A single tin complex, a preparation method thereof, a patterning composition, a method for forming a pattern, and a patterned film

Abstract

This application relates to the technical field of metal-organic hybrid patterning materials, and specifically relates to a single tin complex, a preparation method thereof, a patterning composition, a method for forming a pattern, and a patterned thin film. The structure of the single tin complex is shown in the following formula (1): #imgabs0# Formula (1); wherein, X is sulfur or selenium, R1 is a substituted or unsubstituted C1 to C20 alkyl group, and R2 to R5 are each independently selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group. The single tin complex is a five-coordinate metal compound with large steric hindrance, which can prevent the metal tin from being attacked by water molecules in the environment and undergoing hydrolysis to produce precipitation, has good stability and good solubility in a variety of organic solvents.

Description

Technical Field

[0001] The present application relates to the technical field of metal-organic hybrid patterning materials, and particularly relates to a single tin complex, a preparation method thereof, a patterning composition, a method for forming a pattern, and a patterned film. Background Art

[0002] With the development of chips and their manufacturing processes, the integration of chip structures has been significantly improved, and the requirements for the critical dimensions of their patterning processes have also been continuously reduced. The patterning process generally includes the following steps: (1) depositing a substrate material on a wafer; (2) coating a patterning material film layer on the substrate material; (3) irradiating the patterning material film layer with a light source through a mask plate with a predetermined pattern, so that the irradiated area and the non-irradiated area form a structure with a solubility difference. Optionally, after baking, this solubility difference is further enhanced; (4) developing through a suitable solvent to selectively dissolve one of the irradiated area or the non-irradiated area of the patterning material film layer, and realizing the same or opposite pattern as the template on the substrate material; (5) through etching, the patterning material remaining on the wafer selectively protects the underlying material from being etched or slowly etched, realizing the transfer of the pattern to the underlying material, and finally realizing the expected pattern on the substrate material.

[0003] Traditional patterning materials based on organic polymers and photosensitive small molecule compositions have basically reached their limit resolution. Therefore, the industry urgently needs to find new patterning materials to meet the continuously shrinking requirements for critical dimensions. Since some metals have higher absorption under soft X-rays or electron beams with wavelengths less than 15 nm compared to traditional organic materials, which is beneficial to the improvement of material sensitivity, and metal-organic hybrid materials containing metals have better etching resistance than traditional organic materials, and can also ensure the transfer of patterns after the etching process at low film thickness, while avoiding the collapse of high-film-thickness and small-size patterns. At the same time, metal-organic hybrid patterning materials with metal-oxide clusters and metal complexes as the core structure can avoid the problem of affecting the line edge roughness due to their own particle size after the dissolution of macromolecules due to the natural characteristics of small molecules. Therefore, metal-organic hybrid patterning materials with metal-oxide clusters and metal complexes as the core structure are considered to have the potential to simultaneously achieve better patterning resolution, line edge roughness, and sensitivity under soft X-rays or electron beams. However, existing metal-organic hybrid patterning materials often have problems such as poor solubility and poor solution stability. Summary of the Invention

[0004] Based on this, the present application provides a monotin complex, a preparation method thereof, a patterning composition, a method for forming a pattern, and a patterned film. The monotin complex has good solubility in various organic solvents and is not prone to precipitation and crystallization. The patterning composition solution prepared therefrom has good stability and can achieve excellent sensitivity, pattern resolution, and low line edge roughness under exposure to soft X-rays or electron beams.

[0005] The present application provides a monotin complex, the structure of which is shown in the following formula (1): ;

[0006] Wherein, X is sulfur or selenium, R1 is a substituted or unsubstituted C1-C20 alkyl group, and R2 to R5 are each independently selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group.

[0007] This monotin complex is a pentacoordinate metal compound with large steric hindrance, which can prevent the metal tin from being attacked by water molecules in the environment and undergoing hydrolysis to produce precipitation, thereby affecting its stability.

