CN111704704A - Ultrahigh-resolution anti-etching metal-containing block copolymer, and preparation and application thereof - Google Patents
Ultrahigh-resolution anti-etching metal-containing block copolymer, and preparation and application thereof Download PDFInfo
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The invention relates to an ultrahigh resolution anti-etching metal-containing block copolymer and preparation and application thereof, wherein the block copolymer comprises a first block and a second block, the first block takes alkyl chain (C is more than or equal to 1) as a spacer group and organic metal group as methacrylate or acrylate side chain metal compound containing a metal unit as a monomer, and the second block takes fluorine-containing methacrylate or acrylate compound as a monomer. Compared with the prior art, the first block and the second block in the block copolymer have larger difference of chemical components, so that the block copolymer has the advantages of good etching contrast, convenient pattern transfer, high assembly speed, low defect rate and the like.
Description
Technical Field
The invention belongs to the technical field of photoetching materials, and relates to a highly ordered ultrahigh resolution anti-etching organic metal-containing segmented copolymer, and preparation and application thereof, wherein the copolymer has high resolution (<5nm line width) and high anti-etching performance.
Background
Integrated Circuits (ICs) are one of the most critical technologies in the information age, and from daily life to industrial production, all devices related to electronic operations cannot be separated from chips, and as the integration degree of chips is continuously improved, the functions of electronic devices are becoming more and more powerful, and mobile phones are also coming into the 3G, 4G, and even 5G ages. In 1965, Gordon Moore, one of the founders of intel, proposed an empirical rule that the number of transistors per unit area on an integrated circuit would double every 18 to 24 months, and at the same time the performance of the integrated circuit would double, which is the well-known Moore's Law. In the fabrication of integrated circuits, it is the continuing progress in photolithographic (photolithographic) technology that supports the continued evolution of moore's law. The functions of the chip can be continuously improved without departing from the development of photoetching technology materials and processes.
How many circuits can be inherited on a chip is determined by the spacing between lines on the chip, i.e., the resolution. In the field of integrated circuits, feature sizes (features sizes) refer to the smallest final dimensions of a semiconductor device. The development of moore's law has led to the reduction of feature sizes in devices in the semiconductor industry, where the determining factor is the resolution of the lithographic process. The traditional top-down (top-down) lithography process is as follows: firstly, spin-coating photoresist on a silicon wafer, exposing through a photoetching machine after a series of pretreatment, shrinking the pattern on a mask on photosensitive resin, and selectively removing the exposed part through the development operation of post-treatment so as to form the pattern.
In the conventional lithography field, the resolution R is mainly determined by the wavelength λ, the numerical aperture and the process constant k, and is limited by the physical limitation of the optical resolution, and the relationship is:
according to the formula, the photoetching technology improves the resolution ratio of the process by continuously shortening the wavelength, increasing the numerical aperture and the like. According to the development of the technology, the photoresist is mainly classified into g/i line, KrF (248nm), ArF/immersion ArF (193nm), EUV (13.5nm) photoresist. Immersion ArF and EUV photoresists are currently the most advanced.
At present, ArF and EUV lithography are mainly adopted at the leading edge of the industry, and by combining with an immersion type exposure technology, a double (multiple) exposure technology and the like, semiconductor production nodes are promoted from 32nm, 20nm, 16nm, 14nm, 10nm and even below 7nm, the most advanced semiconductor manufacturing technology in the world is a 5nm node of TSMC (transistor-metal-semiconductor memory), the EUV lithography technology with the wavelength of 13.5nm is used for the first time, and the resolution can reach 13nm line width.
However, conventional lithography is approaching its physical limit, the development cost of lithography process is high, the process flow is complicated, the design of lithography material is limited, and although EUV lithography can achieve higher resolution, EUV lithography is limited by its high instrument price (about 1.2 billion dollar for EUV lithography machine) and low throughput (through-out). Therefore, there is a need for a scheme that can achieve both precision and throughput as a next generation of graphics conversion technology for integrated circuit production.
A technology of forming a pattern conversion template to manufacture a related semiconductor device by using a Directed Self-assembly (DSA) technique of a block copolymer, in which a nanopattern is obtained by microphase separation between different blocks using a block copolymer obtained by polymerizing two or more chemically different monomers. Compared with the traditional photoetching technology, the DSA technology using the block copolymer does not need a light source and a mask plate, can obtain a large-range ordered pattern, and has the advantages of low cost, high resolution, high productivity and the like.
The traditional DSA material still has a plurality of defects, polystyrene polymethyl methacrylate block copolymer (PS-b-PMMA) cannot obtain a microphase separation structure smaller than 10nm due to lower Flory-Huggins interaction parameter (chi), and a reported high-chi block copolymer system can obtain a pattern with higher resolution, but the material is completely organic, so that the material has poor anti-etching performance, and cannot provide enough etching contrast for pattern transfer printing, thereby influencing the application of the DSA material in the actual production of a photoetching process. The etching resistance of the material can be improved by doping metal, but due to the uncontrollable property of the doping process, defects can be introduced into the formed pattern, and the performance of the material is influenced. It is necessary to develop a high-etching-resistance DSA material with high resolution and low defect rate.
