Tetranuclear-based organotin complex and application thereof in photoetching

Abstract

The invention relates to a tetranuclear-based organic tin complex as shown in a formula (I) and application of the tetranuclear-based organic tin complex in photoetching. The compound shown in the formula (I) can be used as a single-component photoresist, and can also be used as an additive to be added into an existing single-component organic tin complex photoresist. When being used as a single-component photoresist, the single-component photoresist has high sensitivity and high resolution. When being used as an additive, the single-component organic tin complex photoresist can promote the generation of a pattern of the single-component organic tin complex photoresist, and the sensitivity of the single-component organic tin complex photoresist is remarkably improved. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of lithography materials, and particularly relates to a class of organic tin complexes based on quadrupole and their applications in lithography. Background Art

[0002] Since Moore's Law was proposed, the innovation of lithography technology has been driving the development of the large-scale integrated circuit manufacturing industry. In the lithography process, a photoresist is spin-coated on a substrate, and then undergoes a series of chemical changes under the action of light, radiation, or electrons. The solubility difference between the exposed area and the unexposed area of the photoresist is generated, and a designed photoresist pattern is formed after development and other steps. Under the theoretical support of the Rayleigh criterion, lithography technology mainly achieves higher resolution by reducing the wavelength of the exposure light source to improve the integration of semiconductor devices. Nowadays, the light source has developed from near-ultraviolet light (436 nm) to extreme-ultraviolet light (13.5 nm), and extreme ultraviolet lithography (EUVL) has been applied to advanced lithography processes. In addition to EUV lithography, electron beam lithography (EBL) is also one of the high-resolution lithography technologies. In addition to achieving high-resolution lithography patterns, the electron beam lithography process of photoresist can also provide a reference for the EUV lithography process.

[0003] Photoresist is the most critical material in this process. For different exposure light sources, researchers need to develop different new photoresists. Therefore, the development of new photoresists that match the light source and the new process node is the primary task to promote the development of lithography technology. To match EUV lithography technology, EUV photoresists are required to have high sensitivity and high etching resistance. This is because the power of EUV light sources is limited, and the EUV light wavelength is short. Under the same dose, the number of photons is lower and the statistical noise is larger than that of the previous generation of light sources. In addition, the photoresist film thickness used in high-resolution lithography is low, which makes the optical path of EUV light in the film shorter and requires a higher absorption coefficient of the material. The thin film thickness also requires the photoresist to have sufficient high etching resistance to support the subsequent etching process.

[0004] To meet the requirement of improving the absorption of extreme ultraviolet light, one of the solutions is to introduce metal elements with high absorption cross-sections for extreme ultraviolet light into the photoresist. The introduction of metal elements simultaneously improves the absorption efficiency of the material and the etching resistance of the photoresist. Currently, a variety of photoresists containing metal elements have been successfully developed, and these metal elements include tin (Sn), zinc (Zn), zirconium (Zr), hafnium (Hf), etc. Among these photoresists, the photoresist with an organotin complex as the main material has advantages such as high sensitivity, small molecular size, and single particle size distribution. Classified according to the number of metal elements in the complex molecule, organotin complexes with mono-nuclear, tetra-nuclear, dodeca-nuclear and other structures have been reported. Among them, the number of reports on photoresists with tetra-nuclear organotin complexes as the main material is limited, and compared with other types of organotin complex photoresists, the sensitivity and resolution performance of this type of photoresist still need to be improved. Therefore, developing a photoresist with high sensitivity and high resolution performance based on tetra-nuclear organotin complexes has theoretical and practical significance for in-depth study of the extreme ultraviolet lithography mechanism and filling the technological gap. Summary of the Invention

[0005] To solve the above problems, the present invention provides a tetra-nuclear based organotin complex, which can be used as the main material of a non-chemically amplified photoresist or an additive in a photoresist composition containing an organotin complex.

[0006] The technical solution of the present invention is as follows: A compound represented by the following formula (I):

[0007] Wherein: each R s is the same or different and independently selected from C 1-15 alkyl, C 2-15 alkenyl, phenyl or benzyl; each R 1 is the same or different and independently selected from halo C 1-15 alkyl, the following groups which are unsubstituted or optionally substituted by 1-3 Ra groups: -CO-C 6-20 aryl, -CO-5-20 membered heteroaryl; Ra is selected from the following groups: -OH, -N(C 1-15 alkyl) 2 , -NHC 1-15 alkyl; R 2 is selected from H, C 1-15 alkyl, C 1-15 alkoxy; m is selected from 1, 2, 3, 4 or 5; n is selected from 0, 1, 2, 3 or 4; and the sum of m and n is 5.

