An "isotropic" zinc-based hybrid compound, its preparation method, and its application in photoresist

Abstract

The present invention belongs to the field of materials / photoresists and relates to an "isotropic" zinc-based hybrid compound, a preparation method thereof, and an application in photoresists, so as to solve the problem of decreased film-forming properties of zinc-based hybrid compounds with a single structure in the prepared photoresist. The compound is prepared in one step using p-bromobenzoic acid and zinc acetate dihydrate as raw materials, has a molecular formula of C9H9BrO5Zn, belongs to the orthorhombic system, has a space group of Pna21, and has a unit cell length, width, and height of 8.0560(7)Å, 5.7165(6)Å, and 25.226(2)Å, respectively; α=β=γ=90°. The compound can be directly used as the sole component and mixed with an organic solvent to prepare an "isotropic" zinc-based hybrid photoresist film, and the photoresist film can be used in the field of membrane science or photolithography. The compound has good stability, and the photoresist film has good solubility, film-forming properties, adhesion, thermal stability, is easy to store, and has a stable structure.

Description

Technical Field

[0001] The invention belongs to the field of materials / photoresists and relates to an "isotropic" zinc-based hybrid compound, a preparation method thereof and an application thereof in photoresists. Background Art

[0002] The mass production of integrated circuits (ICs) has significantly boosted the development of the microelectronics and semiconductor industries. However, photoresists have always played a crucial role in the development of ICs. Robert N. Noyce and Jack Kilby first invented the silicon-based IC by integrating electronic components such as transistors, resistors, capacitors, and inductors onto germanium and silicon substrates, respectively (Noyce 1964, Garcia, Jara et al. 2014). With the advancement of technology, the demand for ICs has continued to increase. Gordon E. Moore proposed Moore's Law (Moore 1995): The number of components on a chip doubles every 18-24 months, while performance also doubles, while the price remains constant. Higher lithographic resolution allows for smaller device critical dimensions and higher IC integration, which necessitates the development of higher-performing photoresists.

[0003] Photoresist, one of the most important components of photolithographic materials, is a thin film material whose structure changes after exposure to radiation, such as light or electron beams, leading to changes in solubility in the developer. Structurally, photoresist is a class of light-sensitive polymers or small molecules, such as molecular glass structures with high glass transition temperatures, as well as metal-containing clusters, complexes, or nanoparticles. When exposed to light or radiation of a certain wavelength, a series of photochemical or radiochemical reactions occur, altering the internal structure of the photoresist and thus the material's properties. This leads to a solubility difference in the developer between the exposed and unexposed portions, and subsequently, a pattern is produced through development and baking procedures.

[0004] The main technical parameters of photoresist are resolution, sensitivity and line edge roughness. According to the photoresist line edge roughness formula: It is known that concentration gradients affect the line roughness of patterns. In typical non-chemical amplification photoresists (n-CARs), polymer molecules are prone to molecular entanglement, resulting in poor line roughness. Therefore, in photoresist design, small molecules are selected as photoresist molecules to meet the requirements of future advanced lithography technologies.

[0005] Currently reported zinc-based hybrid photoresists are primarily centered around zinc-oxygen cluster structures, which are nanoscale in solution. Xu Hong (Xu, Sakai et al. 2018) studied zinc-based oxygen clusters centered around a double zinc core, exploring the potential for asymmetric zinc-oxygen clusters with improved EUV resolution. The zinc-based photoresists reported by Yeh (Yeh, Liu et al. 2017) were primarily prepared via a sol-gel process. To further explore their specific chemical structures, zinc-based hybrid compounds centered around Zn4O have been subsequently studied. Thakur (Thakur, Bliem et al. 2020) proposed in their results report that trifluoromethyl acrylic acid was used to replace acrylic acid through ligand replacement to obtain a metal oxygen cluster compound with Zn4O as the central structure. Although this article reported the specific structure of the material and obtained the ratio of metal to ligand, the structural consistency of the product needs to be investigated; then they explored the effect of methyl acrylic acid ligands with different substituents on the photolithography effect. Finally, the material was a mixture in the photoresist and the film-forming properties were also reduced (Thakur, Vockenhuber et al. 2022).

