A metal-substituted metallocene derivative and its preparation method and application

Abstract

The present invention relates to a metal-substituted dimetallocene derivative shown in formula (A), and a preparation method and use thereof. In the compound, Ra and Rb are the same or different, and are independently selected from H, halogen or acid-sensitive groups, and at least one of the Ra and Rb is the same or different, and is independently selected from H, OH or acid-sensitive groups, and at least one R is selected from acid-sensitive groups; the Z is selected from trivalent metals, tetravalent metals or lanthanide tetravalent metals. The present invention also relates to a photoresist composition comprising the metal-substituted dimetallocene derivative shown in formula (A), which can be used in modern lithography processes such as 248nm lithography, 193nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography (NIL) and electron beam lithography (EBL).

Description

Technical Field

[0001] The invention belongs to the technical field of photoresists, and in particular relates to a metal-substituted metallocene derivative and a preparation method and application thereof, especially application in photoresists. Background Art

[0002] The modern world is full of integrated circuits and other microelectronic devices. The scale of integrated circuits has evolved from small-scale integrated circuits with only a few transistors on a chip, to large-scale integrated circuits with hundreds or thousands of transistors on a single chip, and now to very large-scale integrated circuits with more than millions of transistors on a single chip.

[0003] The reduction of chip feature size depends largely on the advancement of lithography technology. Lithography technology is the technology of transferring circuit features to a single crystal surface or a dielectric layer such as a silicon wafer during the integrated circuit manufacturing process. As the foundation of the development of the modern semiconductor industry, lithography technology has promoted the development of information technology.

[0004] Since the 1980s, photolithography technology has developed from ultraviolet (UV, G line 436nm and I line 365nm) to deep ultraviolet (DUV, 248nm and 193nm), and has now developed to extreme ultraviolet (EUV, 13.5nm).

[0005] The exposure light source used in early ultraviolet lithography (G line and I line) was a high-pressure mercury lamp, which is still used in lithography processes of 0.3μm or larger sizes. In the early 1990s, deep ultraviolet lithography (EUV) using excimer lasers such as KrF (248nm) and ArF (193nm) as light sources began to be widely used in industry; currently, the highest resolution lithography technology used in large-scale production in the semiconductor industry at home and abroad is 193nm lithography and electron beam lithography, and EUV technology, as the future development direction, and its corresponding photoresist and lithography process have become the hot spots and difficulties of lithography research.

[0006] The photoresist of the EUV system must have the characteristics of low absorbance, high transparency, high etching resistance, high resolution, high sensitivity, low exposure dose, high environmental stability, low gas generation and low line edge roughness. In the early lithography technology, polymer photoresist was the most widely used. However, when the polymer photoresist system is applied to EUV lithography, due to its large molecular volume, the resolution of the lithography pattern cannot be less than the volume of its molecules, resulting in high line edge roughness and low resolution. Therefore, the existing polymer photoresist is difficult to use for EUV lithography.

[0007] In order to achieve higher resolution, new organic / inorganic hybrid photoresist materials have been developed. Due to their high etching resistance, high EUV absorption characteristics, simple preparation, good thermal stability, strong etching resistance and other advantages, they have become the most promising photoresist materials in the next generation of high-resolution lithography and have received widespread attention. At the same time, it has been proved that EUV photoresist materials based on this type of material will have great development space.

[0008] Therefore, it is necessary to develop different types of organic-inorganic hybrid photoresist host materials. Summary of the invention

[0009] The present invention provides a metal-substituted metallocene derivative having a structure shown in formula (A):

[0010]

[0011] Wherein, Ra, Rb are the same or different and are independently selected from H, halogen or The halogen is F, Cl, I or Br;

[0012] At least one of Ra and Rb is

[0013] Said The R's are the same or different and are independently selected from H, OH or an acid-sensitive group, and at least one R is selected from an acid-sensitive group;

[0014] Said is the connection site;

[0015] The Z is selected from a trivalent metal, a tetravalent metal or a lanthanide tetravalent metal, the trivalent metal is, for example, Gd or Dy; the tetravalent metal is, for example, Ti, Hf, Zr, Mo, V, Nb, U, Cr or Pt; the lanthanide tetravalent metal is, for example, La or Ce.

