Photosensitive material film, patterned film, patterned substrate, semiconductor device and preparation method thereof

Abstract

The invention provides a photosensitive material film, a patterned film, a patterned substrate, a semiconductor device and a preparation method thereof, the photosensitive material film comprises an amorphous organic metal compound, and the amorphous organic metal compound comprises a metal cluster skeleton and a polydentate ligand in coordination connection with the metal cluster skeleton; the metal cluster skeleton comprises metal atoms or comprises metal atoms and oxygen atoms; the polydentate ligand comprises at least two coordination atoms, and the polydentate ligand is in coordination connection with metal atoms in the metal cluster framework through the coordination atoms. The photosensitive material film provided by the invention can form an irregular reticular framework molecular structure, the coordination bond in the structure is weak in bond energy, good in solubility and small in rigidity, the prepared pattern is high in resolution, low in edge roughness and low in required exposure energy, and the photosensitive material film is applied to preparation of semiconductor devices, so that the comprehensive performance of the semiconductor devices can be improved.

Description

Technical Field

[0001] The present application relates to the field of semiconductor preparation, and specifically to a photosensitive material film, a patterned film, a patterned substrate, a semiconductor device and a preparation method thereof. Background Art

[0002] With the continuous development of semiconductor technology, the industry has put forward higher requirements for the computing power of semiconductors, and the patterning process determines the performance of semiconductors. The resolution of traditional resin patterning compositions has reached its limit and is not suitable for the preparation of patterns with smaller critical dimensions. In the prior art, metal cluster materials can be used to form photosensitive material films to obtain patterns with high resolution and small critical dimensions, thereby improving the performance of semiconductor devices. However, the photosensitive material films obtained by the existing metal cluster patterning compositions have technical problems such as strong structural rigidity, large pores, poor solubility, poor film forming properties, poor edge roughness of the obtained patterned films, poor film uniformity, large required exposure dose, and poor exposure effect. Therefore, there is a need for a photosensitive material film with low structural rigidity, good solubility, small required exposure dose, and excellent exposure performance, which can produce a patterned film with high pattern resolution, low edge roughness, and high uniformity. Summary of the Invention

[0003] In view of this, the present application provides a photosensitive material film, a patterned film, a patterned substrate, a semiconductor device and a preparation method thereof. The photosensitive material film includes an amorphous organic metal compound and is a random metal-based network structure. The coordination bond energy in the structure is weak, the solubility is good, the stability is high, and the exposure performance is excellent, which is beneficial to improving the resolution of the obtained pattern and reducing the edge roughness of the pattern.

[0004] In the first aspect, the present application provides a photosensitive material film, the photosensitive material film comprising an amorphous organometallic compound, the amorphous organometallic compound comprising a metal cluster skeleton and a multidentate ligand coordinatedly connected to the metal cluster skeleton; the metal cluster skeleton comprises metal atoms or metal atoms and oxygen atoms; each of the multidentate ligands comprises at least two coordinating atoms, and the multidentate ligands are coordinatedly connected to the metal atoms in the metal cluster skeleton via the coordinating atoms. The photosensitive material film provided by the present application comprises an amorphous organometallic compound, which is a random metal-based network structure with weak coordination bond energy, good solubility, and high stability, which is conducive to forming a patterned film layer with good uniformity, excellent exposure effect, high pattern resolution, low edge roughness, and improved overall performance of semiconductor devices.

[0005] Optionally, the surface roughness of the photosensitive material film is less than or equal to 0.4 nm. The photosensitive material film provided in this application has low surface roughness and high film uniformity, which is conducive to the formation of a patterned film layer and improves the resolution and fineness of the obtained pattern.

[0006] Optionally, the amorphous organometallic compound has a random metal-based network structure; in the amorphous organometallic compound, the metal cluster skeleton and the multidentate ligand are connected and aggregated in an irregular manner. Thus, the amorphous organometallic compound provided by the present application has low rigidity, weak coordination bond energy, and good solubility. The resulting photosensitive material film has excellent film-forming properties, and the resulting pattern has high resolution, low edge roughness, high uniformity, and requires a low exposure dose.

[0007] Optionally, the chemical formula of the metal cluster skeleton is M a O b R c , 1≤a≤10, 0≤b≤20, 0≤c≤60, where a, b, and c are all integers, M represents the metal atom, and R represents an organic ligand. This improves the solubility and stability of the photosensitive material film, while also increasing the resolution of the exposed pattern and reducing the edge roughness of the pattern.

[0008] Optionally, the organic ligand includes one or more of a substituted or unsubstituted alkyl group or one containing heteroatoms in the main chain, a substituted or unsubstituted alkenyl group or one containing heteroatoms in the main chain, a substituted or unsubstituted alkynyl group or one containing heteroatoms in the main chain, a substituted or unsubstituted heteroalkyl group, or a substituted or unsubstituted aryl group. The selection of the above organic ligands is beneficial for increasing the polarity of the organic ligand, thereby improving the solubility of the photosensitive material film in the solvent.

[0009] Optionally, the organic ligand is connected to the metal atoms in the metal cluster skeleton via carbon atoms, and the number of carbon atoms in the organic ligand is 1 to 30. An appropriate number of carbon atoms can improve the solubility and stability of the photosensitive material film in the solvent, improve the resolution of the pattern after exposure, and reduce the roughness of the pattern.

[0010] Optionally, M includes one or more of indium, tin, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, palladium, platinum, silver, cadmium, antimony, tellurium, hafnium, tungsten, gold, lead, and bismuth. This helps improve the solubility of the photosensitive material film in the solvent and reduces the edge roughness of the resulting pattern.

[0011] Optionally, the chemical formula of the multidentate ligand is Ra(X) d(G)e, Ra is a substituted or unsubstituted alkyl group, X is the coordinating atom, and the coordinating atom includes one or more of an oxygen atom and a nitrogen atom. G represents a hydroxyl group and / or an amino group in the multidentate ligand that does not participate in the coordination connection. d ≥ 2, e ≥ 0, d and e are integers, and the number of carbon atoms in the multidentate ligand is greater than or equal to 2. The multidentate ligand is used to connect with the metal atoms in the metal cluster skeleton, which is conducive to forming a network framework molecular structure. This structure can be dissolved in polar solvents, thereby improving the solubility of the photosensitive material film. At the same time, it can be dissolved in a highly polar developer during exposure and development, decomposing into small molecules, which is conducive to improving the resolution of the pattern and reducing its roughness.

[0012] Optionally, in the amorphous organometallic compound, the ratio of the number of the metal cluster skeleton to the number of the multidentate ligand is 1:(0.1-10). A suitable ratio of the number of the metal cluster skeleton to the multidentate ligand can improve the solubility of the photosensitive material film, facilitate the formation of a random network framework structure, and further enhance the film uniformity of the photosensitive material film.

[0013] Secondly, the present application provides a method for preparing a photosensitive material film, comprising: mixing a metal cluster skeleton precursor, a multidentate ligand precursor, and a solvent to obtain a photosensitive material solution; coating the photosensitive material solution and drying to form a photosensitive material film; the multidentate ligand precursor comprises one or more of a diol, a diamine, a polyol, a polyamine, and an alcoholamine. The preparation method provided by the present application is novel, the preparation process is simple, and the prepared photosensitive material film has good stability, high solubility, and excellent exposure performance.

