Organic compound, patterning composition, patterning method, patterned film, patterned substrate and electronic component

Abstract

The invention provides an organic metal cluster, a patterning composition, a patterning method, a patterned film, a patterned substrate and an electronic component, the organic metal cluster comprises a metal oxide inner core and an organic ligand coordinated with the metal oxide inner core, the molecular general formula of the organic metal cluster is MxOy (L1) n (L2) m, M is selected from titanium, zirconium or hafnium, n is greater than or equal to 1, and m is greater than or equal to 1. L1 and L2 are respectively selected from organic ligands capable of coordinating with M, and the organic metal cluster also meets the following condition a or b; a: 1 < = x < = 5, 1 < = y < = 30, y < = 6x, 0 < = n < = 6x, 0 < = m < = 6x, 1 < = n + m < = 6x, and L1 and / or L2 comprises at least one aromatic ring; b: 6 < = x < = 30, 1 < = y < = 180, y < = 6x, 0 < = n < = 6x, 0 < = m < = 6x, 1 < = n + m < = 6x. According to the organic metal cluster disclosed by the invention, the solubility and the sensitivity of the titanium, zirconium or hafnium-based organic cluster are improved through a special molecular design, and the problem that the solubility of the existing titanium-based organic-inorganic hybrid metal oxygen cluster is poor is solved.

Description

[0001] The present application claims priority to the Chinese patent application No. 202510729231.4, filed on May 30, 2025, entitled "An organic compound, a patterning composition, a patterning method, a patterned film, a patterned substrate and an electronic device", the whole content of which is incorporated herein by reference. TECHNICAL FIELD

[0002] The present application relates to the technical field of patterning, in particular to an organic compound, a patterning composition, a patterning method, a patterned film, a patterned substrate and an electronic device. BACKGROUND

[0003] The patterning compound is a key material for micro-pattern processing in microelectronic technology, which is an etch-resistant material whose solubility in the developing solution changes through light irradiation or radiation. The traditional patterning compound is mainly composed of elements such as C, H, O and N. These patterning compounds have problems such as low light absorption efficiency and poor etch resistance. Research has found that metal elements can greatly enhance the absorption efficiency of light sources, so the organic-inorganic hybrid metal oxide cluster type patterning compound can well solve the above problems.

[0004] The existing organic-inorganic hybrid metal oxide cluster type patterning compound mainly uses organic tin as the main structure. This type of material has high toxicity and causes great pollution to wafers and production processes. The use of titanium and its low-pollution metal to replace tin can reduce the pollution of tin materials to semiconductor devices, but the organic-inorganic hybrid metal oxide cluster of titanium and its group has the problem of poor solubility, which makes it difficult to form a uniform film, thus limiting the application of this type of cluster.

[0005] SUMMARY

[0006] The present application provides an organic metal cluster, a patterning composition, a patterning method, a patterned film, a patterned substrate and an electronic device. The organic metal cluster of the present application uses titanium, zirconium or hafnium oxide as the skeleton, has low pollution to semiconductor devices, and improves the solubility and photosensitivity of titanium, zirconium or hafnium-based organic clusters through special molecular design, solving the problem of poor solubility of existing titanium-based organic-inorganic hybrid metal oxide clusters.

[0007] In detail, the first aspect of the present application provides an organic metal cluster, which comprises a metal oxide core and an organic ligand coordinated with the metal oxide core, and the molecular general formula is: M x O y (L1) n (L2) mwherein M is selected from titanium, zirconium or hafnium, L1and L2are respectively selected from organic ligands capable of coordinating with M, and the organometallic cluster further satisfies the following condition a or b:

[0008] a: 1≤x≤5, 1≤y≤30, y≤6x, 0≤n≤6x, 0≤m≤6x, 1≤n+m≤6x, the L1and / or L2include at least one aromatic ring;

[0009] b: 6≤x≤30, 1≤y≤180, y≤6x, 0≤n≤6x, 0≤m≤6x, 1≤n+m≤6x.

[0010] The organometallic cluster of the present application takes titanium, zirconium or hafnium oxide as the core, avoiding the problems of toxicity and pollution in the existing metal oxide cluster type with organotin as the main structure. The present application also improves the solubility of the organometallic cluster taking titanium, zirconium or hafnium oxide as the core through special molecules.

[0011] In a possible implementation, the L1and L2include coordination atoms capable of coordinating with the M, and the coordination atoms include at least one of O, N, S, Se, P.

[0012] In this case, the patterning material of the present application can have a more stable structure, more excellent radiation sensitivity and more excellent low outgassing, and is easier to obtain.

[0013] In a possible implementation, the organic ligand further includes a radiation-sensitive functional group, and the radiation-sensitive functional group includes at least one of alkenyl, alkynyl, benzyl or epoxy.

[0014] In this case, by introducing the radiation-sensitive functional group in the organic ligand, the photosensitivity of the organometallic cluster is further enhanced, the line edge roughness is improved, and the resolution is improved.

[0015] In a possible implementation, when the organometallic cluster satisfies the condition a, the organic ligand includes magnolol coordination groups and / or Schiff base coordination groups.

[0016] When the organometallic cluster satisfies the condition b, the organic ligand includes methacrylic acid coordination groups.