[0016] According to the present invention, the metal-substituted metallocene derivative has a structure shown in formula (I), formula (II), or formula (III):

[0017]

[0018] wherein X is a trivalent metal, such as Gd or Dy, Y is a tetravalent metal or a lanthanide tetravalent metal, such as Ti, Hf, Zr, Mo, V, Nb, U, Cr, Cr, Pt, La or Ce, M is H or a halogen, and the halogen is F, Cl, I or Br;

[0019] The Rs are the same or different and are independently selected from H, OH or an acid-sensitive group, and at least one R in Formula I, Formula II or Formula III is an acid-sensitive group.

[0020] According to the present invention, the acid-sensitive group is selected from -OC(O)OC 1-20 Alkyl, -OC(O)C 1-20 Alkyl, -OC(O)C 3-20 Cycloalkyl or -O-(CH2) n -C(O)OC 3-20 Cycloalkyl, wherein n is an integer from 0 to 6, and the C 1-20 Alkyl, C 3-20 The cycloalkyl group may be further optionally substituted with one, two or more halogen or C 1-20 Alkyl substitution;

[0021] Preferably, the acid-sensitive group is selected from -OC(O)OC 1-10 Alkyl, -OC(O)C 1-10 Alkyl, -OC(O)C 3-10 Cycloalkyl or -O-(CH2) n -C(O)OC 3-10 Cycloalkyl;

[0022] Preferably, the acid-sensitive group is selected from -OC(O)OC 1-8 Alkyl, -OC(O)C 1-8 Alkyl, -OC(O)C 3-8 Cycloalkyl or -O-(CH2) n -C(O)OC 3-8 Cycloalkyl;

[0023] Preferably, the acid-sensitive group is selected from -OC(O)OC 1-6 Alkyl, -OC(O)C 1-6 Alkyl, -OC(O)C 3-6 Cycloalkyl or -O-(CH2) n -C(O)OC 3-6 Cycloalkyl;

[0024] Specifically, the acid-sensitive group is selected from the following structures:

[0025]

[0026] Said The connection site.

[0027] According to the present invention, the metal-substituted metallocene derivative has the following structural formula:

[0028]

[0029] The present invention also provides a method for preparing the above-mentioned metal-substituted metallocene derivative, comprising: reacting compound (A-3) with compound (A-2) to obtain a compound of formula (A);

[0030]

[0031] Wherein, Z, Ra, Rb, R have the above-mentioned definitions; L is halogen; L1, L2 are the same or different and are independently selected from halogen;

[0032] According to the present invention, the reaction includes first preparing compound (A-2) into a Grignard reagent, for example, reacting (A-2) with magnesium to prepare a corresponding Grignard reagent; preferably, the reaction is carried out in an organic solvent, such as tetrahydrofuran; preferably, the reaction is carried out in the presence of an initiator, for example, the initiator is a Grignard reagent initiator, preferably, the Grignard reagent initiator is 1,2-dibromoethane.

[0033] According to the present invention, the Grignard reagent prepared from the compound (A-2) reacts with the compound (A-3) to obtain the metal-substituted metallocene derivative represented by formula (A). Preferably, the reaction is carried out at room temperature.

[0034] According to the present invention, the compound (A-2) can be prepared by the following method, comprising: reacting the compound (A-1) with R'2O or R'-L3 to obtain the compound (A-2),

[0035]

[0036] Wherein, L3 is selected from halogen, R' is -COOC 1-20 Alkyl, -COC 1-20 Alkyl, -COC 3-20 Cycloalkyl, -(CH2) n -COOC 3-20 Cycloalkyl, wherein n is an integer from 0 to 6, the C 1-20 Alkyl, C 3-20 The cycloalkyl group is further optionally substituted by one, two or more halogen or C 1-20 Alkyl substituted; R1 are the same or different, independently selected from H or OH, and at least one R1 is OH, the OH reacts with R'2O or R'-L3 to form an acid-sensitive group -O-R'; R is as defined above.

