Application of silicon-containing polymer in filling nano-groove structure and silicon-containing polymer and preparation method

Abstract

The present invention relates to an application of a silicon-containing polymer in filling a nano-groove structure, a silicon-containing polymer and a preparation method, and belongs to the technical field of silicon-containing polymers. The invention is used to solve the problems of poor filling ability of existing silicon-containing polymer solutions for filling nano-groove structures, high shrinkage and stress during the formation of SiO2, poor densification, and many filling defects. An application of a silicon-containing polymer in filling a nano-groove structure, wherein the molecular formula of the silicon-containing polymer is Si x N y H z O w C v The unit unsaturation of the silicon-containing polymer is α / 1000, and 3≤α / 1000≤8, #imgabs0#. The silicon-containing polymer for nano-trench structure filling of the present invention is selected to have a specific unit unsaturation. During the SiO2 formation process, the silicon-containing polymer exhibits low shrinkage and low stress, enabling densification and defect-free filling of the nano-trench structure.

Description

Technical Field

[0001] The present invention relates to the technical field of silicon-containing polymers, and in particular to application of silicon-containing polymers in filling nano-groove structures. Background Art

[0002] In the chip manufacturing process, nano-trench isolation structures (STI, DTI, etc.) play a vital and irreplaceable role. They are not only the cornerstone of the chip functional area division, but also the core of ensuring insulation isolation between circuits, minimizing interference, reducing energy consumption, improving integration and enhancing overall reliability. Insulating materials are filled in the nano-trench / hole structure, silicon oxide (SiO x ) has become the first choice of filling material due to its excellent insulation and chemical stability. x Filling materials are prepared using gas phase processes such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). However, as chips develop towards 7 nm, 5 nm and even lower processes and higher integration, the characteristic size of nano-grooves / holes is also shrinking. The use of vapor phase deposition process to fill SiO x It becomes increasingly difficult to prepare SiO by solution method. x The characteristics of easy operation and good fluidity effectively overcome this problem.

[0003] Silicon-containing polymer precursors, such as polysilazane and polysiloxysilazane, can be applied to the nanogrooved structure using a spin-coating process and subsequently converted to SiO2 material through high-temperature annealing. CN115572540A defines polysilazane as having low shrinkage and low wet etch rate characteristics based on refractive index, but this is too one-sided and fails to capture the overall structural characteristics of polysilazane. Existing silicon-containing polymer solutions for nanogrooved structure filling suffer from poor filling capacity and high shrinkage and stress during the SiO2 formation process. Summary of the Invention

[0004] In view of the above analysis, the present invention aims to provide an application of a silicon-containing polymer in filling a nano-groove structure and a silicon-containing polymer and a preparation method, so as to solve at least one of the problems of the existing silicon-containing polymer solution in filling a nano-groove structure, namely, poor filling ability, high shrinkage, high stress, poor densification, and many filling defects during the formation of SiO2.

[0005] In the first aspect, the present invention provides an application of a silicon-containing polymer in filling a nano-groove structure, wherein the molecular formula of the silicon-containing polymer is Si x N y H z O w C v, the unit unsaturation degree of the silicon-containing polymer is α / 1000, and 3≤α / 1000≤8, ;

[0006] Wherein, x is the total number of Si atoms, y is the number of N atoms, z is the number of H atoms, w is the number of O atoms, v is the number of C atoms, and Mn is the number average molecular weight of the silicon-containing polymer.

[0007] Furthermore, the silicon-containing polymer has a number average molecular weight Mn of 800-20,000 g / mol, a weight average molecular weight Mw of 1,000-50,000 g / mol, and a molecular weight distribution PDI of 2-8.

[0008] Furthermore, the characteristic structural units of the silicon-containing polymer satisfy the following relationship:

[0009] 0.2≤SiH3 / SiH m , 0.7≤NH x / SiH3≤3;

[0010] Wherein, SiH3 represents the integrated area of the characteristic peak corresponding to SiH3 in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, and the peak position is 4.34 ppm;

[0011] SiH m Represents the total integrated area of the characteristic peaks corresponding to SiH, SiH2 and SiH3 in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, with the peak position being 4.2~5.3ppm;

[0012] NH x It represents the integrated area corresponding to NH and NH2 groups in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, and the integration range is 1.0~2.0ppm.