[0017] As described above, the organic ligand not only enables the organometallic cluster structure of the present application to have more excellent solubility and high photosensitivity, but also is beneficial to control the molecular size of the organometallic cluster structure to be small due to the small number of carbon atoms, so that the clusters can be arranged more closely, which is beneficial to further improve the resolution of the pattern.

[0018] In one possible implementation, the organic metal cluster comprises at least one compound of the following formulae 1 to 3:

[0019] Ti5O2(L1)4(L2)8, formula 1, wherein L1 is a magnolol ligand, and L2 is an isopropyl alcohol ligand;

[0020] Ti4O2(L1)6(L2)4, formula 2, wherein L1 comprises a Schiff base ligand and a magnolol ligand, and L2 comprises a hexafluoroisopropanol and a N,N dimethylformamide ligand;

[0021] Ti9O8(L1)4(L2) 16 formula 3, wherein L1 is a methacrylic acid ligand, and L is an isopropyl alcohol ligand.

[0022] The second aspect of the present application provides a patterning composition comprising a solvent and the organic metal cluster of the first aspect.

[0023] In the patterning composition of the present application, the organic metal cluster is easily dissolved in the solvent, which facilitates film coating, and the formed coating film layer has a smooth surface, a film thickness that is easy to adjust, and development conditions that meet the requirements of the patterning process, thus facilitating application.

[0024] The third aspect of the present application provides a method for patterning a substrate surface, comprising:

[0025] providing a substrate;

[0026] forming a patterning material layer on a surface of the substrate using the organic metal cluster of the first aspect or the patterning composition of the second aspect, and performing local exposure on the patterning material layer;

[0027] developing the exposed patterning material layer using a developing solution to form a patterned film on the substrate.

[0028] The method for patterning a substrate surface described above can obtain a high-quality pattern, thereby improving the precision of components and the preparation efficiency.

[0029] The fourth aspect of the present application provides a patterned film, which is formed using the patterning composition of the second aspect or obtained using the patterning method of the third aspect.

[0030] The patterned film of the present application can be used as a high-precision mask plate in the patterning process of integrated circuits, and the pattern of the patterned film can be transferred to a substrate such as a silicon wafer by etching, so as to form a preset pattern on the substrate.

[0031] The fifth aspect of the present application provides a patterned substrate, wherein the pattern on the patterned substrate is formed by the patterned composition according to the second aspect or obtained by the patterned method according to the third aspect.

[0032] The patterned substrate of the present application can be used in the preparation of electronic components such as chips, thereby improving the precision and quality of device fabrication and further improving the performance of electronic components.

[0033] The sixth aspect of the present application provides an electronic component, which is prepared by the patterned film according to the fourth aspect or by the steps of the patterned substrate according to the sixth aspect.

[0034] The electronic component of the present application can further improve the precision and preparation efficiency of the electronic component due to the preparation of the patterned film or the patterned substrate.

[0035] The organic metal cluster provided by the present application has titanium, zirconium or hafnium oxide as a skeleton, has low pollution to semiconductor devices, and improves the solubility and photosensitivity of titanium, zirconium or hafnium-based organic clusters through special molecular design, thereby solving the poor solubility problem of existing titanium-based organic-inorganic hybrid metal oxide clusters. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 The figure is a schematic diagram of the single crystal structure of the organic metal cluster of Example 1 of the present application;

[0037] Figure 2 The figure is a powder diffraction spectrum of the organic metal cluster of Example 1 of the present application;

[0038] Figure 3 The figure is an infrared spectrum of the organic metal cluster of Example 1 of the present application;

[0039] Figure 4 The figure is a schematic diagram of the single crystal structure of the organic metal cluster of Example 3 of the present application;

[0040] Figure 5 The figure is a powder diffraction spectrum of the organic metal cluster of Example 1 of the present application;

[0041] Figure 6 The figure is a schematic diagram of the single crystal structure of the organic metal cluster of Example 4 of the present application;

[0042] Figure 7 The figure is a powder diffraction spectrum of the organic metal cluster of Example 4 of the present application;

[0043] Figure 8 The figure is a schematic diagram of the single crystal structure of the organic metal cluster of Comparative Example 1;

[0044] Figure 9 The figure is an SEM characterization result of the pattern formed by the method of Test Example 1;

[0045] Figure 10 SEM characterization result graph of the pattern formed by the method of test example 1;

[0046] Figure 11 SEM characterization result graph of the pattern formed by the method of test example 3;

[0047] Figure 12 AFM characterization result graph of the pattern formed by the method of test example 4. DETAILED DESCRIPTION

[0048] In order to make the purposes, technical solutions and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0049] In order to better understand the technical solutions of the present application, some key processes and terms involved in the present application are explained as follows:

[0050] Developer: Developer is a pure or mixed solvent that can dissolve the area that is soluble after the solubility of the patterned material caused by exposure changes.

[0051] Positive patterned compound: During the exposure process, the chemical structure of the positive patterned compound changes, so that the exposed area becomes more soluble in the developer, and the exposed part is washed away by the developer, forming a positive pattern.

[0052] Negative patterned compound: During the exposure process, the chemical structure of the negative patterned compound changes, so that the exposed area becomes insoluble in the developer, and the unexposed area is washed away by the developer, forming a negative pattern.

