Tetranuclear-based organotin complexes and their applications in photolithography

Abstract

The present invention relates to a tetranuclear organotin complex represented by formula (I) and its application in photolithography. The compound represented by formula (I) 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 exhibits high sensitivity and high resolution. When used as an additive, it can promote the formation of single-component organotin complex photoresist patterns, significantly improving the sensitivity of the single-component organotin complex photoresist.

Description

Technical Field

[0001] The present invention belongs to the technical field of photolithography materials, and in particular relates to a class of tetranuclear-based organotin complexes and applications thereof in photolithography. Background Art

[0002] Since the advent of Moore's Law, innovations in photolithography have driven the development of large-scale integrated circuit manufacturing. During the photolithography process, photoresist is spin-coated onto a substrate. Light, radiation, or electrons then cause a series of chemical changes, resulting in solubility differences between exposed and unexposed areas. After development and other steps, the designed photoresist pattern is formed. Under the theoretical support of the Rayleigh criterion, photolithography primarily achieves higher resolution by reducing the wavelength of the exposure light source, thereby increasing the integration density of semiconductor devices. Today, light sources have evolved from near-ultraviolet (436 nm) to extreme ultraviolet (13.5 nm), and extreme ultraviolet lithography (EUVL) has been adopted in advanced photolithography processes. In addition to EUV lithography, electron-beam lithography (EBL) is also a high-resolution lithography technique. In addition to achieving high-resolution patterns, EBL processes for photoresist also provide a reference for EUV lithography.

[0003] Photoresist is the most critical material in this process. For different exposure light sources, researchers need to develop different new photoresists. Therefore, developing new photoresists that match the light source and new process nodes is the top priority for promoting the development of photolithography technology. To match extreme ultraviolet lithography technology, extreme ultraviolet photoresist is required to have high sensitivity and high etching resistance. This is because the power of the extreme ultraviolet light source is limited, and the wavelength of extreme ultraviolet light is short. At the same dose, the number of photons is lower than that of the previous generation of light sources and the statistical noise is greater. In addition, the photoresist film used in high-resolution lithography is low in thickness, which makes the optical path of extreme ultraviolet light in the film shorter and requires a higher material absorption coefficient. The thin film thickness also requires the photoresist to have sufficiently high etching resistance to support subsequent etching processes.

[0004] To meet the requirements for enhanced absorption of EUV light, one solution is to incorporate metal elements with high absorption cross-sections into photoresists. The introduction of metal elements simultaneously improves the material's absorption efficiency and the photoresist's etch resistance. Currently, a variety of photoresists containing metal elements have been successfully developed, including tin (Sn), zinc (Zn), zirconium (Zr), and hafnium (Hf). Among these photoresists, those based on organotin complexes offer advantages such as high sensitivity, small molecular size, and uniform particle size distribution. Organotin complexes with mononuclear, tetranuclear, and dodecanuclear structures have been reported, depending on the number of metal elements in the complex molecule. However, reports on photoresists based on tetranuclear organotin complexes are limited, and compared to other organotin complex photoresists, this type of photoresist still needs to improve in terms of sensitivity and resolution. Therefore, the development of photoresists with high sensitivity and resolution based on tetranuclear organotin complexes has both theoretical and practical significance for further research into the mechanisms of EUV lithography and for filling gaps in the technology. Summary of the Invention

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

[0006] The technical solutions of the present invention are as follows:

[0007] A compound represented by the following formula (I):

[0008]

[0009] Among them: Each R s The same or different, each independently selected from C 1-15 Alkyl, C 2-15 alkenyl, phenyl or benzyl;

[0010] Each R1 is the same or different and is independently selected from halogenated C 1-15 Alkyl, 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;

[0011] R2 is selected from H, C 1-15 Alkyl, C 1-15 alkoxy;

[0012] m is selected from 1, 2, 3, 4 or 5;

[0013] n is selected from 0, 1, 2, 3 or 4;

[0014] And the sum of m and n is 5.