[0008] In some embodiments of the present invention, R s is selected from C 1-6 alkyl, C 2-6 alkenyl, benzyl or phenyl; In some embodiments of the present invention, R 1 is selected from halo C 1-6 alkyl, -CO-C 6-14 aryl(OH)-N(C 1-6 alkyl) 2 , -CO-5-14-membered heteroaryl(OH)-N(C 1-6 alkyl) 2 , -CO-C 6-14 aryl(OH)-NHC 1-6 alkyl, -CO-5-14-membered heteroaryl(OH)-NHC 1-6 alkyl; In some embodiments of the present invention, R 2 is selected from H, C 1-6 alkyl, C 1-6 alkoxy; In some embodiments of the present invention, m is selected from 1 or 2; In some embodiments of the present invention, n is selected from 3 or 4; In some embodiments of the present invention, all R s in the general formula (I) are the same.

[0009] In some embodiments of the present invention, all R 1 in the general formula (I) are the same.

[0010] In some embodiments of the present invention, R s are the same and are selected from one of methyl, ethyl, propyl, n-butyl, vinyl, propenyl, benzyl or phenyl; R 1 are the same and are selected from halomethyl, haloethyl, -CO-phenyl(OH)-N(C 1-3 alkyl) 2 , -CO-5-6-membered heteroaryl(OH)-N(C 1-3 alkyl) 2 , where represents the connecting site; R 2 is selected from H; m is selected from 1 or 2; n is selected from 4 or 3.

[0011] In some embodiments of the present invention, R s are the same and are selected from methyl, ethyl, propyl or n-butyl; R 1identical, selected from fluoromethyl, chloromethyl, bromomethyl, iodomethyl, fluoroethyl, chloroethyl, bromoethyl, iodoethyl or 。

[0012] In some embodiments of the present invention, the compound represented by formula (I) has a symmetric structure.

[0013] In some embodiments of the present invention, formula (I) is selected from the structure represented by the following formula (II):

[0014] wherein, R 11 and R 12 each independently have the definition of R 1 described above; R 13 , R 14 and R 15 have the definition of R 2 described above.

[0015] As an example, the compound represented by formula (I) is selected from the following compounds: 。

[0016] The present invention also provides a method for preparing the compound represented by formula (I) above, comprising the following steps: The compound represented by formula (I-1) reacts with the compound represented by formula (I-2) to obtain the compound represented by formula (I);

[0017] wherein, R 1 , R 2 , R s , m and n have the definitions as described above.

[0018] According to an embodiment of the present invention, the method for preparing the compound represented by formula (I) comprises: dispersing the compound represented by formula (I-1) and the compound represented by formula (I-2) in a molar ratio of 3:1 - 1:1 in an organic solvent, and reacting at 100 - 150 °C for 1 - 12 h.

[0019] According to an embodiment of the present invention, the method further comprises: removing the water generated during the reaction through a Dean-Stark water separator; after the reaction is completed, filtering off the insoluble matter after the reaction solution is cooled to room temperature; concentrating the filtrate under reduced pressure to 5 - 20 mL, and allowing crystals to precipitate by standing at -20 °C for 8 - 36 h; filtering to separate the solid, washing with a poor solvent and then drying.

[0020] According to an embodiment of the present invention, the ratio of the compound represented by formula (I-2) to the organic solvent is 1 g: 20 - 70 mL; the organic solvent is at least one of benzene, toluene, o-xylene, p-xylene, and m-xylene; the poor solvent used for washing the solid is at least one of absolute ethanol, ether, petroleum ether, and acetonitrile.

[0021] The present invention also provides the use of the compound represented by the above formula (I) for preparing a photoresist.

[0022] According to an embodiment of the present invention, the photoresist is a negative photoresist.

[0023] According to an embodiment of the present invention, the compound represented by formula (I) in the photoresist is used as a matrix material.

[0024] According to an embodiment of the present invention, the photoresist is a single-component photoresist and does not contain a photoacid generator.

[0025] The present invention also provides a photoresist composition, which includes: the compound represented by formula (I), a solvent, and optionally a photoresist matrix material.

[0026] In some embodiments of the present invention, the photoresist composition consists of the compound represented by formula (I) and a solvent.

[0027] In some embodiments of the present invention, the photoresist composition consists of a photoresist matrix material, the compound represented by formula (I), and a solvent.

[0028] In some embodiments of the present invention, the photoresist composition includes: a photoresist matrix material, the compound represented by formula (I), and a solvent; the photoresist matrix material is any organic tin complex photoresist matrix material known in the prior art; for example, the matrix material of a single-component organic tin complex photoresist; the compound represented by formula (I) is used as an additive.