Disclosure of Invention
The invention aims to provide an ultrahigh-resolution anti-etching metal-containing block copolymer, and preparation and application thereof. The block copolymer can realize the resolution of 5nm and below, can be rapidly self-assembled, and has the responsiveness to a magnetic field and high etching contrast.
The purpose of the invention can be realized by the following technical scheme:
an ultra-high resolution etch-resistant metal-containing block copolymer, said block copolymer comprising a first block and a second block, said first block being polymerized from a monomer of formula (1) and/or a monomer of formula (2):
wherein R is1Is hydrogen or methyl, x1、x2Each independently selected from integers of 1 to 20, E1、E2Is an organometallic containing group;
the second block is obtained by polymerizing a monomer of formula (3):
wherein R is2Selected from one of the following groups: C1-C30 alkyl containing substituent, C3-C30 cycloalkyl containing substituent, fluorine-containing aromatic ring, R3Selected from one of the following groups: C1-C40 alkyl containing substituent, C3-C30 containing substituentA cycloalkyl group; the substituent is halogen-containing substituent.
Further, the block copolymer is a diblock copolymer or a triblock copolymer, the diblock copolymer is an A-B type block copolymer, the triblock copolymer is an A-B-A type block copolymer or a B-A-B type block copolymer, A represents a first block, and B represents a second block. The halogen-containing block moiety of the block copolymer may be a homopolymer of one halogen-containing monomer or a copolymer of a plurality of halogen-containing monomers.
Further, said E1、E2Each independently selected from a group of formula (4), formula (5), formula (6) or formula (7):
-Ar1-M1-Ar2(4)
-Ar7-M4-(L2)a3(7)
wherein M is1、M2、M3、M4Each independently selected from the following metal elements: fe. Co, Ni, Zr, Hf, Ta, Pt, Nb, Ti, Sn, Cr, Mn, W;
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7each independently selected from one of the following groups: substituted or unsubstituted cyclopentadiene, substituted or unsubstituted benzene ring, said substitution being by one or more substituents selected from the group consisting of: halogen, alkyl, cycloalkyl, acyl, alkoxy, cyano, hydroxyl, aldehyde, carboxyl and ester;
X1 -is an organic anion or an inorganic anion, the organic anion comprises one or more of dichloro dicyano benzoquinone anion, 7,8, 8-tetracyano-p-benzoquinone dimethane anion, sulfonic acid anion, iodic acid anion, methionine anion or carboxylic acid anion, and the inorganic anion comprises phosphorus hexafluoride anion, boron tetrafluoride anion, antimony hexafluoride anionOne or more of an anion, a halide, an iron tetrabromide anion, an iron tetrachloride anion, a triiodide anion, or a nitrate anion;
a1、a2、a3each independently selected from an integer of 1 or more;
L1、L2each independently selected from the following metal ligands: hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, carboxyl group, carbonyl group, isocyano group, alkenyl group, alkynyl group, amino group, nitro group, thiol group, amide group, ether group, and alcohol group.
Further, said E1、E2Contains cyclopentadiene or benzene ring structure unit and central metal element iron. Preferably, the substituents on the aromatic ring are a single substituent or multiple substituents; the charge number of the organometallic ion is 0 or 1; more preferably, the substituents on the aromatic ring are selected from H, alkyl, methoxy, cyano, hydroxyl, carboxyl, ester, amine and/or halogen.
Further, the halogen comprises one or more of F, Cl, Br or I, preferably F.
Further, the halogen-containing substituent is a fluorine-containing substituent, and the fluorine-containing substituent includes one or more of a fluorine group, a linear fluorine-containing hydrocarbon group, a branched fluorine-containing hydrocarbon group, a cyclic fluorine-containing hydrocarbon group, a linear fluorine-containing alkyl ether group, a branched fluorine-containing alkyl ether group, a cyclic fluorine-containing alkyl ether group, or a aromatic fluorine-containing group. The fluorine substitution in the fluorine-containing substituent includes perfluoro substitution or semifluoro substitution.