[0006] Given the good absorption properties of zinc, there is a need for a class of zinc-based hybrid compounds with clear structure, good stability, simple synthesis process, and inexpensive raw materials. Summary of the Invention

[0007] In response to the above problems, the present invention proposes an "isotropic" zinc-based hybrid compound, a preparation method thereof, and its application in photoresist. The zinc-based hybrid compound described in the present invention has an "isotropic structure" similar to that of a polymer, has good chemical stability and a high thermal decomposition temperature, can meet the requirements of different advanced photolithography technologies, and when the zinc-based hybrid compound is used as the main component of the photoresist, the compound undergoes a chemical reaction during the exposure process, and can achieve patterning during the development process. The innovation of the present invention lies in: its application in the field of photoresist is a new application. The compound prepared by the present invention has a clear structure, can also solve the problem of thermal stability of photoresist, and is easy to implement, has good repeatability, good stability, and can greatly reduce costs.

[0008] In order to achieve the above object, the technical solution of the present invention is achieved as follows:

[0009] An isotactic zinc-based hybrid compound is prepared in one step using p-bromobenzoic acid and zinc acetate dihydrate as raw materials. The molecular formula is C9H9BrO5Zn, and the compound belongs to the orthorhombic system with a space group of Pna21. The length, width, and height of the unit cell are respectively and α=β=γ=90°. This compound can be directly used as a component of photoresist as the only component.

[0010] Furthermore, the preparation method of the "isotropic" zinc-based hybrid compound is as follows: zinc acetate dihydrate is dissolved in an organic solvent, stirred and heated, and recorded as solution A; p-bromobenzoic acid and triethylamine are mixed at room temperature and dispersed in toluene, and recorded as solution B; then solution B is added to solution A while stirring, and reacted to obtain the "isotropic" zinc-based hybrid compound.

[0011] Furthermore, the organic solvent is toluene or ethyl acetate; the stirring and heating temperature is 50-120°C; the molar ratio of zinc acetate dihydrate to p-bromobenzoic acid is 1:(1-4), and the molar ratio of p-bromobenzoic acid to triethylamine is 1:(0.5-1.2); the stirring temperature is 50-120°C, the reaction temperature is 50-120°C, and the reaction time is 6-48h.

[0012] An "isotropic" zinc-based hybrid photoresist coating comprises 1 to 20 parts by weight of an "isotropic" zinc-based hybrid compound and 80 to 90 parts by weight of an organic solvent, wherein the organic solvent is any one of esters, alcohols, benzenes or ethers; the "isotropic" zinc-based hybrid photoresist is a negative photoresist film having a thickness of 10 to 80 nm.

[0013] Preferably, the "isostructural" zinc-based hybrid photoresist coating comprises 2 to 10 parts by weight of an "isostructural" zinc-based hybrid compound and 90 to 98 parts by weight of an organic solvent.

[0014] Preferably, the "isotactic" zinc-based hybrid photoresist is a negative photoresist with a thickness of 40 to 80 nm. More preferably, the "isotactic" zinc-based hybrid photoresist is a negative photoresist with a thickness of 60 nm.

[0015] Furthermore, the organic solvent is a mixture of any one or more of toluene, ethyl acetate, ethyl lactate, methanol, ethanol, isopropyl alcohol, propylene glycol monoacetate, chloroform, dichloromethane, cyclohexanone, or petroleum ether. The type and proportion of the organic solvents affect the coating properties of the photoresist composition. Therefore, adjusting the proportion and type of the organic solvents can improve their solubility in the matrix molecules.

[0016] Furthermore, the preparation method of the "isotactic" zinc-based hybrid photoresist film comprises: dissolving the "isotactic" zinc-based hybrid compound in an organic solvent, filtering through micropores to obtain a spin-coating solution; and forming the spin-coating solution into a film on a substrate to obtain the "isotactic" zinc-based hybrid photoresist film. The film is smooth, dense, and uniform.

