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

Abstract

The invention relates to application of a silicon-containing polymer in filling of a nano groove structure, the silicon-containing polymer and a preparation method, belongs to the technical field of silicon-containing polymers, and aims to solve the problems that when an existing silicon-containing polymer solution is used for filling of the nano groove structure, the filling capacity is poor, in the SiO2 forming process, the shrinkage rate and stress are high, the compactness is poor, and the service life is short. And filling defects are many. According to the application of the silicon-containing polymer in filling of the nanometer groove structure, the molecular formula of the silicon-containing polymer is SixNyHzOwCv, the unit unsaturation degree of the silicon-containing polymer is alpha / 1000, and alpha / 1000 is larger than or equal to 3 and smaller than or equal to 8. According to the silicon-containing polymer for filling the nano groove structure, the silicon-containing polymer with specific unit unsaturation is screened, and in the process of forming SiO2, the silicon-containing polymer has the advantages of low shrinkage rate, low stress, densification of the nano groove structure and zero-defect filling.

Description

Technical Field

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

[0002] In the process of chip manufacturing, nano-groove isolation structures (such as STI, DTI, etc.) play a crucial and irreplaceable role. They are not only the cornerstone for dividing chip functional areas, but also the core for ensuring insulation isolation between circuits, minimizing interference, reducing energy consumption, improving integration, and enhancing overall reliability. When filling an insulating material in a nano-groove / hole structure, silicon oxide (SiO x ) is the preferred filling material due to its excellent insulation and chemical stability. Usually, the preparation of SiO x filling materials adopts gas-phase process technologies such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). However, as chips develop towards 7 nm, 5 nm or even lower processes and higher integration, the feature size of nano-grooves / holes is continuously reduced, and it becomes increasingly difficult to fill SiO x using the gas-phase deposition process. The solution method for preparing SiO x has the characteristics of simple operation and good fluidity, effectively overcoming this problem.

[0003] Silicon-containing polymer precursors, such as polysilazane, polysiloxysilazane, etc., can be spin-coated on a nano-groove structure wafer, and then converted into SiO2 material through high-temperature annealing. CN115572540A defines polysilazane with characteristics of low shrinkage rate and low wet etching rate from the refractive index angle, but it is too one-sided and cannot reflect the overall structural characteristics of polysilazane. When the existing silicon-containing polymer solution is used to fill a nano-groove structure, there are problems such as poor filling ability, high shrinkage rate, high stress, poor densification, and many filling defects during the formation of SiO2. 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, a silicon-containing polymer, and a preparation method, so as to solve at least one of the problems such as poor filling ability, high shrinkage rate, high stress, poor densification, and many filling defects when the existing silicon-containing polymer solution is used to fill a nano-groove structure.

[0005] In a first aspect, the present invention provides an application of a silicon-containing polymer in filling a nano-groove structure, and 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, ; where 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.

[0006] Furthermore, the number-average molecular weight Mn of the silicon-containing polymer is 800 - 20000 g / mol, the weight-average molecular weight Mw is 1000 - 50000 g / mol, and the molecular weight distribution PDI is 2 - 8.

[0007] Furthermore, the characteristic structural unit of the silicon-containing polymer satisfies the following relationship: 0.2 ≤ SiH3 / SiH m , 0.7 ≤ NH x / SiH3 ≤ 3; where SiH3 represents the integral area of the characteristic peak corresponding to SiH3 in the 1H NMR spectrum of the silicon-containing polymer, and the peak position is at 4.34 ppm; SiH m represents the total integral area of the characteristic peaks corresponding to SiH, SiH2, and SiH3 in the 1H NMR spectrum of the silicon-containing polymer, and the peak position is at 4.2 - 5.3 ppm; NH x represents the integral area corresponding to the N-H and NH2 groups in the 1H NMR spectrum of the silicon-containing polymer, and the integral range is 1.0 - 2.0 ppm.

[0008] Furthermore, the characteristic structural unit of the silicon-containing polymer satisfies the following relationship: 0.3 ≤ N / NH n ≤ 0.7, where N represents the number of N atoms with all three bonds connected to Si atoms in the silicon-containing polymer, and NH n represents the number of N atoms with H atoms on N in the silicon-containing polymer.

[0009] Furthermore, the application specifically includes the following steps: (1) Prepare the silicon-containing polymer; (2) Add a catalyst to the silicon-containing polymer, coat it on a substrate with a nano-groove structure, bake until the solvent completely evaporates, and then perform high-temperature annealing treatment.

[0010] 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, an ammonolysis condensation reaction is carried out, and further post-polymerization treatment is carried out to obtain the silicon-containing polymer.

[0011] Further, the temperature of the post-polymerization treatment is 50°C to 100°C, and the time is 5 to 10 h.