[0008] For the monotin complex described above, R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, and ethylcyclohexyl.

[0009] For the monotin complex described above, R2 to R5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0010] For the monotin complex described above, the structure of the monotin complex is shown as follows:

[0011] The present application also provides a preparation method of the above monotin complex, which at least includes the step of reacting an organotin compound shown by formula (2) with organic compounds shown by formula (3) and formula (4);

[0012] Wherein, the structural formula of the organotin compound is: Formula (2), and the structural formula of the organic compound is: Formula (3), (4);

[0013] In the above formulas (2), (3), and (4), X is sulfur or selenium, R1 is a substituted or unsubstituted C1-C20 alkyl group, R2 to R5 are each independently selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, R6 to R 11Each independently selected from substituted or unsubstituted C1 to C20 alkyl groups. In this preparation method, there is no special requirement for the addition order of the organotin compound and the organic compound. The two can either react directly or react in an organic solvent, with simple and convenient operation.

[0014] According to the above-mentioned preparation method, the reaction temperature is -20°C to 40°C. For example, 0°C to 40°C, 20°C to 40°C, etc. can be selected. In actual operation, for the convenience of operation, the reaction is usually carried out at room temperature.

[0015] This application also provides a patterning composition, including the above-mentioned monotin complex and a solvent. The patterning composition has good solution stability and can achieve excellent sensitivity, pattern resolution, and low line edge roughness under the exposure of soft X-rays or electron beams.

[0016] According to the above-mentioned patterning composition, the concentration of the monotin complex in the patterning composition is 10 - 40 mg / mL. Under the same coating conditions, different target film thicknesses can be adjusted by controlling the content of the monotin complex.

[0017] According to the above-mentioned patterning composition, the composition further includes at least a leveling agent and / or a surfactant. When formulating the above-mentioned patterning composition, some additives such as a leveling agent, a surfactant, etc. can be added. The addition of the leveling agent and the surfactant can improve the uniformity of the coated film layer. The contents of the leveling agent and the surfactant can be adjusted according to actual needs.

[0018] This application also provides a method for forming a pattern, at least including the steps of forming a patterned layer using the above-mentioned patterning composition, performing an exposure treatment, and then developing to form a patterned thin film. The above-mentioned patterning composition can be applied to semiconductor patterning processes to obtain high-quality patterns and improve the performance of components such as component precision.

[0019] According to the above-mentioned method for forming a pattern, an electron beam of 5 kV - 125 kV or a soft X-ray with a wavelength less than 15 nm is used for exposure during the exposure treatment.

[0020] According to the above-mentioned method for forming a pattern, the solvent used for development is selected from n-pentane, n-hexane, n-heptane liquids, or n-pentane, n-hexane, n-heptane vapors, and any combination of the above alkanes with ethyl lactate, tetrahydrofuran, 2-pentanone, 3-pentanone, hexanone, 2-heptanone, octanone, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, or 4-methyl-2-pentanol.

[0021] The present application also provides a patterned film, which is formed by the above-mentioned patterning composition or obtained by the above-mentioned method for forming a pattern. The patterned film can be used as a high-precision mask in the integrated circuit patterning process, and can be further transferred onto a substrate by etching, so as to form a preset pattern on the substrate.

[0022] For the above-mentioned patterned film, the resolution of the pattern on the patterned film is below 50 nm, and the edge roughness of the pattern on the patterned film is below 5 nm. Description of the Drawings

[0023] Figure 1 It is the 119Sn nuclear magnetic resonance spectrum of tris(diethylamino)tert-butyltin in deuterated benzene d6 in Example 1 of the present application;

[0024] Figure 2 It is the 1H nuclear magnetic resonance spectrum of tris(diethylamino)tert-butyltin in deuterated benzene d6 in Example 1 of the present application;

[0025] Figure 3 It is the 119Sn nuclear magnetic resonance spectrum of bis(ethylenedithiolato)tert-butyltin in deuterated benzene d6 in Example 1 of the present application;