[0014] Optionally, the chemical formula of the metal cluster skeleton precursor is M a O b R c Z f Z is a group connected to a metal atom and capable of being substituted by the multidentate ligand, N is one or more of a diethylamino group, an alcohol group, a carboxylic acid group, and a halogen group, and f is ≥ 3, where f is an integer. This can form a random network structure, resulting in a uniform photosensitive material film, which is beneficial for reducing the line width roughness of the pattern after exposure.

[0015] Optionally, the solvent includes one or more of an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, tetrahydrofuran, N,N-dimethylformamide, dimethyl adipate, benzene, and toluene. The solvent can improve the coating performance of the photosensitive material solution, facilitate the formation of a uniform photosensitive material film, and improve the uniformity of the pattern after exposure.

[0016] In a third aspect, the present application provides a patterned film, which is obtained by patterning the photosensitive material film described in the first aspect or the photosensitive material film prepared by the preparation method described in the second aspect.

[0017] The patterned film provided in this application has high clarity, good uniformity, and low line width roughness.

[0018] In a fourth aspect, the present application provides a patterned substrate, wherein the patterned substrate is patterned using the photosensitive material film described in the first aspect or the photosensitive material film prepared by the preparation method described in the second aspect. The patterned substrate provided by the present application has a clear pattern and good structural stability.

[0019] Optionally, the line width roughness of the patterned substrate is less than or equal to 4 nm. The lower the edge roughness of the pattern, the higher the fineness of the pattern, which is conducive to improving the overall performance of the semiconductor device.

[0020] Optionally, the critical dimension of the pattern on the patterned substrate is less than or equal to 50 nm, which is beneficial to improving the overall performance of the semiconductor device.

[0021] In a fifth aspect, the present application provides a semiconductor device, which is manufactured by patterning the photosensitive material film described in the first aspect or the photosensitive material film prepared by the preparation method described in the second aspect.

[0022] The semiconductor device provided by this application has high precision and excellent overall performance.

[0023] In a sixth aspect, the present application provides a method for preparing a semiconductor device, comprising: setting a photosensitive material film as described in the first aspect on a substrate, exposing and developing it to form a patterned film on the substrate; preparing a functional layer to obtain a semiconductor device.

[0024] The preparation method of the semiconductor device provided in this application is simple, and the prepared semiconductor device has high precision and excellent comprehensive performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for the embodiments or the description of the prior art. The specific embodiments described here are only used to explain the present application and are not used to limit the present application.

[0026] Figure 1 This is the NMR characterization image of the photosensitive material film provided in Example 1 of the present application;

[0027] Figure 2 This is the NMR characterization image of the photosensitive material film provided in Example 2 of the present application;

[0028] Figure 3 This is the NMR characterization image of the photosensitive material film provided in Example 3 of the present application;

[0029] Figure 4This is the NMR characterization of the metal cluster skeleton precursor provided in Example 1 of the present application;

[0030] Figure 5 This is an infrared spectrum characterization diagram of the photosensitive material film and the multidentate ligand precursor provided in Example 1 of the present application;

[0031] Figure 6 This is an infrared spectrum characterization diagram of the photosensitive material film and the multidentate ligand precursor provided in Example 2 of the present application;

[0032] Figure 7 This is an infrared spectrum characterization diagram of the photosensitive material film and the multidentate ligand precursor provided in Example 3 of the present application;

[0033] Figure 8 This is the XRD diffraction characterization diagram of the photosensitive material film provided in Example 2 of the present application;

[0034] Figure 9 This is the XRD diffraction characterization pattern of Sn-1,2,4-butanetriol;

[0035] Figure 10 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Example 1 of the present application;

[0036] Figure 11 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Example 2 of the present application;

[0037] Figure 12 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Comparative Example 1 of the present application;

[0038] Figure 13 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Comparative Example 2 of the present application;

[0039] Figure 14 This is a graph showing how the line width roughness of the pattern after exposure of the photosensitive material film provided in Example 2 and Comparative Example 2 of the present application changes with the critical dimension (10 nm-22 nm);

[0040] Figure 15 This is a graph showing how the line width roughness of the pattern after exposure of the photosensitive material film provided in Example 2 and Comparative Example 2 of the present application changes with the critical dimension (22nm-32nm);

[0041] Figure 16 This is a graph showing the change in line width roughness of the pattern after exposure of the photosensitive material film provided in Example 2 and Comparative Example 2 of the present application as a function of the critical dimension (35nm-55nm). DETAILED DESCRIPTION

[0042] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0043] In order to better understand the technical solution of this application, some key terms involved in this application are explained as follows:

[0044] 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 through the etching process. The substrate substrate here includes not only silicon wafers, but also other metal layers, dielectric layers, and the above-mentioned substrates with surface modification or added supporting layers.

[0045] Patterning material: also known as photoresist or anti-etching agent, refers to an etching-resistant thin film material whose solubility in the developer changes when irradiated or radiated by light with a wavelength of 10nm-400nm, light with a wavelength of 200nm-350nm, X-rays, electron beams, ion beams, etc.

[0046] Developer: The developer is a pure or mixed solvent that dissolves the soluble areas of the patterned material after the solubility change caused by exposure.

[0047] Positive pattern: After development, the exposed part of the patterned material is washed away by the developer, and the pattern formed is a positive pattern.

[0048] Negative pattern: After development, the unexposed parts of the patterned material are washed away by the developer, and the pattern formed is a negative pattern.

[0049] Spin coating: Spin coating is a high-speed film-forming method that produces uniform thin films and is widely used in the preparation of thin films for semiconductor materials and chemical materials. It uses the centrifugal force generated by rotation to evenly spread sols, solutions, or suspensions onto the substrate surface.

[0050] Mask: During the patterning process, the mask acts as an optical element in the light path. The mask carries the design pattern, and light selectively transmits or reflects through it, projecting the design pattern onto the patterned material film layer.

[0051] With the development of the integrated circuit industry, the market has put forward higher requirements for the computing power per unit area of ​​integrated circuits. This depends largely on breakthroughs in patterning technology in the integrated circuit manufacturing process, especially breakthroughs in patterning compositions. The resolution of traditional resin patterning compositions has reached its limit and is not suitable for the preparation of patterns for integrated circuits with smaller critical dimensions. Therefore, the industry has gradually adopted metal cluster patterning compositions to obtain patterns with higher resolution and smaller critical dimensions to prepare high-performance chips. However, the existing metal cluster patterning compositions have the following problems: the film structure of the photosensitive material is highly rigid, the bond energy is large, the pores are large, the solubility is poor, the film-forming property of the patterned composition is poor, the edge roughness of the pattern finally obtained by exposure is poor, the film uniformity is poor, the required exposure dose is large, and the exposure effect is poor.