[0017] Furthermore, the organic solvent is any one of esters, alcohols, benzenes or ethers; the organic solvent is a mixture of any one or more of toluene, ethyl acetate, ethyl lactate, methanol, ethanol, isopropyl alcohol, propylene glycol monoacetate, chloroform, dichloromethane, cyclohexanone or petroleum ether; the mass ratio of the "isotropic structure" zinc-based hybrid compound to the organic solvent is (1-20):(80-99); the substrate is any one of a silicon wafer, a glass sheet or a quartz wafer; the film forming method is any one of spraying, evaporation, deposition or spin coating; the spin coating parameters are: spin coating speed of 500-5000 rpm, spin coating time of 10-100 s. The pore size of the microporous filtration membrane is 0.22 μm. Preferably, the spin coating speed is 2000 rpm and the spin coating time is 40 s.

[0018] Furthermore, the "isotactic" zinc-based hybrid photoresist film is used in membrane science or lithography, and the lithography includes 248nm lithography, 193nm lithography, extreme ultraviolet lithography or electron beam lithography.

[0019] Furthermore, the photolithography method comprises: subjecting the "isotropic structure" zinc-based hybrid photoresist film to soft baking, exposure, post-baking, development, and hard baking to obtain a photolithography pattern.

[0020] Furthermore, the soft baking temperature is 60-140°C, the soft baking time is 0.1-100s, and the exposure dose at 100keV is 100-1500μC cm -2 The exposure dose at 248nm, 193nm and extreme ultraviolet is 0.1~1500mJ cm -2 The post-baking temperature is 60-140°C, and the post-baking time is 10-100 seconds. The developing agent is any one or more of toluene, ethyl acetate, butyl acetate, propylene glycol monoacetate, ethylene glycol formaldehyde acetate, ethanol, n-propanol, methyl isobutyl ketone, or isopropanol. The developing temperature is room temperature, and the developing time is 5-300 seconds. After the developer is matched with the photoresist described above, it is used to dissolve the unexposed negative photoresist. Preferably, the soft-baking temperature is 110°C, and the soft-baking time is 60 seconds; the post-baking temperature is 110°C, and the post-baking time is 60 seconds.

[0021] The present invention has the following beneficial effects:

[0022] The selected raw materials are cheap and readily available, the synthesis method of the zinc-based hybrid compound is simple, and the prepared product is pure. The designed photoresist molecule is non-chemically amplified, so no photoacid generator is required, and no acid-sensitive groups are required on the ligand unit. It can be in a non-composite form, which is an integrated photoresist that is easy to implement and saves costs. The zinc-oxygen cluster compound of the present invention has good chemical stability and a high thermal decomposition temperature, which can meet the requirements of various advanced photolithography technologies. Moreover, when the zinc-based hybrid compound is used as the main component of the photoresist, the compound undergoes a chemical reaction during the exposure process, which can achieve patterning during the development process. The zinc-oxygen cluster of the present invention is at the molecular level and has the advantage of a clear structure, which is particularly suitable for component analysis before and after exposure and for studying exposure mechanisms. 13 C-NMR studies indicate that the ligand and metal are bound by a coordinate bond, and chemical bond cleavage occurs upon exposure. The zinc oxycluster compound of the present invention has an isotactic structure, with 100% zinc atomic utilization in the zinc salt used, and is soluble in organic solvents commonly used in photoresists. The zinc oxycluster compound of the present invention exhibits no structural change after 100 days of storage under normal conditions. Furthermore, thin films prepared from the photoresist of the present invention exhibit excellent solubility, film-forming properties, adhesion, and thermal stability, are easy to store, and possess a stable structure, meeting the requirements of various photolithographic techniques. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 This is the X-ray single crystal structure analysis of the target compound Zn-PBBA prepared in Example 1 of the present invention.

[0025] Figure 2 The Zn-PBBA zinc oxide cluster prepared in Example 1 of the present invention 1 H-NMR spectrum.

[0026] Figure 3 The Zn-PBBA zinc oxide cluster prepared in Example 1 of the present invention 13 C-NMR spectrum, Note: * indicates the impurity triethylamine.

[0027] Figure 4 This is the FT-IR spectrum of the Zn-PBBA zinc oxide cluster prepared in Example 1 of the present invention.

[0028] Figure 5This is the TGA spectrum of the Zn-PBBA zinc oxide cluster prepared in Example 1 of the present invention.

[0029] Figure 6 This is the DLS spectrum of the Zn-PBBA zinc oxide cluster prepared in Example 1 of the present invention.

