Photosensitive composition

Abstract

The embodiment of the invention provides a photosensitive composition. The photosensitive component in the photosensitive composition provided by the embodiment of the invention comprises a cluster structure formed by combining a novel metal oxygen cluster skeleton taking a tin atom and a rare earth atom as cores with a ligand, has relatively excellent stability and good solubility, and can realize a relatively good exposure effect, so that the photosensitive composition is favorable for high-precision semiconductor devices (such as a semiconductor device, a semiconductor device and the like). And manufacturing a chip).

Description

Technical Field

[0001] The present application relates to the technical field of semiconductor devices, and in particular to a photosensitive composition. Background Art

[0002] As the integration of integrated circuit devices continues to increase, their critical dimensions continue to decrease, prompting the iteration of patterning processes. The patterning process generally transfers the preset pattern to the substrate through a photosensitive composition, which requires the photosensitive composition to have high sensitivity, high resolution and good durability. Traditional resin photosensitive compositions are basically unable to meet the above requirements at the same time. Researchers have gradually focused their attention on metal oxide cluster photosensitive materials, and related technologies are mostly concentrated on photosensitive materials with metal clusters such as Zr, Hf, Zn, Ti, and Sn as the core; among them, Sn-based materials are mainly pure organic tin oxide clusters, however, their exposure performance, solubility and stability still need to be improved. Summary of the invention

[0003] In view of this, the embodiment of the present application provides a photosensitive composition. The metal oxide cluster in the photosensitive composition provided in the embodiment of the present application has a cluster structure formed by a new metal oxide cluster skeleton with tin atoms and rare earth atoms as the core and ligands, which has excellent stability and good solubility, and can achieve a good exposure effect, thereby facilitating the manufacture of high-precision semiconductor devices (e.g., chips).

[0004] In a first aspect, an embodiment of the present application provides a metal oxide cluster, comprising a metal oxide cluster skeleton and a ligand coordinated and connected to the metal oxide cluster skeleton; the metal oxide cluster skeleton comprises tin atoms, rare earth atoms and inorganic oxygen atoms, and at least part of the tin atoms are bridged with at least part of the rare earth atoms by inorganic oxygen atoms; the tin atoms are connected with R groups, and the R groups include one or more of substituted or unsubstituted chain hydrocarbon groups or heteroatoms on the main chain, substituted or unsubstituted cyclic hydrocarbon groups, and halogen atoms; the ligand includes a structure derived from a first monomer, and the first monomer includes one or more of substituted or unsubstituted carboxylic acids or heteroatoms on the main chain, substituted or unsubstituted alcohols or heteroatoms on the main chain, substituted or unsubstituted amines or heteroatoms on the main chain, phosphoric acid, and substituted or unsubstituted phosphonic acid.

[0005] The metal oxide clusters are composed of a metal oxide cluster skeleton composed of organic tin and rare earth atoms as the core and connected with ligands of a specified structure, so that they have high exposure sensitivity and can show high resolution and low edge roughness after irradiation. More importantly, the molecular structure of the metal oxide cluster skeleton includes Sn atoms and rare earth atoms bridged by inorganic oxygen atoms. This special structure can not only effectively improve the structural stability of the metal oxide clusters, but also improve the metastable lifetime of the metal oxide clusters; it can also inhibit the regular arrangement of the metal oxide cluster skeleton in the solvent, so that the metal oxide clusters can maintain an amorphous state in a large range in the photosensitive composition, improve its dispersibility in the solvent, and improve the stability of the photosensitive composition; specifically, in the macroscopic state, the metal oxide clusters can show good thermal stability, and after being dissolved in a solvent, it is not easy to precipitate after long-term storage. The photosensitive composition configured with the solvent can be stored for a long time (one month or more) at room temperature, and can still show better exposure performance after long-term storage.

[0006] In some embodiments of the present application, the number of tin atoms and rare earth atoms in the metal oxide cluster skeleton is independently 1 to 30. In this way, the size of the metal oxide cluster can be controlled within a suitable range, which is beneficial to improving its exposure performance; in addition, the stability of the metal oxide cluster can be effectively improved while the metal oxide cluster has a higher solubility.

[0007] In some embodiments of the present application, the metal oxide cluster skeleton contains a plurality of tin atoms, a plurality of rare earth atoms, and a plurality of inorganic oxygen atoms; each of the rare earth atoms forms a Sn-OMO-Sn inorganic bridging structure, wherein M represents the rare earth atom. The metal oxide cluster skeleton has a Sn-OMO-Sn inorganic bridging structure, which is more conducive to improving the structural stability of the metal oxide cluster and taking into account its solubility in the solvent, for example, it can prolong the storage time of the photosensitive composition.

[0008] In some embodiments of the present application, each of the tin atoms is connected to 1-3 of the R groups. In this way, not only can radiation-sensitive metal oxide clusters be obtained, but they can also be easily synthesized in industry.

[0009] In some embodiments of the present application, the metal oxygen cluster skeleton includes a plurality of inorganic oxygen atoms, and the plurality of inorganic oxygen atoms include inorganic oxygen atoms with a coordination number of 2, inorganic oxygen atoms with a coordination number of 3, and inorganic oxygen atoms with a coordination number of 4. This is more conducive to improving the structural stability of the final metal oxygen cluster.

[0010] In some embodiments of the present application, the rare earth atoms include one or more of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

[0011] In some embodiments of the present application, when the R group is a substituted linear hydrocarbon group or a substituted cyclic hydrocarbon group, the substituents include one or more of halogen, hydroxyl, amino, amido, silyl, and alkoxy. In some embodiments of the present application, the chemical general formula of the metal-oxygen cluster is (R a Sn) x M y O z L n , where 1 ≤ a ≤ 3, 1 ≤ x ≤ 30, 1 ≤ y ≤ 30, 0 < n ≤ 6(x + y), 1 ≤ z ≤ 6(x + y), and a, x, y, z, and n are all integers; M represents the rare earth atom, and L represents the ligand.

[0012] In some embodiments of the present application, the ligand is an organic ligand; the organic ligand has a cyclic structure, and / or the organic ligand has a double bond. In this way, it is beneficial to reduce the exposure dose of the photosensitive composition formed thereby and improve the resolution.

[0013] In some embodiments of the present application, the chemical formula of the metal-oxygen cluster skeleton is (RSn)8O 10 M, and the chemical structure is shown in Formula (1):

[0014] where M represents the rare earth atom.

[0015] In some embodiments of the present application, the ligand is an organic ligand, and the number of carbon atoms of the organic ligand is 1 - 30; and / or when the R group contains carbon atoms, the number of carbon atoms of the R group is 1 - 30.

[0016] The second aspect of the embodiments of the present application provides a preparation method of a metal-oxygen cluster, including:

[0017] Mixing an organotin source, a rare earth element source, the first monomer, and water to obtain a mixture; heating the mixture to react to obtain a metal-oxygen cluster; wherein, based on the sum of the volumes of the water and the first monomer, the volume ratio of the water is ≥ 0.5%; the organotin source and / or the rare earth element source can react with the first monomer.

[0018] In this preparation method, introducing water and controlling the amount of water used can enable water to participate in the reaction during the heating process and generate a special structure of "tin atom - inorganic oxygen atom - rare earth atom" in the metal-oxygen cluster skeleton after reacting with tin atoms and rare earth atoms. The above preparation method has simple steps, strong reliability, and is easy to be industrially produced on a large scale.

[0019] The third aspect of the embodiments of the present application provides a photosensitive composition, including the metal-oxygen cluster provided in the first aspect of the embodiments of the present application and a solvent.

[0020] The photosensitive composition has good coating performance, is easy to coat and form a film, the formed coating film has a smooth surface, the film thickness is easy to adjust, the developing conditions meet the requirements of the patterning process, and is easy to apply; it can be used to form high-resolution, low-roughness high-precision patterns. At the same time, due to the good stability of the metal oxide clusters, the above-mentioned photosensitive composition can be stored for a long time at room temperature, and still exhibits excellent exposure performance after storage.

[0021] The fourth aspect of the embodiment of the present application provides a patterned film, which is formed by the photosensitive composition provided in the third aspect of the embodiment of the present application. The patterned film can be used as a high-precision mask in the patterning process of manufacturing integrated circuits, 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. Since the metal oxide cluster patterning material of the embodiment of the present application has high sensitivity and the molecular size can be controlled at a smaller size, the patterned film obtained by the patterning process of the photosensitive composition of the embodiment of the present application has high resolution and low edge roughness.