[0052] In order to solve the above problems, the present application provides a photosensitive material film, which includes an amorphous organic metal compound, the amorphous organic metal compound includes a metal cluster skeleton and a multidentate ligand coordinated to the metal cluster skeleton, the metal cluster skeleton includes metal atoms or includes metal atoms and oxygen atoms; the multidentate ligand includes at least two coordinating atoms, and the multidentate ligand is coordinated to the metal atoms in the metal cluster skeleton via the coordinating atoms. In the present application, the coordination atoms in the multidentate ligand and the metal atoms in the metal cluster skeleton are coordinated and connected to form an amorphous organic metal compound with a random metal-based network structure. The compound has extremely low crystallinity and low rigidity, and constitutes a photosensitive material film, which can improve the film-forming performance and film uniformity of the photosensitive material film, thereby improving the uniformity of the patterned film; the photosensitive material film includes an amorphous organic metal compound, the coordination bond energy in the amorphous organic metal compound is weak, the solubility is excellent, and it is easy to break in a high-polarity developer to form smaller fragments, which can be better dissolved and removed, and can reduce the roughness of the pattern edge after exposure, improve the resolution of the pattern, and reduce the exposure dose required for the patterning process. Therefore, the photosensitive material film provided by the present application includes an amorphous organic metal compound, the amorphous organic metal compound has low rigidity, weak coordination bond energy, and good solubility, which can improve the film-forming performance of the photosensitive material film, and the obtained pattern has high resolution, low edge roughness, high uniformity, and low required exposure dose.

[0053] In one embodiment of the present application, the surface roughness of the photosensitive material film is less than or equal to 0.4 nm. The amorphous organic metal compound in the photosensitive material film is a random metal-based network structure with uniform distribution, which can avoid large-scale metal agglomeration in the photosensitive material film, reduce the surface roughness of the photosensitive material film, and improve the film uniformity of the photosensitive material film, which is beneficial to the subsequent semiconductor process. Compared with the photosensitive material film composed of crystalline organic metal compounds, the photosensitive material film composed of amorphous organic metal compounds has a significantly reduced surface roughness and high film uniformity, which can improve the overall performance of semiconductor devices. Specifically, the surface roughness of the photosensitive material film can be, but is not limited to, 0.4 nm, 0.35 nm, 0.3 nm, 0.25 nm, 0.2 nm or 0.15 nm. In one embodiment of the present application, the surface roughness of the photosensitive material film can be 0.3 nm, which can further improve the film uniformity of the photosensitive material film. In the present application, the surface roughness test of the photosensitive material film with a size of 2 μm × 2 μm can be performed using an atomic force microscope.

[0054] In one embodiment of the present application, the photosensitive material film is composed of an amorphous organic metal compound. The photosensitive material film is subjected to an XRD test. In the obtained XRD spectrum of the photosensitive material film, no characteristic peak is observed in the spectrum, for example, no characteristic peak is observed in the range of 10°-58°, indicating that the structural regularity and crystallinity of the photosensitive material film are extremely low, and it is an irregular metal-based network structure. The metal cluster skeleton and the multi-dentate ligand are connected and aggregated in an irregular manner to form an irregular network metal-organic framework molecular structure. The photosensitive material film has high solubility, low bond energy, low rigidity, and small pores, which can improve the resolution of the obtained pattern, reduce the line width roughness of the pattern and the required exposure dose, and improve the uniformity of the pattern.

[0055] In one embodiment of the present application, the photosensitive material film includes a crystalline organometallic compound and an amorphous organometallic compound. The amorphous organometallic compound having a random metal-based network structure has low crystallinity and low rigidity, which can appropriately improve the film uniformity of the photosensitive material film and increase the solubility of the photosensitive material film in the developer, thereby reducing the edge roughness of the pattern after exposure, improving the pattern resolution, and appropriately reducing the exposure dose required for the patterning process. In some embodiments, after separating the crystalline organometallic compound, the photosensitive material film without the crystalline organometallic compound can be tested for XRD to obtain an XRD spectrum of the amorphous organometallic compound. The observed absence of characteristic peaks in the obtained XRD spectrum of the amorphous organometallic compound (e.g., within the range of 10°-58°) indicates that the structural regularity and crystallinity of the amorphous organometallic compound are extremely low, indicating that the amorphous organometallic compound has a random metal-based network structure.

[0056] In one embodiment of the present application, the photosensitive material film further includes a free metal cluster skeleton and / or a free multidentate ligand, wherein the amorphous organometallic compound with a random metal-based network structure has low crystallinity and low rigidity, which can appropriately improve the film uniformity of the photosensitive material film, improve the solubility of the photosensitive material film in the developer, and help reduce the edge roughness of the pattern after exposure, improve the pattern resolution, and appropriately reduce the exposure dose required for the patterning process. In some embodiments, the free metal cluster skeleton and / or the free multidentate ligand can be separated, and the XRD of the photosensitive material film without the free metal cluster skeleton and / or the free multidentate ligand is tested to obtain an XRD spectrum of the amorphous organometallic compound. It is observed that there is no characteristic peak in the XRD spectrum of the amorphous organometallic compound (for example, in the range of 10°-58°), indicating that the structural regularity and crystallinity of the amorphous organometallic compound are extremely low, and it is a random metal-based network structure.

[0057] In one embodiment of the present application, the photosensitive material film also includes a free metal cluster skeleton, and / or a free multidentate ligand, and / or a crystalline organic compound. After XRD testing, the obtained photosensitive material film containing the free metal cluster skeleton, and / or the free multidentate ligand, and / or the crystalline organic metal compound has characteristic peaks of the free metal cluster skeleton, and / or the free multidentate ligand, and / or the crystalline organic metal compound in the XRD spectrum (for example, in the range of 10°-58°), and as the number or proportion of the free metal cluster skeleton, and / or the free multidentate ligand, and / or the crystalline organic metal compound gradually decreases, the peak intensity of the characteristic peak of the free metal cluster skeleton, and / or the free multidentate ligand, and / or the crystalline organic metal compound in the range of 10°-58° gradually weakens.

[0058] In one embodiment of the present application, the photosensitive material film further includes other components, such as additives, etc., which can further improve the exposure performance of the photosensitive material film, reduce the pattern edge roughness, and enhance the overall performance of the semiconductor device. In some embodiments, the additives can be separated and the XRD of the amorphous organometallic compound can be tested to obtain the XRD spectrum of the amorphous organometallic compound. It is observed that there are no characteristic peaks in the XRD spectrum of the amorphous organometallic compound (for example, in the range of 10°-58°), indicating that the structural regularity and crystallinity of the amorphous organometallic compound are extremely low, and it is a random metal-based network structure. In the present application, there are no characteristic peaks in the range of 10°-58°. Here, "none" does not mean that there are no characteristic peaks at all. No characteristic peaks refer to the absence of obvious sharp and high-intensity peaks, but there may be miscellaneous peaks or noise peaks generated by the background during the test.

[0059] In one embodiment of the present application, an XRD standard card of a crystalline organometallic compound formed by a metal cluster skeleton and a multidentate ligand coordinated to the metal cluster skeleton can be obtained, and the standard card can be compared with the XRD spectrum of the photosensitive material film formed by the present application to observe whether the XRD spectrum of the photosensitive material film contains the characteristic peak shown in the XRD standard card of the crystalline organometallic compound. If not, it can be explained that the metal cluster skeleton and the multidentate ligand coordinated to the metal cluster skeleton in the photosensitive material film form an amorphous organometallic compound with extremely low crystallinity and a random metal-based network structure.