[0029] According to an embodiment of the present invention, the photoresist matrix material can be the following compound Z-1 ( Collect. Czech. Chem. Commun. , 1997, 62, 279) and / or Z-2 ( Journal of Organometallic Chemistry , 1989, 372, 193): ; Alternatively, the photoresist matrix material can have the following structure described in Patent ZL202311397707.6: .

[0030] According to an embodiment of the present invention, the content of the compound represented by formula (I) in the photoresist composition can be adjusted as needed, and the preferred content is 0.05% - 10% of the total mass of the photoresist composition, such as 0.1% - 8%, such as 1% - 5%.

[0031] According to an embodiment of the present invention, the solvent is, for example, selected from one, two or more of the following substances: 1,2-dichloroethane, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, N,N-dimethylformamide, cyclohexanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, methyl isopentanone.

[0032] According to an embodiment of the present invention, the photoresist composition is a negative photoresist composition.

[0033] The present invention also provides a photoresist coating, which comprises the compound represented by formula (I) as described above, or the compound represented by formula (I) and a photoresist matrix material.

[0034] The present invention also provides a method for preparing the above-mentioned photoresist coating, comprising: applying the photoresist composition as described above on a substrate to obtain the photoresist coating.

[0035] In some embodiments of the present invention, the application method is spin coating.

[0036] In some embodiments of the present invention, the substrate is a silicon wafer substrate.

[0037] Preferably, the photoresist coating is a thin film.

[0038] The present invention also provides the application of the above-mentioned photoresist coating in lithography.

[0039] The present invention also provides the application of the compound represented by formula (I), the photoresist composition or the photoresist coating in lithography.

[0040] According to the present invention, the photoresist coating is used in modern lithography technologies such as 254 nm lithography, 248 nm lithography, 193 nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography or electron beam (EB) lithography, and is preferably used in ultraviolet, extreme ultraviolet and electron beam lithography technologies.

[0041] Advantageous Effects (1) The present invention introduces an electron- or radiation-sensitive group into the ligand of a tetranuclear organotin complex, namely the compound shown in formula (I), and provides the application of the compound of formula (I) as a main material for a single-component non-chemically amplified photoresist. The introduction of the electron- or radiation-sensitive group endows this single-component non-chemically amplified photoresist with high sensitivity and high resolution. Specifically, in the compound shown in formula (I) of the present invention, a halogenated phenyl group or a -phenyl-CO-C 6-20 aryl group, a -phenyl-CO-5- to 20-membered heteroaryl structure is introduced, which can significantly improve its sensitivity and resolution during lithography. Compared with the existing photoresists, such as the photoresist disclosed in ZL202311397707.6 above, the compound of the present invention can obtain a narrower and clearly defined stripe pattern.

[0042] (2) The present invention provides the application of the compound shown in formula (I) as an additive in a photoresist composition. The groups in the ligand of the compound of formula (I) can generate free radicals under the action of electrons or radiation, which is beneficial to intermolecular crosslinking and conducive to the formation of negative lithography patterns. The photoresist composition containing this additive has higher sensitivity during lithography compared to the photoresist composition without this additive.

[0043] (3) The compound shown in formula (I) of the present invention can be spin-coated into a film. When forming a photoresist composition with other organotin complexes, it does not affect the film-forming property of the photoresist material and is conducive to the preparation of the photoresist film.

[0044] In summary, the compound shown in formula (I) of the present invention can be used as a single-component photoresist or added as an additive to an existing single-component organotin complex photoresist. When used as a single-component photoresist, it has high sensitivity and high resolution. When used as an additive, it can promote the formation of patterns of the main material of the organotin complex photoresist mixed with it and significantly improve the sensitivity of the organotin complex photoresist.

[0045] Terms and Definitions Unless otherwise defined, all scientific and technical terms herein have the same meaning as commonly understood by those skilled in the art to which the subject matter of the claims pertains.

[0046] In some substituents, the “ ” represents the connection site.

[0047] “More than” means three or more.

[0048] The term “halomethyl” should be understood as a methyl group mono-substituted, di-substituted or tri-substituted by a halogen, and the halogen refers to fluorine, chlorine, bromine or iodine. The halomethyl group refers to -CH 2 F, -CHF 2 2, -CF 3 3, -CH2 Cl, -CHCl 2 , -CCl 3 , -CH 2 Br, -CHBr 2 , -CBr 3 , -CH 2 I, -CHI 2 , -CI 3 . Among them, monosubstituted halomethyl is preferred.