[0015] In some embodiments of the present invention, R s Selected from C 1-6 Alkyl, C 2-6 alkenyl, benzyl or phenyl;

[0016] In some embodiments of the present invention, R1 is selected from the group consisting of 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;

[0017] In some embodiments of the present invention, R2 is selected from H, C 1-6 Alkyl, C 1-6 alkoxy;

[0018] In some embodiments of the present invention, m is selected from 1 or 2;

[0019] In some embodiments of the present invention, n is selected from 3 or 4;

[0020] In some embodiments of the present invention, all R s All the same.

[0021] In some embodiments of the present invention, all R1 in formula (I) are the same.

[0022] In some embodiments of the present invention, R s The same is selected from one of methyl, ethyl, propyl, n-butyl, vinyl, propenyl, benzyl or phenyl;

[0023] 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, wherein indicates the connection site;

[0024] R2 is selected from H;

[0025] m is selected from 1 or 2;

[0026] n is selected from 4 or 3.

[0027] In some embodiments of the present invention, R s Same, selected from methyl, ethyl, propyl or n-butyl;

[0028] R1 is the same and is selected from fluoromethyl, chloromethyl, bromomethyl, iodomethyl, fluoroethyl, chloroethyl, bromoethyl, iodoethyl or

[0029] .

[0030] In some embodiments of the present invention, the compound represented by formula (I) has a symmetrical structure.

[0031] In some embodiments of the present invention, formula (I) is selected from the structure shown in formula (II) below:

[0032]

[0033] Among them, R 11 and R 12 R1 is independently defined as follows; 13 、R 14 and R 15 Has the definition as described above for R2.

[0034] As an example, the compound represented by formula (I) is selected from the following compounds:

[0035] .

[0036] The present invention also provides a method for preparing the compound represented by the above formula (I), comprising the following steps:

[0037] The compound represented by formula (I-1) reacts with the compound represented by formula (I-2) to obtain the compound represented by formula (I);

[0038]

[0039] Among them, R1, R2, R s , m and n have the definitions described above.

[0040] According to an embodiment of the present invention, the preparation method of 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 hours.

[0041] According to an embodiment of the present invention, the method further includes: removing water generated during the reaction through a Dean-Stark water trap; after the reaction is completed, the reaction solution is cooled to room temperature and then filtered to remove insoluble matter; concentrating the filtrate under reduced pressure to 5-20 mL, and standing at -20 ° C for 8-36 h to allow crystals to precipitate; filtering and separating the solid, washing with a poor solvent, and then drying.

[0042] 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 anhydrous ethanol, ether, petroleum ether, and acetonitrile.

[0043] The present invention also provides use of the compound represented by the above formula (I) in preparing photoresist.

[0044] According to an embodiment of the present invention, the photoresist is a negative photoresist.

[0045] According to an embodiment of the present invention, the compound represented by formula (I) in the photoresist is used as a host material.

[0046] According to an embodiment of the present invention, the photoresist is a single-component photoresist and does not contain a photoacid generator.

[0047] The present invention also provides a photoresist composition, which comprises: a compound represented by formula (I), a solvent, and an optional photoresist main material.

[0048] In some embodiments of the present invention, the photoresist composition consists of a compound represented by formula (I) and a solvent.

[0049] In some embodiments of the present invention, the photoresist composition is composed of a photoresist host material, a compound represented by formula (I) and a solvent.

[0050] In some embodiments of the present invention, the photoresist composition includes: a photoresist main material, a compound represented by formula (I) and a solvent; the photoresist main material is any organotin complex photoresist main material known in the prior art; for example, the main material of a single-component organotin complex photoresist; the compound represented by formula (I) serves as an additive.

[0051] According to an embodiment of the present invention, the photoresist main material may be the following compound Z-1 ( Collect. Czech. Chem. Commun. ,1997, 62, 279) and / or Z-2 ( Journal of Organometallic Chemistry ,1989, 372, 193):

[0052] ;

[0053] Alternatively, the photoresist main material may be the following structure described in Patent ZL202311397707.6:

[0054] .