[0060] In one embodiment of the present application, the chemical formula of the metal cluster skeleton is M a O b R c , 1≤a≤10, 0≤b≤20, 0≤c≤60, a, b, c are all integers, M represents the metal atom in the metal cluster skeleton, and R represents an organic ligand. In this way, the solubility and stability of the photosensitive material film are improved, while the resolution of the pattern after exposure is improved and the edge roughness of the pattern is reduced. In one embodiment of the present application, when b is 0, the metal cluster skeleton includes metal atoms. In another embodiment of the present application, when b is not 0, the metal cluster includes metal atoms and oxygen atoms, and inorganic MO bonds can be formed between the metal atoms and the oxygen atoms. For example, three metal atoms (M) and one oxygen atom can constitute an M3O cluster.

[0061] In one embodiment of the present application, the metal atoms may be, but are not limited to, one or more of indium, tin, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, palladium, platinum, silver, cadmium, antimony, tellurium, hafnium, tungsten, gold, lead, and bismuth. In one embodiment of the present application, the metal atoms may be one or more of indium, tin, antimony, titanium, zinc, hafnium, and zirconium, which is beneficial for improving the solubility of the photosensitive material film in the solvent.

[0062] In one embodiment of the present application, when c is 0, the metal cluster skeleton does not include organic ligands, and the metal atoms are connected to oxygen atoms and / or metal atoms are connected to multidentate ligands; when c is not 0, the metal cluster skeleton is connected to organic ligands, and the metal atoms and organic ligands are coordinated and connected through carbon atoms.

[0063] In one embodiment of the present application, the organic ligand R may be, but is not limited to, one or more of an alkyl group that is substituted or unsubstituted or contains heteroatoms on the main chain, an alkenyl group that is substituted or unsubstituted or contains heteroatoms on the main chain, an alkynyl group that is substituted or unsubstituted or contains heteroatoms on the main chain, a substituted or unsubstituted heteroalkyl group, and a substituted or unsubstituted aryl group. The heteroatom may be one or more of an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom. When the organic ligand is a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted cycloalkyl group, a substituted heteroalkyl group, or a substituted aryl group, the substituent group may be a halogen, an aromatic group, a hydroxyl group, an ether group, an amino group, an amide group, or a silane group. The above-mentioned substituent groups are beneficial to improving the polarity of the organic ligand, thereby improving the solubility of the photosensitive material film in the solvent.

[0064] In one embodiment of the present application, the alkyl group may include a straight-chain alkyl group or a branched-chain alkyl group. Specifically, the alkyl group may include, but is not limited to, one or more of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 4-methylbutyl group, a 2,2-dimethylpropyl group, a n-hexyl group, a heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylpentyl group, a 5-methylpentyl group, a 2-ethylbutyl group, a 3-ethylbutyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. In one embodiment of the present application, the alkyl group may be a 4-methylbutyl group. In another embodiment of the present application, the alkyl group may be a pentyl group.

[0065] In one embodiment of the present application, the alkenyl group may include a straight chain alkenyl group or a branched chain alkenyl group. Specifically, the alkenyl group may include, but is not limited to, one or more of vinyl, propenyl, isopropenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl, heptenyl, octenyl, nonenyl, and decenyl. In one embodiment of the present application, the alkenyl group may be propenyl. In another embodiment of the present application, the alkenyl group may be pentadienyl.

[0066] In one embodiment of the present application, the alkynyl group may include a straight-chain alkynyl group or a branched-chain alkynyl group. Specifically, the alkynyl group may include, but is not limited to, one or more of ethynyl, propynyl, butynyl, pentynyl, and hexynyl. In one embodiment of the present application, the alkynyl group may be a propynyl group. In another embodiment of the present application, the alkynyl group may be a pentynyl group.

[0067] In one embodiment of the present application, the cycloalkyl group may be a cyclic alkyl group having a single ring or multiple rings including fused, bridged, and spiro ring systems. Specifically, the cycloalkyl group may include, but is not limited to, one or more of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and adamantyl. In one embodiment of the present application, the cycloalkyl group may be a cyclopropyl group. In another embodiment of the present application, the cycloalkyl group may be a cyclohexyl group.

[0068] When the atoms constituting the ring contain other heteroatoms in addition to carbon atoms, a heterocyclic group is formed. In one embodiment of the present application, the heterocyclic group may include, but is not limited to, one or more of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, and pyridazine. In one embodiment of the present application, the heterocyclic group may be pyrrole. In another embodiment of the present application, the heterocyclic group may be pyridine.

[0069] In one embodiment of the present application, the aryl group may include, but is not limited to, one or more of phenyl, naphthyl, and anthracenyl. In one embodiment of the present application, the aryl group may be phenyl. In another embodiment of the present application, the aryl group may be naphthyl.

[0070] In one embodiment of the present application, the number of carbon atoms of the organic ligand is 1-30. The appropriate number of carbon atoms can improve the solubility and stability of the photosensitive material film in the solvent, improve the resolution of the pattern after exposure, and reduce the roughness of the pattern. Specifically, the number of carbon atoms of the organic ligand can be, but is not limited to, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28 or 30, etc. In one embodiment of the present application, the organic ligand can be a substituted or unsubstituted oxy group with 1-30 carbon atoms or a heteroatom-containing main chain, a substituted or unsubstituted alkenyl group with a heteroatom-containing main chain, or a substituted or unsubstituted alkynyl group with a heteroatom-containing main chain. In another embodiment of the present application, the organic ligand can be a substituted or unsubstituted aryl group with 6-30 carbon atoms. In yet another embodiment of the present application, the organic ligand can be a substituted or unsubstituted cycloalkyl group with 3-30 carbon atoms or a substituted or unsubstituted heterocyclic group.

[0071] In the present application, the multidentate ligand includes two or more coordinating atoms, and the coordinating atoms include one or more oxygen atoms and nitrogen atoms, which are formed by removing hydrogen atoms from hydroxyl groups and / or amino groups in the multidentate ligand. The multidentate ligand is connected to the metal atoms in the metal cluster skeleton through the coordinating atoms, which is conducive to the formation of an amorphous organic metal compound with a network framework molecular structure; and the coordination bond energy is relatively weak, and can be dissolved in polar solvents, thereby improving the solubility of the photosensitive material film; during exposure and development, it can be dissolved in a highly polar developer and decomposed into small molecules, which is conducive to improving the resolution of the pattern and reducing its roughness.

[0072] In one embodiment of the present application, the chemical formula of the multidentate ligand is Ra(X) d (G) e, wherein Ra is a substituted or unsubstituted alkyl group, Y represents a hydroxyl group and / or an amino group that does not participate in the coordination connection in the multidentate ligand, X is a coordinating atom, d≥2, e≥0, d and e are integers, and the number of carbon atoms of the multidentate ligand is greater than or equal to 2. Specifically, the number of carbon atoms of the multidentate ligand can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. A smaller number of carbon atoms is beneficial for controlling the molecules of the patterned composition to remain in a smaller size. In one embodiment of the present application, the number of carbon atoms of the multidentate ligand is 2-13. In another embodiment of the present application, the number of carbon atoms of the multidentate ligand is 10-20.

[0073] In one embodiment of the present application, when e is 0, all hydroxyl groups and / or amino groups in the multidentate ligand are connected to the metal atom to form a coordination bond. In another embodiment of the present application, when e is not 0, some hydroxyl groups and / or amino groups in the multidentate ligand are connected to the metal atom to form a coordination bond, and some hydroxyl groups and / or amino groups do not participate in the reaction.