Preferably, the monomer of the first block is selected from one of the following compounds:
further, the block copolymer has one or more of the following characteristics:
1) the polydispersity PDI of the block copolymer is less than or equal to 1.30, preferably less than or equal to 1.25, more preferably less than or equal to 1.15, and most preferably less than or equal to 1.10;
2) the number average molecular weight of the block copolymer is 1000-250000, preferably 2000-50000, more preferably 2000-30000, more preferably 2000-10000;
3) the annealing temperature required by the phase separation and self-assembly of the block copolymer is less than or equal to 250 ℃, preferably less than or equal to 200 ℃, more preferably less than or equal to 180 ℃, more preferably less than or equal to 160 ℃, and most preferably less than or equal to 140 ℃;
4) the annealing time required by the phase separation and self-assembly of the block copolymer is less than or equal to 24 hours, preferably less than or equal to 20 hours, more preferably less than or equal to 12 hours, more preferably less than or equal to 10 hours, and more preferably less than or equal to 1 hour;
5) the assembly distance of the product obtained by the self-assembly of the block copolymer is less than or equal to 50nm, preferably less than or equal to 20nm, more preferably less than or equal to 10nm, and most preferably less than or equal to 5nm (i.e. half-pitch is less than or equal to 5 nm);
6) the block copolymer contains a metal block in O2In a gas
Preferably
More preferably
A preparation method of an ultra-high resolution anti-etching metal-containing block copolymer is characterized in that the block copolymer is prepared by anionic Polymerization, Nitroxide-Mediated Free Radical Polymerization (NMP), Atom Transfer Radical Polymerization (ATRP) or Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT).
When the block copolymer is prepared, a first block monomer and a second block monomer are selected, and the block copolymer is obtained through polymerization reaction. Wherein the molar ratio of the first block monomer to the second block monomer is (1-500) to (1-500); preferably, the molar ratio is (3-100) to (3-100); more preferably, the molar ratio is (5-60) to (5-60).
Or selecting a first block monomer, a second block monomer and a third block monomer to obtain a block copolymer through a polymerization reaction, wherein the molar ratio of the first block monomer to the second block monomer to the third block monomer is (1-500) to (1-500); preferably, the molar ratio is (3-100): (3-100); more preferably, the molar ratio is (5-60): (5-60).
The application of the ultra-high resolution anti-etching metal-containing block copolymer in the field of semiconductor lithography can be used in lithography materials.
A lithographic material comprising said ultra-high resolution etch-resistant metal-containing block copolymer.
The first block takes alkyl chain (C is more than or equal to 1) as a spacer, an organic metal group as methacrylate or acrylate side chain metal compound containing a metal unit as a monomer, and the second block takes fluorine-containing methacrylate or acrylate compound as a monomer.
In the invention, the ultrahigh-resolution etching-resistant metal-containing block copolymer can realize excellent phase separation and rapid patterning with high resolution (such as 5nm) in a shorter time (such as 1h), and the formed pattern has higher etching contrast. Meanwhile, due to the introduction of organic metal, the material has potential magnetic field responsiveness, can realize self-assembly under the action of an external field, and reduces the assembly defect rate. Can be applied to the field of semiconductor lithography and further applied to nano catalysis, nano energy storage devices and nano biological medicines.
Compared with the prior art, the invention has the following characteristics:
1) the ultrahigh resolution anti-etching metal-containing block copolymer has strong anti-etching capability and high assembly speed, can meet the requirements of small-size components, can realize patterns with ultrahigh resolution (such as 5nm and below), and has excellent phase separation capability and larger etching contrast.
2) By adjusting the molar ratio of the monomers, different assembly structures with the same hexagonal columnar phase, bicontinuous phase and lamellar phase can be obtained; different assembly sizes can be obtained by regulating and controlling the molecular weight (namely the polymerization degree) of the polymer; the segmented copolymer has self-repairing performance to a certain degree in the rapid assembly process; the preparation method is simple, safe and low in cost, and can prepare the block copolymer with smaller PDI.
Drawings
FIG. 1 shows the NMR of PHFBMA-b-PMAEFC obtained in example 11H-NMR spectrum;
FIG. 2 is a GPC chart of PHFBMA-b-PMAEFC prepared in example 1;
FIG. 3 is a SAXS plot of PHFBMA-b-PMAEFC obtained in example 1 after a short quench;
FIG. 4 is a TEM image of PHFBMA-b-PMAEFC prepared in example 1;
FIG. 5 is an SEM picture of PHFBMA-b-PMAEFC prepared in example 1;
FIG. 6 shows NMR spectra of PHFBMA-b-PFMMA obtained in example 21H-NMR spectrum;
FIG. 7 is a GPC chart of PPHFBMA-b-PFMMA obtained in example 2;
FIG. 8 is a SAXS map obtained after short quenching of PHFBMA-b-PFMMA obtained in example 2;
FIG. 9 shows the NMR of PPFPMA-b-PMAEFC obtained in example 31H-NMR spectrum;
FIG. 10 is a GPC chart of PPFPMA-b-PMAEFC produced in example 3;
FIG. 11 is a SAXS plot of PPFPMA-b-PMAEFC obtained after a short quench time for example 3;
FIG. 12 shows the NMR of PPDFMA-b-PMAEFC obtained in example 41H-NMR spectrum；
FIG. 13 is a GPC chart of PPDFMA-b-PMAEFC obtained in example 4;
FIG. 14 is a SAXS plot obtained after a short quench of PPDFMA-b-PMAEFC obtained in example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
a super-resolution high-molecular nano material containing metal DSA comprises a block copolymer and is prepared from a metal-containing block and a fluorine-containing block by using a RAFT method, wherein the block copolymer capable of resisting etching is prepared by using 2-Cyano-2-propyl benzodithio (2-Cyano-2-propyl benzodithio, CPDB) as a chain transfer agent, Azodiisobutyronitrile (AIBN) as an initiator, 1H-perfluorobutyl methacrylate (1H, 1H-hexafluoro butyl methacrylate, BMA) as a monomer and hexafluoroisopropanol as a solvent, HFBMA, CPDB, AIBN and hexafluoroisopropanol are added into a Schlenk reaction tube, and after deoxygenation, the HFBMA, CPDB, AIBN and hexafluoroisopropanol react at 50-80 ℃ for 2-30 hours and then are precipitated and dried by using methanol for later use. The obtained fluorine-containing monomer homopolymer is used as a macromolecular chain transfer agent, AIBN is used as an initiator, ferrocene formyloxyethyl methacrylate (2- (Methacryloyloxy) ethyl ferrocenecarboxylate, MAEFC) is used as a monomer, Cyclohexanone is used as a solvent, MAEFC and the macromolecular chain transfer agent poly (1H, 1H-perfluorobutyl methacrylate) (Macro-CTA), AIBN and Cyclohexanone (Cyclohexanone) are added into a Schlenk reaction tube, oxygen is removed, reaction is carried out at 50-90 ℃ for 2-50 hours, and then n-hexane is used for precipitation and drying, and then relevant tests are carried out.