[0026] Figure 4 It is the 1H nuclear magnetic resonance spectrum of bis(ethylenedithiolato)tert-butyltin in deuterated benzene d6 in Example 1 of the present application;

[0027] Figure 5 It is the crystal structure of bis(ethylenedithiolato)tert-butyltin in Example 1 of the present application;

[0028] Figure 6 It is the line width of the pattern containing bis(propylenedithiolato)tert-butyltin in different exposure doses in Example 3 of the present application;

[0029] Figure 7 It is the scanning electron microscope image of the pattern containing bis(propylenedithiolato)tert-butyltin in different exposure doses in Example 3 of the present application, wherein (a) line width = 30 nm, period = 60 nm, electron beam exposure dose = 440 μC / cm 2 ; (b) line width = 16 nm, period = 40 nm, electron beam exposure dose = 360 μC / cm 2 . Detailed Embodiments

[0030] To make the objectives, technical solutions, and advantages of this application clearer, the following will, in conjunction with the embodiments of this application, clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the described embodiments are some, but not all, of the embodiments of this application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in this application without creative efforts fall within the scope of protection of this application.

[0031] Based on the existing problems with the stability of metal-organic hybrid materials, single-metal precursor complexes are prone to hydrolysis during storage, resulting in precipitation, while cluster molecules are prone to orientation and aggregation sedimentation, and the precipitation of solids from the formulation solution leads to an increase in defects, affecting the patterning performance and reliability of the materials. This application uses dithiol (or diselenol) to form a coordination compound with a single-tin metal core, forming a mononuclear organometallic material with good solubility, stability, sensitivity, and resolution.

[0032] To better understand this application, some key terms in this application are explained as follows:

[0033] Critical dimension: The smallest feature size on a silicon wafer, the ability to distinguish adjacent graphic features, and is usually used to measure resolution.

[0034] Pitch: The spacing of periodic graphic repetition.

[0035] Patterning material: Also known as photoresist, it is a light-sensitive mixed liquid. After exposure, its solubility in the developing solution changes.

[0036] Exposure: During the exposure process of the patterning material, it is irradiated by a specific wavelength light source (such as an electron beam, ion beam, etc.). These light sources react with the photosensitive components in the patterning material, resulting in changes in the solubility or chemical properties of the patterning material. Specifically, the exposed part of the patterning material undergoes chemical changes under light irradiation, while the unexposed part remains unchanged.

[0037] Development: It is to use the developer to dissolve and remove the unexposed part or the exposed part of the patterning material, thereby presenting the desired pattern.

[0038] The single-tin complex provided by this application has the following structure as shown in formula (1) below: Formula (1);

[0039] Wherein, X is sulfur or selenium, R1 is a substituted or unsubstituted C1 to C20 alkyl group, and R2 to R5 are each independently selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group.

[0040] This mono-tin complex is a five-coordinate metal compound with large steric hindrance, which can prevent the metal tin from being attacked by water molecules in the environment and undergoing hydrolysis to produce precipitation, thus affecting its stability.

[0041] In the mono-tin complex shown in the above formula (1), different R groups can regulate the reactivity of the compound. To ensure the stability of the complex, R1 is selected from substituted or unsubstituted C1-C20 alkyl groups. For example, in some specific embodiments, R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, and ethylcyclohexyl. R2-R5 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, wherein different R2-R5 groups can further regulate the crystallinity and solubility of the compound. For example, in some specific embodiments, R2 to R5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0042] In some specific embodiments, the structure of the mono-tin complex is shown as follows:

[0043] This application also provides a preparation method of the above mono-tin complex, which at least includes the step of reacting the organotin compound shown by formula (2) with the organic compounds shown by formula (3) and formula (4); wherein, the structural formula of the organotin compound is: Formula (2), and the structural formula of the organic compound is: Formula (3), (4); in the above formulas (2), (3), and (4), X is sulfur or selenium, R1 is a substituted or unsubstituted C1 to C20 alkyl group, R2 to R5 are each independently selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl groups, and R6 to R 11 are each independently selected from substituted or unsubstituted C1 to C20 alkyl groups.