[0074] In one embodiment of the present application, in an amorphous organometallic compound, the metal atoms of the metal cluster skeleton are connected by the coordinating atoms in the multidentate ligand and are connected and aggregated in an irregular manner. In the process of patterning a photosensitive material film containing the amorphous organometallic compound, after exposure, the coordination connection between the metal cluster skeleton and the multidentate ligand is broken in the exposed area, a cross-linking reaction occurs, and a cross-linked structure is formed, resulting in a decrease in the solubility of the photosensitive material film in the exposed area, making it difficult to be dissolved and removed by a high-polarity developer; at the same time, in the non-exposed area, the coordination connection between the multidentate ligand and the metal cluster skeleton remains unchanged. Then, when the developer is used for development, the photosensitive material film in the non-exposed area dissociates to form smaller molecules with higher solubility, thereby reducing the edge roughness of the exposed area, improving the resolution and uniformity of the pattern, and reducing the required exposure dose.

[0075] In one embodiment of the present application, the multidentate ligand is connected to the metal atom in the metal cluster skeleton through a coordinating atom. In the multidentate ligand, the coordinating atom is formed by removing hydrogen atoms from alcoholic hydroxyl groups and / or amino groups, and a multidentate ligand includes at least two coordinating atoms, two coordinating atoms can be coordinated and connected with two different metal atoms, and two coordinating atoms can also be connected to the same metal atom. In one embodiment of the present application, the multidentate ligand includes three coordinating atoms, two of which are coordinated and connected with the same or different metal atoms, and the remaining one coordinating atom does not participate in the coordination connection, and forms a hydroxyl group or an amino group with a hydrogen atom, so that the solubility of the amorphous organometallic compound in the solvent can be further improved, a photosensitive material solution with high uniformity can be formed, and the uniformity of the photosensitive material film and the patterned film can be improved.

[0076] In one embodiment of the present application, the metal atom is connected to an organic ligand different from the polyol ligand, and the organic ligand is connected to the metal atom through a carbon coordination atom to form a metal cluster skeleton. This coordination connection breaks during the exposure process and undergoes a cross-linking reaction with the inorganic oxygen atoms present in the solvent to form a metal atom-oxygen atom-metal atom (MOM) cross-linking site, which reduces the solubility of the patterned composition in the exposed area and makes it difficult to dissolve. In one embodiment of the present application, the photosensitive material film includes a plurality of metal atoms, wherein some of the metal atoms may be connected to one or more organic ligands, and the multiple organic ligands may be connected to the same metal atom or to different metal atoms; some of the metal cluster skeletons may also not be connected to organic ligands.

[0077] In one embodiment of the present application, in the amorphous organometallic compound, the ratio of the number of metal cluster skeletons and multidentate ligands is 1: (0.1-10). The appropriate ratio of the number of metal cluster skeletons and multidentate ligands can improve the solubility of the photosensitive material film, which is conducive to the formation of an irregular network framework structure. Specifically, the ratio of the number of metal cluster skeletons and multidentate ligands can be, but is not limited to, 1: 0.1, 1: 0.5, 1: 1, 1: 2, 1: 4, 1: 6, 1: 8 or 1: 10, etc. In one embodiment of the present application, the ratio of the number of metal cluster skeletons and multidentate ligands can be 1: (0.1-6). In another embodiment of the present application, the ratio of the number of metal cluster skeletons and multidentate ligands can be 1: (5-10).

[0078] The present application provides a method for preparing a photosensitive material film, comprising:

[0079] S101: mixing a metal cluster skeleton precursor, a multidentate ligand precursor, and a solvent to obtain a photosensitive material solution;

[0080] S102: applying a photosensitive material solution and drying to form a photosensitive material film;

[0081] The multidentate ligand precursor includes one or more of a diol, a diamine, a polyol, a polyamine, and an alcoholamine. The preparation method provided in this application is novel and simple. The resulting photosensitive material film is easily soluble in a highly polar developer, facilitating the formation of a patterned film layer. The film exhibits good stability and excellent exposure quality, resulting in a high-resolution pattern with low edge roughness.

[0082] In one embodiment of the present application, the chemical formula of the metal cluster skeleton precursor is M a O b R c Z f, wherein Z is a group connected to the metal atom and capable of being replaced by a multidentate ligand, f≥3, and f is an integer. During the coating process of the photosensitive material solution, the metal cluster skeleton precursor and the multidentate ligand precursor react, and the hydroxyl and / or amino groups in the non-volatile multidentate ligand react with the volatile Z group in the metal cluster skeleton precursor, thereby connecting the coordinating atoms in the multidentate ligand and the metal atoms in the metal cluster skeleton to form a coordination bond. The reaction speed is extremely fast and tends to form an irregular network structure. The photosensitive material film has good uniformity and the pattern line width roughness after exposure is low. Specifically, Z can include, but is not limited to, one or more of diethylamino, alcohol groups, carboxylic acid groups, and halogens; illustratively, the alcohol group can be, but is not limited to, ethanol, isopropanol, tert-butanol, etc., and the carboxylic acid group can be, but is not limited to, formic acid, acetic acid, etc. In one embodiment of the present application, Z can be diethylamino (-N(CH3)2), the chemical formula of the metal cluster skeleton precursor can be tBuSn(N(CH3)2)3, and the multidentate ligand precursor is 1,3-propylene glycol. During the reaction, the hydroxyl group in the multidentate ligand precursor undergoes a replacement reaction with Sn-(N(CH3)2)3 to form a Sn-O structure.

[0083] In one embodiment of the present application, the solvent can improve the coating performance of the photosensitive material solution, facilitate the formation of a uniform photosensitive material film, and improve the uniformity of the pattern after exposure. Specifically, the solvent can include, but is not limited to, one or more of alcohol solvents, ketone solvents, ether solvents, ester solvents, tetrahydrofuran, N,N-dimethylformamide, dimethyl adipate, benzene, and toluene; illustratively, the solvent includes one or more of methanol, n-butanol, 4-methyl-2-pentanol, chloroform, 5-methyl-2-hexanone, and cyclohexanone. In one embodiment of the present application, the solvent can be a ketone solvent. In another embodiment of the present application, the solvent can be toluene.

[0084] In one embodiment of the present application, the photosensitive material solution may further include other additives, such as a leveling agent, to improve the coating performance of the photosensitive material solution. Those skilled in the art may determine the amount of the additives added to the patterning composition based on actual production needs.

[0085] In one embodiment of the present application, the photosensitive material film undergoes a chemical reaction when irradiated with light, soft X-rays, or electron beams within a wavelength range of 1-15 nm. The exposure dose required for the light or soft X-rays within a wavelength range of 1-15 nm to act on the amorphous organometallic compound in the photosensitive material film may be 10-300 mJ / cm 2 The exposure dose required for electron beam irradiation on the amorphous organic metal compound in the photosensitive material film can be 50μC / cm 2 -5000μC / cm 2In some embodiments, the wavelength of the exposure light source may be 1 nm, 3 nm, 5 nm, 7 nm, 10 nm, or 13.5 nm. In some embodiments of the present application, the exposure dose required for light or soft X-rays with a wavelength in the range of 1-15 nm to act on the photosensitive material film may be 10 mJ / cm 2 -300 mJ / 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 photosensitive material film can be 50μC / 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 .