The synthesis steps are as follows:
taking the obtained product to carry out GPC,1H-NMR of19F-NMR measurements, as shown in FIG. 1, from polymers1It can be seen from the H-NMR spectrum that the characteristic H peaks of the block PHFBMA and the block PMAEFC correspond to the structures shown.
As shown in FIG. 2, GPC analysis showed that data for molecular weights and molecular weight distributions of the series of block copolymers produced were available, indicating successful synthesis of narrow distribution block copolymers.
The associated characterization data for representative block copolymers obtained by the analysis are shown in table 1.
TABLE 1 characterization data for PHFBMA-b-PMAEFC type block copolymers
Taking part of the product to carry out low-temperature rapid assembly quenching, dissolving the obtained block copolymer with Tetrahydrofuran (THF), then dripping-plating (drop-cast) or spin-coating (spin-coating) on a silicon wafer (Si), baking the silicon wafer on a hot plate (hot-plate) at a low temperature after the solvent is volatilized, quenching the silicon wafer by a cold plate (chill plate) after rapid annealing, and further testing SAXS, a Transmission Electron Microscope (TEM) and a Scanning Electron Microscope (SEM) on the obtained sample. The SAXS results obtained after 12h 160 degree annealing are shown in fig. 3, where the assembly size is calculated by the position of the primary peak of the SAXS spectrum. The calculation formula is as follows: d is 2 pi/q, wherein q is the peak position of the primary peak.
The assembled morphology of the block copolymer is confirmed by the results of a transmission electron microscope and a scanning electron microscope, and the TEM and SEM results are shown in FIGS. 4 and 5, and the material presents images of a hexagonal columnar structure and a layered structure.
Example 2:
a super-resolution high-molecular nano material containing metal DSA comprises a block copolymer and is prepared from a metal-containing block and a fluorine-containing block by using a RAFT method, wherein the block copolymer capable of resisting etching is prepared by using 2-Cyano-2-propyl benzodithio (2-Cyano-2-propyl benzodithio, CPDB) as a chain transfer agent, Azodiisobutyronitrile (AIBN) as an initiator, 1H-perfluorobutyl methacrylate (1H, 1H-hexafluoro butyl methacrylate, BMA) as a monomer and hexafluoroisopropanol as a solvent, HFBMA, CPDB, AIBN and hexafluoroisopropanol are added into a Schlenk reaction tube, and after deoxygenation, the HFBMA, CPDB, AIBN and hexafluoroisopropanol react at 50-80 ℃ for 2-30 hours and then are precipitated and dried by using methanol for later use. The obtained fluorine-containing monomer homopolymer is used as a macromolecular chain transfer agent, AIBN is used as an initiator, Ferrocenyl Methyl Methacrylate (FMMA) is used as a monomer, Cyclohexanone is used as a solvent, FMMA and the macromolecular chain transfer agent poly (1H, 1H-perfluorobutyl methacrylate) (Macro-CTA), AIBN and Cyclohexanone are added into a Schlenk reaction tube, oxygen is removed, reaction is carried out at 50-90 ℃ for 2-50 hours, and then n-hexane is used for precipitation and drying, and then relevant tests are carried out.
The synthesis steps are as follows:
taking the obtained product to carry out GPC,1H-NMR of19F-NMR measurements, as shown in FIG. 6, from polymers1It can be seen from the H-NMR spectrum that the characteristic H peaks of the PHFBMA block and the PFMMA block correspond to the structures shown.
As shown in fig. 7, GPC analysis showed that data for molecular weight and molecular weight distribution of the series of block copolymers produced was available, indicating successful synthesis of narrow distribution block copolymers.