[0030] Figure 7 This is the HOMO-LUMO spectrum of the Zn-PBBA zinc oxide cluster prepared in Example 1 of the present invention.

[0031] Figure 8 This is the c-axis stacking model of the Zn-PBBA zinc oxide cluster prepared in Example 1 of the present invention.

[0032] Figure 9 An atomic force microscope (AFM) image (9A) of the mechanical scratch measurement of the film thickness of the Zn-PBBA photoresist prepared in Example 1 of the present invention and a line distribution of the film thickness derived by software (9B) are shown.

[0033] Figure 10 These are optical microscope (OM) images of 1 μm (10A), 0.9 μm (10B), 0.8 μm (10C), 0.7 μm (10D), 0.6 μm (10E), and 0.4 μm (10F) stripe patterns obtained by deep ultraviolet exposure of the negative photoresist in Example 4 of the present invention.

[0034] Figure 11 Graph showing the relationship between the thickness of the photoresist film and the exposure dose in Example 4 of the present invention.

[0035] Figure 12 These are atomic force microscope (AFM) images of 500nm (12A), 300nm (12B), 100nm (12C), 90nm (12D), 70nm (12E), and 50nm (12F) stripe patterns obtained by electron beam exposure of the negative photoresist in Example 4 of the present invention.

[0036] Figure 13 This is a comparison diagram of the post-lithography patterns of the negative photoresist (13A) in Example 4 of the present invention and the negative photoresist (13B) prepared in Comparative Example 1. DETAILED DESCRIPTION

[0037] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without creative work are within the scope of protection of the present invention.

[0038] Example 1

[0039] A method for preparing an "isotactic" zinc-based hybrid compound comprises the following steps:

[0040] Zinc acetate dihydrate (Zn(OAc)2·2H2O, 1.0 g, 5.45 mol) was dispersed in toluene (10 mL), stirred, and heated to 65°C. This solution is designated as Solution A. Parabromobenzoic acid (PBBA, 1.87 g, 9.3 mol) and triethylamine (0.35 g, 6.9 mol) were mixed at room temperature and dispersed in toluene (10 mL). This mixture was designated as Solution B. Solution B was added to Solution A with stirring at 65°C and heated at 65°C for 24 hours. After cooling to room temperature, a homogeneous solution was obtained. The toluene was removed by rotary evaporation, and the resulting sample was dried under vacuum at 50°C for 12 hours, yielding approximately 1.7 g of the compound Zn-PBBA.

[0041] The prepared compound Zn-PBBA has the molecular formula C9H9BrO5Zn and the crystal structure is as follows Figure 1 It belongs to the orthorhombic system, with a space group of Pna21. The length, width and height of the unit cell are and α=β=γ=90°. The basic characterization data of the prepared zinc oxide cluster Zn-PBBA are as follows:

[0042] Figure 2 : 1 H-NMR (600MHz, DMSO-d6) δ7.60 (Ar-H), δ6.50 (Ar-H), 1.83 (-CH3);

[0043] Figure 3 : Note: * indicates the impurity triethylamine.

[0044] Figure 4 :FT-IR:3002cm -1 (vAr-H),2942cm -1 (v-CH3),1654-1588cm -1 (ν as COO),1560(νC=C bending),1396cm -1 (νCH3+ν s COO),1276,839cm -1 (Ar-H bending),771cm -1 (aromaticC-H bending).

[0045] Example 2

[0046] A method for preparing an "isotactic" zinc-based hybrid compound comprises the following steps:

[0047] Zinc acetate dihydrate (Zn(OAc)2·2H2O, 1.0 g, 5.45 mol) was dispersed in ethyl acetate (10 mL), stirred, and heated to 50°C. This solution is designated as Solution A. Parabromobenzoic acid (PBBA, 1.1 g, 5.45 mol) and triethylamine (0.14 g, 2.725 mol) were mixed at room temperature and dispersed in toluene (10 mL). This mixture was designated as Solution B. Solution B was added to Solution A with stirring at 50°C and heated at 50°C for 48 h. After the solution cooled to room temperature, a homogeneous solution was obtained. The toluene was removed by rotary evaporation, and the resulting sample was dried and then vacuum-dried at 50°C for 12 h.