[0022] The fifth aspect of the embodiment of the present application provides a patterned substrate, which is obtained by etching a substrate having a patterned film provided by the fourth aspect of the embodiment of the present application on its surface. The patterned substrate can be used for the preparation of semiconductor devices such as chips, improving the device manufacturing accuracy and quality, and thus improving the performance of semiconductor devices.

[0023] The sixth aspect of the embodiment of the present application provides a semiconductor device, the semiconductor device comprising a patterned substrate and a functional layer disposed on the patterned substrate; the patterned substrate is obtained by etching a substrate having a patterned film provided by the fourth aspect of the embodiment of the present application on its surface. The semiconductor device provided by the embodiment of the present application has high precision.

[0024] A seventh aspect of the present application provides a method for preparing a semiconductor device, comprising:

[0025] Applying the photosensitive composition provided in the third aspect of the embodiment of the present application on a substrate to form a film layer on the substrate;

[0026] Exposing and developing the film layer through a photomask to form a patterned film on the substrate;

[0027] Etching to obtain a patterned substrate;

[0028] A functional layer is prepared to obtain a semiconductor device.

[0029] The preparation method has strong process reliability and is easy to realize large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The precise structural diagram of the metal oxide cluster provided in one embodiment of the present application;

[0031] Figure 2 X-ray diffraction (XRD) spectra of the metal oxide clusters prepared in Examples 1 to 6 of the present application;

[0032] Figure 3 The UV-visible spectra of the metal oxide clusters prepared in Examples 1 to 6 of the present application;

[0033] Figure 4 Thermogravimetric curves of metal oxide clusters prepared in Examples 1 to 6 of the present application;

[0034] FIG. 5A to FIG. 5F Scanning Electron Microscope (SEM) photos of patterned films of metal oxide clusters prepared in Examples 1 to 6 obtained in Exposure Performance Test 1;

[0035] Figure 5G The SEM image of the patterned film obtained in the comparative example of exposure performance test 1;

[0036] Fig. 6A , Figure 6B They are respectively height sensor images of an atomic force microscope (AFM) of a patterned film of the metal oxide cluster prepared in Example 1 of the present application obtained in the exposure performance test 2;

[0037] Fig. 7A , Figure 7B They are respectively AFM height sensor images of the patterned film of the metal oxide cluster prepared in Example 1 of the present application obtained in the exposure performance test 3;

[0038] Fig. 8A This is a SEM photograph of a patterned film of the metal oxide cluster prepared in Example 1 of the present application obtained in exposure performance test 4;

[0039] Figure 8B This is a SEM photograph of the patterned film obtained in comparative example 4 for exposure performance test. DETAILED DESCRIPTION

[0040] As the market's requirements for the integration of semiconductor devices become higher and higher, the critical dimension (CD) of semiconductor devices is also reduced. The manufacturing process of semiconductor devices generally includes: coating a photosensitive composition on a substrate to form a film layer, then irradiating the film layer through a mask, and then developing to form a patterned film on the substrate; etching the substrate with the patterned film, transferring the pattern of the patterned film to the substrate, and obtaining a patterned substrate with a preset pattern. It can be seen that the precise transfer of the preset pattern is a key link in the manufacturing process of semiconductor devices, and the resolution of the photosensitive composition is particularly important; and the traditional organic resin sensory composition has basically approached its limit resolution, so the industry urgently needs to find new photosensitive materials to meet the increasingly smaller critical dimension patterning requirements. Metal cluster photosensitive materials have gradually attracted the attention of R&D personnel due to their higher exposure performance potential, but the stability, solubility and exposure performance of metal clusters in related technologies still need to be improved.

[0041] To solve the above technical problems, an embodiment of the present application provides a photosensitive material, which is a metal oxide cluster with a new structure, which has excellent stability, good solubility, and excellent exposure performance, for example, higher resolution and lower edge roughness, and can achieve a line width ratio of 1:1.

[0042] In order to better illustrate the technical solution of this application, the key terms involved in this application are explained as follows:

[0043] Patterning: lithography, patterning process, and lithography process are important steps in the semiconductor device manufacturing process. The exposure and development process of this step depicts the collective graphic structure on the patterned material, and the pattern on the mask is transferred to the substrate substrate through the etching process. Here, the substrate substrate and the substrate include not only silicon wafers, but also other metal layers, dielectric layers, and the above-mentioned substrates with surface modification or added supporting layers.

[0044] Photosensitive material: An etch-resistant material whose solubility in the developer changes after exposure to radiation.

[0045] Developer: The developer is a pure or mixed solvent that dissolves the soluble areas of the photosensitive material after the solubility change caused by exposure.

[0046] Positive pattern: After development, the exposed part of the photosensitive material is washed away by the developer, and the pattern formed is a positive pattern.

[0047] Negative pattern: After development, the unexposed part of the photosensitive material is washed away by the developer, and the pattern formed is a negative pattern.

[0048] Spin coating process: Spin coating is a high-speed film forming method that can obtain uniform thin films. Its uniformity is widely used in the preparation of thin films such as semiconductor materials and chemical materials. It uses the centrifugal force generated by rotation to evenly spread sols, solutions or suspensions on the substrate surface.

[0049] Mask: During the patterning process, the mask is an optical element in the light path. The mask carries the design pattern, and the light selectively transmits or reflects through it, so that the design pattern can be projected onto the photosensitive material film layer.

[0050] The embodiment of the present application provides a metal oxygen cluster, which includes a metal oxygen cluster skeleton and a ligand coordinated and connected to the metal oxygen cluster skeleton; the metal oxygen cluster skeleton includes tin atoms, rare earth atoms and inorganic oxygen atoms, and at least part of the tin atoms and at least part of the rare earth atoms are bridged by inorganic oxygen atoms;

[0051] The tin atom is connected to an R group, and the R group includes one or more of a substituted or unsubstituted chain hydrocarbon group or a chain hydrocarbon group containing heteroatoms on the main chain, a substituted or unsubstituted cyclic hydrocarbon group, and a halogen atom;

[0052] The ligand includes a structure derived from a first monomer, which includes one or more of a substituted or unsubstituted carboxylic acid or one containing heteroatoms on the main chain, a substituted or unsubstituted alcohol or one containing heteroatoms on the main chain, a substituted or unsubstituted amine or one containing heteroatoms on the main chain, phosphoric acid, or a substituted or unsubstituted phosphonic acid.

[0053] The metal oxide cluster provided in the embodiment of the present application has a metal oxide cluster skeleton composed of organic tin and rare earth atoms as the core and is connected with a ligand of a specified structure, so that it has a high exposure sensitivity, and can show a high resolution and low edge roughness after irradiation. More importantly, the molecular structure of its metal oxide cluster skeleton includes Sn atoms and rare earth atoms bridged by inorganic oxygen atoms. This special structure can not only effectively improve the structural stability of the metal oxide cluster, but also improve the metastable life of the metal oxide cluster; it can also inhibit the regular arrangement of the metal oxide cluster skeleton in the solvent, so that the metal oxide cluster can maintain an amorphous state in a large range in the photosensitive composition, improve its dispersibility in the solvent, and improve the stability of the photosensitive composition; specifically, in the macroscopic state, the above-mentioned metal oxide cluster can show good thermal stability, and after being dissolved in a solvent, it is not easy to precipitate after long-term storage. The photosensitive composition configured with the solvent can be stored for a long time (one month or more) at room temperature, and can still show better exposure performance after long-term storage. The metal oxide cluster has a metal oxide cluster skeleton of Sn-rare earth atoms as its core, and is highly sensitive to light sources of various wavelengths, such as light sources with wavelengths of 100nm-400nm, 10nm-14nm, 1-15nm soft X-rays, and electron beams. The metal oxide cluster provided in the embodiment of the present application is used in the preparation of integrated circuit devices such as chips, and high-quality patterns can be obtained, thereby improving the integration, reliability, and preparation efficiency of integrated circuit devices.

[0054] In some embodiments of the present application, the number of tin atoms and rare earth atoms in the metal oxide cluster skeleton is independently 1 to 30. By controlling the number of tin atoms and rare earth atoms in the metal oxide cluster within the above range, the size of the metal oxide cluster can be controlled within a suitable range, which is conducive to improving the resolution of the pattern formed after exposure and reducing the edge roughness of the pattern; in addition, it is also conducive to the presence of an appropriate amount of tin atoms and rare earth atoms bridged by inorganic oxygen atoms in the metal oxide cluster, while effectively improving the stability of the metal oxide cluster and taking into account higher solubility. Specifically, the number of tin atoms in the metal oxide cluster skeleton can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30; the number of rare earth atoms in the metal oxide cluster skeleton can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30. In some embodiments of the present application, the metal oxide cluster skeleton includes a plurality of tin atoms, a plurality of rare earth atoms and a plurality of inorganic oxygen atoms.