[0055] 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 preferably the content is 0.05%-10% of the total mass of the photoresist composition, such as 0.1%-8%, such as 1%-5%.

[0056] 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 methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), ethyl lactate, N,N-dimethylformamide, cyclohexanone, ethyl n-amyl ketone, ethyl isoamyl ketone, ethanol, acetonitrile, isopropanol, acetone, methyl n-amyl ketone, and methyl isoamyl ketone.

[0057] According to an embodiment of the present invention, the photoresist composition is a negative photoresist composition.

[0058] 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 main material.

[0059] The present invention also provides a method for preparing the above-mentioned photoresist coating, comprising: applying the above-mentioned photoresist composition on a substrate to prepare the same.

[0060] In some embodiments of the present invention, the applying method is spin coating.

[0061] In some embodiments of the present invention, the substrate is a silicon wafer substrate.

[0062] Preferably, the photoresist coating is a thin film.

[0063] The present invention also provides use of the above-mentioned photoresist coating in photolithography.

[0064] The present invention also provides the use of the compound represented by the above formula (I), the photoresist composition or the photoresist coating in photolithography.

[0065] 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, preferably in ultraviolet, extreme ultraviolet and electron beam lithography.

[0066] Beneficial effects

[0067] (1) The present invention introduces an electron or radiation sensitive group into the ligand of a tetranuclear organotin complex, i.e., a compound represented by formula (I), and provides the use of the compound represented by formula (I) as a main material for a single-component non-chemically amplified photoresist. The introduction of the electron or radiation sensitive group enables the single-component non-chemically amplified photoresist to have high sensitivity and high resolution. Specifically, the compound represented by formula (I) of the present invention introduces a halogenated phenyl group or a -phenyl-CO-C 6-20 The aryl, -phenyl-CO-5-20 membered heteroaryl structure can significantly improve the sensitivity and resolution of its photolithography. Compared with existing photoresists, such as the photoresist disclosed in ZL202311397707.6, the compound of the present invention can obtain narrower and clearer stripe patterns.

[0068] (2) The present invention provides the use of a compound represented by formula (I) as an additive in a photoresist composition. The groups in the ligands of the compound represented by formula (I) can generate free radicals under the action of electrons or radiation, which facilitates intermolecular crosslinking and facilitates the formation of negative photolithographic patterns. Compared to photoresist compositions not containing the additive, photoresist compositions containing the additive have higher sensitivity during photolithography.

[0069] (3) The compound represented by formula (I) of the present invention can be spin-coated to form a film. When it is combined with other organic tin complexes to form a photoresist composition, it does not affect the film-forming properties of the photoresist material, thereby facilitating the preparation of the photoresist film.

[0070] In summary, the compound represented by formula (I) of the present invention can be used as a single-component photoresist or as an additive to existing single-component organotin complex photoresists. When used as a single-component photoresist, it exhibits high sensitivity and resolution. When used as an additive, it can promote the formation of patterns in the mixed organotin complex photoresist matrix, significantly improving the sensitivity of the organotin complex photoresist.

[0071] Terms and Definitions

[0072] Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.

[0073] Some substituents ” represents the connection site.

[0074] "More" means three or more.

[0075] The term "halomethyl" is understood to mean a methyl group that is mono-, di- or tri-substituted by halogen, wherein halogen refers to fluorine, chlorine, bromine or iodine. The halomethyl group refers to -CH2F, -CHF2, -CF3, -CH2Cl, -CHCl2, -CCl3, -CH2Br, -CHBr2, -CBr3, -CH2I, -CHI2 or -CI3. Monosubstituted halomethyl groups are preferred.

[0076] The term "C 1-15 "Alkyl" should be understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 15 carbon atoms, preferably "C 1-6 Alkyl". "C 1-6 "Alkyl" means straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, etc. or isomers thereof.