[0013] Furthermore, the characteristic structural units of the silicon-containing polymer satisfy the following relationship:

[0014] 0.3≤N / NH n ≤0.7, where N represents the number of N atoms in the silicon-containing polymer with three bonds connected to Si atoms, NH n Represents the number of nitrogen atoms containing hydrogen atoms in the silicon-containing polymer.

[0015] Furthermore, the application specifically includes the following steps:

[0016] (1) Preparation of silicon-containing polymers;

[0017] (2) Adding a catalyst to the silicon-containing polymer, coating it on a substrate with a nano-groove structure, baking it until the solvent is completely volatilized, and then performing a high-temperature annealing treatment.

[0018] Furthermore, in step (1), the silicon-containing polymer is prepared by the following method: under an inert gas, a solvent, a chlorosilane and an amine compound are sequentially added to a reaction vessel to carry out an aminolysis condensation reaction, and then further post-polymerization treatment is carried out to obtain the silicon-containing polymer.

[0019] Furthermore, the post-polymerization treatment is carried out at a temperature of 50° C. to 100° C. and for a time of 5 to 10 hours.

[0020] Furthermore, in step (2), the amount of the catalyst added is 0-5% of the mass of the silicon-containing polymer.

[0021] In a second aspect, the present invention provides a method for preparing the silicon-containing polymer, comprising: adding a solvent, a chlorosilane and an amine compound to a reaction vessel in sequence under an inert gas, carrying out an aminolysis condensation reaction, and then performing further post-polymerization treatment to obtain the silicon-containing polymer.

[0022] Furthermore, in step (2), the baking temperature is 80-200°C.

[0023] Furthermore, the high temperature annealing temperature is 300-1000° C., and the annealing time is 1-200 min.

[0024] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0025] (1) The silicon-containing polymer of the present invention selects a specific unit unsaturation, reveals the characteristic structure of the silicon-containing polymer from the molecular structure level, and provides index parameters suitable for groove structure filling and conversion to form SiO2. Meeting the unit unsaturation of 3≤α / 1000≤8 can provide a more universal molecular level characterization method for the structure of the silicon-containing polymer, and provide a reference basis for the selection of silicon-containing polymers that meet the requirements of pore structure filling;

[0026] (2) The silicon-containing polymer for filling the nano-groove structure of the present invention is selected by screening silicon-containing polymers with specific unit unsaturation. In the process of forming SiO2, it has low shrinkage and low stress, ensuring the densification and defect-free filling of the nano-groove structure.

[0027] In the present invention, the above-mentioned technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of the present invention will be described in the following description, and some advantages will become apparent from the description or be learned through practice of the present invention. The objectives and other advantages of the present invention can be realized and obtained through the contents particularly pointed out in the description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings are only used for the purpose of illustrating specific embodiments and are not to be considered as limiting the present invention. Throughout the drawings, the same reference symbols denote the same components.

[0029] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer prepared in Example 1 of the present invention;

[0030] Figure 2 This is the silicon nuclear magnetic resonance spectrum of the silicon-containing polymer prepared in Example 1 of the present invention;

[0031] Figure 3 This is the two-dimensional nuclear magnetic resonance spectrum of the silicon-containing polymer prepared in Example 1 of the present invention;

[0032] Figure 4 This is a schematic structural diagram of the silicon-containing polymer prepared in Example 1 of the present invention;

[0033] Figure 5 This is an SEM photograph of a trench structure filled with the silicon-containing polymer solution of Example 1;

[0034] Figure 6 This is an SEM photograph of the trench structure filled with the silicon-containing polymer solution of Comparative Example 1. DETAILED DESCRIPTION

[0035] The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein the accompanying drawings constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not used to limit the scope of the present invention.

[0036] A specific embodiment of the present invention discloses the use of a silicon-containing polymer in filling a nano-groove structure, wherein the molecular formula of the silicon-containing polymer is Si x N y H z O w C v The unit unsaturation degree of the silicon-containing polymer is α / 1000, and 3≤α / 1000≤8, for example, α / 1000 is 3, 4, 5, 6, 7, 8, ;

[0037] Wherein, x is the total number of Si atoms, y is the number of N atoms, z is the number of H atoms, w is the number of O atoms, v is the number of C atoms, and Mn is the number average molecular weight of the silicon-containing polymer.