[0055] In the embodiment of the present application, the greater the proportion of Sn atoms and rare earth atoms bridged by inorganic oxygen in a single metal oxide cluster skeleton, the more conducive to improving the stability of the metal oxide cluster, but the solubility of the metal oxide cluster will be slightly affected; specifically, the number of rare earth atoms bridged by inorganic oxygen atoms and Sn atoms in a single metal oxide cluster skeleton can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30. In the metal oxide cluster skeleton provided in the embodiment of the present application, all inorganic oxygen atoms can bridge tin atoms and rare earth atoms at the same time; or part of the inorganic oxygen atoms can bridge tin atoms and rare earth atoms, and another part of the inorganic oxygen atoms can bridge rare earth atoms and rare earth atoms, and / or another part of the inorganic oxygen atoms can bridge tin atoms and tin atoms. In some embodiments, the metal oxide cluster skeleton includes a plurality of tin atoms, a plurality of rare earth atoms M, and a plurality of oxygen atoms; each rare earth atom M forms a Sn-OMO-Sn inorganic bridging structure. The metal oxide cluster skeleton has a Sn-OMO-Sn inorganic bridging structure, which is more conducive to improving the structural stability of the metal oxide cluster and taking into account its solubility in the solvent, for example, it can prolong the storage time of the photosensitive composition.

[0056] In some embodiments of the present application, the coordination number of the inorganic oxygen atom is a positive integer of 2-4. Specifically, the coordination number of the inorganic oxygen atom can be, for example, 2, 3, or 4. In some specific embodiments, the metal oxygen cluster skeleton includes a plurality of inorganic oxygen atoms, and the plurality of inorganic oxygen atoms include inorganic oxygen atoms with a coordination number of 2, inorganic oxygen atoms with a coordination number of 3, and inorganic oxygen atoms with a coordination number of 4. In this way, it is more conducive to improving the structural stability of the final metal oxygen cluster. For inorganic oxygen atoms with a coordination number of 4, a single inorganic oxygen atom can be connected to one rare earth atom and three tin atoms, or it can be connected to two rare earth atoms and two tin atoms, or it can be connected to one tin atom and three rare earth atoms. In this way, it is conducive to maintaining the solubility and structural stability of the metal oxygen cluster at a high level. In addition, for inorganic oxygen atoms with a coordination number of 2, one tin atom and one rare earth atom can be bridged, or two tin atoms can be bridged. Similarly, for inorganic oxygen atoms with a coordination number of 3, three metal atoms can be bridged, and the metal atoms include tin atoms and / or rare earth atoms. The metal oxide clusters with the above structure are easy to synthesize in industry and have stable structures.

[0057] In the embodiment of the present application, the R group may be a halogen atom, or a substituted or unsubstituted chain hydrocarbon group containing heteroatoms on the main chain, or a substituted or unsubstituted cyclic hydrocarbon group; when the metal oxide cluster skeleton contains multiple tin atoms, the structures of the R groups connected by the multiple tin atoms may be completely the same or different. Specifically, the above-mentioned halogen atoms may be, for example, F atoms, Cl atoms, Br atoms, I atoms, and halogen atoms have a high absorption efficiency for soft X-ray photons, which is beneficial to improve the photosensitivity of the metal oxide cluster. The above-mentioned hydrocarbon group may be, for example, an alkyl group, an alkenyl group, an alkynyl group, and the above-mentioned cyclic hydrocarbon group may be, for example, an aryl group, a cycloalkyl group, a cycloalkenyl group, etc. In the embodiment of the present application, when the R group is a hydrocarbon group containing heteroatoms on the main chain, the heteroatoms may be, for example, one or more of O atoms, S atoms, N atoms, and Si atoms. When the R group is a substituted hydrocarbon group or a substituted cycloalkyl group, the substituent may be, for example, a halogen, a hydroxyl group, an amine group, an amide group, a silane group, an alkoxy group, etc. These substituent groups are beneficial to improving the polarity, thereby improving the solubility of the metal oxide cluster in polar solvents and the uniformity of the film layer formed by the coating.

[0058] In some embodiments of the present application, when the R group contains carbon atoms, the number of carbon atoms in the R group is 1-30. In some embodiments of the present application, when the R group is a substituted or unsubstituted chain hydrocarbon group with a carbon number of 1-30 or containing heteroatoms on the main chain; in this way, it is beneficial to ensure that the solubility of the metal oxygen cluster is better. In some embodiments of the present application, the R group can be a straight chain alkyl or branched chain alkyl group that is substituted or unsubstituted or contains heteroatoms on the main chain, wherein the branched chain alkyl group can effectively protect the substitution site due to the large steric hindrance, reduce the water sensitivity of the metal oxygen cluster, and obtain better storage stability. In some embodiments, the R group is a haloalkyl group. The halogen can be F, Cl, Br, I. In other embodiments, the R group is an alkoxy-substituted hydrocarbon group. In some embodiments, the R group is a methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl (i.e., tertiary butyl), tertiary pentyl or neopentyl group that is substituted or unsubstituted or contains heteroatoms on the main chain. In some embodiments, R is substituted or unsubstituted cyclopropyl, cyclopentyl, cyclohexyl, etc.

[0059] In some embodiments of the present application, in the metal oxide cluster skeleton, each tin atom is connected to 1-3 R groups. Specifically, a single tin atom can be connected to 1, 2 or 3 R groups. In this way, not only can radiation-sensitive metal oxide clusters be obtained, but also they can be easily synthesized industrially. In the metal oxide cluster skeleton of the embodiment of the present application, the coordination number of a single tin atom can be 5, 6 or other, for example, and the number of R groups connected to a single tin atom does not significantly affect the exposure performance and stability of the metal oxide cluster. In the embodiment of the present application, when a single tin atom is connected to multiple R groups, the structures of the multiple R groups can be exactly the same or different.

[0060] In the embodiments of the present application, the chemical general formula of the metal-oxygen cluster can be expressed as (R a Sn) x M y O z L n , where 1≤a≤3, 1≤x≤30, 1≤y≤30, 0<n≤6(x + y), 1≤z≤6(x + y), and a, x, y, z, and n are all integers; M represents a rare earth atom, and L represents a ligand. In the embodiments of the present application, the metal-oxygen cluster has multiple ligands to obtain a neutral metal-oxygen cluster, and it is easy to prepare the metal-oxygen cluster. The specific number of ligands is jointly affected by the number of tin atoms and rare earth atoms in the metal-oxygen cluster, the number of tin atoms and rare earth atoms bridged by inorganic oxygen atoms, the coordination number of rare earth atoms, the coordination number of tin atoms, and the connection mode of ligands. In the embodiments of the present application, the coordination number of rare earth atoms can be, for example, 5, 6, 7, 8, 9.

[0061] In some embodiments of the present application, the ligand L is an organic ligand. In this way, it is more conducive to enhancing the affinity between the cluster and organic solvent molecules, more conducive to the solubility of the metal-oxygen cluster in organic solvents, and the uniformity of the film layer formed by coating the prepared photosensitive composition.

[0062] In the embodiments of the present application, the ligand L is coordinatively connected to the metal-oxygen cluster framework; specifically, the ligand can form a chemical bond with a tin atom, or the ligand L can form a chemical bond with a rare earth atom, or a single ligand L can simultaneously form a chemical bond with a tin atom and a rare earth atom. In some specific embodiments, a single ligand L simultaneously forms a chemical bond with a tin atom and a rare earth atom. It is easy to synthesize and prepare industrially. For example, the ligand L can be * 1 -O-CH2CH2-O-* 2 , * 1 the marked position is connected to the tin atom, and * 2 the marked position is connected to the rare earth atom.