[0053] Spin coating process: Spin coating is a high-speed film forming method that can obtain uniform thin films, and uniformity is widely used in thin film preparation of semiconductor materials and chemical materials. It uses centrifugal force generated by rotation to uniformly spread sol, solution or suspension on the substrate surface.

[0054] Mask plate: In the patterning process, the mask is an optical element in the optical path, and the mask carries a design pattern. Light is selectively transmitted or reflected through it, and the design pattern can be transmitted on the patterned material film layer.

[0055] Patterning: lithography, patterning process, lithography process, is an important step in the semiconductor device manufacturing process, which exposes and develops the process to draw a set of patterns on the patterning material, and the pattern on the mask is transferred to the substrate by etching process. The substrate includes not only silicon wafers, but also other metal layers, dielectric layers, and the above-mentioned substrates with surface modification or additional layers.

[0056] The patterning process includes: (1) forming a patterning material film layer on the substrate by using a patterning compound; (2) selectively exposing the patterning material film layer; (3) developing the exposed patterning material film layer to remove part of the patterning material film layer; (4) etching the substrate with the remaining patterning material film layer as a protective layer.

[0057] In step (1), the patterning material film layer is formed on the substrate by mixing the organometallic cluster with a suitable solvent to form a solution with a certain concentration. The solution concentration can be adjusted according to the film thickness requirement. Generally, the higher the solution concentration, the thicker the film layer. According to the size of the substrate, a certain amount of solution is spin-coated on the substrate to form a patterning material film layer with a thickness of less than 100 nm. The solvent remaining in the film layer is usually removed by baking before selective exposure.

[0058] In step (2), a mask can be used for selective exposure. The patterning material film layer is selectively irradiated by a single wavelength or mixed wavelength ray in the range of 1-15 nm Soft X-ray through the mask to transfer the pattern on the mask to the patterning material film layer. After selective irradiation of the patterning material film layer, the chemical properties of the irradiated part change and the solubility changes.

[0059] In step (3), the irradiated patterning material film layer is cleaned with a developing solution, and the cleaning time is 10-300 seconds, which can be single-step cleaning or multi-step cleaning. In step (4), the pattern formed by the photoresist selectively protects the substrate during etching. After etching under certain conditions, the photoresist and the unprotected substrate are etched, but the etching rate of the protected area is slower than that of the unprotected area, and finally a pattern is formed on the substrate.

[0060] It can be seen that step (1) mixes the organometallic cluster with a suitable solvent to form a photoresist solution with a certain concentration, which is the basis of the patterning process. If the solubility of the organometallic cluster is poor, it will directly lead to the failure of the subsequent process. Therefore, in order to provide an organometallic cluster with excellent solubility and low toxicity, the following solutions are provided:

[0061] In a first aspect, the present application provides an organometallic cluster, the organometallic cluster comprising a metal oxide core and organic ligands coordinated to the metal oxide core, and having a general formula of: M x O y (L1) n (L2) m wherein M is selected from titanium, zirconium or hafnium, L1 and L2 are respectively selected from organic ligands capable of coordinating to M, and the organometallic cluster further satisfies one of the following conditions a or b:

[0062] a: 1≤x≤5, 1≤y≤30, y≤6x, 0≤n≤6x, 0≤m≤6x, 1≤n+m≤6x, the L1 and / or L2 comprises at least one aromatic ring;

[0063] b: 6≤x≤30, 1≤y≤180, y≤6x, 0≤n≤6x, 0≤m≤6x, 1≤n+m≤6x.

[0064] The organometallic cluster of the present application takes titanium, zirconium or hafnium oxide as the core, avoiding the problems of toxicity and pollution in the prior art metal oxide cluster type mainly structured by organotin. In addition, the solubility of the organometallic cluster taking titanium, zirconium or hafnium oxide as the core is improved by special molecules. In detail, when condition a is satisfied, the TiO core in the structure of the organometallic cluster is reduced, the proportion of the organic ligand on the outside is increased and the proportion of the organic component in the organometallic cluster is increased, which facilitates mutual dissolution with the organic solvent and further improves the solubility. When condition b is satisfied, the symmetry of the structure of the organometallic cluster is low, there is no central symmetry axis, it is difficult to stack in a regular manner, and only a triclinic system is formed in the crystal, thereby facilitating the improvement of the solubility.

[0065] In a possible implementation, the L1 and L2 comprise coordination atoms capable of coordinating to the M, and the coordination atoms comprise at least one of O, N, S, Se and P.

[0066] In this case, the patterning material of the present application can have a more stable structure, more excellent radiation sensitivity and more excellent low outgassing property, and is more easily obtained.

[0067] In some embodiments, the organic ligand of the present application comprises L1 and L2, L1 comprises a coordination functional group capable of coordinating with M and a reaction functional group, the coordination functional group comprises the coordination atom, the coordination functional group comprises at least one of carboxyl, amino, hydroxyl, phenol, nitrile, alcohol amine, amide, carbonyl and the like, the reaction functional group is capable of chemical reaction under 1-15 nm soft X-ray or electron beam, the solubility of the cluster is changed after the reaction, and then a pattern is formed on the surface of the film layer, the reaction type comprises at least one of cross-linking, bond breaking, exchange and separation, and the like; the reaction functional group comprises at least one of alkenyl, alkynyl, benzyl, epoxy and the like; L2 is mainly used to provide steric hindrance to control the size of the inner core, and exemplarily, the L2 comprises at least one of carboxyl, amino, hydroxyl, phenol, nitrile, alcohol amine, amide, carbonyl and the like.