[0012] Further, in step (2), the addition amount of the catalyst is 0 to 5% of the mass of the silicon-containing polymer.

[0013] In a second aspect, the present invention provides a method for preparing the silicon-containing polymer, including: under an inert gas, sequentially adding a solvent, a chlorosilane, and an amine compound into a reaction vessel, performing an ammonolysis condensation reaction, and then performing a further post-polymerization treatment to obtain the silicon-containing polymer.

[0014] Further, in step (2), the baking temperature is 80 to 200°C.

[0015] Further, the temperature of the high-temperature annealing is 300 to 1000°C, and the annealing time is 1 to 200 min.

[0016] Compared with the prior art, the present invention can at least achieve one of the following beneficial effects: (1) The silicon-containing polymer of the present invention selects a specific unit of unsaturation, reveals the characteristic structure of the silicon-containing polymer from the molecular structure level, provides index parameters applicable to the filling of trench structures and the transformation to form SiO2, and 3 ≤ α / 1000 ≤ 8 units of unsaturation can provide a more general characterization method at the molecular level for the structure of the silicon-containing polymer, providing a reference basis for the selection of silicon-containing polymers that meet the filling of pore structures; (2) The silicon-containing polymer for filling nano-trench structures of the present invention, by screening silicon-containing polymers with specific units of unsaturation, has a low shrinkage rate and low stress during the formation of SiO2, ensuring dense and defect-free filling of the nano-trench structures.

[0017] In the present invention, the above technical solutions can also be combined with each other to achieve more preferred combination schemes. Other features and advantages of the present invention will be described in the subsequent description, and some advantages can be made obvious from the description, or understood by implementing the present invention. The objectives and other advantages of the present invention can be achieved and obtained through the content specifically pointed out in the description and the drawings. Description of the Drawings

[0018] The drawings are only for the purpose of showing specific embodiments, and are not considered as limiting the present invention. Throughout the drawings, the same reference signs represent the same components; Figure 1 1H NMR spectrum of the silicon-containing polymer prepared in Example 1 of the present invention; Figure 21H NMR spectrum of the silicon-containing polymer prepared in Example 1 of the present invention; Figure 3 2D NMR spectrum of the silicon-containing polymer prepared in Example 1 of the present invention; Figure 4 Schematic structural diagram of the silicon-containing polymer prepared in Example 1 of the present invention; Figure 5 SEM photograph of the trench structure filled with the silicon-containing polymer solution of Example 1; Figure 6 SEM photograph of the trench structure filled with the silicon-containing polymer solution of Comparative Example 1. Detailed Description of the Invention

[0019] The preferred embodiments of the present invention will be specifically described below with reference to the accompanying drawings. The accompanying drawings form a part of the present invention and are used together with the embodiments of the present invention to explain the principles of the present invention, rather than to limit the scope of the present invention.

[0020] A specific embodiment of the present invention discloses an application of a silicon-containing polymer in filling a nano-trench structure. 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. For example, α / 1000 is 3, 4, 5, 6, 7, 8, ; where 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.

[0021] Preferably, x is 26 - 402, y is 24 - 380, z is 69 - 898, w is 0 - 8, and v is 0 - 22.

[0022] Compared with the prior art, the silicon-containing polymer of the present invention selects a specific unit unsaturation to reveal the characteristic structure of the silicon-containing polymer from the molecular structure level, and provides index parameters suitable for trench structure filling and conversion into SiO2. Since all the chemical bonds of the silicon-containing polymer are 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 degree of ring formation and the higher the degree of crosslinking within the molecule. The lower the α / 1000, the lower the degree of ring formation and the lower the degree of crosslinking within the molecule. A unit unsaturation satisfying 3 ≤ α / 1000 ≤ 8 can provide a more general characterization method at the molecular level for the structure of the silicon-containing polymer, and provide a reference basis for the selection of silicon-containing polymers that meet the pore structure filling.

[0023] The silicon-containing polymer for filling nano-groove structures of the present invention has a low shrinkage rate and low stress during the formation of SiO2 by screening silicon-containing polymers with specific unit unsaturations, ensuring densification and defect-free filling of nano-groove structures.

[0024] Specifically, the number-average molecular weight Mn of the silicon-containing polymer is 800 to 20,000 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, 10,000 g / mol, 11,000 g / mol, 12,000 g / mol, 13,000 g / mol, 14,000 g / mol, 15,000 g / mol, 16,000 g / mol, 17,000 g / mol, 18,000 g / mol, 19,000 g / mol, and the weight-average molecular weight Mw is 1000 to 50,000 g / mol, for example, 5000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, and the molecular weight distribution PDI is 2 to 8, for example, 3, 4, 5, 6, 7.

