Single tin complex and preparation method thereof, patterning composition, pattern forming method and patterning film

Abstract

The invention relates to the technical field of metal-organic hybrid patterned materials, in particular to a single tin complex and a preparation method thereof, a patterned composition, a pattern forming method and a patterned film. The structure of the single tin complex is as shown in a formula (1): # imgabs0 # formula (1); wherein X is sulfur or selenium, R1 is substituted or unsubstituted C1 to C20 alkyl, and R2 to R5 are each independently selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl. The single-tin complex is a five-coordinate metal compound, is large in steric hindrance, can prevent metal tin from being attacked by water molecules in the environment to be hydrolyzed and generate precipitates, and is good in stability and good in solubility in various organic solvents.

Description

Technical Field

[0001] The present application relates to the technical field of metal-organic hybrid patterned materials, and in particular to a single tin complex and a preparation method thereof, a patterned 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 its patterning process have been continuously reduced. The patterning process generally includes the following steps: (1) depositing a base material on a wafer; (2) coating a patterned material film layer on the base material; (3) irradiating the patterned material film layer with a light source through a mask with a predetermined pattern, so that the irradiated area and the unirradiated area form a structure with a solubility difference, and optionally, after baking, this solubility difference is further enhanced; (4) selectively dissolving one of the patterned material films in the irradiated area or the unirradiated area through a suitable solvent development, and realizing a pattern on the base material that is the same or opposite to the template; (5) through etching, the patterned material retained on the wafer selectively protects the underlying material from being etched or slowly etches, so as to realize the transfer of the pattern to the underlying material, and finally realize the desired pattern on the base material.

[0003] Traditional patterning materials based on organic polymers and photosensitive small molecule compositions have basically reached their limit resolution, so the industry is in urgent need of finding new patterning materials to meet the requirements of continuously shrinking key dimensions. Since some metals have higher absorption than traditional organic materials under soft X-rays or electron beams with a wavelength less than 15nm, it is beneficial to improve the sensitivity of the material, and metal-containing organic hybrid materials have better etching resistance than traditional organic materials. At low film thickness, they can also ensure the transfer of patterns after the etching process, while avoiding the collapse of high film thickness and small-size patterns. In addition, metal-organic hybrid patterning materials with metal oxide clusters and metal complexes as the core structure can avoid the problem of line edge roughness affected by their own particle size after the dissolution of large molecules due to their 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 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 single tin complex and a preparation method thereof, a patterned composition, a method for forming a pattern and a patterned film. The single tin complex has good solubility in a variety of organic solvents and is not easy to precipitate and crystallize. The patterned composition solution prepared therefrom has good stability and can achieve better sensitivity and pattern resolution and lower line edge roughness under exposure to soft X-rays or electron beams.

[0005] The present application provides a single tin 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 to C20 alkyl group, and R2 to R5 are each independently selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group.

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

[0008] In the above-mentioned monotin complex, 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] In the above-mentioned monotin complex, R2 to R5 are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0010] From the above-mentioned single tin complex, the structure of the single tin complex is as follows:

[0011] The present application also provides a method for preparing the above-mentioned monotin complex, which at least comprises the steps of reacting an organic tin compound represented by formula (2) with an organic compound represented by formula (3) or formula (4);

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

[0013] In the above formulae (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, a substituted or unsubstituted C1 to C20 alkyl group, and R6 to R7 are each independently selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group. 11Each is independently selected from substituted or unsubstituted C1 to C20 alkyl groups. In the preparation method, there is no special requirement for the order of adding the organotin compound and the organic compound, and the two can react directly or in an organic solvent, which is simple and convenient to operate.

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

[0015] The present application also provides a patterning composition, comprising the above-mentioned monotin complex and a solvent. The patterning composition has good solution stability and can achieve better sensitivity and pattern resolution and lower line edge roughness under soft X-ray or electron beam exposure.

[0016] According to the patterned composition described above, the concentration of the single tin complex in the patterned composition is 10-40 mg / mL. Under the same coating conditions, the adjustment of different target film thicknesses can be achieved by regulating the content of the single tin complex.

[0017] The patterned composition described above further includes at least a leveling agent and / or a surfactant. When preparing the patterned composition, some additives such as a leveling agent, a surfactant, etc. may be added. The addition of the leveling agent and the surfactant may improve the uniformity of the coating film layer. The content of the leveling agent and the surfactant may be adjusted according to actual needs.

[0018] The present application also provides a method for forming a pattern, which at least includes the steps of forming a patterned layer using the above-mentioned patterned composition, exposing it to light, and developing it to form a patterned film. The above-mentioned patterned composition can be applied to semiconductor patterning processes to obtain high-quality patterns and improve the performance of components such as precision.