[0037] According to an embodiment of the present invention, the reaction is carried out in the presence of an acid binding agent, which is an organic base and / or an inorganic base;

[0038] Preferably, the organic base is triethylamine, DIEA and / or pyridine; the inorganic base is sodium acetate, sodium carbonate and / or potassium carbonate;

[0039] The present invention also provides a photoresist composition, which comprises the metal-substituted metallocene derivative represented by formula (A) of the present invention.

[0040] The present invention also provides a positive photoresist composition, which comprises: (a) a matrix component, wherein the matrix component comprises the metal-site-substituted metallocene derivative; and (b) a photoacid generator.

[0041] Preferably, the positive photoresist composition further comprises: (c) an organic base; and (d) an organic solvent.

[0042] According to an embodiment of the present invention, in the photoresist composition, the matrix component may be composed of one, two or more of the metal-substituted metallocene derivatives shown in formula (A).

[0043] According to an embodiment of the present invention, in the positive photoresist composition, the mass of the matrix component accounts for 2%-30% of the total mass of the photoresist composition, preferably 2.4-25%, preferably 5-20%, and illustratively 3%, 8% or 10%.

[0044] The ratio of the matrix component to the photoresist can affect the viscosity of the photoresist solution, and further affect the thickness of the coating. If a film of different thickness is required, a photoresist composition containing different mass fractions of the matrix component can be selected.

[0045] The component (b) photoacid generator in the photoresist composition of the present invention affects the photosensitivity of the photoresist. Therefore, different types of photoacid generators and different proportions of photoacid generators can be selected to control the photosensitivity of the photoresist.

[0046] According to an embodiment of the present invention, the photoacid generator is, for example, a bistrichloromethyl-s-triazine derivative, an onium salt compound, a sultone compound or a sulfonate compound;

[0047] Preferably, the photoacid generator is selected from one, two or more of the following structures:

[0048]

[0049] Among them, R1'-R 10 'same or different, independently selected from H, C 1-20 Alkyl, ester, amide, carboxyl, aldehyde or hydroxyl groups;

[0050] m is any integer selected from 2 to 6;

[0051] According to an embodiment of the present invention, the mass of the photoacid generator component (b) in the photoresist composition accounts for 2%-30% of the mass of the matrix component (a), preferably 3-30%, preferably 5-25%, for example 10%.

[0052] The organic base as component (c) in the photoresist composition of the present invention serves to neutralize the acid diffused in the unexposed area.

[0053] According to an embodiment of the present invention, the organic base is a nitrogen-containing organic amine compound, preferably, one, two or more of methylamine, dimethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, hexamethylenediamine, benzylamine and cyclohexylamine.

[0054] According to an embodiment of the present invention, in the photoresist composition, the mass of the component (c) organic base accounts for 0.02%-8% of the mass of the matrix component (a) in the photoresist composition, preferably, 0.05-8%, preferably, 0.08-7%, for example, 1-5%. Adjusting the ratio of the organic base can control the edge roughness of the exposed area and the unexposed area.

[0055] According to an embodiment of the present invention, the component (d) organic solvent is selected from alkanes, esters, ethers or halogenated alkane compounds. Preferably, the organic solvent is at least one of 1,2,3-trichloropropane, anisole, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, ethyl lactate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, neopentyl acetate, butyl acetate, diethylene glycol ethyl ether, dichloromethane and tetrahydrofuran.

[0056] According to an embodiment of the present invention, the mass of the organic solvent accounts for 70%-99% of the total mass of the photoresist. The type and proportion of the solvent affect the coating properties of the photoresist composition. Therefore, adjusting the proportion and type of the solvent can improve the solubility of the solvent in the matrix molecules.

[0057] According to an embodiment of the present invention, the photoresist composition further comprises additives, such as sensitizers, surfactants, dyes, stabilizers, etc. The above additives can endow the photoresist composition with good film-forming properties, stability, sensitivity, and the like.

[0058] The present invention also provides use of the photoresist composition, which is used in photolithography technology.

[0059] According to the present invention, the photoresist composition is used for 248 nm lithography, 193 nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography (NIL) and electron beam lithography (EBL).