[0025] Specifically, the characteristic structural units of the silicon-containing polymer satisfy the following relationships: 0.2 ≤ SiH3 / SiH m , for example, SiH3 / SiH m is 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, for example, N / NH n is 0.32, 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; Among them, SiH3 represents the integrated area of the characteristic peak corresponding to SiH3 in the 1H NMR spectrum of the silicon-containing polymer, and the peak position is at 4.34 ppm; SiH m represents the total integrated area of the characteristic peaks corresponding to SiH, SiH2 and SiH3 in the 1H NMR spectrum of the silicon-containing polymer, and the peak position is at 4.2 - 5.3 ppm; N represents the number of N atoms in the silicon-containing polymer whose three bonds are all connected to Si atoms, and NH n represents the number of N atoms in the silicon-containing polymer that contain H atoms on N; NH x represents the integrated area corresponding to the N-H and NH2 groups in the 1H NMR spectrum of the silicon-containing polymer, and the integration interval is 1.0 - 2.0 ppm.

[0026] It should be noted that in the above relational expressions, N and NH n are calculated based on the integration of the two-dimensional NMR spectrum of the silicon-containing polymer. For the calculation of NH x , the N-H peak overlaps with the peak of the solvent used to dissolve the silicon-containing polymer during the test, and it is necessary to correct it by subtracting the integration of the characteristic peak at the known position of the solvent.

[0027] Specifically, the above application specifically includes the following steps: (1) Prepare a silicon-containing polymer solution; (2) Add a catalyst to the silicon-containing polymer solution, coat it on a substrate with a nano-groove structure, bake until the solvent completely volatilizes, and then perform high-temperature annealing treatment.

[0028] 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 successively added to a reaction vessel, an ammonolysis condensation reaction is carried out, and further post-polymerization treatment is carried out to obtain the silicon-containing polymer solution.

[0029] Specifically, the temperature of the ammonolysis 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 20 h, for example, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h. The temperature of the post-polymerization treatment 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 10 h, for example, 5.5 h, 6.0 h, 6.5 h, 7.0 h, 7.5 h, 8.0 h, 8.5 h, 9.0 h, 9.5 h. Specifically, the inert atmosphere is one or more of nitrogen, argon, and helium.

[0030] Specifically, the solvent includes at least one of hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, ketone solvents, aromatic solvents, and ester solvents; Preferably, the hydrocarbon solvent is selected from at least one of n-hexane, heptane, octane, decane, petroleum ether, dichloromethane, chloroform, and dichloroethylene, but not limited thereto; The halogenated hydrocarbon solvent is selected from the halogenated hydrocarbon solvents corresponding to the hydrocarbon solvents. 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 solvents corresponding to the hydrocarbon solvents; The ether solvent is selected from at least one of diethyl ether and n-butyl ether, but not limited thereto; The ketone solvent is selected from at least one of acetone, cyclohexanone, methyl ethyl ketone, and isophorone, but not limited thereto; The aromatic solvent is selected from at least one of toluene, o-xylene, p-xylene, m-xylene, and chlorobenzene, but not limited thereto; The ester solvent is selected from at least one of ethyl acetate, butyl butyrate, amyl acetate, and octyl acetate, but not limited thereto.

[0031] Specifically, the chlorosilane includes at least one of dihydrodichlorosilane, trichlorosilane, tetrachlorosilane, methyldichlorosilane, dimethyldichlorosilane, methylvinyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, γ-chloropropyltrichlorosilane, 3-aminopropyltrichlorosilane, and epoxypropyltrichlorosilane, but not limited thereto.

[0032] Specifically, the amine compound includes at least one of ammonia, methylamine, ethylamine, propylamine, and butylamine, but not limited thereto.

[0033] Specifically, the molar ratio of the solvent, chlorosilane and amine compound is 100: 1 to 10 (for example, 2, 3, 4, 5, 6, 7, 8, 9): 3 to 50 (for example, 5, 10, 15, 20, 25, 30, 35, 40, 45).

[0034] Specifically, the catalyst includes a metal catalyst and / or an amine catalyst.

[0035] Preferably, the amine catalyst is selected from at least one of aliphatic amines, alicyclic amines, alkanolamines, aromatic amines, etc.

[0036] More preferably, the aliphatic amine can be selected from at least one of diethylamine, triethylamine and triethylenetetramine; The alicyclic amine can be selected from at least one of triethylenediamine, piperazine, piperidine, morpholine, etc.; The alkanolamine can be selected from at least one of N,N'-diethylethanolamine, N,N'-dimethyl ethanolamine, diisopropanolamine, etc.; The aromatic amine can be selected from at least one of aniline, benzidine, o-phenylenediamine and N,N'-dimethylaniline, etc.