[0038] Preferably, x is 26-402, y is 24-380, z is 69-898, w is 0-8, and v is 0-22.

[0039] Compared to the prior art, the silicon-containing polymer of the present invention selects a specific unit of unsaturation, revealing the characteristic structure of the silicon-containing polymer at the molecular level, and providing index parameters suitable for trench structure filling and conversion to SiO2. Since the chemical bonds of the silicon-containing polymer are all single bonds, the α / 1000 value represents the ratio of linear rings in the silicon-containing polymer. The higher the α / 1000 value, the higher the cyclicity of the silicon-containing polymer and the higher the degree of intramolecular crosslinking. The lower the α / 1000 value, the lower the cyclicity of the silicon-containing polymer and the lower the degree of intramolecular crosslinking. Meeting the requirement of 3≤α / 1000≤8 units of unsaturation provides a more universal molecular-level characterization method for the structure of the silicon-containing polymer, providing a reference for the selection of silicon-containing polymers that meet the requirements of pore structure filling.

[0040] The silicon-containing polymer for filling the nano-groove structure of the present invention is prepared by screening a silicon-containing polymer with a specific unit unsaturation, and has low shrinkage and low stress during the formation of SiO2, thereby ensuring densification and defect-free filling of the nano-groove structure.

[0041] Specifically, the number average molecular weight Mn of the silicon-containing polymer is 800-20000 g / mol, for example, 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, 10000 g / mol, 11000 g / mol, 12000 g / mol, 13000 g / mol, 14000 g / mol, 15000 g / mol, 16000 g / mol, 17000 g / mol, 18000 g / mol, 19000 g / mol, the weight average molecular weight Mw is 1000~50000 g / mol, for example, 5000 g / mol, 10000 g / mol, 15000 g / mol, 20000 g / mol, 25000 g / mol, 30000 g / mol, 35000 g / mol, 40000 g / mol, 45000 g / mol, and the molecular weight distribution PDI is 2~8, for example, 3, 4, 5, 6, 7.

[0042] Specifically, the characteristic structural unit of the silicon-containing polymer satisfies the following relationship:

[0043] 0.2≤SiH3 / SiH m , for example, SiH3 / SiH m 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.3≤N / NH n ≤0.7, e.g., N / NH n0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.44, 0.46, 0.48, 0.50, 0.52, 0.54, 0.56, 0.58, 0.60, 0.62, 0.64, 0.66, 0.68, 0.7≤NH x / SiH3≤3, for example, NH x / SiH3 is 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.05, 1.10, 1.15, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9;

[0044] Wherein, SiH3 represents the integrated area of the characteristic peak corresponding to SiH3 in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, and the peak position is 4.34 ppm;

[0045] SiH m Represents the total integrated area of the characteristic peaks corresponding to SiH, SiH2 and SiH3 in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, with the peak position being 4.2~5.3ppm;

[0046] N represents the number of N atoms in the silicon-containing polymer whose three bonds are connected to Si atoms. n Represents the number of N atoms with H atoms on N of silicon-containing polymers;

[0047] NH x It represents the integrated area corresponding to NH and NH2 groups in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, and the integration range is 1.0~2.0ppm.

[0048] It should be noted that N and NH in the above relationship n The calculation is based on the integration of the two-dimensional NMR spectrum of the silicon-containing polymer. x The NH peak during calculation overlaps with the peak of the solvent dissolving the silicon-containing polymer during testing, and a subtraction correction is required by integrating the characteristic peaks at known positions of the solvent.

[0049] Specifically, the application includes the following steps:

[0050] (1) Preparing a silicon-containing polymer solution;

[0051] (2) Adding a catalyst to the silicon-containing polymer solution, coating the solution on a substrate with a nano-groove structure, baking the solution until the solvent is completely volatilized, and then performing a high-temperature annealing treatment.

[0052] Specifically, in step (1), the silicon-containing polymer solution is prepared by the following method: under an inert gas, a solvent, a chlorosilane and an amine compound are sequentially added to a reaction vessel to carry out an aminolysis condensation reaction, and then further post-polymerization treatment is carried out to obtain the silicon-containing polymer solution.