[0068] In a possible implementation, the organic ligand comprises a radiation-sensitive functional group, the radiation-sensitive functional group comprises at least one of alkenyl, alkynyl, benzyl or epoxy.

[0069] In this case, by introducing the radiation-sensitive functional group in the organic ligand, the photosensitivity of the organometallic cluster is further enhanced, the line edge roughness is improved, and the resolution is improved.

[0070] In some embodiments, the organic ligand of the present application comprises L1 and L2, L1 comprises a coordination functional group capable of coordinating with M and a radiation-sensitive functional group, the coordination functional group comprises the coordination atom, the coordination functional group comprises at least one of carboxyl, amino, hydroxyl, phenol, nitrile, alcohol amine, amide, carbonyl and the like, the radiation-sensitive functional group is capable of chemical reaction under 1-15 nm soft X-ray or electron beam, the solubility of the cluster is changed after the reaction, and then a pattern is formed on the surface of the film layer, the reaction type comprises at least one of cross-linking, bond breaking, exchange and separation, and the like; the reaction functional group comprises at least one of alkenyl, alkynyl, benzyl, epoxy and the like; L2 is mainly used to provide steric hindrance to control the size of the inner core, and exemplarily, the L2 comprises at least one of carboxyl, amino, hydroxyl, phenol, nitrile, alcohol amine, amide, carbonyl and the like.

[0071] In a possible implementation, when the organometallic cluster satisfies the condition a, the organic ligand comprises magnolol coordination group and / or Schiff base coordination group.

[0072] When the organometallic cluster satisfies the condition b, the organic ligand comprises methacrylic acid coordination group.

[0073] The organic ligand as described above not only can obtain the organic metal cluster structure of the present application, but also has more excellent solubility and high photosensitivity, and due to the less number of carbon atoms, the molecular size of the organic metal cluster structure can be controlled to be small, so that the clusters can be arranged more closely, and the resolution of the pattern can be further improved.

[0074] In a possible implementation, the L1 and / or L2 includes at least one substituent of fluorine, chlorine, bromine, iodine, and sulfur.

[0075] In this case, due to the different electronegativities of the substituents, the polarity of the organic metal cluster can be affected, and the solubility of the organic metal cluster can be further improved. For example, fluorine and chlorine have high electronegativity, and the introduction of these elements can increase the polarity of the organic metal cluster, thereby improving the solubility of the organic metal cluster in a polar solvent (such as water or alcohol).

[0076] In addition, the substituents can improve the light absorption capacity of the organic metal cluster. This is because the outer electrons of fluorine, chlorine, bromine, iodine, and sulfur are more than those of carbon and hydrogen, and the light absorption rate is high. After absorbing light, more secondary electrons can be generated, thereby reducing the exposure dose.

[0077] In a possible implementation, the molecular formula of the organic metal cluster is Ti5O2(L1)4(L2)8, where L1 is magnolol coordination base, and L2 is isopropanol coordination base.

[0078] In a possible implementation, the crystal state of the organic metal cluster has a triclinic crystal system, a P-1 space group, a cell parameter a of 13. 1 A, a cell parameter b of 13. 1 A, a cell parameter c of 13. 1 A, an α of 80. 11°, a β of 83. 98°, a γ of 81. 01°, and a V of 1, 800. 1 A3. b is 13. 1 A, c is 13. 1 A, α is 80. 11°, β is 83. 98°, γ is 81. 01°, and V is 1, 800. 1 A3.

[0079] In a possible implementation, the molecular formula of the organic metal cluster is Ti4O2(L1)6(L2)4, where L1 includes Schiff base coordination base and magnolol coordination base, and L2 includes hexafluoroisopropanol and N, N dimethylformamide coordination base.

[0080] In a possible implementation, the crystal state of the organic metal cluster has a monoclinic crystal system, a P1 21 / n 1 space group, a cell parameter a of 13. 1 A, a cell parameter b of 13. 1 A, a cell parameter c of 13. 1 A, an α of 90°, a β of 92. 13°, a γ of 90°, and a V of 1, 800. 1 A3. b is 13. 1 A, c is 13. 1 A, α is 90°, β is 92. 13°, γ is 90°, and V is 1, 800. 1 A3.

[0081] In a possible implementation, the organic metal cluster has a molecular formula of Ti9O8(L1)4(L2) 16 wherein L1 is a methacrylic coordination group, and L is an isopropyl alcohol coordination group.

[0082] In a possible implementation, the crystal state of the organic metal cluster has a triclinic crystal system, a P-1 space group, a cell parameter a of b is c is α is 87.65, β is 88.16°, γ is 72.023°, and V is

[0083] In a possible implementation, the method for preparing the organic metal cluster comprises the following steps:

[0084] The M source and the organic ligand are dissolved in a solvent, stirred, filtered, reacted at 200°C or below for at least 1 hour, and the solvent is removed to obtain the organic metal cluster.

[0085] In some implementations, in order to improve the yield of the organic metal cluster, the reaction is performed at 40°C-100°C for at least 1 hour.