[0049] The term "C 1-15 alkyl" should be understood to mean a straight-chain or branched-chain saturated monovalent hydrocarbon group having 1 to 15 carbon atoms, preferably "C 1-6 alkyl". "C 1-6 alkyl" means straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, etc. or their isomers.

[0050] The term "C 2-15 alkenyl" should be understood to mean a straight-chain or branched-chain monovalent hydrocarbon group which contains one or more double bonds and has 2, 3, 4, 5, 6, 7, 8, 9, 10, 11... or 15 carbon atoms, especially 2 or 3 carbon atoms ("C 2-3"Alkenyl"), it should be understood that in the case where the alkenyl contains more than one double bond, the double bonds may be separated from each other or conjugated. The alkenyl is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl, (Z)-1-methylbut-2-enyl, (E)-3-methylbut-1-enyl, (Z)-3-methylbut-1-enyl, (E)-2-methylbut-1-enyl, (Z)-2-methylbut-1-enyl, (E)-1-methylbut-1-enyl, (Z)-1-methylbut-1-enyl, 1,1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.

[0051] The term "C 1-15 alkoxy" should be understood as -O-C 1-15 alkyl, preferably "-O-C 1-12 alkyl", where C 1-15 alkyl has the above definition.

[0052] The term "C 6-20 aryl" should be understood to represent a monocyclic, bicyclic or tricyclic hydrocarbon ring that is monovalent aromatic or partially aromatic and has 6 to 20 carbon atoms, preferably "C 6-14 aryl". The term "C 6-14 aryl" should be understood to preferably represent a monocyclic, bicyclic or tricyclic hydrocarbon ring that is monovalent aromatic or partially aromatic and has 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms ("C 6-14 aryl"), especially a ring having 6 carbon atoms ("C 6 aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9"aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 "aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 "aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 "aryl"), such as anthryl. When the C 6-20 aryl is substituted, it may be mono-substituted or multi-substituted. And there is no restriction on the substitution site, for example, it may be ortho-substituted, para-substituted or meta-substituted.

[0053] The term "5-20 membered heteroaryl" should be understood to include such a monovalent monocyclic, bicyclic or tricyclic aromatic ring system: having 5 to 20 ring atoms and containing 1-5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" should be understood to include such a monovalent monocyclic, bicyclic or tricyclic aromatic ring system: having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, especially 5 or 6 or 9 or 10 carbon atoms, and containing 1-5, preferably 1-3 heteroatoms independently selected from N, O and S. And, additionally, it may be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, etc. and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzoisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo derivatives, such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or azocinyl, indolizinyl, purinyl, etc. and their benzo derivatives; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc.

[0054] The above definition of the term "C 1-15 alkyl" also applies to other groups containing C 1-15 alkyl, such as -CO-C 6-20 aryl(OH)-NHC 1-15 alkyl, etc.

[0055] Similarly, C 6-20 aryl and 5-20 membered heteroaryl have the same definition throughout the text. Brief Description of the Drawings

[0056] Figure 1 It is the thermogravimetric curve of Compound I-1 in Example 1 of the present invention.

[0057] Figure 2 It is the atomic force microscope (AFM) image of compound I-1 in Example 1 of the present invention.

[0058] Figure 3 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period is 2 μm) of the host material of compound I-1 in Example 1 of the present invention.

[0059] Figure 4 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period is 60 nm) of the host material of compound I-1 in Example 1 of the present invention.

[0060] Figure 5 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period is 50 nm) of the host material of compound I-1 in Example 1 of the present invention.

[0061] Figure 6 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period is 44 nm) of the host material of compound I-1 in Example 1 of the present invention.

[0062] Figure 7 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period is 40 nm) of the host material of compound I-1 in Example 1 of the present invention.

[0063] Figure 8 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period 80 nm) of the host material of compound I-3 in Example 3 of the present invention.

[0064] Figure 9 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period 50 nm) with compound Z-1 as the host material.

[0065] Figure 10 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period is 50 nm) of the photoresist composition with compound I-1 in Example 1 of the present invention as an additive.

[0066] Figure 11 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period 40 nm) of the host material of compound Z-1.

[0067] Figure 12 It is the scanning electron microscope (SEM) image of the negative resist film formation lithography stripes (exposure period is 40 nm) of the photoresist composition with compound I-1 in Example 1 of the present invention as an additive. Detailed implementation mode

[0068] The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0069] Unless otherwise specified, the raw materials and reagents used in the following embodiments are all commercially available products or can be prepared by known methods.