[0086] In one embodiment of the present application, the critical dimension (CD) of the pattern obtained by the above-mentioned photosensitive material film is less than or equal to 50nm, which is beneficial to improving the overall performance of the semiconductor device. Specifically, the critical dimension of the pattern can be, but is not limited to, 50nm, 45nm, 40nm, 35nm, 30nm, 25nm, 20nm, 15nm or 10nm. In one embodiment of the present application, the critical dimension of the pattern can be 20nm-50nm. In another embodiment of the present application, the critical dimension of the pattern can be 10nm-30nm. In the present application, the critical dimension (CD) of the patterned film can be tested by SEM or atomic force microscope (Atomic Force Microscope, AFM). In some embodiments, the pattern can constitute a patterned film or a patterned substrate.

[0087] In one embodiment of the present application, the line width roughness of the pattern obtained by the above-mentioned photosensitive material film is less than or equal to 4nm. The lower the line width roughness, the lower the edge roughness of the pattern, and the higher the fineness of the pattern, which is beneficial to improving the overall performance of the semiconductor device. Specifically, the line width roughness of the pattern can be, but is not limited to, 4nm, 3.5nm, 3nm, 2.5nm, 2nm, 1.5nm or 1nm. In one embodiment of the present application, the line width roughness of the pattern can be 3nm-4nm. In another embodiment of the present application, the line width roughness of the pattern can be 2nm-3.5nm. In some embodiments, the pattern can constitute a patterned film or a patterned substrate.

[0088] The present application also provides a patterned film, which is patterned using the photosensitive material film provided in any of the above embodiments, or a photosensitive material film produced by the preparation method described in any of the above embodiments. This patterned film can be used to prepare a mask in a semiconductor manufacturing process, facilitating the subsequent transfer of the pattern of the patterned film to a substrate such as a wafer through exposure and other processes, thereby forming a pattern corresponding to the mask on the substrate. The patterned composition provided in this application has high stability and good exposure effect, and the resulting mask pattern is clear and has high contrast, which facilitates the transfer of the pattern.

[0089] In one embodiment of the present application, a method for preparing a patterned film includes: coating a photosensitive material solution on a substrate to form a photosensitive material film; exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate surface.

[0090] The present application also provides a patterned substrate, which is patterned by patterning the photosensitive material film provided by any of the above-mentioned embodiments or the photosensitive material film prepared by the preparation method described in any of the above-mentioned embodiments. The patterned substrate can be used in the preparation of semiconductor devices, thereby improving the production progress and quality of semiconductor devices and helping to improve the overall performance of semiconductor devices.

[0091] In one embodiment of the present application, a method for preparing a patterned substrate includes: forming a patterned film on a substrate, and transferring a pattern of the patterned film onto the substrate to obtain a patterned substrate.

[0092] In one embodiment of the present application, the pattern formed by the photosensitive material film selectively protects the underlying substrate material during the etching step. Under certain etching conditions, the unprotected substrate material is etched, but the protected area is etched more slowly than the unprotected area, ultimately forming a pattern on the substrate material, thereby transferring the pattern to the substrate. Specifically, the etching process can be performed by HF etching, ion etching, or ion implantation to transfer the pattern to the substrate.

[0093] The present application provides a semiconductor device, which is manufactured using any of the photosensitive material films described above, or using the patterned film described in any of the above embodiments, or using the patterned substrate described in any of the above embodiments. The semiconductor device provided in this application has high precision, which is beneficial for improving the overall performance of the semiconductor device.

[0094] In one embodiment of the present application, the semiconductor device comprises: a structure obtained by etching or electron injection into a patterned substrate. In one embodiment of the present application, the semiconductor device is a structure obtained by etching or electron injection into a patterned substrate, the substrate being a silicon wafer.

[0095] In this application, there is no limitation on the specific type of semiconductor device. In one embodiment of this application, the semiconductor device may be an integrated circuit device such as a chip. During the chip preparation process, other functional layers may be prepared after completing the aforementioned patterning process.

[0096] The present application also provides a method for preparing a semiconductor device, comprising:

[0097] S201: placing the photosensitive material film described in any one of the above embodiments on a substrate, and forming a patterned film on the substrate after exposure and development;

[0098] S202: Prepare a functional layer to obtain a semiconductor device.

[0099] The preparation method provided in this application is simple, and the semiconductor device produced has excellent comprehensive performance, which is conducive to its commercial application.

[0100] In one embodiment of the present application, the substrate is selected based on actual needs. Specifically, the substrate may be, but is not limited to, a silicon wafer or a silicon wafer covered with a coating. For example, the coating may be an anti-reflective coating, an anti-etching coating, an epitaxial layer, a metal layer, a dielectric layer, a modified layer, or a supporting layer. Usually, other coatings can be obtained by pre-treating the substrate. The pre-treatment method can be: subjecting the silicon wafer substrate to O2 plasma surface hydrophilic activation; or cleaning in Piranha solution (H2O: 30% ammonia water: 30% H2O2 = 5:1:1) for 15 minutes to 20 minutes, and then washing with deionized water and isopropyl alcohol to complete the hydrophilic treatment; or using evaporation or spin coating to cover the substrate with hexamethyldisilazane (Hexamethyldisilazane, HMDS) to perform surface hydrophobic treatment on the substrate; the hydrophobic treatment can be after the hydrophilic treatment; or adding a bottom antireflection coating (BARC), a bottom carbon-containing coating (SOC), or a bottom silicon-containing coating (SOG).

[0101] In one embodiment of the present application, the substrate may be cleaned before coating to remove impurities and dust on the substrate surface. Specifically, the cleaning method may include, but is not limited to, using a solvent, acid, ultrasound, or spray cleaning. In one embodiment of the present application, the cleaning method may be ultrasonic cleaning.

[0102] In one embodiment of the present application, the light source for exposure may be, but is not limited to, light with a wavelength of 10 nm to 380 nm, X-rays, electron beams, ion beams, and the like.

[0103] In one embodiment of the present application, a baking treatment may be performed after coating and before exposure to remove excess solvent in the film layer and improve the structural reliability of the patterned composition; a baking treatment may also be performed after exposure and before development to promote the chemical reaction in the etch-resistant coating. The baking temperature is 60°C-200°C, and the baking time is 20s-120s. Specifically, the baking temperature may be, but is not limited to, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C or 200°C, and the baking time may be, but is not limited to, 20s, 40s, 60s, 80s, 100s or 120s. In one embodiment of the present application, the baking temperature may be 60°C-150°C, and the baking time may be 20s-80s. In one embodiment of the present application, the baking temperature may be 100°C-200°C, and the baking time may be 70s-120s.

[0104] In one embodiment of the present application, a developer solution is used for development. Since the chemical properties and solubility of the exposed regions of the photosensitive material film change, the exposed photosensitive material film needs to be cleaned with a developer solution to produce a patterned film. The cleaning time ranges from 10s to 300s and can be categorized as single-step or multi-step cleaning. After cleaning, the exposed regions of the photosensitive material film remain intact, indicating negative development, resulting in a negative pattern. In this case, the photosensitive material solution is a negative photosensitive material solution.