The associated characterization data for representative block copolymers obtained by the analysis are shown in table 2.
TABLE 2 characterization data of PHFBMA-b-PFMMA-based block copolymers
And (3) taking part of the product to carry out low-temperature rapid assembly quenching, dissolving the obtained block copolymer by THF, then dripping-plating (drop-cast) or spin-coating (spin-coating) on a silicon wafer (Si), baking the silicon wafer on a hot plate (hot-plate) at a low temperature after the solvent is volatilized, quenching by a cold plate (chill plate) after rapid annealing, and further carrying out SAXS test on the obtained sample. The SAXS results obtained after 12h 160 degree annealing are shown in fig. 8, where the assembly size is calculated by the position of the primary peak of the SAXS spectrum. The calculation formula is as follows: d is 2 pi/q, wherein q is the peak position of the primary peak.
Example 3:
a super-resolution high-molecular nano material containing metal DSA comprises a block copolymer consisting of a metal-containing block and a fluorine-containing block, and the block copolymer capable of resisting etching is prepared by using a RAFT method, wherein 2-Cyano-2-propyl-benzodithio (CPDB) is used as a chain transfer agent, Azobisisobutyronitrile (AIBN) is used as an initiator, perfluorophenyl methacrylate (PFPMA) is used as a monomer, hexafluoroisopropanol is used as a solvent, PFPMA, CPDB, AIBN and hexafluoroisopropanol are added into a Schlenk reaction tube, and after oxygen removal, the materials are precipitated and dried by methanol at 50-80 ℃ for 2-30 hours for later use. The obtained fluorine-containing monomer homopolymer is used as a macromolecular chain transfer agent, AIBN is used as an initiator, ferrocene methyl formyloxyethyl methacrylate (2- (Methacryloyloxy) ethyl Ferrocenecarboxylate, MAEFC) is used as a monomer, Cyclohexanone is used as a solvent, the monomer containing MAEFC, the macromolecular chain transfer agent perfluorophenyl polymethacrylate (PFPPMA, Macro-CTA), AIBN and Cyclohexanone (cyclohexoxanone) are added into a Schlenk reaction tube, after oxygen removal, the reaction is carried out for 2 to 50 hours at 50 to 90 ℃, and then normal hexane is used for precipitation and drying, and then relevant tests are carried out.
The synthesis steps are as follows:
taking the obtained product to carry out GPC,1H-NMR of19F-NMR measurements, as shown in FIG. 9, from polymers1It can be seen from the H-NMR spectrum that the characteristic H peaks of the block PPFPMA and the block PMAEFC correspond to the structures shown.
As shown in FIG. 10, GPC analysis showed that the data molecular weight and molecular weight distribution of the obtained block copolymer could be obtained, indicating successful synthesis of a narrow distribution block copolymer. The number average molecular weight was found to be 8070 kg. mol-1The molecular weight distribution (PDI) was 1.20.
And (3) taking part of the product to carry out low-temperature rapid assembly quenching, dissolving the obtained block copolymer by THF, then dripping-plating (drop-cast) or spin-coating (spin-coating) on a silicon wafer (Si), baking the silicon wafer on a hot plate (hot-plate) at a low temperature after the solvent is volatilized, quenching by a cold plate (chill plate) after rapid annealing, and further carrying out SAXS test on the obtained sample. SAXS results obtained after 12h 160 degree annealing are shown in fig. 11, where the assembly size is calculated by the position of the primary peak of the SAXS spectrum. The calculation formula is as follows: d is 2 pi/q, wherein q is the peak position of the primary peak. The full-pitch obtained after the assembly is 12.8nm, namely the half-pitch is 6.4 nm.
Example 4:
a super-resolution high-molecular nano material containing metal DSA comprises a block copolymer consisting of a metal block and a fluorine-containing block, wherein the block copolymer capable of resisting etching is prepared by an anion polymerization method, triisobutylaluminum is used as a drying agent, 2- (Methacryloyloxy) ethyl ferrocenecarboxlate (MAEFC) is used as a monomer, Tetrahydrofuran (THF) is used as a solvent, butyl lithium is used as an initiator, the THF, triisobutylaluminum and MAEFC are added into a dried double-arm glass bottle for treatment for 0.5h, the reaction bottle is transferred into a reaction bottle, the reaction bottle is restored to the room temperature and is uniformly stirred, and then the reaction bottle is placed in a cold bath at-80-0 ℃ and is cooled for 15 min. Adding 0.5-0.6 mL sec-BuLi (1.3M, solvent is n-hexane), and reacting for 15-120 minutes at-80-0 ℃. And (2) reducing the temperature of the dried 1H,1H-PERFLUOROOCTYL methacrylate (1H, 1H-PERFUOROOCTYL METHACRYLATE, PDFMA) monomer to-60-0 ℃, dripping the monomer into a reaction system, reacting for 5-120 minutes at-80-0 ℃, quenching, precipitating with n-hexane, drying for later use, and performing related tests.