[0044] When preparing the above mono-tin complex, the reaction temperature is usually -20°C - 40°C. For example, 0°C - 40°C, 20°C - 40°C, etc. can be selected. In actual operation, for the convenience of operation, the reaction can be carried out under room temperature conditions.

[0045] When preparing the above mono-tin complex, there is no special requirement for the addition order of the organotin compound and the organic compound. The two can react directly or in an organic solvent.

[0046] For example, in some specific embodiments, the organic compounds shown in formula (3) and formula (4) are added dropwise to the liquid of the organotin compound shown in formula (2) or an organic solvent containing this compound for reaction. It can be understood that the purpose of the organic solvent is to provide an anhydrous reaction environment, and its selection is not restricted. For example, in some specific embodiments, the organic solvent is deuterated benzene-d6, tetrahydrofuran, n-pentane, n-hexane, n-heptane, etc.

[0047] The present application also provides a patterning composition, which includes the above-mentioned mono-tin complex and a solvent. This patterning composition can be applied to high-resolution patterning processes such as electron beam or soft X-ray exposure.

[0048] In this patterning composition, the concentration of the mono-tin complex is usually 10 mg / mL - 40 mg / mL. For example, it can be 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, or the range between any two of the above parameters. Under the same coating conditions, different target film thicknesses can be adjusted by controlling the content of the mono-tin complex.

[0049] In order to further improve other properties such as the uniformity of the film layer, other commonly used additives for patterning can also be added to the above-mentioned patterning composition, such as leveling agents, surfactants, etc. The specific addition amount can be adjusted according to actual needs.

[0050] The present application also provides a method for forming a pattern, which at least includes the steps of forming a patterned layer by using the above-mentioned patterning composition, and after exposure treatment, developing to form a patterned thin film.

[0051] For example, in some specific embodiments, the method for forming a pattern is as follows:

[0052] (1) The surface of the wafer substrate may be a silicon nitride layer, a polysilicon layer or a silicon oxide layer. A substrate material is spin-coated or evaporated on the wafer surface. The substrate material may be one or a combination of SOG, SOC, SiARC, HMDS. After drying and baking, a bottom layer material for patterning treatment is formed.

[0053] (2) The above-mentioned patterning composition is coated or deposited on the bottom layer material to form a patterned material film layer. The specific deposition method is not restricted. For example, a conventional solution spin-coating method can be used, or the precursor material (i.e., the mono-tin complex) can be transported to the substrate cavity by gas phase for vapor deposition, including the deposition of volatiles, chemical vapor deposition or atomic layer deposition. The film layer thickness can be adjusted by the concentration of the solution.

[0054] (3) The light source selectively irradiates the patterned material film through a mask with a predetermined pattern, so that a structure with solubility difference is formed in the irradiated area or the unirradiated area. Further, baking can also be performed to enhance the solubility difference. Electron beam or soft X-ray exposure is used for the exposure.

[0055] (4) Through development with an organic solvent, one of the patterned material films in the irradiated area or the unirradiated area is selectively dissolved, and a pattern identical or opposite to the template is achieved on the substrate material. Further, reheating and baking can also be performed to further solidify the material forming the pattern. In addition, vapor development can also be carried out using the volatiles of the organic solvent.

[0056] (5) Through etching, the patterned material remaining on the wafer selectively protects the underlying material from being etched or etched slowly, realizing the transfer of the pattern to the underlying material, and finally achieving the desired pattern on the substrate material.

[0057] For the patterned composition containing the single tin complex provided in this application, an electron beam of 5 kV - 125 kV or soft X-ray exposure with a wavelength less than 15 nm can be used during the exposure treatment.