[0053] Specifically, the temperature of the aminolysis condensation reaction is -30 to 50°C, for example, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, and the reaction time is 0.5 to 20h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, the post-polymerization treatment temperature is 50°C to 100°C, for example, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, and the time is 5 to 10h, for example, 5.5h, 6.0h, 6.5h, 7.0h, 7.5h, 8.0h, 8.5h, 9.0h, 9.5h. Specifically, the inert atmosphere is one or more of nitrogen, argon, and helium.

[0054] Specifically, the solvent includes at least one of hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, ketone solvents, aromatic solvents, and ester solvents;

[0055] Preferably, the hydrocarbon solvent is selected from at least one of n-hexane, heptane, octane, decane, petroleum ether, dichloromethane, chloroform, and dichloroethylene, but is not limited thereto;

[0056] The halogenated hydrocarbon solvent is selected from the halogenated hydrocarbon solvent corresponding to the hydrocarbon solvent. For example, when the hydrocarbon solvent is selected from n-hexane, the halogenated hydrocarbon solvent can be selected from halogenated n-hexane. The same applies to other halogenated hydrocarbon solvents selected from the halogenated hydrocarbon solvent corresponding to the hydrocarbon solvent.

[0057] The ether solvent is selected from at least one of diethyl ether and n-butyl ether, but is not limited thereto;

[0058] The ketone solvent is selected from at least one of acetone, cyclohexanone, methyl ethyl ketone, and isophorone, but is not limited thereto;

[0059] The aromatic solvent is selected from at least one of toluene, o-xylene, p-xylene, m-xylene, and chlorobenzene, but is not limited thereto;

[0060] The ester solvent is selected from at least one of ethyl acetate, butyl butyrate, amyl acetate, and octyl acetate, but is not limited thereto.

[0061] Specifically, the chlorosilane includes at least one of dihydrodichlorosilane, trichlorosilane, tetrachlorosilane, methyldichlorosilane, dimethyldichlorosilane, methylvinyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, γ-chloropropyltrichlorosilane, 3-aminopropyltrichlorosilane, and epoxypropyltrichlorosilane, but is not limited thereto.

[0062] Specifically, the amine compound includes at least one of ammonia, methylamine, ethylamine, propylamine, and butylamine, but is not limited thereto.

[0063] Specifically, the molar ratio of the solvent, chlorosilane and amine compound is 100: 1-10 (e.g., 2, 3, 4, 5, 6, 7, 8, 9): 3-50 (e.g., 5, 10, 15, 20, 25, 30, 35, 40, 45).

[0064] Specifically, the catalyst includes a metal catalyst and / or an amine catalyst.

[0065] Preferably, the amine catalyst is selected from at least one of aliphatic amines, alicyclic amines, alcohol amines and aromatic amines.

[0066] More preferably, the fatty amine may be selected from at least one of diethylamine, triethylamine and triethylenetetramine;

[0067] The alicyclic amine may be selected from at least one of triethylenediamine, piperazine, piperidine, morpholine, etc.;

[0068] The alcoholamine can be selected from at least one of N,N'-diethylethanolamine, N,N'-dimethylethanolamine, diisopropanolamine, etc.;

[0069] The aromatic amine may be at least one selected from aniline, benzidine, o-phenylenediamine, N,N'-dimethylaniline, and the like.

[0070] Preferably, the metal catalyst can be selected from at least one of an organic tin catalyst and a palladium catalyst;

[0071] More preferably, the organotin catalyst can be selected from at least one of dibutyltin dilaurate, triphenyltin and stannous octoate;

[0072] The palladium catalyst can be selected from at least one of carbon / palladium, palladium propionate, and palladium chloride.

[0073] Specifically, in step (2), the amount of the catalyst added is 0-5% of the mass of the silicon-containing polymer solution, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%.

[0074] It should be noted that a catalyst can be added as needed. The catalyst can increase the speed of conversion into a film. In particular, when the amount of catalyst added is 0, it takes a longer time to complete the curing.

[0075] Specifically, the baking temperature is 80-200°C, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C.

[0076] Specifically, the temperature of the high temperature annealing is 300~1000℃, for example, 400℃, 500℃, 600℃, 700℃, 800℃, and 900℃, and the annealing time is 1~200min, for example, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min, 180min, and 190min.