The synthesis steps are as follows:
taking the obtained product to carry out GPC,1H-NMR of19F-NMR measurements, as shown in FIG. 12, from polymers1It can be seen from the H-NMR spectrum that the characteristic H peaks of the block PPFPMA and the block PMAEFC correspond to the structures shown.
As shown in fig. 13, GPC analysis showed that the data molecular weight and molecular weight distribution of the resulting block copolymer were obtained, demonstrating the successful synthesis of a narrow distribution block copolymer. The number average molecular weight was found to be 14101kg & mol-1The molecular weight distribution (PDI) was 1.10.
And (3) taking part of the product to carry out low-temperature rapid assembly quenching, dissolving the obtained block copolymer by THF, then dripping-plating (drop-cast) or spin-coating (spin-coating) on a silicon wafer (Si), baking the silicon wafer on a hot plate (hot-plate) at a low temperature after the solvent is volatilized, quenching by a cold plate (chill plate) after rapid annealing, and further carrying out SAXS test on the obtained sample. SAXS results obtained after 12h 160 degree annealing are shown in fig. 14, where the assembly size is calculated by the position of the primary peak of the SAXS spectrum. The calculation formula is as follows: d is 2 pi/q, wherein q is the peak position of the primary peak. The full-pitch obtained after the assembly is 13.52nm, namely the half-pitch is 6.76 nm.
The invention introduces organic metal material into DSA material for semiconductor photoetching to obtain homogeneous metal-containing phase separation micro-region and halogen (fluorine) -containing phase separation micro-region. The two blocks of the used block copolymer have good phase separation effect, the resolution can reach below 10nm (full-pitch), and the material has good etching contrast by introducing metal.
The types and the number of the block copolymer groups, the preparation method of the block copolymer and the like in the above embodiments can be selected according to actual situations and actual requirements, for example:
the ultrahigh resolution etching-resistant metal-containing block copolymer comprises a first block and a second block, wherein the first block is obtained by polymerizing a monomer of formula (1) and/or a monomer of formula (2):
wherein R is1Is hydrogen or methyl, x1、x2Each independently selected from integers of 1 to 20 (e.g., 3, 7, 10, 15, 18), E1、E2Is an organometallic containing group;
the second block is obtained by polymerizing a monomer of formula (3):
wherein R is2Selected from one of the following groups: C1-C30 (such as C5, C10, C15, C20 and C25) alkyl containing substituent, C3-C30 (such as C5, C10, C15, C20 and C25) cycloalkyl containing substituent, fluorine-containing aromatic ring, R3Selected from one of the following groups: C1-C40 (such as C5, C10, C15, C20, C25, C30 and C35) alkyl containing substituent, C3-C30 (such as C5, C10, C15, C20 and C25) cycloalkyl containing substituent; the substituent is a halogen-containing substituent.
The block copolymer is a diblock copolymer or a triblock copolymer, the diblock copolymer is an A-B type block copolymer, the triblock copolymer is an A-B-A type block copolymer or a B-A-B type block copolymer, A represents a first block, and B represents a second block.
E1、E2Each independently selected from a group of formula (4), formula (5), formula (6) or formula (7):
-Ar1-M1-Ar2(4)
-Ar7-M4-(L2)a3(7)
wherein M is1、M2、M3、M4Each independently selected from the following metal elements: fe. Co, Ni, Zr, Hf, Ta, Pt, Nb, Ti, Sn, Cr, Mn, W;
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7each independently selected from one of the following groups: substituted or unsubstituted cyclopentadiene, substituted or unsubstituted benzene ring, substituted with one or more substituents selected from the group consisting of: halogen, alkyl, cycloalkyl, acyl, alkoxy, cyano, hydroxyl, aldehyde, carboxyl and ester;
X1-is an organic anion comprising one or more of dichlorodicyanoquinone anion, 7,8, 8-tetracyanoterephthalenediquinodimethane anion, sulfonic acid anion, iodoic acid anion, methionine anion or carboxylic acid anion, or an inorganic anion comprising one or more of phosphorus hexafluoride anion, boron tetrafluoride anion, antimony hexafluoride anion, halogen anion, iron tetrabromide anion, iron tetrachloride anion, triiodide anion or nitric acid anion;
a1、a2、a3each independently selected from integers of 1 or more (e.g., 3, 5, 7, 9);
L1、L2each independently selected from the following metal ligands: hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, carboxyl group, carbonyl group, isocyano group, alkenyl group, alkynyl group, amino group, nitro group, thiol group, amide group, ether group, and alcohol group.
Preferably, E1、E2Contains cyclopentadiene or benzene ring structure unit and central metal element iron.
Halogen includes one or more of F, Cl, Br, or I.