[0070] Example 1 Prepare compound I-1, and the synthesis route is as follows:

[0071] Experimental procedure: At room temperature, dibutyltin oxide (2.00 g, 8.03 mmol, 1 eq) and 3-chloromethylbenzoic acid (1.37 g, 8.03 mmol, 1 eq) were dispersed in 100 mL of toluene, and stirred at 140 °C for 8 h. The water generated during the reaction was removed through a Dean-Stark water separator. After the reaction was completed, the insoluble substances were removed by suction filtration after cooling to room temperature. After concentrating the filtrate under reduced pressure, crystallization was carried out at -20 °C. After 24 h, the solid was filtered, washed with a small amount of petroleum ether, and dried to obtain 2.37 g of colorless crystals. Melting point 102-103 °C; 1 H NMR (600 MHz, chloroform-d) δ 8.23-7.86 (m, 8H), 7.62-7.44 (m, 8H), 4.71 (s, 8H), 1.88-1.50 (m, 32H), 1.43-1.22 (m, 16H), 0.95-0.72(m, 24H); 119 Sn NMR (224 MHz, chloroform-d) δ -208.91, -210.28; FT-IR (KBr, cm -1 ): 3031, 2959, 2926, 2860, 1620, 1609, 1583, 1559, 1398, 1352, 884, 808, 678, 637, 483, 426; MS(ESI): m / z = 1642.18, calculated value C 64 H 96 O 10 Cl 4 Sn 4 + m / z = 1642.18 ([M] +)。The colorless crystal in this example was determined to be triclinic by single-crystal X-ray diffraction, with a P-1 space group structure.

[0072] Example 2 Compound I-2 was prepared, and the synthetic route is as follows:

[0073] Experimental procedure: At room temperature, dimethyltin oxide (2.00 g, 11.9 mmol, 1 eq) and 3-chloromethylbenzoic acid (2.03 g, 11.9 mmol, 1 eq) were dispersed in 100 mL of toluene and stirred at 140 °C for 8 h. The water generated during the reaction was removed through a Dean-Stark water separator. After the reaction was completed, the insoluble matter was removed by suction filtration after cooling to room temperature. The filtrate was concentrated under reduced pressure and then cooled to -20 °C for crystallization. After 24 h, the solid was filtered, washed with a small amount of petroleum ether, and dried to obtain 3.21 g of colorless crystals. Melting point 112 - 113 °C; 1 H NMR (600 MHz, chloroform-d) δ 8.19 - 7.82 (m, 8H), 7.59 - 7.42 (m, 8H), 4.75 (s, 8H), 1.82 (s, 24H); 119 Sn NMR (224 MHz, chloroform-d) δ -205.11, -207.18; FT-IR (KBr, cm -1 ): 3035, 2957, 2856, 1624, 1602, 1586, 1552, 1395, 879, 802, 680, 632, 484, 432; MS(ESI): m / z = 1304.80, calculated value C 40 H 48 O 10 Cl 4 Sn 4 + m / z = 1304.81 ([M] + ).

[0074] Example 3 Compound I-3 was prepared, and the synthetic route is as follows:

[0075] Experimental procedure: At room temperature, dibutyltin oxide (2.00 g, 8.03 mmol, 1 eq) and 4 - diethylamino ketonic acid (2.52 g, 8.03 mmol, 1 eq) were dispersed in 100 mL of toluene and stirred at 140 °C for 10 h. The water generated during the reaction was removed through a Dean - Stark water separator. After the reaction was completed, the insoluble substances were removed by suction filtration after cooling to room temperature. The filtrate was concentrated under reduced pressure and then cooled to - 20 °C for crystallization. After 24 h, the solid was filtered, washed with a small amount of absolute ethanol, and dried to obtain 1.54 g of colorless crystals. Melting point 154 - 156 °C; 1 H NMR (600 MHz, chloroform - d) δ 12.93 - 12.51 (m, 4H), 8.24 - 7.85 (m, 4H), 7.67 - 7.45 (m, 8H), 7.29 (d, J J J = 6.8 Hz, 4H), 6.83 (d, J J J = 9.2 Hz, 4H), 6.10 (d, 119 J -1 = 16.6 Hz, 4H), 5.98 (d, 104 J 144 = 8.3 Hz, 4H), 3.34 (s, 16H), 1.71 - 1.34 (m, 24H), 1.34 - 1.04 (m, 48H), 0.90 - 0.56 (m, 24H); 119 Sn NMR (224 MHz, chloroform - d) δ - 205.55, - 212.96; FT - IR (KBr, cm -1 - 1 104 ):3066, 2957, 2868, 1630, 1599, 1341, 1228, 1125, 636, 584, 537, 490, 437; MS(ESI): m / z = 2212.66, calculated for C 104 H 144 N 4 O 18 Sn 4 + m / z = 2212.66 ([M + +). The colorless crystal in this example was determined by X - ray single - crystal diffraction to be in the monoclinic crystal system with a C2 / c space - group structure.