[0060] The present invention also provides a method for using the photoresist composition, comprising the following steps: dissolving the photoresist composition and coating it on a substrate to obtain a photoresist film, and then performing photolithography.

[0061] The substrate is, for example, a silicon wafer, and the photolithography includes 248 nm photolithography, 193 nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography (NIL) and electron beam lithography (EBL).

[0062] A photoresist film comprises a metal-substituted metallocene derivative represented by formula (A).

[0063] Terms and Definitions

[0064] Unless otherwise defined, 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.

[0065] "More" means three or more.

[0066] The term "halogen" includes F, Cl, Br or I.

[0067] The term "C 1-20 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms. Preferably "C 1-6 Alkyl", "C 1-6 The term "alkyl" refers to 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, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl, or the like or isomers thereof.

[0068] The term "C 3-20 "Cycloalkyl" should be understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or polycyclic hydrocarbon ring (also called condensed hydrocarbon ring) having 3-20 carbon atoms. Bicyclic or polycyclic cycloalkyl groups include paracyclic cycloalkyl, bridged cycloalkyl and spirocyclic cycloalkyl; the paracyclic refers to a condensed ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing one bond). The bridged ring refers to a condensed ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. The spirocyclic refers to a condensed ring structure formed by two or more cyclic structures sharing one ring atom. For example, the C 3-20The cycloalkyl group may be C 3-8 Monocyclic cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Cycloalkyl, such as decahydronaphthalene; it can also be C 7-12 Bridged ring cycloalkyl, such as norbornane, adamantane, bicyclo[2,2,2]octane.

[0069] Beneficial Effects

[0070] 1. The metal-substituted metallocene derivative of the present invention adopts a metal as the central core structure, and therefore has a higher melting point and glass transition temperature, can meet the requirements of photolithography technology, and has a stable structure, and the film structure does not change during high-temperature baking.

[0071] 2. The metal-substituted metallocene derivative of the present invention is protected by an acid-sensitive group around the metal atomic nucleus structure. Since the acid-sensitive group can undergo a chemical reaction under the action of a photoacid generator to generate a phenol or a carboxyl group, the solubility of the exposed part and the unexposed part in the developer changes, and the exposed part has a greater solubility in the developer while the unexposed part does not dissolve in the developer.

[0072] 3. The metal-substituted metallocene derivative of the present invention can control the ratio of acid-sensitive groups to R groups, and increasing the number of acid-sensitive groups can improve its photosensitivity. Increasing the number of hydroxyl groups in R can increase the glass transition temperature and melting point of the matrix, thereby improving the thermal stability of the matrix.

[0073] 4. The metallocene derivative substituted at the metal position of the present invention has a structure of a three-dimensional asymmetric amorphous small molecule compound, which can be dissolved in an organic solvent commonly used in photoresists. The photoresist composition of the present invention can prepare a uniform film, and the metallocene derivative substituted at the metal position as a matrix component does not separate out during the film making process. Therefore, the film prepared by the photoresist composition of the present invention has good resolution, photosensitivity, adhesion, and is easy to preserve.

[0074] 5. The photoresist composition of the present invention can be used in modern lithography processes such as 248nm lithography, 193nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography (NIL) and electron beam lithography (EBL). BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 This is an electron microscope photograph of the ultraviolet lithography pattern after the photoresist composition of Example 4 is formed into a film;

[0076] Figure 2 This is an electron microscope photograph of a deep ultraviolet lithography pattern after the photoresist composition of Example 7 is formed into a film;

[0077] Figure 3 This is an electron microscope photo of the deep ultraviolet lithography pattern after the photoresist composition of Example 10 is formed into a film DETAILED DESCRIPTION

[0078] The technical scheme 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 exemplary descriptions 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 included in the scope that the present invention is intended to protect.