[0058] The solvents used for development can be selected from n-pentane, n-hexane, n-heptane liquids, or n-pentane, n-hexane, n-heptane vapors, and compositions of any of the above alkanes with ethyl lactate, tetrahydrofuran, 2-pentanone, 3-pentanone, hexanone, 2-heptanone, octanone, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, or 4-methyl-2-pentanol.

[0059] This application provides a patterned thin film, which is obtained from the above-mentioned patterned composition or the above-mentioned method of forming a pattern.

[0060] Further, the resolution of the pattern on the patterned thin film is below 50 nm, and the edge roughness of the patterned thin film is below 5 nm.

[0061] The single tin complex described in this application will be described in detail below in conjunction with specific embodiments.

[0062] Example 1

[0063] [Characterization (1) of Single Tin Complex A1]

[0064] Structural transformation from tris(diethylamino)tert-butyltin precursor to bis(ethylenedithiolato)tert-butyltin: 50.0 mg of tris(diethylamino)tert-butyltin [tBuSn(NEt2)3] was dissolved in deuterated benzene-d6, and then 30.6 mg, i.e., twice the equivalent amount of 1,2-ethanedithiol (C2H6S2), was added.

[0065] 119Sn nuclear magnetic resonance (NMR) and 1H NMR measurements were respectively carried out on the deuterated benzene-d6 solution before and after the addition of 1,2-ethanedithiol, and the results are as Figure 1-4 shown.

[0066] Figure 1 Figure Figure 1-4 is the 119Sn NMR spectrum of tris(diethylamino)tert-butyltin in deuterated benzene-d6, and this spectrum shows a chemical shift at 81.61 ppm. Figure 2 Figure is the 1H NMR spectrum of tris(diethylamino)tert-butyltin in deuterated benzene-d6, and this spectrum shows the following chemical shifts: 1H NMR (400 MHz, deuterated benzene d6) δ 1.08 - 1.18 (18H), 1.18 - 1.43 (9H), 2.90 - 3.33 (12H).

[0067] Figure 3 Figure

[0066] is the 119Sn NMR spectrum of bis(ethylenedithiolato)tert-butyltin, which is obtained after adding 1,2-ethanedithiol to tris(diethylamino)tert-butyltin in deuterated benzene-d6, and this spectrum shows a chemical shift at 27.58 ppm. Figure 4 Figure Figure 1 is the 1H NMR spectrum of bis(ethylenedithiolato)tert-butyltin, which is obtained after adding 1,2-ethanedithiol to tris(diethylamino)tert-butyltin in deuterated benzene-d6. This spectrum shows that the chemical shifts and peak patterns of the diethylamine ligands change. The peak positions shift from 1.13 ppm and 3.13 ppm to 1.05 ppm and 2.58 ppm respectively, and among them, 12 H atoms split from the multiplet coordinated with tin and return to the quartet in the free state.

[0068] It can be seen from the above 119Sn and 1H NMR spectra that the coordination environment of tin metal has changed. After adding two equivalents of 1,2-ethanedithiol, the diethylamine coordinated to tin metal is replaced by 1,2-ethanedithiol, completely converted into free diethylamine, and at the same time, bis(ethylenedithiolato)tert-butyltin (i.e., monotin complex A1) is obtained.

[0069]

Characterization of Monotin Complex A1 (2)

[0070] 2.0 g of tris(diethylamino)tert-butyltin was dissolved in anhydrous tetrahydrofuran, and two equivalents of 1,2-ethanedithiol were added. After standing at room temperature for one month, the precipitated crystals were separated to obtain the crystals of organotin complex A1, and single-crystal X-ray diffraction characterization was carried out. The obtained crystal structure is as Figure 5 shown, and the crystallographic data are shown in Table 1.