[0077] The term "C 2-15 "Alkenyl" is understood to mean a linear or branched monovalent hydrocarbon radical containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 ... or 15 carbon atoms, in particular 2 or 3 carbon atoms ("C 2-3"alkenyl"); it is understood that when the alkenyl group contains more than one double bond, the double bonds may be separated from one another or conjugated. The alkenyl group 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. -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-enyl -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 1-ethylprop-1-enyl, 1-propylvinyl, and 1-isopropylvinyl.

[0078] The term "C 1-15 "Alkoxy" should be understood as -OC 1-15 Alkyl, preferably "-OC 1-12 Alkyl", where C 1-15 Alkyl has the above definition.

[0079] The term "C 6-20 "Aryl" is understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 Aryl". The term "C 6-14 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C10 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 anthracenyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Furthermore, there is no limitation on the position of substitution, and for example, substitution may be at the ortho, para or meta position.

[0080] The term "5-20 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S. And, in each case, may additionally be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or acininyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like.

[0081] The above term “C 1-15 The definition of "alkyl" also applies to other C-containing 1-15 Alkyl groups, such as -CO-C 6-20 Aryl (OH)-NHC 1-15 Alkyl, etc.

[0082] Similarly, C 6-20 Aryl and 5-20 membered heteroaryl have the same definitions throughout the text. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 This is a thermogravimetric curve of compound I-1 in Example 1 of the present invention.

[0084] Figure 2This is an atomic force microscope (AFM) image of compound I-1 in Example 1 of the present invention.

[0085] Figure 3 This is a scanning electron microscope (SEM) image of the photolithography stripes (exposure period of 2 μm) of the negative resist film formed by the main material of Compound I-1 in Example 1 of the present invention.

[0086] Figure 4 This is a scanning electron microscope (SEM) image of the negative resist photolithography stripes (exposure period of 60 nm) of the main material of compound I-1 in Example 1 of the present invention.

[0087] Figure 5 This is a scanning electron microscope (SEM) image of the photolithography stripes (exposure period of 50 nm) of the negative resist film formed by the main material of Compound I-1 in Example 1 of the present invention.

[0088] Figure 6 This is a scanning electron microscope (SEM) image of the negative resist photolithography stripes (exposure period of 44 nm) of the main material of compound I-1 in Example 1 of the present invention.

[0089] Figure 7 This is a scanning electron microscope (SEM) image of the negative resist photolithography stripes (exposure period of 40 nm) of the main material of compound I-1 in Example 1 of the present invention.

[0090] Figure 8 This is a scanning electron microscope (SEM) image of the negative resist photolithography stripes (exposure period 80 nm) of the main material of compound I-3 in Example 3 of the present invention.

[0091] Figure 9 This is a scanning electron microscope (SEM) image of the photolithography stripes (exposure period 50 nm) of the negative resist film formed with compound Z-1 as the main material.

[0092] Figure 10 This is a scanning electron microscope (SEM) image of the negative resist film-forming photolithography stripes (exposure period of 50 nm) of the photoresist composition using Compound I-1 in Example 1 of the present invention as an additive.

[0093] Figure 11 This is a scanning electron microscope (SEM) image of the negative photoresist film lithography stripes (exposure period 40 nm) of the main material of compound Z-1.

[0094] Figure 12 This is a scanning electron microscope (SEM) image of the negative resist film-forming photolithography stripes (exposure period of 40 nm) of the photoresist composition using Compound I-1 in Example 1 of the present invention as an additive. DETAILED DESCRIPTION

[0095] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0096] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0097] Example 1

[0098] Compound I-1 was prepared by the following synthetic route:

[0099]

[0100] Experimental Procedure: Disperse dibutyltin oxide (2.00 g, 8.03 mmol, 1 eq) and 3-chloromethylbenzoic acid (1.37 g, 8.03 mmol, 1 eq) in 100 mL of toluene at room temperature and stir at 140 °C for 8 h. Water produced during the reaction was removed via a Dean-Stark trap. After the reaction was completed, the insoluble material was removed by 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 yield 2.37 g of colorless crystals. Melting point: 102-103 °C. 1 H NMR (600 MHz, deuterated chloroform) 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, deuterated chloroform) 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 Cl4Sn4 + m / z = 1642.18 ([M] +The colorless crystals in this embodiment were determined by X-ray single crystal diffraction to be of triclinic system with a P-1 space group structure.