[0079] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0080] Example 1 Preparation of bis(cyclopentadiene)-4-tert-butyloxycarbonyloxyphenyl-zirconium chloride (IV) (Compound B)

[0081]

[0082] Synthesis of compound G:

[0083] In a three-necked flask (three mouthfuls are connected to airway, constant pressure dropping funnel, rubber mouth stopper respectively), 5.14g4-bromophenol and 6.62g potassium carbonate are added, and then vacuum argon filling circulation is carried out three times, so that the reaction system is carried out under the protection of argon, and then 10mL dichloromethane is added to the bottle and the reaction bottle is placed in a 0 DEG C ice-water bath. 4.91g Boc anhydride is dissolved in 5mL dichloromethane, added dropwise in a three-necked flask, and returned to room temperature after adding for 12 hours. After the reaction is completed, the mixed solution is spin-dried for solvent, washed with saturated salt water, and extracted three times with dichloromethane, and the organic phase is merged, dried with anhydrous magnesium sulfate and filtered, and the concentrated solvent is dried through a silica gel column after filtration. The eluent during the silica gel column is: petroleum ether: dichloromethane = 9: 1, and the product is put into a vacuum drying oven and dried to obtain 5.758g white solid G.

[0084] Synthesis of compound B:

[0085] Under argon protection, 72.09 mg of magnesium stick polished with sandpaper was placed in a 25 mL three-necked flask, 2 mL of tetrahydrofuran and two drops of 1,2-dibromoethane were added, and after successful heating with a hair dryer, 540.26 mg of compound G was dissolved in 3 mL of tetrahydrofuran and added dropwise to the above system. After the addition was complete, the reaction was carried out in an ice bath at 0°C for 2 hours to obtain the Grignard reagent.

[0086] Under argon protection, 584.64 mg of zirconocene dichloride was placed in a 50 mL two-necked bottle, 10 mL of tetrahydrofuran was added and stirred, and the prepared Grignard reagent was added dropwise to the system, and 5 mL of 1,4-dioxane was added after reacting at room temperature for 2 hours, and the reaction was continued at room temperature for 12 hours. After the reaction was completed, the mother liquor was evaporated to remove the solvent, and 30 mL of toluene was added for extraction. After the mixture was passed through diatomaceous earth, the filtrate was evaporated to remove the solvent, and toluene was recrystallized to obtain 0.576 g of pink purple solid compound B. The elemental analysis results were: C, 56.12; H, 5.23.

[0087] Example 2 Preparation of bis(cyclopentadiene)-bis(4-tert-butyloxycarbonyloxyphenyl)hafnium(IV) (Compound C)

[0088]

[0089] Synthesis of compound C:

[0090] Under argon protection, 72.09 mg of magnesium stick (3 mmol) polished with sandpaper was placed in a 25 mL three-necked flask, 2 mL of tetrahydrofuran was added, two drops of 1,2-dibromoethane were added, and after successful heating with a hair dryer, 540.26 mg of compound G in Example 1 was dissolved in 3 mL of tetrahydrofuran and added dropwise to the above system. After the addition was completed, the reaction was carried out in an ice bath at 0°C for 2 hours to obtain a Grignard reagent.

[0091] Under argon protection, 303.21 mg of dichlorodiphenylamine was placed in a 50 mL two-necked bottle, 10 mL of tetrahydrofuran was added and stirred, and the prepared Grignard reagent was added dropwise to the system. After reacting at room temperature for 2 hours, 5 mL of 1,4-dioxane was added and the reaction was continued at room temperature for 12 hours. After the reaction was completed, the mother liquor was evaporated to remove the solvent, 30 mL of toluene was added for extraction, the mixture was passed through diatomaceous earth, the filtrate was evaporated to remove the solvent, and the white solid compound C 0.45 g was obtained by recrystallization from toluene. 1 H NMR (300 MHz, C6D6) δ7.04-6.99 (m, 4H), 6.88-6.86 (m, 2H), 6.76-6.73 (m, 2H), 6.02 (s, 10H), 1.35 (s, 18H). The results of elemental analysis are: C, 56.32; H, 5.24.