[0071] Table 1

[0072]

[0073] From the above results, it can be seen that by simply mixing alkyl tris(diethylamino)tin with ethanedithiol, a thiol-coordinated monotin compound and free diethylamine can be directly generated, and the preparation of the monotin compound shown in formula (1) of this application can be carried out according to this method.

[0074] Example 2

[0075] To 0.2 g of tert-butyl tris(diethylamino)tin, 2 equivalents of 1,2-ethanedithiol were added, and the free diethylamine ligand displaced was removed by vacuum distillation. After detection, the organotin complex A1 was also obtained, and its chemical structural formula is shown as follows: .

[0076] To the above organotin complex A1, the solvent 4-methyl-2-pentanol was added. After sufficient stirring, it was passed through a polytetrafluoroethylene filter with a pore size of 0.2 μm to obtain a patterned material formulation solution B1 with a mass fraction of organotin complex A1 of 2%.

[0077] Example 3

[0078] To 0.2 g of tert-butyl tris(diethylamino)tin, 2 equivalents of 1,2-propanedithiol were added, and the free diethylamine ligand displaced was removed by vacuum distillation to obtain the organotin complex A2, and its chemical structural formula is shown as follows: .

[0079] To the above organotin complex A2, the solvent 4-methyl-2-pentanol was added. After sufficient stirring, it was passed through a polytetrafluoroethylene filter with a pore size of 0.2 μm to obtain a patterned material formulation solution B2 with a mass fraction of organotin complex A2 of 2%.

[0080] Example 4

[0081] To 0.2 g of isopropyl tris(diethylamino)tin, twice the equivalent of 1,2-ethanedithiol was added, and the free diethylamine ligand displaced was removed by vacuum distillation to obtain the organotin complex A3, and its chemical structural formula is shown as follows: .

[0082] To the above organotin complex A3, the solvent propylene glycol monomethyl ether acetate was added to obtain a patterned material formulation solution B3 with a mass fraction of organotin complex of 1%.

[0083] Example 5

[0084] To 0.4 g of n-butyl tris(diethylamino)tin, twice the equivalent of 1,2-butanedithiol was added, and the free diethylamine displaced was removed by vacuum distillation to obtain the organotin complex A4, and its chemical structural formula is shown as follows: .

[0085] The patterned material formulation solution B4 with a mass fraction of 4% of the organotin complex was obtained by adding the solvent methyl 2-hydroxyisobutyrate to the above-mentioned organotin complex A4.

[0086] Comparative Example 1

[0087] Typical tin-oxygen cluster (C4H9Sn) 12 O 14 (OH)6FA2, denoted as a1.

[0088]

Solubility Test

[0089] The mono-tin complexes obtained in Examples 2-5 and the tin-oxygen cluster (C4H9Sn) 12 O 14 (OH)6FA2 in the comparative example were dissolved in organic solvents at different concentrations for solubility tests, and the results are shown in Table 2 below:

[0090] Table 2

[0091]

[0092] Among them, ○ indicates that the solubility is greater than 30 mg / ml; × indicates that the solubility is less than 10 mg / mL.

[0093] From the above results, it can be seen that the mono-tin complexes in the examples have good solubility (>30 mg / ml) in alcohols, ketones, chloroform, alkanes and acetonitrile. The tin-oxygen cluster ((C4H9Sn) 12 O 14 (OH)6FA2) in the comparative example is poorly soluble (<10 mg / ml) in solvents such as alcohols, ketones, chloroform, alkanes and acetonitrile. That is, the solubility of the mono-tin complex structure provided by this application is better in different solvents.

[0094]

Stability Test

[0095] The patterned material formulation solution obtained in the examples was subjected to a stability test, and at the same time, a 4-methyl-2-pentanol solution of tris(diethylamino)tert-butyltin with a mass fraction of 2% was used as a control. After storing at room temperature for 30 days and heating at 40 °C for 14 days, the solution state was observed, and the results are shown in Table 3 below:

[0096] Table 3

[0097]

[0098] From the above results, it can be seen that no precipitation occurred in the solution of the mono-tin complex provided by this application whether it was stored at room temperature for 30 days or stored at 40 °C for 14 days. It shows that the mono-tin complex provided by this application has better stability.