Preferably, the halogen-containing substituent is a fluorine-containing substituent comprising one or more of a fluorine group, a linear fluorine-containing hydrocarbon group, a fluorine-containing branched hydrocarbon group, a fluorine-containing cyclic hydrocarbon group, a fluorine-containing linear alkyl ether group, a fluorine-containing branched alkyl ether group, a fluorine-containing cyclic alkyl ether group, or a fluorine-containing aromatic group.
The block copolymer has one or more of the following characteristics:
1) the polydispersity PDI of the block copolymer is less than or equal to 1.30;
2) the number average molecular weight of the block copolymer is 1000-250000;
3) the annealing temperature required by the phase separation and self-assembly of the block copolymer is less than or equal to 250 ℃;
4) the annealing time required by the phase separation and self-assembly of the block copolymer is less than or equal to 24 hours;
5) the assembly distance of the product obtained by self-assembly of the block copolymer is less than or equal to 50 nm;
6) the block copolymer containing a metal block in O2In a gas
The block copolymer is prepared by anionic polymerization, nitroxide radical polymerization, atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization, and is applied to the field of semiconductor lithography to obtain the lithography material containing the ultrahigh-resolution anti-etching metal-containing block copolymer.
The "first", "second" and "third" of the "first block", "second block" and "third block" referred to herein are only blocks for distinguishing different structures, and no limitation is imposed on the block sequence, that is, the organometallic-containing structural unit portion may be any one of the first block monomer, the second block monomer and the third block monomer.
In the present invention, the initiation terminal generated during the polymerization, such as the initiation terminal sec-butyl generated by anionic polymerization, and 1, 1-diphenylethylene for stabilizing anions in both blocks do not affect the phase separation and assembly structure of the block copolymer.
In a similar manner, in nitroxide radical polymerization
An initiating end;
initiators for Atom Transfer Radical Polymerization (ATRP), such as alkyl halides RX (X ═ Br, Cl), benzyl halides, α -bromo esters, α -haloketones, α -halonitriles;
in the same way, reversible addition-fragmentation chain transfer polymerization (RAFT) disulfides and trithiolipids, etc.
Therefore, a block copolymer structure containing the above groups is considered equivalent to that containing no groups.
The self-assembly substrate of the invention is not limited to silicon wafers, and other substrates or curved surfaces can also be assembled with highly ordered patterns; the diblock copolymer is taken as an example in the above embodiments, but the invention is not limited to the diblock and triblock copolymers, and may be a tetrablock or even more blocks; the present invention is not limited to linear block copolymers and can be extended to star block copolymers, graft copolymers, and the like.
The characterization means and the instrument model and the parameter information used in the embodiment of the invention are as follows:
1. nuclear magnetic resonance spectrum (1H Nuclear Magnetic Resonance Spectroscopy，1H-NMR，19F-NMR)
The embodiment of the invention uses a 400MHz Fourier transform nuclear magnetic resonance spectrometer (AVANCE III) to determine the specific structure of the material, adopts deuterated chloroform as a solvent, and determines the information of the structure, the component proportion, the polymer molecular weight and the like of the material by integrating the peak of the characteristic peak position of hydrogen atoms in the structural formula.
2. Gel Permeation Chromatograph (GPC)
In the present example, the Number-average Molecular Weight (Mn) and the polydispersity index (PDI) can be corrected by a gel chromatography test (tetrahydrofuran phase) using a general correction method, and styrene is used as a correction reference.
3. Differential Scanning Calorimeter (DSC)
The glass-transition temperature (Tg) of the materials was determined using differential scanning calorimetry Q2000 (DSC). The temperature rise program is that the temperature rises from 0 ℃ to 150 ℃ per minute by 10 ℃, then the temperature falls to 0 ℃ at the same speed and is recorded as a first cycle, the main function is to eliminate the thermal history of the sample, the temperature rise program of the second cycle is still from 0 ℃ to 150 ℃ per minute by ten ℃, and then the temperature falls to zero at the speed of ten ℃ per minute. The DSC images of the present application are all the results of the second cycle measurements.
4. Small-angle X-ray Scattering (SAXS)
The embodiment of the invention uses small-angle X-ray scattering (SAXS) to test the assembly size of the polymer material, and the assembly size is calculated through the peak position of the highest peak. The samples tested were polymer powders or films after quenching.
5. Scanning Electron Microscope (SEM)
Embodiments of the present invention use Scanning Electron Microscopy (SEM) to test the assembly morphology and assembly roughness of polymeric materials. The tested sample is a thin film sample obtained by spin coating a polymer material solution on the surface of a silicon wafer and quenching.
6. Transmission Electron Microscope (Transmission Electron Microscope, TEM)
According to the embodiment of the invention, the assembling morphology of the polymer material is tested by using a Transmission Electron Microscope (TEM), and the assembling morphology of the polymer material is determined through a TEM image. The samples tested were polymer powders after quenching.
7. Magnetism measuring system (MPMS)
The embodiment of the invention uses an MPMS magnetic measurement System (SQUID) to measure the magnetic induction intensity of the polymer material, and the magnetic induction intensity and the paramagnetism of the polymer material are calculated according to the change of the magnetic moment of the polymer material along with the magnetic field intensity. The samples tested were polymer powders after drying.