[0048] Example 3

[0049] A method for preparing an "isotactic" zinc-based hybrid compound comprises the following steps:

[0050] Zinc acetate dihydrate (Zn(OAc)2·2H2O, 1.0 g, 5.45 mol) was dispersed in toluene (10 mL), stirred, and heated to 120°C. This solution is designated as Solution A. Parabromobenzoic acid (PBBA, 4.38 g, 21.8 mol) and triethylamine (1.33 g, 26.16 mol) were mixed at room temperature and dispersed in toluene (10 mL). This mixture was designated as Solution B. Solution B was added to Solution A with stirring at 120°C and heated at 120°C for 6 h. After the solution cooled to room temperature, a homogeneous solution was obtained. The toluene was removed by rotary evaporation, and the resulting sample was dried and then vacuum-dried at 50°C for 12 h.

[0051] Thermal stability test: The completely dried zinc-based hybrid compound was placed in a nitrogen atmosphere for thermogravimetric testing. The experimental results are as follows: Figure 5 As shown, the decomposition temperature of 5 wt.% zinc-based material is 162°C, indicating that the material meets the requirements of conventional photolithography process.

[0052] Solubility Testing: Comparative solubility experiments were conducted on the prepared pure zinc-based hybrid compound. It is soluble in most common laboratory organic solvents, such as dichloromethane, methanol, ethanol, and ethyl acetate. It is insoluble in water but readily soluble in benzene-based solvents, such as toluene, xylene, and chlorobenzene.

[0053] Example 4

[0054] A method for preparing a negative photoresist film, comprising the following steps:

[0055] The prepared pure zinc-based hybrid photoresist (abbreviated as Zn-PBBA) was dissolved in isopropyl alcohol to obtain a 5wt% solution. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a clear spin-coating solution. The film was then spin-coated on a silicon substrate at 2000 rpm for 40 seconds. After spin coating, the film was baked at 110°C for 60 seconds to obtain a negative photoresist film. In all embodiments and comparative examples, after baking process screening, it was preferred that baking at 110°C for 60 seconds could obtain a relatively smooth and uniform film. This condition was used in the following embodiments and comparative examples.

[0056] Particle size analysis test: Dynamic light scattering (DLS) was used to test the particle size distribution of the compound in the photoresist prepared in Example 4. The experimental results are shown in Figure 2. Figure 6 As shown, the hydrodynamic radius of the photoresist in isopropyl alcohol is 0.710 nm.

[0057] Frontier orbital simulation calculation: Gaussian calculation was used to obtain the highest occupied orbital and lowest unoccupied orbital energies of the structure in Example 1. The experimental results are as follows: Figure 7 As shown, the HOMO-LUMO band gap is -6.5 eV.

[0058] Figure 8 and Figure 9 It is a study of film thickness. Figure 8 The arrangement of compounds in the film is simulated by software. Figure 9 A. The thin film prepared in Example 4 was scratched on a silicon wafer with a spin-coated photoresist using a syringe needle tip, and the depth of the scratch was measured using an AFM probe scan to characterize the film thickness. Figure 9 B is the distribution of film thickness derived from the software, and the measurement result is 56.0 nm.

[0059] Comparative Example 1

[0060] A representative comparative example was selected, holding all other variables constant in all failed experimental cases. The following negative photoresist film formulation was prepared: Zn-PBBA was dissolved in ethyl acetate to prepare a 5 wt% solution. This solution was filtered through a 0.22 μm pore filter to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate at 2000 rpm for 40 seconds. After spin coating, the film was baked at 110°C for 60 seconds, resulting in a thickness of approximately 60 nm.

[0061] Example 5

[0062] A method for preparing a negative photoresist film, comprising the following steps:

[0063] The prepared pure zinc-based hybrid photoresist (abbreviated as Zn-PBBA) was dissolved in isopropanol to prepare a 1 wt% solution. The solution was then filtered through a 0.22 μm pore filter to obtain a clear, transparent spin-coating solution. This solution was then spin-coated onto a silicon substrate at 500 rpm for 100 seconds. After spin coating, the solution was baked at 110°C for 60 seconds to obtain a negative photoresist film.