[0092] Example 3 Bis(3-tert-butoxycarbonyloxy-4-(1-methyladamantyloxycarbonylmethoxy)phenyl)-bis(cyclopentadienyl)hafnium (Compound F)

[0093]

[0094] Synthesis of compound D:

[0095] In a three-necked flask (the three flasks are connected to an airway, a constant pressure dropping funnel, and a rubber stopper), 5.64g of 4-bromo-1,2-dihydroxybenzene and 6.62g of potassium carbonate are added, and then the vacuum is evacuated and argon is circulated three times to make the reaction system under the protection of argon. Then 10mL of dichloromethane is added to the bottle and the reaction bottle is placed in an ice-water bath at 0°C. 4.91g of Boc anhydride is dissolved in 5mL of dichloromethane and added dropwise to the above system. After adding, it is returned to room temperature and reacted for 12 hours. After the reaction is completed, the mixed solution is spin-dried with solvent, washed with saturated brine, and extracted three times with dichloromethane. Combine the organic phases, dry over anhydrous magnesium sulfate and filter, filter and concentrate the solvent to dry through a silica gel column, the eluent is: petroleum ether: dichloromethane = 9:1, the product is placed in a vacuum drying oven and dried to obtain 6.52g of white solid compound D.

[0096] Synthesis of compound E:

[0097] In a three-necked flask (the three flasks are connected to an airway, a constant pressure dropping funnel, and a rubber stopper), add 2.89g of compound D and 2.2g of potassium carbonate, then evacuate and fill with argon for three cycles to make the reaction system under the protection of argon, then add 16mL of tetrahydrofuran to the flask and place the reaction flask in a 0°C ice-water bath. Then add 3.63g of methyl chloroacetate and 7.5mL of tetrahydrofuran (anhydrous) solution dropwise, and after the addition is complete, move to 35°C to react for 24 hours. Filter the reaction solution, spin dry the filtrate, separate by column chromatography, and recrystallize from ethanol to obtain 3.76g of compound E.

[0098] Synthesis of compound F:

[0099] Under argon protection, 72.09 mg of magnesium stick polished with sandpaper was placed in a 25 mL three-necked flask, 2 mL of tetrahydrofuran and two drops of 1,2-dibromoethane were added, and after successful heating with a hair dryer, 988.8 mg of compound E was dissolved in 3 mL of tetrahydrofuran and added dropwise to the above system. After the addition was complete, the reaction was carried out in an ice bath at 0°C for 2 hours to obtain the Grignard reagent.

[0100] Under argon protection, 303.21 mg of dichlorodi(cyclopentadienyl)hafnium was placed in a 50 mL two-necked bottle, 10 mL of tetrahydrofuran was added and stirred, and the prepared Grignard reagent was added dropwise to the system. After reacting at room temperature for 2 hours, 5 mL of 1,4-dioxane was added and the reaction was continued at room temperature for 12 hours. After the reaction was completed, the mother liquor was evaporated to remove the solvent, 30 mL of toluene was added for extraction, the mixture was passed through diatomaceous earth, the filtrate was evaporated to remove the solvent, and 0.637 g of white solid compound F was obtained by recrystallization from toluene. The elemental analysis results of compound F are: C, 62.03; H, 6.23.

[0101] Example 4: Photoresist composition based on compound B prepared in Example 1

[0102] Photoresist composition:

[0103] (1) Matrix: 30 mg of compound B prepared in Example 1;

[0104] (2) Photoacid generator: 1.4mg;

[0105] (3) Organic base: trioctylamine 0.1 mg;

[0106] (4) Organic solvent: 1.2 mL of dichloromethane.

[0107] Example 5: Photoresist composition based on compound B prepared in Example 1 Photoresist composition:

[0108] (1) Matrix: Compound B 48 mg,

[0109] (2) Photoacid generator:

[0110] 1.0mg and 1.0mg,

[0111] (3) Organic base: trioctylamine 0.05 mg,

[0112] (4) Organic solvent: 2.4 mL of dichloromethane.

[0113] Example 6: Photoresist composition based on compound B prepared in Example 1

[0114] Photoresist composition:

[0115] (1) Matrix: Compound B 48 mg,

[0116] (2) Photoacid generator:

[0117] 1.0mg and 1.0mg,

[0118] (3) Organic base: trioctylamine 0.05 mg,

[0119] (4) Organic solvent: 2.4 mL of tetrahydrofuran.