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

[0020] According to the method for forming a pattern as described above, the solvent used for development is selected from n-pentane, n-hexane, n-heptane liquid, or n-pentane, n-hexane, n-heptane vapor, and a combination 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.

[0021] The present application also provides a patterned film, which is formed by the above-mentioned patterned 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 process of making integrated circuit patterning, and can be further transferred to a substrate by etching to form a preset pattern on the substrate.

[0022] According to the patterned film described above, the resolution of the pattern on the patterned film is less than 50 nm, and the edge roughness of the pattern on the patterned film is less than 5 nm. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0024] Figure 2 1H NMR spectrum of tri(diethylamino)tert-butyltin in deuterated benzene d6 in Example 1 of the present application;

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

[0026] Figure 4 1H NMR spectrum of di(ethylenedithiol)tert-butyltin in deuterated benzene d6 in Example 1 of the present application;

[0027] Figure 5 The crystal structure of di(ethylenedithiol)tert-butyltin in Example 1 of the present application;

[0028] Figure 6 The line width of the pattern containing di(propylenedithiol) tert-butyltin in Example 3 of the present application at different exposure doses;

[0029] Figure 7 The scanning electron microscope images of the pattern containing di(propylenedithiol) tert-butyltin in Example 3 of the present application at different exposure doses, 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 DESCRIPTION

[0030] In order to make the purpose, technical solutions and advantages of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below in combination with the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0031] Based on the fact that existing metal-organic hybrid materials have major stability problems, single metal precursor complexes are easily hydrolyzed during storage to produce precipitation, while cluster molecules are easily oriented and arranged, resulting in aggregation and sedimentation. Solids precipitate from the formula solution, resulting in increased defects, affecting the patterning performance and reliability of the material. This application uses dithiol (or selenol) to form a coordination compound with a single tin metal core to form a single-core organic metal material with good solubility, stability, sensitivity and resolution.

[0032] In order to better understand this application, some key terms of this application are explained as follows:

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

[0034] Pitch: The pitch at which a periodic pattern is repeated.

[0035] Patterning material: also known as photoresist, is a light-sensitive mixed liquid whose solubility in the developing solution changes after exposure.

[0036] Exposure: During the exposure process, the patterned material will be irradiated by a light source of a specific wavelength (such as an electron beam, ion beam, etc.), which will react with the photosensitive components in the patterned material, causing the solubility or chemical properties of the patterned material to change. Specifically, the patterned material in the exposed part will undergo chemical changes under light, while the unexposed part will remain the same.

[0037] Development: The process of using a developer to dissolve and remove the unexposed or exposed parts of the patterned material to present the desired pattern.

[0038] The structure of the single tin complex provided in the present application is shown in the following formula (1): 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] The monotin complex is a five-coordinated metal compound with large steric hindrance, which can prevent the metal tin from being attacked by water molecules in the environment and hydrolyzed to produce precipitation, thereby affecting its stability.

[0041] In the monotin complex represented by the above formula (1), different R groups can regulate the reactivity of the compound. In order 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 single tin complex is as follows:

[0043] The present application also provides a method for preparing the above-mentioned monotin complex, which at least comprises the step of reacting an organic tin compound represented by formula (2) with an organic compound represented by formula (3) or formula (4); wherein the structural formula of the organic tin compound is: Formula (2), 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, a substituted or unsubstituted C1 to C20 alkyl group, and R6 to R 11 Each is independently selected from a substituted or unsubstituted C1 to C20 alkyl group.

[0044] When the above-mentioned monotin complex is prepared, the reaction temperature is usually -20°C-40°C, for example, 0°C-40°C, 20°C-40°C, etc. In actual operation, for the convenience of operation, the reaction can be carried out at room temperature.

[0045] When preparing the above-mentioned monotin complex, there is no special requirement for the order of adding 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 matter represented by formula (3) or formula (4) is added dropwise to the liquid of the organic tin compound represented by formula (2) or an organic solvent containing the compound to carry out the reaction. It is understood that the purpose of the organic solvent is to provide an anhydrous reaction environment, and its selection is not limited. 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 comprises the above-mentioned single tin complex and a solvent. The patterning composition can be applied to a high-resolution patterning process of electron beam or soft X-ray exposure.

[0048] In the patterned composition, the concentration of the single tin complex is generally 10 mg / mL-40 mg / mL, for example, 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL or a range between any two of the above parameters. Under the same coating conditions, the adjustment of different target film thicknesses can be achieved by regulating the content of the single tin complex.