[0086] The method for preparing the organic metal cluster provided in the application has a simple process and is easy to be industrialized.

[0087] In a second aspect, the application provides a patterning composition comprising a solvent and the organic metal cluster of the first aspect.

[0088] In the patterning composition, the organic metal cluster is dissolved in the solvent, which is convenient for film coating, and the formed coating film layer has a smooth surface, a film thickness that is easy to adjust, and a development condition that meets the requirements of the patterning process, and is convenient for application.

[0089] In the implementations of the application, the organic metal cluster can comprise one or more of the above-described organic metal clusters.

[0090] In the implementations of the application, the solvent can comprise one or more of, but is not limited to, N,N-dimethylformamide (DMF) or ethyl lactate, and propylene glycol methyl ether acetate. The above-described solvent can better dissolve the organic metal cluster to achieve a target concentration, form a uniform coating liquid, and be suitable for film coating.

[0091] Exemplarily, the above-described alcohol solvent can be, but is not limited to, 4-methyl-2-pentanol; and the ester solvent can be, but is not limited to, propylene glycol methyl ether acetate.

[0092] In some embodiments, the concentration of the organic metal cluster is 1 mg / mL to 100 mg / mL. In some embodiments, the concentration of the organic metal cluster is 5 mg / mL to 20 mg / mL. In some embodiments, the concentration of the organic metal cluster is 1 mg / mL, 5 mg / mL, 10 mg / mL, 15 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL, 80 mg / mL, 90 mg / mL, or 100 mg / mL. The concentration is suitable to ensure high efficiency and high quality of the patterning process.

[0093] In some embodiments, other additives can be added to the patterning composition to improve the overall performance of the patterning composition. The other additives can include one or more of leveling agents and surfactants. The addition of the leveling agents and surfactants can improve the uniformity of the coating film. The content of the other additives in the patterning composition can be adjusted according to actual needs.

[0094] In a third aspect, the present application provides a method for patterning a surface of a substrate, comprising:

[0095] providing a substrate;

[0096] forming a layer of patterning material on a surface of the substrate using the organic metal cluster of the first aspect or the patterning composition of the second aspect, and performing local exposure on the layer of patterning material;

[0097] developing the exposed film layer using a developing solution to form a patterned film on the substrate.

[0098] It should be noted that the substrate can be selected according to specific needs, for example, it can be a silicon wafer, or a silicon wafer covered with other coatings, which can be an anti-reflection coating, an etch-resistant coating, an epitaxial layer, a metal layer, a dielectric layer, a modification layer or a matching layer. Generally, the other coating can be obtained by pretreating the substrate. The pretreatment method can be: performing O2 plasma surface hydrophilic activation on the silicon wafer substrate; or washing in Piranha solution (H2O: 30% ammonia water: 30% H2O2=5:1:1) for 15-20 minutes, and then washing with deionized water and isopropanol to complete the hydrophilic treatment; or using evaporation or spin coating to cover hexamethyldisilazane (HMDS) on the substrate to perform surface hydrophobic treatment; the hydrophobic treatment can be after the hydrophilic treatment; or adding a bottom anti-reflection layer (BARC), a bottom carbon-containing coating (SOC), or a bottom silicon-containing coating (SOG).

[0099] In the embodiments of the present application, the above-mentioned use of the organic metal cluster of the first aspect or the patterning composition of the second aspect to form a patterned material layer on a surface of the substrate specifically includes the following processes:

[0100] According to the size of the substrate, an appropriate amount of volume of the patterning composition is spin-coated on the substrate to form a patterned material film layer with a thickness of 5-200 nm, and the surface roughness of the film layer can be less than 2 nm. For example, a 4-inch substrate can be spin-coated with 1-5 mL of the patterning composition;

[0101] After spin coating, the solvent remaining in the film layer can be selectively removed by an baking process before exposure. The baking temperature can be between 60-200°C, and the time can be between 20-120s.

[0102] In the embodiments of the present application, the patterned material layer is partially exposed, specifically including the following processes:

[0103] The patterned material film layer is exposed to an exposure light source through a mask plate;

[0104] In some embodiments, the patterned material film layer can be selectively irradiated by a light source through a mask plate to reflect the pattern on the mask plate to the patterned material film layer. After the patterned material film layer is selectively exposed to the light source, the exposed part undergoes a chemical reaction and changes in solubility.

[0105] In some embodiments, the patterned material film is baked after exposure and before development. The baking temperature is between 60 °C and 200 °C, and the baking time is between 20 s and 120 s. The baking operation can facilitate the completion of the chemical reactions that are not completed in the film.

[0106] In some embodiments, the developer used in the development of the exposed film is selected based on the properties of the organic metal. For example, the developer can be selected from organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents with additives, and the like. In some embodiments, the developer can be a 0.5-5% tetramethylammonium hydroxide (TMAH) aqueous solution, or a ketone, an alcohol, an ether, an ester, a lactone, a high-boiling alcohol, or the like. For example, the ketone can be cyclohexanone or methyl-2-n-pentyl ketone; the alcohol can be at least one of 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; the ether can be at least one of propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; the ester can be at least one of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; and the lactone can be gamma-butyrolactone. The high-boiling alcohol can be at least one of diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol. The developer can be in contact with the exposed film for 10 s to 120 s. After development, a water rinse can be optionally added, which can be performed for 20 s to 120 s. The rinse can make the film cleaner. A baking operation can also be optionally added, which can be performed at a temperature of 60 °C to 200 °C for 20 s to 120 s. The baking operation can make the pattern more stable and less likely to collapse.