[0077] Preferably, the baking atmosphere can be air, nitrogen, argon, or a mixture of two or more thereof.

[0078] Preferably, the high temperature annealing atmosphere is a humid atmosphere, the humid gas is introduced into the high temperature furnace through a steam generator, and the carrier gas of the humid gas is selected from air, nitrogen, argon or a mixture of two or more thereof.

[0079] Another specific embodiment of the present invention discloses a silicon-containing polymer. The molecular formula of the silicon-containing polymer is Si x N y H z O w C v , the unit unsaturation degree of the silicon-containing polymer is α / 1000, and 3≤α / 1000≤8, ;

[0080] Wherein, x is the total number of Si atoms, y is the number of N atoms, z is the number of H atoms, w is the number of O atoms, v is the number of C atoms, and Mn is the number average molecular weight of the silicon-containing polymer.

[0081] Another specific embodiment of the present invention discloses a method for preparing the silicon-containing polymer, comprising: adding a solvent, a chlorosilane, and an amine compound to a reaction vessel in sequence under an inert gas, carrying out an aminolysis condensation reaction, and then performing further post-polymerization treatment to obtain the silicon-containing polymer.

[0082] The technical solution of the present invention is further explained below in conjunction with specific embodiments.

[0083] Synthesis example 1

[0084] 500 g of pyridine was added to a 1 L pressure-resistant glass reactor, cooled to -5°C, and 10 L of dichlorosilane was added at a rate of 100 mL / min. Subsequently, 50 L of ammonia was introduced at a rate of 200 mL / min, and the reaction system was stirred for 2 hours. The exhaust valve was then opened, and dry nitrogen was continuously introduced into the reaction system for 1 hour to remove unreacted ammonia. The filtrate was separated using a 0.1 μm PTFE (polytetrafluoroethylene) positive pressure filter. 300 g of ultra-dry n-butyl ether was added, and the pyridine in the solution was evaporated using a rotary evaporator. This process was repeated three times. Finally, the solution was diluted to a 20% concentration. Particulate matter was removed from the solution using a 0.05 μm PTFE filter cartridge to obtain a silicon-containing polymer solution.

[0085] Example 1

[0086] The preparation method of a silicon-containing polymer solution in this embodiment is the same as that in Synthesis Example 1, except that the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 50°C for 10 h, and then the subsequent operations are performed.

[0087] The hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer prepared in this example is as follows: Figure 1 As shown, the silicon NMR spectrum is as Figure 2 As shown, the two-dimensional NMR spectrum is Figure 3 As shown, the structural diagram of the silicon-containing polymer prepared in this embodiment is shown in FIG. Figure 4 As shown, it is a typical wire loop structure.

[0088] Example 2

[0089] The method for preparing a silicon-containing polymer solution in this embodiment is the same as that in Synthesis Example 1, except that the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 70°C for 5 hours, and then the subsequent operations are performed.

[0090] Example 3

[0091] The method for preparing a silicon-containing polymer solution in this embodiment is the same as that in Synthesis Example 1, except that the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 70°C for 10 h, and then the subsequent operations are performed.

[0092] Example 4

[0093] The method for preparing a silicon-containing polymer solution in this embodiment is the same as that in Synthesis Example 1, except that the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 90°C for 5 hours, and then the subsequent operations are performed.

[0094] Example 5

[0095] The method for preparing a silicon-containing polymer solution in this embodiment is the same as that in Synthesis Example 1, except that the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 90°C for 10 h, and then the subsequent operations are performed.

[0096] Example 6

[0097] The method for preparing a silicon-containing polymer solution in this example is the same as that in Synthesis Example 1, except that 5g of dimethyldichlorosilane is added to the pyridine solution and thoroughly stirred before proceeding with the subsequent reactions. Finally, the filtrate is transferred to a 1000ml three-necked flask under N2 protection and heated at 70°C for 10 hours before proceeding with the subsequent reactions.

[0098] Example 7

[0099] The method for preparing a silicon-containing polymer solution in this embodiment is the same as that in Synthesis Example 1, except that the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 50°C for 5 hours, and then the subsequent operations are performed.