[0076] Example 4 To prepare compound I - 4, the synthetic route is as follows:

[0077] Experimental procedure: At room temperature, dimethyltin oxide (2.00 g, 11.9 mmol, 1 eq) and 4-diethylamino ketonic acid (3.73 g, 11.9 mmol, 1 eq) were dispersed in 100 mL of toluene and stirred at 140 °C for 10 h. The water generated during the reaction was removed through a Dean-Stark water separator. After the reaction was completed, the insoluble substances were removed by suction filtration after cooling to room temperature. After concentrating the filtrate under reduced pressure, crystallization was carried out at -20 °C. After 24 h, the solid was filtered, washed with a small amount of absolute ethanol, and dried to obtain 1.68 g of colorless crystals. The yield was 30%, and the melting point was 170 - 173 °C; 1 H NMR (600 MHz, chloroform-d) δ 12.89 - 12.47(m, 4H), 8.20 - 7.86 (m, 4H), 7.64 - 7.50 (m, 8H), 7.28 (d, J = 6.8 Hz, 4H), 6.84(d, J = 9.2 Hz, 4H), 6.12 (d, J = 16.6 Hz, 4H), 5.95 (d, J = 8.3 Hz, 4H), 3.32 (s,16H), 1.72 (s, 24H), 1.14 (s, 24H); 119 Sn NMR (224 MHz, chloroform-d) δ -203.12, -207.56; FT-IR (KBr, cm -1 ):3058, 2956, 2857, 1635, 1600, 1228, 1120, 638, 574,548, 477, 428; MS(ESI): m / z = 1876.28, calculated value C 80 H 96 N 4 O 18 Sn 4 + m / z = 1876.28 ([M] + ).

[0078] Example 5 Determine the thermal stability of compound I-1 in Example 1. The thermogravimetric analysis of the compound in Example 1 is shown in Figure 1 . The results show that the thermal decomposition temperature of compound I-1 is above 200 °C, indicating good thermal stability.

[0079] Example 6 A photoresist composition comprising Compound I-1 obtained in Example 1 and 1,2-dichloroethane. The specific preparation method is as follows: Dissolve Compound I-1 prepared in Example 1 in 1,2-dichloroethane to prepare a solution with a concentration of 15 mg / mL. Filter it three times through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution, spin coat and form a film on an untreated silicon substrate, and analyze the film uniformity with an atomic force microscope AFM, see attached Figure 2 . From Figure 2 it can be seen that the surface of the obtained film is flat, and its root mean square roughness Rq is 0.3 nm.

[0080] <The compound of the present invention as the main material of the photoresist> Example 7 A negative photoresist formulation and its use in ultraviolet lithography: Dissolve Compound I-1 of Example 1 in 1,2-dichloroethane to prepare a solution with a mass concentration of 15 mg / mL. Filter it three times through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. Spin coat the spin coating solution on a silicon substrate to form a film, bake it at 80 °C for 2 minutes, perform an exposure experiment on the prepared film (mercury lamp with a wavelength of 254 nm), the target pattern of the mask used is dense stripes with a period of 2 μm and a duty cycle of 1:1, the exposure time is 45 s, and then develop it with n-hexane to obtain clear stripes, see Figure 3 . From Figure 3 it can be known that the width of the lithography stripe is about 1.4 μm.

[0081] Example 8 A negative photoresist formulation and its use in electron beam lithography: Dissolve Compound I-1 of Example 1 in 1,2-dichloroethane to prepare a solution with a mass concentration of 8 mg / mL. Filter it three times through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. Spin coat the spin coating solution on a silicon substrate to form a film, bake it at 80 °C for 2 minutes, perform an EBL exposure experiment on the prepared film, use dense lines with a period of 60 nm and a duty cycle of 1:1 as the layout, the exposure dose is 1200 μC / cm 2 , and then develop it with n-hexane to obtain clear stripes without obvious defects, see Figure 4 . From Figure 4 it can be known that the width of the lithography stripe is 30 nm.

[0082] Example 9 A negative photoresist formulation and its use in electron beam lithography: Compound I-1 of Example 1 was dissolved in 1,2-dichloroethane to prepare a solution with a mass concentration of 8 mg / mL. It was filtered three times through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating solution was spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film was subjected to an EBL exposure experiment. Dense lines with a period of 50 nm and a duty cycle of 1:1 were used as the layout, and the exposure dose was 1200 μC / cm 2 , and then developed using n-hexane to obtain stripes with clear contours and no obvious defects, as shown in Figure 5 . From Figure 5 , it can be seen that the width of the lithography stripe is 25 nm.

