist upper layer film; etching the BARC film and the resist middle layer film by using the resist upper layer film having the formed pattern as a mask; etching the resist underlayer film by using the resist middle layer film having the formed pattern as a mask; further etching the body to be processed by using the resist underlayer film having the formed pattern as a mask, whereby the pattern is formed in the body to be processed.
14. A patterning process comprising: forming a resist underlayer film on a body to be processed by using the composition for forming a resist underlayer film according to claim 1 ; forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; forming a resist upper layer film on the inorganic hard mask intermediate film by using a resist upper layer film composition which is a photoresist composition; forming a circuit pattern on the resist upper layer film; etching the inorganic hard mask intermediate film by using the resist upper layer film having the formed pattern as a mask; etching the resist underlayer film by using the inorganic hard mask intermediate film having the formed pattern as a mask; further etching the body to be processed by using the resist underlayer film having the formed pattern as a mask, whereby the pattern is formed in the body to be processed.
15. A patterning process comprising: forming a resist underlayer film on a body to be processed by using the composition for forming a resist underlayer film according to claim 1 ; forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; forming an organic antireflective film (BARC) on the inorganic hard mask intermediate film; forming a resist upper layer film on the BARC by using a resist upper layer film composition which is a photoresist composition and thereby forming a 4-layered resist film; forming a circuit pattern on the resist upper layer film; etching the BARC film and the inorganic hard mask intermediate film by using the resist upper layer film having the formed pattern as a mask; etching the resist underlayer film by using the inorganic hard mask intermediate film having the formed pattern as a mask; further etching the body to be processed by using the resist underlayer film having the formed pattern as a mask, whereby the pattern is formed in the body to be processed.
16. The patterning process according to claim 14 , wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.
17. The patterning process according to claim 12 , wherein the resist upper layer film is patterned by a photolithography with a wavelength ranging from 10 nm to 300 nm, a direct drawing by electron beam, a nanoimprinting, or a combination thereof.
18. The patterning process according to claim 12 , wherein a development method in the patterning process is an alkaline development or a development with an organic solvent.
19. The patterning process according to claim 12 , wherein the body to be processed is a semiconductor apparatus substrate or the semiconductor apparatus substrate coated with any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film.
20. The patterning process according to claim 19 , wherein the metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.