[0107] After development, the resulting pattern can be observed using SEM or AFM, and the resolution of the resulting pattern can be between 3 nm and 100 nm. In some embodiments, the method further comprises etching the substrate after development to transfer the pattern of the patterned film to the substrate to obtain a patterned substrate.

[0108] In a fourth aspect, the present application provides a patterned film formed using the patterned composition of the second aspect or obtained using the method of the third aspect.

[0109] The patterned film of the embodiments of the present application can be used as a high-precision mask plate in the process of manufacturing integrated circuit pattern, and the pattern of the patterned film can be transferred to a substrate such as a silicon wafer by etching to form a preset pattern on the substrate.

[0110] The metal organic cluster provided by the embodiments of the present application has good exposure performance, and the patterned film prepared therefrom has high resolution, low edge roughness and high critical dimension uniformity.

[0111] Specifically, in some embodiments of the present application, the resolution of the patterned film is ≤100 nm. For example, 3 nm-100 nm. Specifically, the resolution of the patterned film may, for example, be 3 nm, 4 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, etc.

[0112] In a fifth aspect, the present application provides a patterned substrate, wherein the pattern on the patterned substrate is formed by the patterned composition of the second aspect or obtained by the patterned method of the third aspect.

[0113] The patterned substrate of the embodiments of the present application can be used in the preparation of electronic components such as chips to improve the precision and quality of device manufacturing and thus improve the performance of electronic components. Specifically, in the embodiments of the present application, the resolution of the pattern on the patterned substrate is ≤100 nm. In some embodiments, the resolution of the pattern can be 3 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm.

[0114] In some embodiments of the present application, the critical dimension uniformity CDU of the pattern on the patterned substrate is less than or equal to 10% of the critical dimension CD. Specifically, the CDU of the pattern on the patterned substrate may, for example, be 0, 1% CD, 2% CD, 3% CD, 4% CD, 5% CD, 6% CD, 7% CD, 8% CD, 9% CD, 10% CD.

[0115] In some embodiments of the present application, the method for preparing the patterned substrate comprises:

[0116] The patterned film is formed on the substrate, and the pattern of the patterned film is transferred to the substrate to obtain a patterned substrate. The process of forming the patterned film can be referred to the description above, which will not be described here again.

[0117] In a sixth aspect, the present application provides an electronic component, comprising: a patterned film prepared according to the fourth aspect, or a step of preparing a patterned substrate according to the fifth aspect.

[0118] In the embodiments of the present application, the structure of the semiconductor device is not particularly limited, and a person skilled in the art can design according to the actual application needs and the composition provided in the embodiments of the present application.

[0119] In some embodiments of the present application, the semiconductor device comprises a structure obtained by etching or electron injection on a patterned substrate.

[0120] In some specific embodiments of the present application, the semiconductor device is a structure obtained by etching or electron injection on a patterned substrate with a silicon wafer as the substrate.

[0121] In the embodiments of the present application, the specific type of semiconductor device is not limited; in some embodiments of the present application, the semiconductor device can be an integrated circuit device including a chip. In the preparation process of the chip, other functional layers can be prepared after the aforementioned patterning process is completed.

[0122] In the following, the technical solutions of the present application are further described through specific embodiments.

[0123] Unless otherwise specified, the materials or reagents used in the present application can be purchased or prepared by methods known in the art.

[0124] Example 1

[0125] The present embodiment provides an organometallic cluster, the molecule of which is: Ti5O2(L1)4(L2)8, wherein L1 is magnolol ligand, and L2 is isopropanol ligand. Figure 1 The single crystal structure of the organometallic cluster is shown in the figure.

[0126] The preparation process comprises: mixing 0.25 mL of isopropyl titanate with 0.2 g of magnolol, adding 4 mL of isopropanol, stirring and dissolving, and then reacting at 65°C for 48 hours to obtain a crude product. After filtration, washing and drying, the final product is obtained. The single crystal structure is shown in Figure 1 The core is Ti5O2 structure, and the outside is coordinated by isopropanol and magnolol.

[0127] The product is characterized, and the powder diffraction spectrum is shown in Figure 2 As can be seen from Figure 2 The actual measured powder diffraction peak position is basically consistent with the theoretically calculated peak position, which proves that the structure is Ti5O2(C 18 H 16O2)4(C3H7O)8, the product was characterized by elemental analysis, the theoretical elemental content (wt%): C: 64.0; H: 6.71; the actual elemental content (wt%): C: 62.7; H: 6.9, which proved that the purity of the product was greater than 90%.

[0128] Example 2

[0129] This example provides an organic metal cluster, the molecule of which is: Ti4O2(L1)6(L2)4, wherein L1 is two Schiff base coordination groups and four magnolol coordination groups, and L2 is two hexafluoroisopropanol and two N,N dimethylformamide (DMF) coordination groups.