[0063] In the embodiment of the present application, the ligand L includes a structure derived from the first monomer, and the first monomer includes a substituted or unsubstituted carboxylic acid (carboxylic acid) containing heteroatoms on the main chain, a substituted or unsubstituted alcohol (alcohol) containing heteroatoms on the main chain, a substituted or unsubstituted amine (amine) containing heteroatoms on the main chain, phosphoric acid, a substituted or unsubstituted phosphonic acid (phosphoric acid) or one or more. When a single metal oxygen cluster contains multiple ligands, the multiple ligands can be the same or different. The ligand L can be connected to the metal oxygen cluster skeleton by coordination through oxygen atoms, nitrogen atoms, sulfur atoms or phosphorus atoms. The ligand L can better achieve the regulation of the solubility of the metal oxygen cluster, which is beneficial to the improvement of film thickness, film roughness, resolution, film adhesion and corrosion resistance; controlling the number of ligands L can further regulate the exposure dose and pattern resolution. In the ligand L, the heteroatom can be one or more of oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms. When the first monomer is a substituted carboxylic acid, a substituted alcohol, a substituted amine, or a substituted phosphonic acid, the substituent group may be a halogen, an aromatic group, a hydroxyl group, an ether group, an amine group, an amide group, a silane group, an alkoxy group, and the like. These substituent groups are beneficial to improving the polarity of the ligand L, thereby improving the solubility of the metal oxygen cluster in the polar solvent and the uniformity of the film layer formed by coating the obtained photosensitive composition. Specifically, the first monomer may be a carboxylic acid, an amine, an alcohol amine, an alcohol acid, a phosphoric acid, a phosphonic acid, an alcohol, and the like. Exemplarily, the amine may be diethylamine; the alcohol amine may be diethanolamine, and the like; the phosphonic acid may be methylphosphonic acid, and the like. In the embodiment of the present application, in the first monomer, the carboxylic acid may be an acid containing two carboxyl groups, for example, iminodiacetic acid, 5-norbornene-2,3-dicarboxylic acid; the alcohol may be, for example, ethylene glycol, and the like. In one embodiment, the ligand L is *-O-R1-O-, *-OC-R2-CO-, *OC-R3-N*-R4-CO, and the positions marked with * represent the connection sites. R1, R2, R3, and R4 can be, for example, alkylene, alkenylene, or a cyclic structure.

[0064] In some embodiments of the present application, the ligand L is an organic ligand, and the number of carbon atoms of the organic ligand is 1-30. In some specific embodiments, the number of carbon atoms of the organic ligand L is 1-20. Fewer carbon atoms are beneficial to control the molecules of the metal oxygen cluster to remain in a smaller size. Specifically, the number of carbon atoms of the organic ligand L can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30.

[0065] In some embodiments of the present application, the organic ligand L has a cyclic structure. The introduction of a cyclic rigid structure can give the metal oxide clusters a higher etching resistance, and has good penetration to light sources with a wavelength of 10nm-14nm, and does not affect the absorption of photons by the central metal. Specifically, the above-mentioned cyclic structure can be, for example, a carbon ring, such as a structure derived from a carbon ring with a stereo configuration: for example, a structure obtained by losing one or two hydrogen atoms from a carbon ring with a stereo configuration. In some other embodiments of the present application, the organic ligand L has a double bond, for example, a carbon-carbon double bond. The presence of a double bond can provide more reactive sites, which is beneficial to increase the degree of polymerization of the metal oxide clusters after irradiation, so as to increase the solubility difference between the metal oxide clusters in the exposed area and the metal oxide clusters in the non-exposed area in the developer, and further improve the quality of the pattern formed by the metal oxide clusters. In some specific embodiments of the present application, the organic ligand L has both a cyclic structure and a double bond; it is beneficial to reduce the exposure dose and improve the resolution. Specifically, the organic ligand L may include *-O-CH2CH2-O-*, a structure derived from bicyclo[2,2,1]-heptene, and a structure derived from iminodiac acid; illustratively, the structure derived from bicyclo[2,2,1]-heptene may be, for example, a structure obtained when both carboxyl groups of 5-norbornene-2,3-dicarboxylic acid lose -OH and a hydrogen atom on the N atom, and the structure derived from iminodiac acid may be a structure obtained when both carboxyl groups of iminodiacetic acid lose -OH.

[0066] In an embodiment of the present application, the rare earth atoms include one or more of Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium) and Lu (lutetium). In some embodiments of the present application, the rare earth atoms are selected from one or more of Yb, Er, Ho, Sm, Eu, and Y. In some specific embodiments, the rare earth atoms include Er and / or Ho; Er and Ho are more conducive to improving the exposure resolution of metal oxide clusters. In an embodiment of the present application, when a single metal oxide cluster skeleton has multiple rare earth atoms, the multiple rare earth atoms may be the same or different.

[0067] In some embodiments of the present application, the chemical formula of the metal oxygen cluster skeleton is (RSn)8O 10 M, chemical structure is shown in formula (1):

[0068] Wherein, M represents a rare earth atom, and the R group includes one or more of a substituted or unsubstituted hydrocarbon group or a halogen atom containing a heteroatom on the main chain; please refer to the above description for details, which will not be repeated here. In formula (1), multiple R groups can be the same or different groups. No hydrogen atoms are shown in the structure shown in formula (1).

[0069] In some embodiments, the chemical formula of the metal oxide cluster is [(C4H9)Sn]8MO 10 (OCH2CH2O)2(CO-C7H8CO)2(COCH2NHCH2CO)2. In some specific embodiments, the chemical formula of the metal oxygen cluster is [nBuSn]8M(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2, and its precise structure is shown in Figure 1 As shown; wherein, nBu is n-butyl; μ2 represents a coordination number of 2, μ3 represents a coordination number of 3, μ4 represents a coordination number of 4, IDA is a structure obtained when both carboxyl groups of iminodiacetic acid lose -OH, EG is a structure obtained when both hydroxyl groups of ethylene glycol lose hydrogen atoms, NE is a structure obtained when both carboxyl groups of 5-norbornene-2,3-dicarboxylic acid lose -OH and a hydrogen atom on the N atom; M is any one of Y, Sm, Eu, Ho, Er, and Yb.

[0070] The metal oxide clusters provided in the embodiments of the present application will undergo a chemical reaction under the irradiation of a 100nm-400nm light source, a 10nm-14nm light source, a soft X-ray or an electron beam exposure light source. After the metal oxide clusters undergo a chemical reaction under the irradiation of the light source, their solubility will change, and their photosensitivity is high, which can effectively improve the pattern resolution. In some embodiments, the wavelength of the exposure light source can be 1nm, 3nm, 5nm, 7nm, 10nm, 13.5nm. In some embodiments of the present application, the exposure dose required for the 10nm-14nm light source and soft X-ray to act on the metal oxide clusters can be 10-300mJ / cm 2 , for example 10mJ / cm 2 、50mJ / cm 2 、100mJ / cm 2 、150mJ / cm 2 、200mJ / cm 2 、250mJ / cm 2 、300mJ / cm 2 The exposure dose required for electron beam irradiation on the metal oxide clusters can be 50 μC / cm 2 -5000μC / cm 2 , for example, it can be 50μC / cm 2 , 500μC / cm 2 、1000μC / cm 2 、2000μC / cm 2 、3000μC / cm 2 、4000μC / cm 2 、5000μC / cm 2.

[0071] The metal oxide clusters provided in the embodiments of the present application can be detected by nuclear magnetic resonance, mass spectrometry and other detection methods, and can also be directly detected or auxiliary proved by methods such as X-ray powder diffraction and X-ray single crystal diffraction.

[0072] Accordingly, the present application also provides a method for preparing a metal oxide cluster, comprising:

[0073] S1. Mix an organic tin source, a rare earth element source, a first monomer and water to obtain a mixture; wherein, based on the sum of the volumes of the water and the first monomer, the volume proportion of the water is ≥0.5%; the organic tin source and / or the rare earth element source can react with the first monomer; in some embodiments, the organic tin source and the rare earth element source can be added to the first monomer and mixed thoroughly to obtain a mixture.

[0074] S2. The mixture is heated to react to obtain metal oxide clusters.

[0075] In the preparation method provided in the embodiment of the present application, water is introduced and the amount of water is controlled, so that during the heating process, water participates in the reaction and reacts with tin atoms and rare earth atoms to generate a special structure of "tin atom-inorganic oxygen atom-rare earth atom" in the metal oxygen cluster skeleton. Specifically, based on the sum of the volumes of water and the first monomer, the volume proportion of water can be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, 2.2%, 2.5%, 2.8%, 3.0%, 3.2%, 3.5%, 3.8%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%.

[0076] Among them, the organic tin source has a group connected to the tin atom that can be replaced by a ligand, or has a group connected to the tin atom that can react with a rare earth element source. The group can be a diethylamine group, an alcohol group, a carboxylic acid group, a halogen, etc. Amine groups are, for example, diethylamine and dimethylamine; alcohol groups are, for example, tert-butyl alcohol and 4-methyl-2-pentanol; carboxylic acid groups are, for example, formate, acetate, methacrylate, etc.; halogens are, for example, fluorine, chlorine, bromine, and iodine. The general chemical formula of the organic tin source can be expressed as RSnX n , R is the same as R in the metal oxide cluster skeleton, X represents a group connected to the tin atom that can be replaced by a ligand, and n can be an integer from 1 to 5. In a specific embodiment, the organic tin source is trichlorobutyltin.