[0064] Example 6

[0065] A method for preparing a negative photoresist film, comprising the following steps:

[0066] The prepared pure zinc-based hybrid photoresist (abbreviated as Zn-PBBA) was dissolved in isopropanol to prepare a 20 wt% solution. The solution was then filtered through a 0.22 μm pore filter to obtain a clear, transparent spin-coating solution. This solution was then spin-coated onto a silicon substrate at 5000 rpm for 10 seconds. After spin coating, the solution was baked at 110°C for 60 seconds to obtain a negative photoresist film.

[0067] Application Example 1

[0068] The steps for preparing the photolithographic pattern are as follows:

[0069] The "isotactic" zinc-based hybrid photoresist film was soft-baked, exposed, post-baked, developed, and hard-baked to obtain a photolithographic pattern. The soft-baking temperature was 110°C, the soft-baking time was 60s, and the exposure dose was 69mJ cm -2 The post-baking temperature is 110°C and the post-baking time is 60 seconds. The developing agent is any one or more of isopropyl alcohol, the developing temperature is room temperature, and the developing time is 5 seconds. After drying with nitrogen, the film is hardened at 110°C for 30 seconds.

[0070] Figure 10 This is the result of photolithography of the photoresist film prepared in Example 4 under a mercury lamp. Figure 10 A to Figure 10 F is an optical microscope image of the photoresist after exposure at the same dose. The best development result is as follows Figure 10 Finally, the developing conditions were determined as follows: isopropyl alcohol as the developing solution, developing time 5s, and after drying with nitrogen, the film was hardened at 110℃ for 30s.

[0071] The sensitivity test was conducted under the optimal photolithography conditions obtained in Application Example 1. The relationship between the film thickness after AFM probe scanning and the exposure dose is shown in the figure below. Figure 11 As shown in the figure, the optimal dose of the prepared photoresist film is 69mJ cm -2 . Figure 12 A to Figure 12 F is an optical micrograph of the photoresist after exposure at the same dose. Figure 12The exposure results of the exposure experiment on the film prepared in Example 4 on an electron beam exposure machine under the optimal dose are as follows: isopropyl alcohol solution for 5 seconds, nitrogen blowing for 2 seconds, and baking at 110°C for 60 seconds. Figure 12 A-12F shows that the lines are well developed, and the maximum stripe width can be 50nm, indicating that the prepared photoresist has high-resolution imaging capabilities. Given the excellent physical and chemical properties of the zinc oxy clusters used in the present invention, its photolithographic effect is expected to be further explored and verified.

[0072] The purpose of setting up the comparative example is to illustrate that the results of the two adhesive solutions prepared in the comparative example and Example 4 after development are different. Figure 13 shown.

[0073] Repeated exposure experiments on the photoresist films prepared by the present invention demonstrated that the required exposure dose was essentially the same for each exposure. These results demonstrate the stability of the synthesized zinc-based hybrid compound, allowing for similar exposure doses across batches of photoresist films. Ensuring the precise formulation of the zinc-based hybrid compound into photoresist films allows for experimental repeatability.

[0074] Application Example 2

[0075] The steps for preparing the photolithographic pattern are as follows:

[0076] The "isotropic" zinc-based hybrid photoresist film was soft-baked, exposed, post-baked, developed, and hard-baked to obtain a photolithographic pattern. The soft-baking temperature was 60°C, the soft-baking time was 100s, and the exposure dose was 100μC cm at 100keV. -2 The exposure time is 120 seconds; the post-baking temperature is 110°C and the post-baking time is 60 seconds; the developing agent is any one or more of isopropyl alcohol, the developing temperature is room temperature, and the developing time is 5 seconds. After drying with nitrogen, the film is hardened at 110°C for 30 seconds.

[0077] Application Example 3

[0078] The steps for preparing the photolithographic pattern are as follows:

[0079] The "isotropic" zinc-based hybrid photoresist film was soft-baked, exposed, post-baked, developed, and hard-baked to obtain a photolithographic pattern. The soft-baking temperature was 140°C, the soft-baking time was 10s, and the exposure dose was 1500μC cm at 100keV. -2 The post-baking temperature is 110°C and the post-baking time is 60 seconds. The developing agent is any one or more of isopropyl alcohol, the developing temperature is room temperature, and the developing time is 5 seconds. After drying with nitrogen, the film is hardened at 110°C for 30 seconds.