[0083] Example 10 A negative photoresist formulation and its use in extreme ultraviolet lithography: Compound I-1 of Example 1 was dissolved in 1,2-dichloroethane to prepare a solution with a mass concentration of 8 mg / mL. It was filtered three times through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating solution was spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film was subjected to an EUV exposure experiment (SSRF). The target pattern of the grating used was dense lines with a period of 44 nm and a duty cycle of 1:1, and the exposure dose was 39 mJ / cm 2 , and then developed using n-hexane to obtain stripes with clear contours and no obvious defects, as shown in Figure 6 . From Figure 6 , it can be seen that the width of the lithography stripe is 22 nm.

[0084] Example 11 A negative photoresist formulation and its use in extreme ultraviolet lithography: Compound I-1 of Example 1 was dissolved in 1,2-dichloroethane to prepare a solution with a mass concentration of 8 mg / mL. It was filtered three times through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating solution was spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film was subjected to an EUV exposure experiment. The target pattern of the grating used was dense lines with a period of 40 nm and a duty cycle of 1:1, and the exposure dose was 39 mJ / cm 2 , and then developed using n-hexane to obtain stripes with clear contours and no obvious defects, as shown in Figure 7 . From Figure 7 , it can be seen that the width of the lithography stripe is 20 nm.

[0085] Example 12 A negative photoresist formulation and its use in electron beam lithography: Compound I-3 of Example 3 was dissolved in toluene to prepare a solution with a mass concentration of 30 mg / mL. It was filtered three times through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. The spin-coating solution was spin-coated on a silicon substrate to form a film, baked at 100 °C for 3 minutes, and the prepared film was subjected to an EBL exposure experiment. Dense lines with a period of 80 nm and a duty cycle of 1:3 were used as the layout, and the exposure dose was 2000 μC / cm 2 , and then developed using a mixed solvent of chlorocyclohexane:n-hexane = 1:6 (v / v) to obtain a striped pattern as Figure 8 shown. As Figure 8 can be seen, the width of the photolithography stripes is approximately 29 nm.

[0086] <The compound of the present invention as a photoresist additive> Example 13 A negative photoresist formulation and its use in electron beam lithography: Compound I-1 of Example 1 was used as an additive and mixed with Compound Z-1, and dissolved in 1,2-dichloroethane. The concentration of Compound Z-1 was 10 mg / mL, and the concentration of Compound I-1 was 3 mg / mL. It was filtered three times through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. The spin-coating solution was spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film was subjected to an EBL exposure experiment. Dense lines with a period of 50 nm and a duty cycle of 1:1 were used as the layout, and the exposure dose was 1000 μC / cm 2 , and then developed using n-hexane to obtain stripes with clear structure and no obvious defects, as shown in Figure 10 . As Figure 10 can be seen, the period of the photolithography stripes is 50 nm.

[0087] A negative photoresist formulation using Compound Z-1 as the main material of a single-component photoresist and its use in electron beam lithography: Compound Z-1 was dissolved in 1,2-dichloroethane to prepare a solution with a mass concentration of 10 mg / mL of Compound Z-1. It was filtered three times through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. The spin-coating solution was spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film was subjected to an EBL exposure experiment. Dense lines with a period of 50 nm and a duty cycle of 1:1 were used as the layout, and the exposure dose was 3200 μC / cm 2 , and then developed using n-hexane to obtain the stripes as Figure 9 shown. As Figure 9 can be seen, the period of the photolithography stripes is 50 nm.

[0088] It can be seen that, when the compound of the present invention is used as an additive and mixed with a photoresist matrix material to form a photoresist, compared with the photoresist without adding the compound of the present invention, on the premise of obtaining stripes without obvious defects, the photoresist with the compound of the present invention added requires a much lower exposure dose during exposure, indicating that the compound of the present invention can significantly improve the sensitivity of the photoresist as an additive.

[0089] Example 14 A negative photoresist formulation and its use in extreme ultraviolet lithography: The compound I-1 of Example 1 was used as an additive and mixed with compound Z-1, and dissolved in 1,2-dichloroethane. The concentration of compound Z-1 was 8 mg / mL, and the concentration of compound I-1 was 2 mg / mL. It was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating solution was spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film was subjected to an EUV exposure experiment. The target pattern of the grating used was dense lines with a period of 40 nm and a duty cycle of 1:1, and the exposure dose was 32 mJ / cm 2 , and then developed with n-hexane to obtain a pattern without obvious defects, as shown in Figure 12 . It can be seen from Figure 12 that the period of the photolithographic stripes is 40 nm.