[0077] Among them, the rare earth element source can be a rare earth salt. The first monomer can be one or more of carboxylic acids, alcohols, amines, alcohol acids, alcohol amines, phosphoric acids, and phosphonic acids containing ligands. For details, please refer to the description of the first monomer in the previous text, which will not be repeated here. In some specific embodiments, the first monomer includes one or more of ethylene glycol, iminodiacetic acid, and 5-norbornene-2,3-dicarboxylic acid.

[0078] In order to avoid the introduction of impurities, the water is deionized water.

[0079] In the embodiment of the present application, the relative amounts of tin atoms and rare earth atoms in the metal oxide cluster framework can be adjusted by adjusting the relative amounts of the rare earth element source and the organic tin source added.

[0080] In some embodiments of the present application, the temperature of the heating reaction may be 60°C-120°C. Controlling the temperature of the heating reaction within the above range is conducive to the rightward reaction, improving the yield of metal oxygen clusters, and ensuring a higher product purity. Specifically, the temperature of the heating reaction may be, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, etc.

[0081] The heating reaction time can be more than 12 hours, or more than 24 hours, for example, 1-7 days, or longer. After the reaction is completed, it can be cooled to room temperature to allow the product to crystallize, or the reaction solution can be accelerated to evaporate under negative pressure to allow crystals to precipitate, and then purified by recrystallization to obtain a solid product with a purity of more than 95%.

[0082] The method for preparing the metal oxide clusters provided in the embodiments of the present application has a simple process and is easy for industrial production.

[0083] The present application also provides a photosensitive composition, which includes the metal oxide clusters and a solvent described above in the present application. In the photosensitive composition, the metal oxide clusters can be well dissolved in the solvent, and the photosensitive composition has good coating properties and is easy to coat and form a film. The formed coating film has a smooth surface, the film thickness is easy to adjust, and the developing conditions meet the requirements of the patterning process, which is easy to use; it can be used to form high-resolution, low-roughness, high-precision patterns. At the same time, due to the good stability of the metal oxide clusters, the above-mentioned photosensitive composition can be stored for a long time at room temperature, and still exhibits excellent exposure performance after storage. For example, electron beam irradiation can achieve a critical dimension of 50nm, a line width ratio of 1:1, and an edge roughness LER≤15nm; using soft X-rays below 15nm as the light source for irradiation can achieve a critical dimension of 35nm and a line width ratio of 1:1. With Fig. 6A For example, Fig. 6AThe photosensitive composition prepared in Example is exposed to light and is formed into an intermittently arranged stripe pattern. The line width ratio is the ratio of the width of the stripe pattern to the interval size.

[0084] In the embodiment of the present application, the photosensitive composition may include one or more of the above-mentioned metal oxide clusters.

[0085] In the embodiment of the present application, the solvent may be one or more of an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl adipate (DMA), benzene, and toluene. The above solvents can dissolve metal oxygen clusters well, reach the target concentration, and form a uniform coating liquid suitable for coating and film formation. The alcohol solvent may be, but is not limited to, 4-methyl-2-pentanol; the ester solvent may be, but is not limited to, propylene glycol methyl ether acetate.

[0086] In the embodiment of the present application, in the photosensitive composition, the concentration of the above-mentioned metal oxygen clusters is 1mg / mL-100mg / mL. In some embodiments, the concentration of the above-mentioned metal oxygen clusters in the photosensitive composition is 5mg / mL-30mg / mL. In some embodiments, the concentration of the above-mentioned metal oxygen clusters in the photosensitive composition is 1mg / mL, 5mg / mL, 10mg / mL, 15mg / mL, 20mg / mL, 30mg / mL, 40mg / mL, 50mg / mL, 60mg / mL, 70mg / mL, 80mg / mL, 90mg / mL, 100mg / mL. The appropriate concentration of metal oxygen clusters is beneficial to the film-forming property of the photosensitive composition, for example, it is beneficial to form a film layer with suitable thickness and excellent uniformity, so as to effectively ensure the high efficiency and high quality of the patterning process. In an embodiment of the present application, the patterned composition can be subjected to freeze-drying or other treatments to remove the solvent, the solid substance obtained after freeze-drying is dissolved in a quantitative deuterated reagent and subjected to nuclear magnetic resonance testing, the nuclear magnetic resonance test results are normalized, and then the content of metal oxygen clusters in the photosensitive composition is calculated and determined.

[0087] In the embodiment of the present application, in order to improve the comprehensive performance of the photosensitive composition, the photosensitive composition may further include other additives, and the other additives may include one or more of a leveling agent and a surfactant. The addition of a leveling agent and a surfactant can improve the uniformity of the coating film layer. The content of other additives in the photosensitive composition can be adjusted according to actual needs.

[0088] The present application also provides the application of the metal oxide cluster or photosensitive composition in the field of patterning. The metal oxide cluster or photosensitive composition can be applied to semiconductor patterning process to obtain high-quality patterns and improve the precision and production efficiency of components.

[0089] The present application also provides a patterning method, wherein the patterning process includes:

[0090] S101, coating the photosensitive composition of the embodiment of the present application on a substrate to form a patterned material film layer on the substrate;

[0091] Specifically, one or more metal oxide clusters of the embodiments of the present application may be dissolved in a suitable solvent to form a solution of a certain concentration, i.e., a photosensitive composition, to which one or more other components such as a leveling agent and a surfactant may be selectively added. In the embodiment of the present application, the solvent may be one or more of an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl adipate (DMA), benzene, and toluene. The amount of solvent added can be adjusted according to the film thickness requirements, and generally the higher the solution concentration, the thicker the corresponding film layer. In the photosensitive composition, the concentration of the above-mentioned metal oxide cluster patterning material can be 1mg / mL-100mg / mL.

[0092] In the embodiment of the present application, the substrate can be selected according to specific needs, and can be a silicon wafer, or a silicon wafer covered by other coatings, and the other coatings can be anti-reflective coatings, anti-etching coatings, epitaxial layers, metal layers, dielectric layers, modified layers or supporting layers. Usually, other coatings can be obtained by pre-treating the substrate, and the pre-treatment method can be: subjecting the silicon wafer substrate to O2 plasma surface hydrophilic activation; 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 (Hexamethyldisilazane, HMDS) on the substrate to perform surface hydrophobic treatment on the substrate; the hydrophobic treatment can be after the hydrophilic treatment; or adding a bottom anti-reflective layer, a bottom carbon-containing coating, or a bottom silicon-containing coating.

[0093] According to the size of the substrate, a suitable volume of the photosensitive composition is applied to the substrate by spin coating to form a patterned material film layer with a thickness of 5nm-200nm, and the surface roughness of the film layer can be less than 2nm. For example, a 4-inch substrate can be spin coated with 1-5mL of the photosensitive composition. Since the metal oxide cluster patterned material of the embodiment of the present application has high sensitivity, a smaller thickness can be set to achieve high-quality patterning.

[0094] In the embodiment of the present application, after spin coating and before exposure, a baking process can be selectively performed to remove the solvent remaining in the patterned material film layer. The baking temperature can be between 60° C. and 200° C., and the baking time can be between 20s and 120s.

[0095] S102, exposing the patterned material film layer to an exposure light source through a photomask;

[0096] Specifically, the exposure light source may be the light source described above, which will not be described in detail here. In some embodiments, any single wavelength ray or mixed wavelength ray in the range of 1-15nm X-ray may be used to selectively irradiate the patterned material film layer through reflection from the mask plate, so as to transfer the pattern on the mask to the patterned material film layer. The exposure dose of the irradiation light source may be 10-300mJ / cm 2 The dose of electron beam irradiation can be 50μC / cm 2 -5000μC / cm 2 After the patterned material film layer is selectively exposed by the light source, a chemical reaction occurs in the exposed part and the solubility changes.

[0097] In the embodiment of the present application, the patterned material film layer can be selectively baked after exposure and before development, and the baking temperature is between 60° C. and 200° C., and the time is between 20s and 120s. The baking operation can promote the further completion of unfinished chemical reactions in the film layer.

[0098] S103 , using a developer to develop the exposed patterned material film layer to form a patterned film on the substrate.