[0101] Example 2

[0102] Compound I-2 was prepared by the following synthetic route:

[0103]

[0104] Experimental Procedure: Disperse dimethyltin oxide (2.00 g, 11.9 mmol, 1 eq) and 3-chloromethylbenzoic acid (2.03 g, 11.9 mmol, 1 eq) in 100 mL of toluene at room temperature and stir at 140 °C for 8 h. The water produced during the reaction was removed via a Dean-Stark trap. After the reaction was completed, the insoluble material was removed by 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 yield 3.21 g of colorless crystals. Melting point: 112-113 °C. 1 H NMR (600 MHz, deuterated chloroform) 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, deuterated chloroform) 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 Cl4Sn4 + m / z = 1304.81 ([M] + ).

[0105] Example 3

[0106] Compound I-3 was prepared by the following synthetic route:

[0107]

[0108] Experimental Procedure: Disperse dibutyltin oxide (2.00 g, 8.03 mmol, 1 eq) and 4-diethylaminoketoic acid (2.52 g, 8.03 mmol, 1 eq) in 100 mL of toluene at room temperature and stir at 140 °C for 10 h. Water produced during the reaction was removed via a Dean-Stark trap. After the reaction was completed, the insoluble material was removed by 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 anhydrous ethanol, and dried to yield 1.54 g of colorless crystals. Melting point: 154-156 °C. 1 H NMR (600 MHz, deuterated chloroform) δ 12.93-12.51 (m, 4H), 8.24-7.85 (m, 4H), 7.67-7.45 (m, 8H), 7.29 (d, J = 6.8 Hz, 4H), 6.83 (d, J = 9.2Hz, 4H), 6.10 (d, J = 16.6 Hz, 4H), 5.98 (d, J = 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, deuterated chloroform) δ -205.55, -212.96; FT-IR (KBr, cm -1 ): 3066, 2957, 2868, 1630, 1599,1341, 1228, 1125, 636, 584, 537, 490, 437; MS (ESI): m / z = 2212.66, calculated value C 104 H 144 N4O 18 Sn4 + m / z = 2212.66 ([M] + ). X-ray single crystal diffraction analysis showed that the colorless crystal in this embodiment is a monoclinic crystal system with a C2 / c space group structure.

[0109] Example 4

[0110] Compound I-4 was prepared by the following synthetic route:

[0111]

[0112] Experimental Procedure: Disperse dimethyltin oxide (2.00 g, 11.9 mmol, 1 eq) and 4-diethylaminoketoic acid (3.73 g, 11.9 mmol, 1 eq) in 100 mL of toluene at room temperature and stir at 140 °C for 10 h. Water produced during the reaction was removed via a Dean-Stark trap. After the reaction was completed, the insoluble material was removed by 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 anhydrous ethanol, and dried to yield 1.68 g of colorless crystals. Yield: 30%; melting point: 170-173 °C. 1 H NMR (600 MHz, deuterated chloroform) 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, deuterated chloroform) 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 N4O 18 Sn4 + m / z = 1876.28 ([M] + ).

[0113] Example 5

[0114] The thermal stability of compound I-1 in Example 1 was determined. Thermogravimetric analysis of the compound in Example 1 is shown in FIG. Figure 1 The results showed that the thermal decomposition temperature of compound I-1 was above 200 °C, indicating good thermal stability.