[0090] A negative photoresist formulation with compound Z-1 as the single-component photoresist matrix material and its use in extreme ultraviolet lithography: Compound Z-1 was dissolved in 1,2-dichloroethane to prepare a solution with a mass concentration of 8 mg / mL of compound Z-1. It was filtered three times through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating solution was spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film was subjected to an EUV exposure experiment. The target pattern of the grating used was dense lines with a period of 40 nm and a duty cycle of 1:1, and the exposure dose was 122 mJ / cm 2 , and then developed with n-hexane to obtain the Figure 11 shown stripes. It can be seen from Figure 11 that the period of the photolithographic stripes is 40 nm.

[0091] It can be seen that, when the compound of the present invention is used as an additive and mixed with a photoresist matrix material to form a photoresist, compared with the photoresist without adding the compound of the present invention, on the premise of obtaining stripes without obvious defects, the photoresist with the compound of the present invention added requires a much lower exposure dose during exposure, indicating that the compound of the present invention can significantly improve the sensitivity of the photoresist as an additive.

[0092] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. The compound represented by formula (I): in: Each R s The same or different, each independently selected from C 1-15 Alkyl, C 2-15 alkenyl, phenyl or benzyl; Each R1 is the same or different and is independently selected from halogenated C 1-15 Alkyl, unsubstituted or optionally substituted by 1 to 3 Ra groups: -CO-C 6-20 Aryl, -CO-5-20 membered heteroaryl; Ra is selected from the following groups: -OH, -N(C 1-15 Alkyl)2, -NHC 1-15 alkyl; R2 is selected from H, C 1-15 Alkyl, C 1-15 Alkoxy; m is selected from 1, 2, 3, 4 or 5; n is selected from 0, 1, 2, 3 or 4; And the sum of m and n is 5.

2. The compound according to claim 1, wherein R s Selected from C 1-6 Alkyl, C 2-6 alkenyl, benzyl or phenyl; R1 is selected from halogenated C 1-6 Alkyl, -CO-C 6-14 Aryl (OH)-N (C 1-6 Alkyl)2, -CO-5-14 membered heteroaryl (OH)-N(C 1-6 Alkyl)2, -CO-C 6-14 Aryl (OH)-NHC 1-6 Alkyl, -CO-5-14 membered heteroaryl (OH)-NHC 1-6 alkyl; R2 is selected from H, C 1-6 Alkyl, C 1-6 Alkoxy; m is selected from 1 or 2; n is selected from 3 or 4.

3. The compound according to claim 1, wherein R s The same is selected from one of methyl, ethyl, propyl, n-butyl, vinyl, propenyl, benzyl or phenyl; R1 is the same and is selected from halomethyl, haloethyl, -CO-phenyl(OH)-N(C 1-3 Alkyl)2, -CO-5-6 membered heteroaryl (OH)-N(C 1-3 Alkyl)2, where * indicates the connection site; R2 is selected from H; m is selected from 1 or 2; n is selected from 4 or 3.

4. The compound according to claim 1, wherein R s Same, selected from methyl, ethyl, propyl or n-butyl; R1 is the same and is selected from fluoromethyl, chloromethyl, bromomethyl, iodomethyl, fluoroethyl, chloroethyl, bromoethyl, iodoethyl or 。 5. The compound according to any one of claims 1 to 4, wherein The compound represented by formula (I) is selected from the following compounds: 。 6. A method for preparing the compound according to any one of claims 1 to 5, wherein: The steps include: The compound represented by formula (I-1) reacts with the compound represented by formula (I-2) to obtain the compound represented by formula (I); Among them, R1, R2, R s , m and n have the definitions given in any one of claims 1-5.

7. A photoresist composition comprising: The compound represented by formula (I) according to any one of claims 1 to 5, a solvent, and an optional photoresist host material; The photoresist main material is any main material of a single-component organic tin complex photoresist known in the prior art.

8. The photoresist composition according to claim 7, wherein the photoresist main material is the following compound Z-1 and / or Z-2: ； Alternatively, the photoresist main material has the following structure: 。 9. A photoresist coating, comprising the compound of formula (I) according to any one of claims 1 to 5, or the compound of formula (I) according to any one of claims 1 to 5 and a photoresist main material; The photoresist main material is any main material of a single-component organic tin complex photoresist known in the prior art.

10. Use of the compound represented by formula (I) according to any one of claims 1 to 5, the photoresist composition according to claim 7 or 8, or the photoresist coating according to claim 9 in photolithography; The photolithography is 254 nm photolithography, 248 nm photolithography, 193 nm photolithography, extreme ultraviolet photolithography, nanoimprint photolithography or electron beam (EB) photolithography.

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