[0099] Since the chemical properties and solubility of the exposed portion of the patterned material film layer change, the irradiated metal oxide cluster patterned material is cleaned by a developer, and the cleaning time ranges from 10s to 300s, which can be single-step cleaning or multi-step cleaning.

[0100] In the development process, a suitable developer can be selected according to the properties of the metal oxide clusters, and the developer can be selected from organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing additives, etc. Specifically, in some embodiments of the present application, the developer can be a tetramethylammonium hydroxide (TMAH) aqueous solution with a concentration of 0.5-5%, or it can be an organic solvent such as ketones, alcohols, ethers, esters, lactones, high-boiling alcohols, etc., wherein ketones can be, for example, cyclohexanone, 4-methyl-2-pentanone, methyl-2-n-pentyl ketone; alcohols can be, for example, isopropanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and diacetone alcohol; ethers can be, for example, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether , ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, tert-butyl acetate, tert-butyl propionate and propylene glycol monotert-butyl ether acetate; lactones such as γ-butyrolactone; high boiling point alcohol solvents such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, 1,3-butanediol. The developer can be a mixture of one or more of the above solvents. Among them, the developer is in contact with the exposed film layer for a development time of 10s-120s. After development, a water rinsing process can be optionally added, and the rinsing time can be 20s-120s. Rinse can make the film layer cleaner; a baking process can also be optionally added, and the baking temperature can be between 60-200°C and the time can be between 20s-120s; baking can make the pattern structure more stable and not easy to collapse.

[0101] In some embodiments, the metal oxide cluster patterning material is [nBuSn]8M(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2, and the developer can be a mixture of isopropyl alcohol and 4-methyl-2-pentanone (volume ratio range 10:1-1:10).

[0102] After development, the obtained pattern can be observed using a scanning electron microscope (SEM) or an atomic force microscope (AFM). The obtained pattern resolution is between 3nm-100nm, and the line width ratio is 1:1; the pattern resolution is, for example, ≤50nm, further ≤35nm; the critical size is ≤50nm, further ≤35nm.

[0103] S104, etching the substrate after development to transfer the pattern of the patterned film to the substrate to obtain a patterned substrate;

[0104] The pattern formed by the metal oxide cluster patterned material selectively protects the underlying substrate material during the etching step. After etching under certain conditions, the metal oxide cluster patterned material and the unprotected substrate material are etched, but the etching speed of the protected area by the metal oxide cluster patterned material is slower than that of the unprotected area, and finally a pattern is formed on the substrate material, that is, the pattern is transferred to the substrate. The etching process can specifically transfer the pattern to the substrate through HF etching, ion etching or ion implantation process.

[0105] The patterning method provided in the embodiment of the present application can be applied to the patterning process of the semiconductor integrated circuit manufacturing process by adopting the photosensitive composition of the embodiment of the present application to obtain a smaller chip patterning critical dimension, which is conducive to the development of high-integration and high-precision semiconductors.

[0106] The present application also provides a patterned film, which is formed by the photosensitive composition of the present application or obtained by the patterning method. The patterned film can be used as a high-precision mask 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 to form a preset pattern on the substrate. Since the metal oxide cluster patterning material of the present application embodiment has high sensitivity and the molecular size can be controlled at a smaller size, the patterned film obtained by the patterning process of the photosensitive composition of the present application embodiment has a high resolution and low edge roughness. Specifically, in the present application embodiment, the resolution of the pattern on the patterned film is within the range of 3nm-100nm, for example, ≤50nm, and further ≤35nm. In some embodiments, the resolution of the pattern can be 3nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm.

[0107] The present application embodiment also provides a patterned substrate, and the pattern on the patterned substrate is formed by the photosensitive composition of the present application embodiment or obtained by the above-mentioned patterning method. The patterned substrate can be used for the preparation of semiconductor devices such as chips, improves the precision and quality of device manufacturing, and thus improves the performance of semiconductor devices. Specifically, in the embodiment of the present application, the resolution of the pattern on the patterned substrate is within the range of 3nm-100nm. In some embodiments, the resolution of the pattern can be 3nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm.

[0108] The embodiment of the present application also provides a semiconductor device, including a patterned substrate and a functional layer arranged on the patterned substrate; the patterned substrate is obtained by etching a substrate having the aforementioned patterned film provided by the embodiment of the present application on its surface.

[0109] The semiconductor device provided in the embodiment of the present application has high precision. In the embodiment of the present application, there is no special limitation on the structure of the semiconductor device, and those skilled in the art can design it according to the actual application needs and prepare it according to the photosensitive composition provided in the embodiment of the present application.

[0110] In some implementations of the present application, the semiconductor device includes: a structure obtained by etching or electron injection into a patterned substrate.

[0111] In some specific embodiments of the present application, the semiconductor device is a structure obtained by etching or electron injection into a patterned substrate whose substrate is a silicon wafer.

[0112] In the embodiments of the present application, there is no limitation on the specific type of semiconductor device. In some embodiments of the present application, the semiconductor device may be an integrated circuit device including a chip. In the process of preparing the chip, other functional layers may be prepared after the aforementioned patterning process is completed.

[0113] The present application also provides a method for preparing a semiconductor device, comprising:

[0114] The photosensitive composition provided in the embodiment of the present application is coated on a substrate to form a film layer on the substrate;

[0115] developing the film layer through a photomask to form a patterned film on a substrate;

[0116] Etching to obtain a patterned substrate;

[0117] The functional layer is prepared to obtain a semiconductor device. The process parameters involved in the above process can all be referred to the relevant description of the method for preparing the patterned film in the above text, and will not be repeated here.

[0118] In some embodiments of the present application, after forming a patterned film on a substrate, the method for preparing the semiconductor device further comprises:

[0119] The patterned substrate is etched or electrons are injected to form a pattern on the surface of the patterned substrate, thereby forming a structure required for the semiconductor device on the surface of the substrate to obtain a semiconductor device.

[0120] The preparation method has strong process reliability and is easy to realize large-scale industrial production.

[0121] The technical solution of the present application is further explained below in conjunction with specific embodiments.

[0122] Example 1

[0123] Dissolve 1 mmol of tin trichloride and 0.3 mmol of a rare earth salt (specifically ytterbium salt) in 4 mL of iminodiacetic acid, 2 mL of ethylene glycol and 0.5 mL of deionized water to obtain a mixture;

[0124] The mixture was heated at 80°C for four days and then cooled to room temperature. Crystals precipitated and the product was collected after drying to obtain a metal oxygen cluster (nBuSn)8Yb(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2; for the sake of convenience, it is recorded as Sn8Yb.

[0125] Example 2

[0126] Dissolve 1 mmol of tin trichloride and 0.3 mmol of a rare earth salt (specifically an erbium salt) in 4 mL of iminodiacetic acid, 2 mL of ethylene glycol and 0.5 mL of deionized water to obtain a mixture;

[0127] The mixture was heated at 80°C for four days and then cooled to room temperature. Crystals precipitated and the product was collected after drying to obtain a metal oxygen cluster (nBuSn)8Er(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2; for the sake of convenience, it is recorded as Sn8Er.

[0128] Example 3

[0129] Dissolve 1 mmol of tin trichloride and 0.3 mmol of a rare earth salt (specifically a holmium salt) in 4 mL of iminodiacetic acid, 2 mL of ethylene glycol and 0.5 mL of deionized water to obtain a mixture;

[0130] The mixture was heated at 80°C for four days and then cooled to room temperature. Crystals precipitated and the product was collected after drying to obtain a metal oxygen cluster (nBuSn)8Ho(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2; for the sake of convenience, it is recorded as Sn8Ho.

[0131] Example 4

[0132] Dissolve 1 mmol of tin trichloride and 0.3 mmol of a rare earth salt (specifically a samarium salt) in 4 mL of iminodiacetic acid, 2 mL of ethylene glycol and 0.5 mL of deionized water to obtain a mixture;

[0133] The mixture was heated at 80°C for four days and then cooled to room temperature. Crystals precipitated and the product was collected after drying to obtain a metal oxygen cluster (nBuSn)8Sm(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2; for the sake of convenience, it is recorded as Sn8Sm.

[0134] Example 5

[0135] Dissolve 1 mmol of tin trichloride and 0.3 mmol of a rare earth salt (specifically a europium salt) in 4 mL of iminodiacetic acid, 2 mL of ethylene glycol and 0.5 mL of deionized water to obtain a mixture;

[0136] The mixture was heated at 80°C for four days and then cooled to room temperature. Crystals precipitated and the product was collected after drying to obtain a metal oxygen cluster (nBuSn)8Eu(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2; for the sake of convenience, it is recorded as Sn8Eu.