[0130] The preparation process comprises: mixing 0.25 mL of isopropyl titanate with 0.1 g of magnolol and 0.04 g of 2-{[(E)-(3-ethynylphenyl) nitroso] methyl} phenol (the structure of which is shown in the following formula I), adding 3 mL of a mixed solvent of hexafluoroisopropanol and 100 uL of DMF, stirring and dissolving, and then reacting at 40°C for 72 hours to obtain the product. After filtration, washing and drying, the final product is obtained, the single crystal structure of which is shown in Figure 4 , the core of which is a Ti4O2 structure, and the outside is coordinated by magnolol and hexafluoroisopropanol.

[0131]

[0132] The product was characterized, Figure 5 The powder diffraction pattern of the product is shown in the figure, from which it can be seen that the actual measured powder diffraction peak position is basically consistent with the theoretically calculated peak position, proving that the structure is Ti4O2(C 15 H 11 NO)2(C 18 H 16 O2)4(C3HF6O)2(C3H7NO)2.

[0133] Example 3

[0134] This example provides an organic metal cluster, the molecule of which is: Ti9O8(L1)4(L2) 16 , wherein L1 is a methacrylic acid coordination group, and L2 is an isopropanol coordination group.

[0135] The preparation process comprises: mixing tetrabutyl titanate (2 mL, 5.9 mmol) and methacrylic acid (4 mL, 46.4 mmol) in 20 mL of isopropanol at room temperature, dissolving, ultrasonicating for 15 minutes, and then heating at 60°C for 2 days. The colorless transparent square crystal is obtained after cooling at room temperature. The product is obtained after filtration, washing and drying. The single crystal structure of which is shown in Figure 6 , the core of which is a Ti9O8 structure, and the outside is coordinated by L1 methacrylic acid and isopropanol.

[0136] The product was characterized, Figure 7 The powder diffraction pattern of the product was obtained, and it was found that the actual measured powder diffraction peak position was basically consistent with the theoretically calculated peak position, proving that the structure of the product was Ti9O8(OC3H7)4(O2C4H5) 16 .

[0137] Comparative Example 1

[0138] This example provides an organometallic cluster, the molecule of which is: Ti8O8(C4H5O2) 16 .

[0139] The preparation process comprises: mixing and dissolving tetrabutyl titanate (2 mL, 5.9 mmol) and methacrylic acid (4 mL, 46.4 mmol) in 20 mL of acetonitrile at room temperature, and reacting for 2 days to obtain colorless transparent square crystals. The product is obtained after filtration, washing and drying. The single crystal structure is shown in Figure 8 , the core is a Ti8O8 structure, and the outside is coordinated by methacrylic acid.

[0140] Test Example 1

[0141] The method for patterning the organometallic cluster obtained in Example 1 comprises the following steps:

[0142] a) Preparation of a patterned composition solution: 10 mg of the organometallic cluster is dissolved in 1 mL of PGMEA solvent, the solution is filtered to remove particles, and is directly spin-coated on a silicon wafer having a hydrophilic surface to form a material coating layer with a thickness of about 30 nm.

[0143] d) Pre-exposure baking (PAB): 100°C, baking for 1 minute.

[0144] e) Radiation exposure: In this example, electron beam lithography (EBL) is used to expose the patterned material layer, and the dose is 1500 uC / cm2.

[0145] f) Development: The developing solution in this example is PGMEA, and the developing solution is contacted with the exposed film layer for 60 s.

[0146] g) Pattern characterization: Scanning atomic force microscopy (AFM) and electron microscopy (SEM) are used to characterize the patterned material layer after exposure and development.

[0147] The SEM characterization results of the pattern formed by the above steps are shown in Figure 9 , and the resolution can reach CD 40 nm.

[0148] Test Example 2

[0149] The method of patterning using the organometallic cluster obtained in Example 2 comprises the following steps:

[0150] a) Preparation of the solution of the patterning composition: 20 mg of the organometallic cluster is dissolved in 1 mL of cyclohexanone solvent, the solution is filtered to remove particles, and is directly spin-coated on a silicon wafer with a hydrophilic surface to form a material coating layer with a thickness of about 30 nm.

[0151] b) Pre-exposure baking (PAB): 100°C, baking for 1 minute.

[0152] c) Radiation exposure: The exposure of the material layer for patterning is performed using electron beam lithography (EBL) in the present application, and the dose is 600 uC / cm2.

[0153] d) Development: The developing solution in this example is PGMEA, and the developing solution is contacted with the post-exposure film layer for a developing time of 60 s.

[0154] e) Pattern characterization: The material layer after exposure and development is characterized using a scanning atomic force microscope (AFM) and an electron microscope (SEM).

[0155] The SEM characterization results of the pattern formed through the above steps are shown in Figure 10 , and the resolution can reach CD 80 nm.

[0156] Test Example 3

[0157] The method of patterning using the organometallic cluster obtained in Example 3 comprises the following steps:

[0158] a) Preparation of the solution of the patterning composition: 20 mg of the organometallic cluster is dissolved in 1 mL of a mixed solvent of PGMEA and methanol, the solution is filtered to remove particles, and is directly spin-coated on a silicon wafer with a hydrophilic surface to form a material coating layer with a thickness of about 30 nm.

[0159] b) Pre-exposure baking (PAB): 100°C, baking for 1 minute.

[0160] c) Radiation exposure: The exposure of the material layer for patterning is performed using electron beam lithography (EBL) in the present application, and the dose is 600 uC / cm2.