[0100] Example 8

[0101] The method for preparing a silicon-containing polymer solution in this embodiment is the same as that in Synthesis Example 1, except that the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 100°C for 10 h, and then the subsequent operations are performed.

[0102] Comparative Example 1

[0103] The preparation method of a silicon-containing polymer solution in this comparative example is the same as that in Synthesis Example 1, that is, no further post-polymerization treatment is performed.

[0104] Comparative Example 2

[0105] The preparation method of a silicon-containing polymer solution in this comparative example is the same as that in Example 1, except that the solution is heated at 90° C. for 20 h.

[0106] Comparative Example 3

[0107] The preparation method of a silicon-containing polymer solution in this comparative example is the same as that in Example 1, except that the solution is heated at 110° C. for 10 h.

[0108] Test Example 1

[0109] The basic structural characterization of the silicon-containing polymer solutions prepared in Examples 1-8 and Comparative Examples 1-3 was tested respectively, and the results are shown in Table 1.

[0110] The testing method for the basic structure of the silicon-containing polymer in the present invention is as follows:

[0111] (1) The molecular weight of the product was determined using a gel permeation chromatograph (GPC; 2414, Waters). The test temperature was 20°C, the mobile phase was THF, the flow rate was 1 mL / min, and the standard sample was polystyrene.

[0112] (2) The H NMR spectrum, Si NMR spectrum, and two-dimensional spectrum of the product were measured using a Bruker AV 600 nuclear magnetic resonance spectrometer. The deuterated reagent used was deuterated chloroform, and the relaxation reagent used was chromium metal acetylacetonate.

[0113] (3) X-ray photoelectron spectroscopy (XPS, VG Scientific) was used to analyze the relative contents of Si, N, and O elements in the product. During the test, 300W Al Ka excitation was used and the base pressure was 3×10 -9 mbar. The solvent in the silicon-containing polymer solution was first removed by vacuum distillation, and then the sample was transferred to a glove box. To prevent oxidation, a dedicated sealed container was used to transfer the sample from the glove box to the XPS analyzer, under N2 protection throughout the process.

[0114]

[0115] Test Example 2

[0116] The properties of the silicon-containing polymer solutions prepared in Examples 1-8 and Comparative Examples 1-3 were tested, as shown in Table 2. The specific testing methods are as follows:

[0117] (1) 0.5 mL of each of the silicon-containing polymer solutions prepared in Examples 1-8 and Comparative Examples 1-3 was spin-coated on a 4-inch silicon wafer to form a silicon-containing polymer film, wherein the spin-coating speed was 1000 rpm / s and the time was 30 s; the silicon wafer was transferred to a hot plate at 150°C and baked for 3 min to evaporate the solvent, the thickness of the baked film was measured by an ellipsometer (M-2000V, JA Woollam), and the curvature radius R1 of the film was measured by a thin film stress gauge (Toho FLX-2320-S); the silicon wafer was then transferred to a high-temperature furnace and subjected to high-temperature moisture annealing at 600°C for 2 h to form a SiO2 film, and the thickness and curvature radius R2 of the film were then measured again. Based on the changes in the thickness and curvature of the film before and after annealing, the shrinkage rate and internal stress during the material conversion process were calculated.

[0118] Shrinkage rate = (thickness before conversion - thickness after conversion) / thickness before conversion × 100%;

[0119] Internal stress test formula,

[0120]

[0121] Where σ is the average stress of the dielectric layer (Pa); E / (1-ν) is the biaxial elastic modulus of the substrate, which is 1.805×10 11 Pa; h is the substrate thickness (m); T is the dielectric layer thickness (m); R is the curvature radius (m).

[0122] Wet etching rate: The SiO2 film prepared by the above method was placed in a 1v% hydrofluoric acid solvent, taken out at regular intervals to test its thickness change, and its etching rate was calculated.

[0123] Nanogroove filling: The process is the same as the above spin coating and conversion process, but the substrate is replaced with a silicon structure wafer (groove wafer) with a groove size of 50nm wide and 250nm deep. After the conversion is completed, the cross-sectional state is observed using SEM.

[0124] The SEM photograph of the groove structure filled with the silicon-containing polymer solution prepared in Example 1 is as follows: Figure 5 As shown in FIG, the filling result has no defects such as voids and cracks. The SEM photo of the groove structure filled with the silicon polymer solution prepared in Comparative Example 1 is shown in FIG. Figure 6 As shown, there is an obvious cracking problem in the filled surface filling layer.