[0137] Example 6

[0138] Dissolve 1 mmol of tin trichloride and 0.3 mmol of a rare earth salt (specifically, a yttrium salt) in 4 mL of iminodiacetic acid, 2 mL of ethylene glycol and 0.5 mL of deionized water to obtain a mixture;

[0139] The mixture was heated at 80°C for four days and then cooled to room temperature. Crystals precipitated and the product was collected after drying to obtain a metal oxide cluster (nBuSn)8Y(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2; for the sake of convenience, it is recorded as Sn8Y.

[0140] Analysis and testing of metal oxygen clusters

[0141] (1) X-ray Diffraction (XRD) Test: XRD powder test was performed on the metal oxide clusters prepared in each embodiment, using a copper target (the incident wavelength of the X-ray was λ = 0.154056 nm); the XRD diffraction spectra of the products (metal oxide clusters) prepared in Examples 1 to 6 are summarized in Figure 2 middle.

[0142] (2) UV-visible spectrum analysis: The metal oxide clusters prepared in Examples 1 to 6 were subjected to UV-visible spectrum analysis. The UV-visible spectra of the products (metal oxide clusters) prepared in each Example are summarized in Figure 3 middle.

[0143] (3) Elemental analysis: The metal oxygen clusters prepared in Examples 1 to 3 were analyzed by an elemental analyzer to determine the mass proportions of C, H and N in the products prepared in the examples. The results are summarized in Table 1. The theoretical mass proportions of the above C, H and N elements in the corresponding metal oxygen clusters were calculated to calculate the purity of the product. From the results in Table 1, it was found that the purity of the metal oxygen clusters prepared in the examples of the present application was ≥95%.

[0144] (4) Thermal Stability Analysis: The metal oxide clusters prepared in Examples 1 to 6 were subjected to thermogravimetric analysis (TGA) in a nitrogen atmosphere. The thermogravimetric curves of the metal oxide clusters in each example under air are summarized in Figure 4 middle.

[0145] Table 1

[0146]

[0147]

[0148] Preparation of photosensitive composition

[0149] 15 mg of (nBuSn)8M(μ2-O)(μ2-OH)5(μ3-O)2(μ4-O)2(IDA)2(EG)2(NE)2 prepared in the above embodiments was dissolved in 1 mL of N,N-dimethylformamide (DMF), and the solution was filtered after complete dissolution to form a photosensitive composition.

[0150] Photosensitive composition stability test:

[0151] The photosensitive compositions obtained in Example 3 (Sn8Ho) were stored at room temperature (25°C) and the crystallization and precipitation of the solutions were observed. 12 O 14 The cluster was dissolved in 1 mL of DMF for stability test as comparative example 1. The results are shown in Table 2.

[0152] Table 2

[0153] serial number 7 days 30 days Example 1 + +++ Comparative Example 1 - -

[0154] It should be noted that, in Table 2, “-” indicates that the solution is clear without precipitation, “+” indicates that the solution is clear with a small amount of precipitation, and “+++” indicates that there is a large amount of precipitation in the solution.

[0155] From the results in Table 2, it can be seen that the photosensitive composition of Example 1 of the present application can maintain a clear solution without precipitation after being stored at 25°C for more than 30 days, while Comparative Example 1 has a small amount of precipitation after being stored at 25°C for 7 days and a large amount of precipitation after being stored for 1 month. This shows that the solution stability of the photosensitive composition of the present application example is significantly improved.

[0156] Exposure performance test 1:

[0157] (1) Hydrophobic treatment of silicon wafer: HMDS is evenly coated on the surface of silicon wafer by evaporation or spin coating;

[0158] (2) Film preparation: Spin-coating an appropriate amount of the filtered photosensitive composition onto the surface of the silicon substrate to form a patterned material film layer;

[0159] (3) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0160] (4) Radiation exposure: Electron beam lithography (EBL) was used to expose the patterned material film layer through a mask (line width 100 nm); the dose of electron beam irradiation was 80 μC / cm 2 -100μC / cm 2 ;

[0161] (5) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0162] (6) Development: A mixed solution of isopropyl alcohol and 4-methyl-2-heptanone (volume ratio of 1:1) was used for development for 60 seconds to form a patterned film on the silicon wafer.

[0163] The pattern of the patterned film obtained after the exposure and development was characterized using a scanning electron microscope (SEM). Figure 5A , Figure 5B , Figure 5C , Figure 5D , Figure 5E , Fig. 5F The SEM images of the patterned films obtained in Examples 1 to 6 of the present application are shown in sequence; FIG. 5A to FIG. 5FIt can be seen that the minimum line width LW (Line Width) of the patterned films obtained in Examples 1 to 6 of the present application are 117nm, 107nm, 97nm, 90nm, 83nm, and 95nm, respectively. That is, the CD of the patterned films obtained in Examples 1 to 6 are 117nm, 107nm, 97nm, 90nm, 83nm, and 95nm, respectively; the line width roughness LWR (Line Width Roughness) are 23.34nm, 16.79nm, 24.64nm, 20.47nm, 25.09nm, and 49.77nm, respectively, and the edge roughness LER are 14.49nm, 12.73nm, 15.11nm, 15.06nm, 17.96nm, and 28.72nm, respectively.

[0164] Exposure test 1 comparison

[0165] The metal oxygen cluster is replaced by a Sn4 cluster structure without rare earth atoms. The structure is a tin oxygen cluster coordinated by a dialkyl group and an organic cyclic carboxylic acid, the center of which is composed of four metal tin atoms connected by two bridging oxygens and peripheral ligands such as cycloalkyl and alkenyl groups. The specific structure is shown in formula (2);

[0166]

[0167] Take 15 mg of Sn4 cluster structure, dissolve it in 1 mL of chloroform, filter the solution after it is completely dissolved, and form a photosensitive composition of exposure test 1 comparative example, and perform exposure performance test:

[0168] (1) Hydrophobic treatment of silicon wafer: HMDS is evenly coated on the surface of silicon wafer by evaporation or spin coating;

[0169] (2) Film preparation: spin coating an appropriate amount of the filtered photosensitive composition onto the surface of the silicon substrate to form a patterned material film layer;

[0170] (3) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0171] (4) Radiation exposure: Electron beam lithography (EBL) was used to expose the patterned material film layer through a mask (line width 100 nm); the dose of electron beam irradiation was 80 μC / cm 2 -100μC / cm 2 ;

[0172] (5) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0173] (6) Development: A mixed solution of isopropyl alcohol (IPA) and deionized water (DIW) (volume ratio of 3:1) was used for development for 60 seconds to form a patterned film on the silicon wafer. The SEM photo is shown in Figure 5G .

[0174] from Figure 5G It can be seen that the photosensitive composition of exposure test comparative example 1 cannot achieve a line width ratio of 1:1 under electron beam irradiation, and has a problem of poor resolution.

[0175] Exposure performance test 2:

[0176] (1) Hydrophobic treatment of silicon wafer: HMDS is evenly coated on the surface of silicon wafer by evaporation or spin coating;

[0177] (2) Film preparation: Spin-coat an appropriate amount of the filtered photosensitive composition of Example 3 onto the surface of the silicon substrate to form a patterned material film layer;

[0178] (3) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0179] (4) Radiation exposure: The patterned material film layer was exposed to a mask (line width 50 nm) using electron beam lithography (EBL), and the L / S ratios of the preset patterns were 1L / 1S and 1L / 2S (L is the line width and is 50 nm; S is the line spacing, specifically Space refers to the strip spacing); the dose of electron beam irradiation was 600 μC / cm 2 ;

[0180] (5) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0181] (6) Development: A mixed solution of isopropyl alcohol and 4-methyl-2-heptanone (volume ratio 1:1) was used for development for 60 seconds to form a patterned film on the silicon wafer.

[0182] AFM was used to characterize the pattern of the patterned film obtained after the exposure and development. Fig. 6A , Figure 6B The AFM height sensor images of the patterned films of 1L / 1S and 1L / 2S under the above exposure doses in Example 1 of the present application are respectively; Fig. 6A , Figure 6B It can be seen that the LW of the patterned film is 50 nm.