[0080] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An "isotactic" zinc-based hybrid compound, characterized in that: The zinc-based hybrid compound is prepared in one step using p-bromobenzoic acid and zinc acetate dihydrate as raw materials. Its molecular formula is C9H9BrO5Zn, it belongs to the orthorhombic crystal system, the space group is Pna21, and the length, width and height of its unit cell are 8.0560(7) Å, 5.7165(6) Å and 25.226(2) Å, respectively; α=β=γ=90°.

2. The method for preparing the "isotropic" zinc-based hybrid compound according to claim 1, characterized in that: Zinc acetate dihydrate is dissolved in an organic solvent, stirred, and heated, referred to as solution A. p-Bromobenzoic acid and triethylamine are mixed at room temperature and dispersed in toluene, referred to as solution B. Solution B is then added to solution A with stirring, and the reaction proceeds to obtain an "isotactic" zinc-based hybrid compound.

3. The method for preparing the "isomorphic" zinc-based hybrid compound according to claim 2, characterized in that: The organic solvent is toluene or ethyl acetate; the stirring and heating temperature is 50-120°C; the molar ratio of zinc acetate dihydrate to p-bromobenzoic acid is 1:(1-4), and the molar ratio of p-bromobenzoic acid to triethylamine is 1:(0.5-1.2); the stirring temperature is 50-120°C, the reaction temperature is 50-120°C, and the reaction time is 6-48 hours.

4. An "isotropic" zinc-based hybrid photoresist film, characterized by: The invention comprises 1 to 20 parts by weight of the "isotropic" zinc-based hybrid compound according to claim 1 and 80 to 90 parts by weight of an organic solvent, wherein the organic solvent is any one of esters, alcohols, benzenes or ethers; the "isotropic" zinc-based hybrid photoresist film is a negative photoresist film having a thickness of 10 to 80 nm.

5. The "isotropic" zinc-based hybrid photoresist film according to claim 4, characterized in that: The organic solvent is a mixture of any one or more of toluene, ethyl acetate, ethyl lactate, methanol, ethanol, isopropanol, propylene glycol monoacetate, or petroleum ether.

6. The method for preparing the "isotropic" zinc-based hybrid photoresist film according to claim 4 or 5, characterized in that: The "isotropic" zinc-based hybrid compound is dissolved in an organic solvent and filtered through micropores to obtain a spin coating solution; the spin coating solution is formed into a film on a substrate to obtain an "isotropic" zinc-based hybrid photoresist film.

7. The method for preparing an "isotropic" zinc-based hybrid photoresist film according to claim 6, characterized in that: The organic solvent is any one of esters, alcohols, benzenes or ethers; the mass ratio of the "isotropic" zinc-based hybrid compound to the organic solvent is (1-20):(80-99); the substrate is any one of a silicon wafer, a glass sheet or a quartz wafer; the film forming method is any one of spraying, evaporation, deposition or spin coating; the spin coating parameters are: a spin coating speed of 500-5000 rpm and a spin coating time of 10-100 s.

8. Use of the "isotropic" zinc-based hybrid photoresist film according to claim 4 or 5 in photolithography, characterized in that: The photolithography includes 248nm photolithography, 193nm photolithography, extreme ultraviolet photolithography or electron beam photolithography.

9. The use according to claim 8, characterized in that The photolithography method comprises the following steps: soft-baking, exposing, post-baking, developing, and hard-baking a "completely isotropic" zinc-based hybrid photoresist film to obtain a photolithographic pattern.

10. The use according to claim 9, characterized in that: The soft baking temperature is 60-140°C, the soft baking time is 0.1-100 s, and the exposure dose is 100-1500 μC cm at 100 keV. -2 The exposure dose at 248nm, 193nm and extreme ultraviolet is 0.1 to 1500 mJ cm -2 The post-baking temperature is 60 to 140°C, and the post-baking time is 10 to 100 seconds. The developing agent is any one or more of toluene, ethyl acetate, butyl acetate, propylene glycol monoacetate, ethylene glycol formaldehyde acetate, ethanol, n-propanol, methyl isobutyl ketone or isopropanol. The developing temperature is room temperature, and the developing time is 5 to 300 seconds.

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