[0125]

[0126] As shown in Table 2 above, the silicon-containing polymers prepared in Examples 1 to 8 can achieve uniform and defect-free filling of the trench structure, and have lower shrinkage, internal stress, and wet etching rate than Comparative Examples 1 to 3.

[0127] The SiO2 formed in the method of the present invention has a shrinkage rate of 16.8-18.2%, an internal stress of 120-165 MPa, and a wet etching rate of 12.0-15.4%.

[0128] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. An application of a silicon-containing polymer in filling a nano-groove structure, characterized in that: The molecular formula of the silicon-containing polymer is , the unit unsaturation of the silicon-containing polymer is ,and , ; Wherein, x is the total number of Si atoms, y is the number of N atoms, z is the number of H atoms, w is the number of O atoms, v is the number of C atoms, and Mn is the number average molecular weight of the silicon-containing polymer; The silicon-containing polymer has a number average molecular weight Mn of 800 to 20,000 g / mol, a weight average molecular weight Mw of 1,000 to 50,000 g / mol, and a molecular weight distribution PDI of 2 to 8; The characteristic structural units of the silicon-containing polymer satisfy the following relationship: ； Wherein, SiH3 represents the integrated area of the characteristic peak corresponding to SiH3 in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, and the peak position is 4.34 ppm; NH x represents the integrated area corresponding to NH and NH2 groups in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, with the integration range being 1.0-2.0 ppm; N represents the number of N atoms in the silicon-containing polymer whose three bonds are connected to Si atoms. n Represents the number of nitrogen atoms containing hydrogen atoms in the silicon-containing polymer.

2. The use of a silicon-containing polymer in filling a nano-groove structure according to claim 1, characterized in that: The silicon-containing polymer has a number average molecular weight Mn of 1000-19000 g / mol, a weight average molecular weight Mw of 5000-45000 g / mol, and a molecular weight distribution PDI of 3-7.

3. The use of a silicon-containing polymer in filling a nano-groove structure according to claim 1, characterized in that: The characteristic structural units of the silicon-containing polymer satisfy the following relationship: ； Wherein, SiH3 represents the integrated area of the characteristic peak corresponding to SiH3 in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, and the peak position is 4.34 ppm; SiH m Represents the total integrated area of the characteristic peaks corresponding to SiH, SiH2 and SiH3 in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, with the peak position being 4.2~5.3ppm; NH x It represents the integrated area corresponding to NH and NH2 groups in the hydrogen nuclear magnetic resonance spectrum of the silicon-containing polymer, and the integration range is 1.0~2.0ppm.

4. The use of a silicon-containing polymer in filling a nano-groove structure according to claim 1, characterized in that: The characteristic structural units of the silicon-containing polymer satisfy the following relationship: , wherein N represents the number of N atoms in the silicon-containing polymer whose three bonds are connected to Si atoms, NH n Represents the number of nitrogen atoms containing hydrogen atoms in the silicon-containing polymer.

5. Use of a silicon-containing polymer according to any one of claims 1 to 4 in filling a nano-groove structure, characterized in that: The application specifically includes the following steps: (1) Preparation of silicon-containing polymers; (2) Adding a catalyst to the silicon-containing polymer, coating it on a substrate with a nano-groove structure, baking it until the solvent is completely volatilized, and then performing a high-temperature annealing treatment.

6. The use of a silicon-containing polymer in filling a nano-groove structure according to claim 5, characterized in that: In step (1), the silicon-containing polymer is prepared by the following method: under an inert gas, a solvent, a chlorosilane and an amine compound are sequentially added to a reaction vessel to carry out an aminolysis condensation reaction, and then further post-polymerization treatment is carried out to obtain the silicon-containing polymer.

7. The use of a silicon-containing polymer in filling a nano-groove structure according to claim 6, characterized in that: The post-polymerization treatment is carried out at a temperature of 50° C. to 100° C. and for a time of 5 to 10 hours.

8. The use of a silicon-containing polymer in filling a nano-groove structure according to claim 5, characterized in that: In step (2), the amount of the catalyst added is 0-5% of the mass of the silicon-containing polymer.

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