[0183] Exposure performance test 3:

[0184] (1) Hydrophobic treatment of silicon wafer: HMDS is evenly coated on the surface of silicon wafer by evaporation or spin coating;

[0185] (2) Film preparation: Spin-coat an appropriate amount of the filtered photosensitive composition of Example 3 onto the surface of the silicon substrate to form a patterned material film layer;

[0186] (3) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0187] (4) Radiation exposure: The patterned material film layer was exposed with a mask (line width 50 nm) using electron beam etching (EBL) technology, and the L / S ratios of the preset patterns were 1L / 2S and 1L / 3S (L is the line width and is 50 nm; S is the line spacing, specifically Space refers to the strip spacing); the electron beam irradiation dose was 800 μC / cm 2 ;

[0188] (5) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0189] (6) Development: A mixed solution of isopropyl alcohol and 4-methyl-2-heptanone (volume ratio 1:1) was used for development for 60 seconds to form a patterned film on the silicon wafer.

[0190] AFM was used to characterize the pattern of the patterned film obtained after the exposure and development. Fig. 7A , Figure 7B The AFM height sensor images of the patterned films of 1L / 2S and 1L / 3S under the above exposure doses in Example 1 of the present application are shown in sequence; Fig. 7A , Figure 7B It can be seen that the LW of the patterned film is 50 nm.

[0191] Exposure performance test 4:

[0192] (1) Hydrophobic treatment of silicon wafer: HMDS is evenly coated on the surface of silicon wafer by evaporation or spin coating;

[0193] (2) Film preparation: Spin-coating an appropriate amount of the filtered photosensitive composition onto the surface of the silicon substrate to form a patterned material film layer;

[0194] (3) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0195] (4) Radiation exposure: The patterned material film layer is exposed to a mask (line width 35 nm) using 13.5 nm soft X-rays, and the L / S ratio of the preset pattern is 1:1; the soft X-ray irradiation dose is 50-100 μC / cm 2 ;

[0196] (5) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0197] (6) Development: A mixed solution of isopropyl alcohol (IPA) and deionized water (DIW) (volume ratio of 3:1) is used for development for 60 seconds to form a patterned film on the silicon wafer.

[0198] The pattern of the patterned film obtained after the above exposure and development was characterized by SEM, see Fig. 8A .

[0199] Exposure performance test 4 comparison

[0200] Take 15 mg of the Sn4 cluster structure represented by formula (2) and dissolve it in 1 mL of chloroform. After it is completely dissolved, filter the solution to form a photosensitive composition of comparative example of exposure test 4. Perform exposure performance test on the photosensitive composition according to steps (1) to (6):

[0201] (1) Hydrophobic treatment of silicon wafer: HMDS is evenly coated on the surface of silicon wafer by evaporation or spin coating;

[0202] (2) Film preparation: spin coating an appropriate amount of the filtered photosensitive composition onto the surface of the silicon substrate to form a patterned material film layer;

[0203] (3) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0204] (4) Radiation exposure: The patterned material film layer is exposed to a mask (line width 35 nm) using 13.5 nm soft X-rays, and the L / S ratio of the preset pattern is 1:1; the soft X-ray irradiation dose is 50-100 μC / cm 2 ;

[0205] (5) Baking: Baking the patterned material film layer at 100° C. for 2 minutes;

[0206] (6) Development: Use a mixture of isopropyl alcohol (IPA) and deionized water (DIW) (volume ratio of 3:1) for development for 60 seconds to form a patterned film on the silicon wafer. Use SEM to characterize the pattern of the patterned film obtained after the above exposure and development. See Figure 8B .

[0207] from Fig. 8A and Figure 8B It can be seen that the metal oxide clusters provided in the embodiment of the present application can achieve 35nm CD under 13.5nm soft X-rays and a line width ratio of 1:1; the critical dimension of the comparative example under 13.5nm soft X-rays is only 50nm, and the morphology is poor.

[0208] It should be understood that the first, second and various numerical numbers involved in this document are only distinguished for the convenience of description and are not used to limit the scope of the present application.

[0209] In this application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone, where A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0210] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0211] In this application, “-” represents a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, which means that the value of a can be between 0.5 and 15, and includes the endpoint values ​​0.5 and 15.

[0212] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

Claims

1. A metal oxide cluster, characterized in that: It includes a metal oxygen cluster skeleton and a ligand coordinated and connected to the metal oxygen cluster skeleton; The metal oxygen cluster skeleton includes tin atoms, rare earth atoms and inorganic oxygen atoms, and at least part of the tin atoms and at least part of the rare earth atoms are bridged by inorganic oxygen atoms; The tin atom is connected to an R group, and the R group includes one or more of a substituted or unsubstituted chain hydrocarbon group or a chain hydrocarbon group containing heteroatoms on the main chain, a substituted or unsubstituted cyclic hydrocarbon group, and a halogen atom; The ligand includes a structure derived from a first monomer, which includes one or more of a substituted or unsubstituted carboxylic acid or one containing heteroatoms on the main chain, a substituted or unsubstituted alcohol or one containing heteroatoms on the main chain, a substituted or unsubstituted amine or one containing heteroatoms on the main chain, phosphoric acid, and a substituted or unsubstituted phosphonic acid.

2. The metal oxide cluster according to claim 1, characterized in that: The number of tin atoms and rare earth atoms in the metal oxide cluster framework is independently 1-30.

3. The metal oxide cluster according to claim 1, characterized in that: The metal oxygen cluster skeleton contains a plurality of tin atoms, a plurality of rare earth atoms and a plurality of inorganic oxygen atoms; Each of the rare earth atoms forms a Sn-OMO-Sn inorganic bridging structure, wherein M represents the rare earth atom.

4. The metal oxide cluster according to claim 1, characterized in that: Each of the tin atoms is bonded to 1 to 3 of the R groups.

5. The metal oxide cluster according to claim 1, characterized in that: The metal oxygen cluster skeleton includes a plurality of inorganic oxygen atoms, and the plurality of inorganic oxygen atoms include inorganic oxygen atoms with a coordination number of 2, inorganic oxygen atoms with a coordination number of 3, and inorganic oxygen atoms with a coordination number of 4.

6. The metal oxide cluster according to claim 1, characterized in that: The rare earth atoms include one or more of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

7. The metal oxide cluster according to claim 1, characterized in that: When the R group is a substituted chain hydrocarbon group or a substituted cyclic hydrocarbon group, the substituent group includes one or more of halogen, hydroxyl, amine, amide, silane, and alkoxy.

8. The metal oxide cluster according to claim 1, characterized in that: The chemical general formula of the metal oxygen cluster is (R a Sn) x M y O z L n , where 1 ≤ a ≤ 3, 1 ≤ x ≤ 30, 1 ≤ y ≤ 30, 0 < n ≤ 6(x + y), 1 ≤ z ≤ 6(x + y), and a, x, y, z, and n are all integers; M represents the rare earth atom, and L represents the ligand.

9. The metal oxide cluster according to claim 1, characterized in that: The ligand is an organic ligand; the organic ligand has a cyclic structure, and / or the organic ligand has a double bond.

10. The metal oxide cluster according to claim 1, characterized in that: The chemical formula of the metal oxygen cluster skeleton is (RSn)8O 10 M, chemical structure is shown in formula (1): Wherein, M represents the rare earth atom.

11. The metal oxide cluster according to claim 1, characterized in that: The ligand is an organic ligand, and the number of carbon atoms of the organic ligand is 1-30; and / or, when the R group contains carbon atoms, the number of carbon atoms of the R group is 1-30.

12. A method for preparing the metal oxide cluster according to any one of claims 1 to 11, characterized in that: include: An organic tin source, a rare earth element source, the first monomer and water are mixed to obtain a mixture; the mixture is heated to react to obtain metal oxide clusters; wherein the volume of the water accounts for ≥0.5% based on the sum of the volumes of the water and the first monomer; the organic tin source and / or the rare earth element source can react with the first monomer.

13. A photosensitive composition, characterized in that: The method comprises the metal oxygen cluster according to any one of claims 1 to 11 and a solvent.

14. A patterned film, characterized in that: The patterned film is formed by the photosensitive composition according to claim 13.

15. A patterned substrate, characterized in that: The patterned substrate is obtained by etching a substrate having the patterned film as claimed in claim 14 on its surface.

16. A semiconductor device, characterized in that: The semiconductor device comprises a patterned substrate and a functional layer arranged on the patterned substrate; the patterned substrate is obtained by etching a substrate having a patterned film as claimed in claim 14 on its surface.

17. A method for preparing a semiconductor device, characterized in that: include: Applying the photosensitive composition according to claim 13 on a substrate to form a film layer on the substrate; Exposing and developing the film layer through a photomask to form a patterned film on the substrate; Etching to obtain a patterned substrate; A functional layer is prepared to obtain a semiconductor device.

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