[0105] In one embodiment of the present application, the developing solution includes a developer. The developer can be selected according to the properties of the photosensitive material film and used in combination to improve the etching effect. The developing time is 10s-120s. Specifically, the developer can include, but is not limited to, organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing other additives, etc.; illustratively, the organic solvent can be, but is not limited to, one or more of ketones, alcohols, ethers, esters, lactones, and high-boiling point alcohols; among them, ketones can be, but are not limited to, cyclohexanone or methyl-2-n-pentyl ketone, etc.; alcohols can be, but are not limited to, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol or diacetone alcohol, etc.; ethers can be, but are not limited to, propylene glycol monohydrate. Methyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, or diethylene glycol dimethyl ether; esters may include, but are not limited to, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, or propylene glycol monotert-butyl ether acetate; lactones may include, but are not limited to, γ-butyrolactone; high-boiling-point alcohol solvents may include, but are not limited to, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol. In one embodiment of the present application, the developer may be a 0.5%-5% aqueous solution of tetramethylammonium hydroxide (TMAH). In some embodiments, post-development, rinsing and baking are further performed to remove impurities on the surface of the patterned film and improve the structural reliability of the patterned film.

[0106] In one embodiment of the present application, after forming a patterned film on a substrate, the method further includes: etching the patterned substrate or injecting electrons to form a pattern on the surface of the patterned substrate, thereby forming a structure required for a semiconductor device on the surface of the substrate to obtain a semiconductor device.

[0107] The effects of the technical solution of this application are further illustrated below through specific examples.

[0108] Example 1

[0109] The metal cluster skeleton precursor (tBuSn(N(CH3)2)3), the multidentate ligand precursor (1,3-propylene glycol) and the solvent (1 ml of n-butanol) are shaken until completely dissolved, and after filtering out the impurity particles, a photosensitive material solution is obtained, and the photosensitive material solution is coated on a substrate to form a photosensitive material film;

[0110] Among them, the ratio of the number of metal cluster skeleton precursors to multidentate ligand precursors is 1:3.

[0111] Example 2

[0112] The difference from Example 1 is that the multidentate ligand precursor is 1,2,4-butanetriol.

[0113] Example 3

[0114] The difference from Example 1 is that the multidentate ligand precursor is triethylene glycol.

[0115] Comparative Example 1

[0116] The difference from Example 1 is that 15 mg of crystalline organometallic compound ((C4H9) 12 Sn 12 O 14 Clusters), the solvent is a mixed solution of 1 ml of 4-methyl-2-pentanone and 10% w formic acid, after obtaining a photosensitive material solution, it is coated on a substrate to form a photosensitive material film.

[0117] Comparative Example 2

[0118] The difference from Example 1 is that 20 mg of crystalline organic metal compound (tBuSn(N(CH3)2)3) and the solvent are a mixed solution of 1 ml of 4-methyl-2-pentanone and 10%w formic acid. After obtaining the photosensitive material solution, it is coated on the substrate to form a photosensitive material film.

[0119] Performance Testing

[0120] The photosensitive material films prepared in Examples 1-3 were subjected to nuclear magnetic resonance characterization. Figure 1 This is the NMR characterization image of the photosensitive material film provided in Example 1 of the present application. Figure 2 This is the NMR characterization image of the photosensitive material film provided in Example 2 of the present application. Figure 3 This is the NMR characterization image of the photosensitive material film provided in Example 3 of the present application. Figure 4 This is the nuclear magnetic resonance characterization of the metal cluster skeleton precursor provided in Example 1 of this application. Figure 1-Figure 4It can be seen that the metal cluster skeleton precursor has a characteristic H spectrum peak of -N(CH3)2 at 2.83ppm, while the photosensitive material films provided in Examples 1-3 have no characteristic peak here, indicating that in Examples 1 and 2, the -N(CH3)2 of tBuSn(N(CH3)2)3 has been completely reacted.

[0121] The photosensitive material films prepared in Examples 1-3 were characterized by infrared spectroscopy. Figure 5 This is an infrared spectrum characterization diagram of the photosensitive material film and the multidentate ligand precursor provided in Example 1 of the present application. Figure 6 This is an infrared spectrum characterization diagram of the photosensitive material film and the multidentate ligand precursor provided in Example 2 of the present application. Figure 7 This is an infrared spectrum characterization diagram of the photosensitive material film and the multidentate ligand precursor provided in Example 3 of the present application. Figure 5-Figure 7 It can be seen that the multidentate ligand precursor (polyol) has an obvious broad peak at the 2900nm-3500nm position, which can be attributed to OH stretching, while the photosensitive material film provided in Examples 1-3 has almost no peak at the 2900nm-3500nm position, indicating that there is basically no -OH component in the photosensitive material film, and the -OH in the multidentate ligand precursor has completely replaced with Sn-NMe2, and a sharper multiple peak appears near 400nm-800nm, which can be attributed to the formation of a Sn-O core structure. Based on nuclear magnetic resonance and infrared spectra, a Sn core provides three or more coordination sites, a polyol ligand provides two or more coordination sites, and the coordination sites of the Sn core and the polyol are not in a free state (the product has no -N(CH3)2 and -OH), and are all in a mutually coordinated state. Therefore, it can be inferred that the photosensitive material films in Examples 1-3 have all formed a network metal-organic framework molecular structure.

[0122] The photosensitive material film prepared in Example 2 was characterized by XRD diffraction. Figure 8 This is the XRD diffraction characterization diagram of the photosensitive material film provided in Example 2 of the present application. Figure 9 This is the XRD diffraction characterization pattern of Sn-1,2,4-butanetriol. Figure 9 Sn-1,2,4-butanetriol is a product of tBuSn(NMe2)3 and 1,2,4-butanetriol. According to the XRD diffraction pattern, Sn-1,2,4-butanetriol crystals have clear and sharp XRD peaks, proving that it has a high crystallinity structure. Figure 8 The photosensitive material film provided in Example 2 of the present application has almost no peak within the range of 10°-58°, and the structural regularity and crystallinity of the cluster structure are extremely low, and it is a random network metal-organic framework molecular structure.

[0123] The photosensitive material films provided in Examples 1-2 and Comparative Examples 1-2 were subjected to patterning performance characterization. Test process:

[0124] 1. The base material is a silicon substrate, which is covered with a uniform layer of SOC (bottom carbon coating) as the bottom material.

[0125] 2. The photosensitive material solution is spin-coated on the surface of the base material to form a photosensitive material film coating, and the thickness of the photosensitive material film is 25 nm.

[0126] 3. Bake (PAB) at 100°C for 1 minute to completely remove the residual solvent in the coating.

[0127] 4. Expose the coating to an electron beam pattern with an exposure dose of 100-500uC / cm 2 , no baking is performed after exposure.

[0128] 5. Develop the coating with 2-heptanone or a mixture of 2-heptanone and 5%w acetic acid for 60 seconds, and rinse with 2-heptanone or a mixture of 2-heptanone and 5%w acetic acid for 10 seconds.