[0120] Example 7: Photoresist composition based on compound C prepared in Example 2

[0121] Photoresist composition:

[0122] (1) Matrix: Compound C 44 mg,

[0123] (2) Photoacid generator:

[0124] 2.0mg,

[0125] (3) Organic base: trioctylamine 0.05 mg,

[0126] (4) Organic solvent: 2 mL of dichloromethane.

[0127] Example 8: Photoresist composition based on compound C prepared in Example 2

[0128] Photoresist composition:

[0129] (1) Matrix: Compound C 32 mg,

[0130] (2) Photoacid generator:

[0131] 1.0mg and 1.0mg,

[0132] (3) Organic base: trioctylamine 0.05 mg,

[0133] (4) Organic solvent: 1.5 mL of tetrahydrofuran.

[0134] Example 9: Photoresist composition based on compound C prepared in Example 2

[0135] Photoresist composition:

[0136] (1) Matrix: Compound C 48 mg,

[0137] (2) Photoacid generator:

[0138] 1.0mg and 1.0mg,

[0139] (3) Organic base: trioctylamine 0.05 mg,

[0140] (4) Organic solvent: 1 mL of tetrahydrofuran and 1 mL of anisole.

[0141] Example 10: Photoresist composition based on compound F prepared in Example 3

[0142] Photoresist composition:

[0143] (1) Matrix: Compound F 45 mg,

[0144] (2) Photoacid generator:

[0145] 2.0mg,

[0146] (3) Organic base: trioctylamine 0.05 mg,

[0147] (4) Organic solvent: 2 mL of dichloromethane.

[0148] Example 11: Photoresist composition based on compound F prepared in Example 3

[0149] Photoresist composition:

[0150] (1) Matrix: Compound F 46 mg,

[0151] (2) Photoacid generator:

[0152] 1.0mg and 1.0mg,

[0153] (3) Organic base: trioctylamine 0.05 mg,

[0154] (4) Organic solvent: 2 mL of dichloromethane.

[0155] Example 12: Photoresist composition based on compound F prepared in Example 3

[0156] Photoresist composition:

[0157] (1) Matrix: Compound F 48 mg,

[0158] (2) Photoacid generator:

[0159] 1.0mg and 1.0mg,

[0160] (3) Organic base: trioctylamine 0.05 mg,

[0161] (4) Organic solvent: 2 mL of tetrahydrofuran.

[0162] Test Example 1

[0163] The photoresist composition of Example 4 was dissolved in dichloromethane as a solvent and then spin-coated on a silicon wafer to obtain a 50-100 nm photoresist film. The photoresist composition had good film-forming properties and a uniform film thickness. A 2.5 μm line width photolithography pattern could be obtained by ultraviolet lithography (see Figure 1 ).

[0164] Test Example 2

[0165] The photoresist composition of Example 7 was dissolved in tetrahydrofuran as a solvent and then spin-coated on a silicon wafer to obtain a 50-100 nm photoresist film. The photoresist composition had good film-forming properties and a uniform film thickness. A lithographic pattern with a line width of 2.82 μm could be obtained by deep ultraviolet lithography (see Figure 2 ).

[0166] Test Example 3

[0167] The photoresist composition of Example 10 was dissolved in dichloromethane as a solvent and then spin-coated on a silicon wafer to obtain a 50-70 nm photoresist film. The photoresist composition had good film-forming properties and a uniform film thickness. A lithographic pattern with a line width of 4.27 μm could be obtained by deep ultraviolet lithography (see Figure 3 ).

[0168] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A compound having a structure shown in formula (A): in, Ra, Rb are the same or different and are independently selected from halogen or And at least one of Ra and Rb is Said The R in the compound are the same or different and are independently selected from H or an acid-sensitive group, and at least one R in the compound is selected from an acid-sensitive group; the acid-sensitive group is selected from -OC(O)OC 1-6 Alkyl, -OC(O)C 1-6 Alkyl, or the following structure: Said is the connection site; The Z is selected from tetravalent metals, and the tetravalent metal is Hf or Zr.

2. The compound according to claim 1, wherein the compound is: in, Y is a tetravalent metal Hf or Zr, M is a halogen; the Rs are the same or different and are independently selected from H or an acid-sensitive group, and at least one R in Formula II or Formula III is an acid-sensitive group, and the acid-sensitive group is as defined in claim 1.