[0049] In order to further improve the uniformity of the film layer and other properties, other additives commonly used in patterning, such as leveling agents, surfactants, etc., may be added to the above-mentioned patterning composition, and the specific amount added may 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 using the above-mentioned patterning composition to form a patterned layer, exposing it to light, and then developing it to form a patterned film.

[0051] For example, in some specific embodiments, the method of forming the 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. The substrate material is spin-coated or evaporated on the wafer surface. The substrate material may be a combination of one or more of SOG, SOC, SiARC, HMDS, etc., dried and baked to form a patterned bottom layer material.

[0053] (2) Coating or depositing the above-mentioned patterned composition on the bottom material to form a patterned material film layer. The specific deposition method is not limited, for example, a conventional solution spin coating method can be used, or the precursor material (i.e., the single tin complex) can be transported to the substrate cavity by gas phase for vapor deposition, including deposition of volatiles, chemical vapor deposition or atomic layer deposition. The film 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 the irradiated area or the unirradiated area forms a structure with a solubility difference. Furthermore, the solubility difference can be enhanced by baking. Exposure is performed by electron beam or soft X-ray exposure.

[0055] (4) Through organic solvent development, one of the patterned material film layers in the irradiated area or the non-irradiated area is selectively dissolved to realize a pattern on the base material that is the same as or opposite to the template. Furthermore, heating and baking can be performed again to further solidify the patterned material. In addition, vapor phase development can also be performed using volatile organic solvents.

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

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

[0058] The solvent used for development can be selected from n-pentane, n-hexane, n-heptane liquid, or n-pentane, n-hexane, n-heptane vapor, and a combination 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] The present application provides a patterned film, which is obtained from the above-mentioned patterned composition or the above-mentioned method for forming a pattern.

[0060] Furthermore, the resolution of the pattern on the patterned film is less than 50 nm, and the edge roughness of the patterned film is less than 5 nm.

[0061] The single tin complex described in the present application is described in detail below in conjunction with specific implementation methods.

[0062] Example 1

[0063]

Characterization of single tin complex A1 (1)

[0064] Structural conversion from tri(diethylamino)tert-butyltin precursor to di(ethylenedithiol)tert-butyltin: 50.0 mg of tri(diethylamino)tert-butyltin [tBuSn(NEt2)3] was dissolved in deuterated benzene-d6, followed by the addition of 30.6 mg, or two equivalents, of 1,2-ethanedithiol (C2H6S2).

[0065] The deuterated benzene-d6 solution was subjected to 119Sn NMR and 1H NMR detection before and after adding 1,2-ethanedithiol. The results are as follows: Figure 1-4 shown.

[0066] Figure 1 This is the 119 Sn NMR spectrum of tri(diethylamino)tert-butyltin in deuterated benzene-d6, which shows a chemical shift at 81.61 ppm. Figure 2 This is the 1H nuclear magnetic resonance spectrum of tri(diethylamino)tert-butyltin in deuterated benzene-d6. The 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 This is the 119 Sn NMR spectrum of di(ethylenedithiol)tert-butyltin after the addition of 1,2-ethanedithiol to tri(diethylamino)tert-butyltin in deuterated benzene-d6. The spectrum shows a chemical shift at 27.58 ppm. Figure 4 This is the 1H NMR spectrum of di(ethylenedithiol)tert-butyltin after adding 1,2-ethanedithiol to tri(diethylamino)tert-butyltin in deuterated benzene-d6. The spectrum shows that the chemical shift and peak shape of the diethylamine ligand have changed. The peak positions have shifted from 1.13 ppm and 3.13 ppm to 1.05 ppm and 2.58 ppm, respectively. The 12 H atoms have recovered from the multiple peak splitting of coordination with tin to the quartet in the free state.

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

[0069]

Characterization of single tin complex A1 (2)

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

[0071] Table 1

[0072]

[0073] From the above results, it can be seen that a thiol-coordinated monotin compound and free diethylamine can be directly generated by simply mixing alkyl tri(diethylamino)tin and ethanedithiol. This method can be used to prepare the monotin compound represented by formula (1) of the present application.

[0074] Example 2

[0075] 2 equivalents of 1,2-ethanedithiol were added to 0.2 g of tri(diethylamino)tert-butyltin, and the displaced free diethylamine ligand was removed by decompression. After testing, the organotin complex A1 was also obtained, and its chemical structure is shown below: .

[0076] Solvent 4-methyl-2-pentanol was added to the above-mentioned organotin complex A1, and after sufficient stirring, the solution was passed through a polytetrafluoroethylene filter with a pore size of 0.2 microns to obtain a patterning material formula solution B1 with a mass fraction of 2% of the organotin complex A1.