[0161] d) Development: The developing solution in this example is PGMEA:MeOH=2:1, and the developing solution is contacted with the post-exposure film layer for a developing time of 60 s.

[0162] e) Pattern characterization: The material layer after exposure and development is characterized using a scanning atomic force microscope (AFM) and an electron microscope (SEM).

[0163] SEM characterization results of the pattern formed by the above steps are shown in Figure 11 The resolution of the patterns formed by the above steps can reach CD 30 nm.

[0164] Test Example 4

[0165] The organic metal cluster obtained by Comparative Example 1 was patterned by referring to the method of Example 1. The results show that the solubility of the organic metal cluster is very poor when performing step a), and it is difficult to form a film, only a micrometer-level square pattern can be exposed, and there are many particles on the pattern, Figure 12 The AFM characterization results of the pattern of this example are shown in

[0166] Dissolution test

[0167] The solubility of the organic metal clusters prepared in the test examples and comparative examples was tested, including the following process:

[0168] Different amounts of organic metal clusters were weighed and dispersed in propylene glycol methyl ether acetate (PGMEA), ethyl acetate (EL), methanol (MeOH), cyclohexanone (CYC), isopropyl alcohol (IPA), methyl isobutyl carbinol (MIBC), propylene glycol methyl ether (PGME), and dimethylformamide (DMF) at 25°C, respectively. After stirring for 30 min, the dissolution of the organic metal clusters was observed. The results are shown in Table 1.

[0169] Table 1: Solubility test results

[0170] PGMEA EL MeOH CYC IPA MIBC PGME DMF Example 1 ++ - + - - - - - Example 2 +++ +++ +++ +++ +++ +++ +++ +++ Example 3 ++ - + - - - - - Comparative Example 1 - - - - - - - +

[0171] “-” represents solubility <1 mg / ml; “+” represents solubility 1-5 mg / ml; “++” represents solubility >5 mg / ml; “+++” represents solubility >10 mg / ml

[0172] As can be seen from Table 1, the solubility of the organic metal cluster of Example 2 in different solvents is higher than that of Comparative Example 1; the solubility of the organic metal clusters of Examples 1 and 3 in solvents PGMEA and MeOH is higher than that of Comparative Example 1.

[0173] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, and are not limited thereto; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions described in the foregoing examples can still be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. An organometallic cluster, characterized in that: The organometallic cluster comprises a metal oxide core and an organic ligand coordinated with the metal oxide core, and its molecular formula is: x O y (L1) n (L2) m , wherein M is selected from titanium, zirconium or hafnium, L1 and L2 are selected from organic ligands capable of coordinating with M, and the organometallic cluster further satisfies the following conditions a or b: a: 1≤x≤5, 1≤y≤30, y≤6x, 0≤n≤6x, 0≤m≤6x, 1≤n+m≤6x, said L1 and / or L2 include at least one aromatic ring; b: 6≤x≤30, 1≤y≤180, y≤6x, 0≤n≤6x, 0≤m≤6x, 1≤n+m≤6x.

2. The organometallic cluster according to claim 1, characterized in that The L1 and L2 include coordinating atoms capable of coordinating with the M, and the coordinating atoms include at least one of O, N, S, Se, and P.

3. The organometallic cluster according to claim 1 or 2, characterized in that The organic ligand further includes a radiation-sensitive functional group, wherein the radiation-sensitive functional group includes at least one of an alkenyl group, an alkynyl group, a benzyl group, or an epoxy group.

4. The organometallic cluster according to any one of claims 1 to 3, characterized in that When the organometallic cluster satisfies the condition a, the organic ligand includes a magnolol ligand and a Schiff base ligand; When the organometallic cluster satisfies the condition b, the organic ligand includes a methacrylic acid ligand.

5. The organometallic cluster according to any one of claims 1 to 4, characterized in that The molecular formula of the organometallic cluster is at least one compound of Formulas 1 to 3: Ti5O2(L1)4(L2)8 formula 1, where L1 is magnolol ligand and L2 is isopropanol ligand; Ti4O2(L1)6(L2)4 formula 2, where L1 includes a Schiff base ligand and a magnolol ligand, and L2 includes a hexafluoroisopropanol ligand and an N,N-dimethylformamide ligand; Ti9O8(L1)4(L2) 16 Formula 3: In Formula 3, L1 is a methacrylic acid ligand, and L is an isopropyl alcohol ligand.

6. A patterned composition, characterized in that The method comprises a solvent and the organic metal cluster according to any one of claims 1 to 5.

7. A method for patterning a substrate surface, characterized in that: include: providing a substrate; forming a patterned material layer on a surface of the substrate using the organometallic cluster according to any one of claims 1 to 5 or the patterned composition according to claim 6, and locally exposing the patterned material layer; The exposed patterned material layer is developed using a developer to form a patterned thin film on the substrate.

8. A patterned film, characterized in that: The patterned film is formed by using the patterning composition according to claim 6 or obtained by using the patterning method according to claim 7.

9. A patterned substrate, characterized in that The pattern on the patterned substrate is formed using the patterning composition according to claim 6 or obtained using the patterning method according to claim 7.

10. An electronic component, characterized in that: include: The method comprises the steps of preparing the patterned film according to claim 8 or preparing the patterned substrate according to claim 9.

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