All raw materials involved in embodiments of the present invention can be purchased commercially.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. An ultra-high resolution etch-resistant metal-containing block copolymer, wherein the block copolymer comprises a first block and a second block, and the first block is obtained by polymerizing a monomer of formula (1) and/or a monomer of formula (2):
wherein R is1Is hydrogen or methyl, x1、x2Each independently selected from integers of 1 to 20, E1、E2Is an organometallic containing group;
the second block is obtained by polymerizing a monomer of formula (3):
wherein R is2Selected from one of the following groups: C1-C30 alkyl containing substituent, C3-C30 cycloalkyl containing substituent, fluorine-containing aromatic ring, R3Selected from one of the following groups: C1-C40 alkyl containing substituent groups, C3-C30 cycloalkyl containing substituent groups; the substituent is halogen-containing substituent.
2. The ultra-high resolution etching-resistant metal-containing block copolymer as claimed in claim 1, wherein the block copolymer is a diblock copolymer or a triblock copolymer, the diblock copolymer is an a-B type block copolymer, the triblock copolymer is an a-B-a type block copolymer or a B-a-B type block copolymer, a represents a first block, and B represents a second block.
3. The ultra-high resolution etch-resistant metal-containing block copolymer of claim 1, wherein E is1、E2Each independently selected from a group of formula (4), formula (5), formula (6) or formula (7):
-Ar1-M1-Ar2(4)
-Ar7-M4-(L2)a3(7)
wherein M is1、M2、M3、M4Each independently selected from the following metal elements: fe. Co, Ni, Zr, Hf, Ta, Pt, Nb, Ti, Sn, Cr, Mn, W;
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7each independently selected from one of the following groups: substituted or unsubstituted cyclopentadiene, substituted or unsubstituted benzene ring, said substitution being by one or more substituents selected from the group consisting of: halogen, alkyl, cycloalkyl, acyl, alkoxy, cyano, hydroxyl, aldehyde, carboxyl and ester;
X1 -is an organic anion comprising one or more of dichlorodicyanoquinone anion, 7,8, 8-tetracyanoterephthalenediquinodimethane anion, sulfonic acid anion, iodoic acid anion, methionine anion, or carboxylic acid anion, or an inorganic anion comprising one or more of phosphorus hexafluoride anion, boron tetrafluoride anion, antimony hexafluoride anion, halogen ion, iron tetrabromide anion, iron tetrachloride anion, triiodide anion, or nitric acid anion;
a1、a2、a3each independently selected from an integer of 1 or more;
L1、L2each independently selected from the following metal ligands: hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, carboxyl group, carbonyl groupAlkyl, isocyano, alkenyl, alkynyl, amino, nitro, thiol, amide, ether, and alcohol.
4. The ultra-high resolution etch-resistant metal-containing block copolymer of claim 3, wherein E is1、E2Contains cyclopentadiene or benzene ring structure unit and central metal element iron.
5. The ultra-high resolution etch-resistant metal-containing block copolymer of claim 1, wherein the halogen comprises one or more of F, Cl, Br, or I.
6. The ultra-high resolution etching-resistant metal-containing block copolymer of claim 5, wherein the halogen-containing substituent is a fluorine-containing substituent, and the fluorine-containing substituent comprises one or more of a fluorine group, a linear fluorine-containing hydrocarbon group, a branched fluorine-containing hydrocarbon group, a cyclic fluorine-containing hydrocarbon group, a linear fluorine-containing alkyl ether group, a branched fluorine-containing alkyl ether group, a cyclic fluorine-containing alkyl ether group, or an aromatic fluorine-containing group.
7. The ultra-high resolution etch-resistant metal-containing block copolymer of claim 1, wherein the block copolymer has one or more of the following characteristics:
1) the polydispersity PDI of the block copolymer is less than or equal to 1.30;
2) the number average molecular weight of the block copolymer is 1000-250000;
3) the annealing temperature required by the phase separation and self-assembly of the block copolymer is less than or equal to 250 ℃;
4) the annealing time required by the phase separation and self-assembly of the block copolymer is less than or equal to 24 hours;
5) the assembly distance of the product obtained by self-assembly of the block copolymer is less than or equal to 50 nm;
6) the block copolymer contains a metal block in O2Etch rate in gas
8. The method for preparing an ultra-high resolution etching-resistant metal-containing block copolymer as claimed in any one of claims 1 to 7, wherein the block copolymer is prepared by anionic polymerization, nitroxide radical polymerization, atom transfer radical polymerization, or reversible addition-fragmentation chain transfer polymerization.
9. Use of the ultra-high resolution etch-resistant metal-containing block copolymer of any one of claims 1 to 7 in the field of semiconductor lithography.
10. A lithographic material comprising the ultra-high resolution etch-resistant metal-containing block copolymer of any of claims 1 to 7.
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