[0077] Example 3

[0078] 2 equivalents of 1,2-propanedithiol were added to 0.2 g of tri(diethylamino)tert-butyltin, and the displaced free diethylamine ligand was removed by decompression to obtain an organotin complex A2, the chemical structure of which is shown below: .

[0079] Solvent 4-methyl-2-pentanol was added to the above-mentioned organotin complex A2, and after sufficient stirring, it was passed through a polytetrafluoroethylene filter with a pore size of 0.2 microns to obtain a patterning material formula solution B2 with a mass fraction of the organotin complex A2 of 2%.

[0080] Example 4

[0081] Two equivalents of 1,2-ethanedithiol were added to 0.2 g of tri(diethylamino)isopropyltin, and the displaced free diethylamine ligand was removed by decompression to obtain an organotin complex A3, the chemical structure of which is shown below: .

[0082] Propylene glycol methyl ether acetate as a solvent was added to the above-mentioned organotin complex A3 to obtain a patterning material formula solution B3 with a mass fraction of 1% of the organotin complex.

[0083] Example 5

[0084] Two equivalents of 1,2-butanedithiol were added to 0.4 g of tri(diethylamino)-n-butyltin, and the displaced free diethylamine was removed by decompression to obtain an organotin complex A4, the chemical structure of which is shown below: .

[0085] A solvent, methyl 2-hydroxyisobutyrate, was added to the above-mentioned organotin complex A4 to obtain a patterning material formula solution B4 with a mass fraction of the organotin complex of 4%.

[0086] Comparative Example 1

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

[0088]

Solubility test

[0089] The single tin complexes obtained in Examples 2-5 and the tin oxide clusters (C4H9Sn) in the comparative example were mixed. 12 O 14 (OH)6FA2 was dissolved in organic solvents at different concentrations for solubility testing. The results are shown in Table 2 below:

[0090] Table 2

[0091]

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

[0093] From the above results, it can be seen that the single tin complex in the example has good solubility (>30mg / ml) in alcohol, ketone, chloroform, alkane and acetonitrile. 12 O 14 (OH)6FA2) is poorly soluble in solvents such as alcohol, ketone, chloroform, alkane and acetonitrile (< 10 mg / ml). That is, the single tin complex structure provided in this application has better solubility in different solvents.

[0094]

Stability test

[0095] The patterned material formula solution obtained in the embodiment was subjected to a stability test, and a 2% by mass solution of tri(diethylamino)tert-butyltin in 4-methyl-2-pentanol was used as a control. After being stored at room temperature for 30 days and heated at 40°C for 14 days, the solution state was observed. The results are shown in Table 3 below:

[0096] Table 3

[0097]

[0098] From the above results, it can be seen that the solution of the monotin complex provided by the present application does not produce precipitation whether it is stored at room temperature for 30 days or at 40° C. for 14 days, which indicates that the monotin complex provided by the present application has better stability.

[0099]

Resolution test

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

[0101] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to 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 shown in the following 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.

2. The single tin complex according to claim 1, characterized in that 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.

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 single tin complex according to claim 1, characterized in that The structure of the single tin complex is shown below: 。 5. A method for preparing the single tin complex according to any one of claims 1 to 4, characterized in that: The method comprises at least the steps of reacting an organic tin compound represented by formula (2) with an organic compound represented by formula (3) or formula (4); Among them, the structural formula of the organotin compound is: Formula (2), the structural formula of the organic compound is: Formula (3) (4); In the above formulae (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, a substituted or unsubstituted C1 to C20 alkyl group, and R6 to R7 are each independently selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group. 11 Each is independently selected from a substituted or unsubstituted C1 to C20 alkyl group.

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

7. A patterned composition, characterized in that The invention comprises the single tin complex according to any one of claims 1 to 4 and a solvent.

8. The patterned composition according to claim 7, characterized in that The concentration of the monotin complex in the patterning composition is 10 mg / mL-40 mg / mL.

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

10. A method for forming a pattern, characterized in that: The method at least comprises the steps of forming a patterned layer using the patterned composition according to any one of claims 7 to 9, and developing the patterned layer to form a patterned film after exposure treatment.

11. The method for forming a pattern according to claim 10, characterized in that: The exposure process uses an electron beam of 5kV-125kV or soft X-ray exposure with a wavelength less than 15nm.

12. The method for 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 liquid, or n-pentane, n-hexane, n-heptane vapor, and a combination 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.

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

14. The patterned film according to claim 13, characterized in that: The resolution of the pattern on the patterned film is less than 50 nm, and the edge roughness of the pattern on the patterned film is less than 5 nm.

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