3. The compound according to claim 1, wherein the acid-sensitive group is:

4. The compound according to claim 1, wherein The compound is selected from the following compounds, 5. The method for preparing the compound according to any one of claims 1 to 4, characterized in that: The steps include: The compound (A-3) is reacted with the compound (A-2) to obtain a compound of formula (A); Wherein, Z, Ra, Rb, R are as defined in any one of claims 1-4; L is halogen; L1 and L2 are the same or different and are independently selected from halogen.

6. The preparation method according to claim 5, characterized in that: The compound (A-2) is first prepared into a Grignard reagent and then reacted with the compound (A-3) to obtain the compound represented by formula (A).

7. A photoresist composition, characterized in that: It comprises the compound represented by formula (A) according to any one of claims 1 to 3.

8. A positive photoresist composition, characterized in that: include: (a) a matrix component, wherein the matrix component is selected from the compound represented by formula (A) according to any one of claims 1 to 4; and (b) a photoacid generator.

9. The positive photoresist composition according to claim 8, characterized in that: The positive photoresist composition further includes: (c) an organic base; and (d) an organic solvent.

10. The positive photoresist composition according to claim 8, characterized in that: The mass of the matrix component accounts for 2%-30% of the total mass of the photoresist composition.

11. The positive photoresist composition according to claim 8, characterized in that: The photoacid generator is a bis(trichloromethyl)-s-triazine derivative, an onium salt compound, a sultone compound or a sulfonate compound.

12. The positive photoresist composition according to claim 11, characterized in that: The photoacid generator is selected from one, two or more of the following structures: Among them, R1 ， -R 10 ， The same or different, independently selected from H, C 1-20 Alkyl, ester, amide, carboxyl, aldehyde or hydroxyl; m is selected from any integer from 2 to 6.

13. The positive photoresist composition according to claim 8, characterized in that: The mass of the photoacid generator component (b) in the photoresist composition accounts for 2%-30% of the mass of the matrix component (a).

14. The positive photoresist composition according to claim 9, characterized in that: The organic base is a nitrogen-containing organic amine compound.

15. The positive photoresist composition according to claim 9, characterized in that: The organic base is one, two or more of methylamine, dimethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, hexamethylenediamine, benzylamine and cyclohexylamine.

16. The positive photoresist composition according to claim 9, characterized in that: In the photoresist composition, the mass of the organic base component (c) accounts for 0.02%-8% of the mass of the matrix component (a) in the photoresist composition.

17. The positive photoresist composition according to claim 9, characterized in that: The organic solvent of component (d) is selected from alkanes, esters, ethers or halogenated alkane compounds.

18. The positive photoresist composition according to claim 17, characterized in that: The organic solvent is at least one of 1,2,3-trichloropropane, anisole, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, ethyl lactate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, neopentyl acetate, butyl acetate, diethylene glycol ethyl ether, dichloromethane, and tetrahydrofuran.

19. The positive photoresist composition according to claim 9, characterized in that: The mass of the organic solvent accounts for 70%-99% of the total mass of the photoresist.

20. The positive photoresist composition according to any one of claims 8 to 19, characterized in that: The photoresist composition further comprises an additive, and the additive is a sensitizer, a surfactant, a dye, or a stabilizer.

21. Use of the compound according to any one of claims 1 to 4 or the photoresist composition according to any one of claims 8 to 20 in photolithography.

22. The use according to claim 21, wherein the lithography is ultraviolet lithography, 248 nm lithography, 193 nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography (NIL) and electron beam lithography (EBL).

23. A method for using the photoresist composition according to any one of claims 8 to 20, comprising the following steps: The photoresist composition is dissolved and then coated on a substrate to obtain a photoresist film, which is then subjected to photolithography.

24. The method of use according to claim 23, wherein the substrate is a silicon wafer; And / or, the lithography is 248 nm lithography, 193 nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography (NIL) and electron beam lithography (EBL).

25. A photoresist film comprising the compound represented by formula (A) according to any one of claims 1 to 4.

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