[0099]

Resolution Test

[0100] The carbon coating material is coated on a silicon wafer substrate and heated on a hot plate at 250 °C for 60 seconds to form a bottom coating with a thickness of 300 nm. Then, the patterned material B2 in Example 3 is coated on the carbon coating and heated on a hot plate at 100 °C for 60 seconds to form a patterned material film layer with a thickness of 20 nm. The patterned material film layer is subjected to electron beam direct writing exposure using an electron beam exposure device with 5 kV. After exposure, it is developed by immersion in n-heptane for 30 seconds to remove the unexposed part, and line patterns with different line widths are obtained at different doses, as Figure 6 shown. Among them, for the line pattern with a period of 60 nm and a line width of 30 nm obtained, the top view of the scanning electron microscope is as shown in Figure 7 (a); for the line pattern with a period of 40 nm and a line width of 16 nm obtained, the top view of the scanning electron microscope is as shown in Figure 7 (b).

[0101] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A single tin complex, characterized in that, Its structure is as shown in the following formula (1): ; Wherein, X is sulfur or selenium, R1 is a C1-C20 alkyl group, and R2 to R5 are each independently selected from hydrogen and C1-C20 alkyl groups.

2. The monotin complex according to claim 1, wherein R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and tert-pentyl.

3. The single tin complex according to claim 1 or 2, characterized in that, R2 to R5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

4. The monotin complex according to claim 1, characterized in that, The structure of the mono-tin complex is shown as follows: 。 5. A method for preparing the monotin complex according to any one of claims 1-4, characterized in that, It at least includes the step of reacting the organo-tin compound shown by formula (2) with the organic compounds shown by formula (3) and formula (4); Among them, the structural formula of the organotin compound is: For formula (2), the structural formula of the organic compound is: For formula (3), (4); In the above formulas (2), (3), and (4), X is sulfur or selenium, R1 is a C1-C20 alkyl group, R2 to R5 are each independently selected from hydrogen and C1-C20 alkyl groups, and R6 to R 11 are each independently selected from C1-C20 alkyl groups.

6. The preparation method of the single tin complex according to claim 5, characterized in that, The reaction temperature of the reaction is -20°C to 40°C.

7. A patterned composition, characterized in that, It includes the mono-tin complex according to any one of claims 1-4 and a solvent.

8. The patterned composition according to claim 7, wherein The concentration of the mono-tin complex in the patterned composition is 10 mg / mL to 40 mg / mL.

9. The patterned composition according to claim 7 or 8, characterized in that, The composition at least further includes a leveling agent and / or a surfactant.

10. A method of forming a pattern, characterized in that, It at least includes the step of forming a patterned layer by using the patterned composition according to any one of claims 7-9, and after exposure treatment, developing to form a patterned film.

11. The method of forming a pattern according to claim 10, wherein During the exposure treatment, an electron beam of 5 kV - 125 kV or soft X-ray exposure with a wavelength less than 15 nm is used.

12. The method of forming a pattern according to claim 10 or 11, characterized in that, The solvent used for development is selected from n-pentane, n-hexane, n-heptane liquids, or n-pentane, n-hexane, n-heptane vapors, and any composition of the above-mentioned alkanes and ethyl lactate, tetrahydrofuran, 2-pentanone, 3-pentanone, hexanone, 2-heptanone, octanone, ethanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, or 4-methyl-2-pentanol.

13. A patterned film, characterized in that, The patterned film is formed by using the patterned composition according to any one of claims 7-9 or obtained by using the method for forming a pattern according to any one of claims 10-12.

14. The patterned film according to claim 13, wherein The resolution of the pattern on the patterned film is below 50 nm, and the edge roughness of the pattern on the patterned film is below 5 nm.

Images