[0129] The pattern of the patterned film after exposure and development was characterized using a scanning electron microscope (SEM). The test results are shown in Table 1. Figure 10 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Example 1 of the present application; Figure 11 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Example 2 of the present application; Figure 12 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Comparative Example 1 of the present application; Figure 13 This is a scanning electron microscope image of the pattern of the photosensitive material film after exposure provided in Comparative Example 2 of this application. Figure 14 This is a graph showing the variation of the line width roughness of the pattern after exposure of the photosensitive material film provided in Example 2 and Comparative Example 2 of the present application with the critical dimension (10nm-22nm). Figure 15 This is a graph showing the variation of the line width roughness of the pattern after exposure of the photosensitive material film provided in Example 2 and Comparative Example 2 of the present application with the critical dimension (22nm-32nm). Figure 16 This is a graph showing the change in line width roughness of the pattern after exposure of the photosensitive material film provided in Example 2 and Comparative Example 2 of the present application as a function of the critical dimension (35nm-55nm).

[0130] Figure 14-16 It can be seen that the LWR (Limit in the Line Width Roughness) changes in Example 2 and Comparative Example 2 in patterns with a critical dimension of 20-55 nm. The roughness of Example 2 in all patterns is lower than that of Comparative Example 2, indicating that the amorphous organometallic compound with a random metal-organic framework molecular structure has the advantage of low roughness.

[0131] Table 1 Exposure performance test

[0132] developer Resolution Average line width roughness (nm) <![CDATA[Exposure dose (μC / cm 2 )]]> Example 1 2-Heptanone + acetic acid 5%w 30nm CD (60nm pitch) 2.9 436 Example 2 2-Heptanone 30nm CD (60nm pitch) 2.7 161.8 Comparative Example 1 2-Heptanone + acetic acid 5%w 30nm CD (60nm pitch) 4.1 439 Comparative Example 2 2-Heptanone 30nm CD (60nm pitch) 3.8 222.47

[0133] According to Examples 1-2 and Comparative Examples 1-2, it can be seen that the photosensitive material film provided by the present application includes an amorphous organic metal compound formed by the coordination connection of the coordinating atoms in the multidentate ligand and the metal atoms in the metal cluster skeleton, which is a random metal-based network structure, forming an irregular network framework molecular structure with high solubility, low rigidity and small pores; the coordination bond energy in this structure is relatively weak, and it is easy to break in a highly polar developer, forming a structure with a smaller molecular size, which can be better dissolved, reducing the roughness of the edge of the pattern obtained, reducing the exposure dose required for patterning, and achieving the same level of resolution as the patterned composition of the prior art.

[0134] In this application, "and / or" describes the relationship between related objects, indicating that three possible relationships exist. For example, "A and / or B" can mean: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the related objects are in an "or" relationship.

[0135] 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.

[0136] 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.

[0137] 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. 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.

[0138] The above is a preferred embodiment of the present application, but it should not be construed as limiting the scope of the present application. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present application, and such improvements and modifications are also considered to be within the scope of protection of the present application.

Claims

1. A photosensitive material film, characterized in that: The photosensitive material film includes an amorphous organic metal compound, and the amorphous organic metal compound includes a metal cluster skeleton and a multidentate ligand coordinated and connected to the metal cluster skeleton; The metal cluster skeleton includes metal atoms or metal atoms and oxygen atoms; the multidentate ligand includes at least two coordination atoms, and the multidentate ligand is coordinated and connected to the metal atoms in the metal cluster skeleton via the coordination atoms.

2. The photosensitive material film according to claim 1, wherein The surface roughness of the photosensitive material film is less than or equal to 0.4 nm.

3. The photosensitive material film according to claim 1, wherein The amorphous organometallic compound is a random metal-based network structure; In the amorphous organometallic compound, the metal cluster skeleton and the multidentate ligand are connected and aggregated in an irregular manner.

4. The photosensitive material film according to claim 1, wherein The chemical formula of the metal cluster skeleton is M a O b R c , 1≤a≤10, 0≤b≤20, 0≤c≤60, a, b, c are all integers, M represents the metal atom, and R represents an organic ligand.

5. The photosensitive material film according to claim 4, wherein The organic ligand includes one or more of substituted or unsubstituted alkyl or alkyl groups containing heteroatoms on the main chain, substituted or unsubstituted alkenyl or alkyl groups containing heteroatoms on the main chain, substituted or unsubstituted alkynyl or alkynyl groups containing heteroatoms on the main chain, substituted or unsubstituted heteroalkyl groups, and substituted or unsubstituted aryl groups; The organic ligand is connected to the metal atom in the metal cluster skeleton via a carbon atom, and the number of carbon atoms in the organic ligand is 1-30.

6. The photosensitive material film according to claim 1, wherein The metal atoms include one or more of indium, tin, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, palladium, platinum, silver, cadmium, antimony, tellurium, hafnium, tungsten, gold, lead and bismuth.

7. The photosensitive material film according to claim 1, wherein The chemical formula of the multidentate ligand is Ra(X) d (G)e, Ra is a substituted or unsubstituted alkyl group, X is the coordinating atom, and the coordinating atom includes one or more of an oxygen atom and a nitrogen atom. G represents a hydroxyl group and / or an amino group that does not participate in the coordination connection in the multidentate ligand. d≥2, e≥0, d and e are integers, and the number of carbon atoms in the multidentate ligand is greater than or equal to 2.

8. The photosensitive material film according to claim 1, wherein In the amorphous organometallic compound, the ratio of the number of the metal cluster skeleton to the number of the multidentate ligand is 1:(0.1-10).

9. A method for preparing a photosensitive material film according to any one of claims 1 to 8, characterized in that: include: mixing a metal cluster skeleton precursor, a multidentate ligand precursor, and a solvent to obtain a photosensitive material solution; Applying the photosensitive material solution and forming a photosensitive material film after drying; The multidentate ligand precursor includes one or more of diols, diamines, polyols, polyamines and alcoholamines.

10. The preparation method according to claim 9, characterized in that The chemical formula of the metal cluster skeleton precursor is M a O b R c Z f , Z is a group connected to the metal atom and capable of being substituted by the multidentate ligand, wherein Z includes one or more of diethylamino, alcohol group, carboxylic acid group, and halogen, f≥3, and f is an integer.

11. The preparation method according to claim 9, wherein The solvent includes one or more of alcohol solvents, ketone solvents, ether solvents, ester solvents, tetrahydrofuran, N,N-dimethylformamide, dimethyl adipate, benzene, and toluene.

12. A patterned film, characterized in that: The patterned film is obtained by patterning the photosensitive material film according to any one of claims 1 to 8 or the photosensitive material film prepared by the preparation method according to any one of claims 9 to 11.

13. A patterned substrate, characterized in that The patterned substrate is obtained by patterning the photosensitive material film according to any one of claims 1 to 8 or the photosensitive material film prepared by the preparation method according to any one of claims 9 to 11.

14. The patterned substrate according to claim 13, wherein The line width roughness of the patterned substrate is less than or equal to 4 nm; The critical dimension of the pattern on the patterned substrate is less than or equal to 50 nm.

15. A semiconductor device, characterized in that: The semiconductor device is manufactured by patterning the photosensitive material film according to any one of claims 1 to 8 or the photosensitive material film prepared by the preparation method according to any one of claims 9 to 11.

16. A method for preparing a semiconductor device, characterized in that: include: Disposing the photosensitive material film according to any one of claims 1 to 8 on a substrate, and forming a patterned film on the substrate after exposure and development; A functional layer is prepared to obtain a semiconductor device.

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