[0115] Example 6

[0116] A photoresist composition comprising Compound I-1 obtained in Example 1 and 1,2-dichloroethane. The specific preparation method is as follows: Compound I-1 obtained in Example 1 is dissolved in 1,2-dichloroethane to obtain a solution with a concentration of 15 mg / mL. The solution is filtered three times using a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution, which is then spin-coated onto an untreated silicon substrate to form a film. The film uniformity is analyzed using an atomic force microscope (AFM). See Appendix. Figure 2 .from Figure 2 It can be seen from the figure that the surface of the obtained film is smooth and its root mean square roughness Rq is 0.3 nm.

[0117] <The compound of the present invention as a photoresist host material>

[0118] Example 7

[0119] A negative photoresist formulation and its use in UV lithography: Compound I-1 of Example 1 was dissolved in 1,2-dichloroethane to prepare a solution with a mass concentration of 15 mg / mL. The solution was filtered three times with 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 exposure experiment (mercury lamp with a wavelength of 254 nm). The target pattern of the mask used was dense stripes with a period of 2 μm and a duty cycle of 1:1. The exposure time was 45 s, and then developed with n-hexane to obtain clearly defined stripes, as shown. Figure 3 .Depend on Figure 3 It can be seen that the width of the photolithography stripe is about 1.4 μm.

[0120] Example 8

[0121] 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. The solution was filtered three times using 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, which was baked at 80 °C for 2 minutes. The prepared film was subjected to an EBL exposure experiment, using dense lines with a period of 60 nm and a duty cycle of 1:1 as the layout, and the exposure dose was 1200 μC / cm 2 , and then developed with n-hexane to obtain stripes with clear outlines and no obvious defects. Figure 4 .Depend on Figure 4 It can be seen that the width of the lithography stripe is 30 nm.

[0122] Example 9

[0123] 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. The solution was filtered three times using 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, which was baked at 80 °C for 2 minutes. The prepared film was subjected to an EBL exposure experiment, using dense lines with a period of 50 nm and a duty cycle of 1:1 as the layout, and the exposure dose was 1200 μC / cm 2 , and then developed with n-hexane to obtain stripes with clear outlines and no obvious defects. Figure 5 .Depend on Figure 5 It can be seen that the width of the lithography stripe is 25 nm.

[0124] Example 10

[0125] 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. The solution was filtered three times using 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, which was baked at 80 °C for 2 minutes. 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. The exposure dose was 39 mJ / cm 2 , and then developed with n-hexane to obtain stripes with clear outlines and no obvious defects. Figure 6 .Depend on Figure 6 It can be seen that the width of the lithography stripe is 22 nm.

[0126] Example 11

[0127] 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. The solution was filtered three times using 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, which was baked at 80 °C for 2 minutes. 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. The exposure dose was 39 mJ / cm 2 , and then developed with n-hexane to obtain stripes with clear outlines and no obvious defects. Figure 7 .Depend on Figure 7 It can be seen that the width of the lithography stripe is 20 nm.

[0128] Example 12

[0129] A negative photoresist formulation and its application 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. The solution was filtered three times using 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 and baked at 100 °C for 3 minutes. The prepared film was subjected to an EBL exposure experiment, using dense lines with a period of 80 nm and a duty cycle of 1:3 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 stripe pattern as shown Figure 8 As shown. Figure 8 It can be seen that the width of the lithography stripe is about 29 nm.

[0130] <Compounds of the Invention as Photoresist Additives>

[0131] Example 13

[0132] A negative photoresist formulation and its use in electron beam lithography: Compound I-1 of Example 1 is mixed with Compound Z-1 as an additive and dissolved in 1,2-dichloroethane. The concentration of Compound Z-1 is 10 mg / mL and the concentration of Compound I-1 is 3 mg / mL. The solution is filtered three times with a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating solution is spin-coated on a silicon substrate to form a film, baked at 80 °C for 2 minutes, and the prepared film is subjected to an EBL exposure experiment. A dense line with a period of 50 nm and a duty cycle of 1:1 is used as the layout, and the exposure dose is 1000 μC / cm 2 , and then developed with n-hexane to obtain stripes with clear structure and no obvious defects. Figure 10 .Depend on Figure 10 It can be seen that the period of the photolithography stripes is 50 nm.

[0133] Compound Z-1 was used as a negative photoresist formulation for a single-component photoresist main material and was used for 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. The solution was filtered three times with 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 and baked at 80°C for 2 minutes. The prepared film was subjected to an EBL exposure experiment, using dense lines with a period of 50 nm and a duty cycle of 1:1 as the layout, and the exposure dose was 3200 μC / cm 2 , then developed with n-hexane to obtain Figure 9 The stripes shown. Figure 9 It can be seen that the period of the photolithography stripes is 50 nm.

[0134] It can be seen that the photoresist formed by mixing the compound of the present invention as an additive with the main material of the photoresist, compared with the photoresist without the compound of the present invention, requires a much lower exposure dose during exposure to obtain stripes without obvious defects, while also obtaining stripes without obvious defects. This shows that the compound of the present invention as an additive can significantly improve the sensitivity of the photoresist.

[0135] Example 14

[0136] A negative photoresist formulation and its use in extreme ultraviolet lithography: Compound I-1 of Example 1 was mixed with Compound Z-1 as an additive 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. The mixture 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. The exposure dose was 32 mJ / cm 2 , and then developed with n-hexane to obtain a pattern without obvious defects, see Figure 12 .Depend on Figure 12 It can be seen that the period of the photolithography stripes is 40 nm.

[0137] Compound Z-1 was used as a negative photoresist formulation for a single-component photoresist main material and was used for 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. The solution was filtered three times with 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 and baked at 80°C for 2 minutes. 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. The exposure dose was 122 mJ / cm 2 , then developed with n-hexane to obtain Figure 11 The stripes shown. Figure 11 It can be seen that the period of the photolithography stripes is 40 nm.

[0138] It can be seen that the photoresist formed by mixing the compound of the present invention as an additive with the main material of the photoresist, compared with the photoresist without the compound of the present invention, requires a much lower exposure dose during exposure to obtain stripes without obvious defects, while also obtaining stripes without obvious defects. This shows that the compound of the present invention as an additive can significantly improve the sensitivity of the photoresist.

[0139] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection 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 1-6 Alkyl, C 2-6 alkenyl, phenyl or benzyl; Each R1 is the same or different and is independently selected from chloro 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.

2. 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 chloromethyl, chloroethyl, -CO-phenyl(OH)-N(C 1-3 Alkyl)2, -CO-5-6 membered heteroaryl (OH)-N(C 1-3 Alkyl)2; R2 is selected from H; m is selected from 1 or 2; n is selected from 4 or 3.

3. 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 chloromethyl, chloroethyl or , where * indicates the connection site.

4. The compound according to any one of claims 1 to 3, wherein The compound represented by formula (I) is selected from the following compounds: 。 5. A method for preparing the compound according to any one of claims 1 to 4, 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 1-4.

6. A photoresist composition comprising: The compound represented by formula (I) according to any one of claims 1 to 4, a solvent, and an optional photoresist host material; The photoresist main material is any main material of a single-component organotin complex photoresist known in the prior art.

7. The photoresist composition according to claim 6, wherein The solvent is selected from one, two or more of the following substances: 1,2-dichloroethane, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, N,N-dimethylformamide, cyclohexanone, ethyl n-amyl ketone, ethyl isoamyl ketone, ethanol, acetonitrile, isopropanol, acetone, methyl n-amyl ketone, and methyl isoamyl ketone.

8. The photoresist composition according to claim 6 or 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 4, or the compound of formula (I) according to any one of claims 1 to 4 and a photoresist host material; The photoresist main material is any main material of a single-component organotin complex photoresist known in the prior art.

10. Use of the compound of formula (I) according to any one of claims 1 to 4, the photoresist composition according to any one of claims 6 to 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 lithography or electron beam lithography.

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