[0037] Preferably, the metal catalyst can be selected from at least one of an organotin catalyst and a palladium catalyst; More preferably, the organotin catalyst can be selected from at least one of dibutyltin dilaurate, triphenyltin and stannous octoate, etc.; The palladium catalyst can be selected from at least one of carbon / palladium, palladium propionate salt and palladium chloride, etc.

[0038] Specifically, in step (2), the addition amount of the catalyst is 0 to 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%.

[0039] It should be noted that the catalyst can be added as needed. The catalyst can increase the speed of film formation by conversion. In particular, when the addition amount of the catalyst is 0, it takes a longer time to complete curing.

[0040] Specifically, the baking temperature is 80 to 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, 200 °C.

[0041] Specifically, the temperature of the high-temperature annealing is 300 to 1000 °C, for example, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C, 900 °C, and the annealing time is 1 to 200 min, for example, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min.

[0042] Preferably, the atmosphere for baking can be air, nitrogen, argon or a mixed gas of two or more of them.

[0043] Preferably, the atmosphere for the high-temperature annealing is a humid atmosphere, and the humidity is introduced into the high-temperature furnace through a steam generator. The carrier gas for the humidity is selected from air, nitrogen, argon or a mixed gas of two or more of them.

[0044] 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, ; 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.

[0045] Another specific embodiment of the present invention discloses a preparation method of the silicon-containing polymer, including: under an inert gas, successively adding a solvent, a chlorosilane and an amine compound into a reaction vessel, carrying out an ammonolysis condensation reaction, and then carrying out a further post-polymerization treatment to obtain the silicon-containing polymer.

[0046] The following further explains the technical solution of the present invention in combination with specific embodiments.

[0047] Synthesis Example 1 Add 500 g of pyridine to a 1 L pressure-resistant glass reactor, cool it down to -5 °C, add 10 L of dichlorosilane at a rate of 100 mL / min, and then continue to introduce 50 L of ammonia gas at a rate of 200 mL / min. Stir the reaction system for another 2 h. Subsequently, open the exhaust valve and continuously introduce dry nitrogen gas into the reaction system for 1 h to remove the unreacted ammonia gas in the reactor. Separate the filtrate using a 0.1-μm PTFE (polytetrafluoroethylene) positive pressure filter. Add 300 g of ultra-dry n-butyl ether to it, evaporate the pyridine in the solution using a rotary evaporator three times, and finally dilute the solution concentration to 20%. Use a PTFE filter element with a pore size of 0.05 μm to remove the particulate matter in the solution to obtain a silicon-containing polymer solution.

[0048] Example 1 A method for preparing a silicon-containing polymer solution in this example 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 and heated at 50 °C for 10 h, and then subsequent operations are carried out.

[0049] The 1H NMR spectrum of the silicon-containing polymer prepared in this example is as Figure 1 shown, and the 29Si NMR spectrum is as Figure 2 shown, and the two-dimensional NMR spectrum is as Figure 3 shown. The structural schematic diagram of the silicon-containing polymer prepared in this example is as Figure 4 shown, which is a typical linear-ring structure.

[0050] Example 2 A method for preparing a silicon-containing polymer solution in this example 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 and heated at 70 °C for 5 h, and then subsequent operations are carried out.

[0051] Example 3 A method for preparing a silicon-containing polymer solution in this example 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 and heated at 70 °C for 10 h, and then subsequent operations are carried out.

[0052] Example 4 A method for preparing a silicon-containing polymer solution in this example 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 and heated at 90 °C for 5 h, and then subsequent operations are carried out.

[0053] Example 5 A method for preparing a silicon-containing polymer solution in this example 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 and heated at 90 °C for 10 h, and then subsequent operations are carried out.

[0054] Example 6 A method for preparing a silicon-containing polymer solution in this example is the same as that in Synthesis Example 1, except that 5 g of dimethyldichlorosilane is added to the pyridine solution, and after stirring well, subsequent reaction operations are carried out. And finally, the filtrate is transferred to a 1000 ml three-necked flask protected by N2, heated at 70 °C for 10 h, and then subsequent operations are carried out.

[0055] Example 7 A method for preparing a silicon-containing polymer solution in this example 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 h, and then subsequent operations are carried out.

[0056] Example 8 A method for preparing a silicon-containing polymer solution in this example 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 subsequent operations are carried out.

[0057] Comparative Example 1 A method for preparing 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 carried out.

[0058] Comparative Example 2 A method for preparing a silicon-containing polymer solution in this comparative example is the same as that in Example 1, except that it is heated at 90 °C for 20 h.

[0059] Comparative Example 3 A method for preparing a silicon-containing polymer solution in this comparative example is the same as that in Example 1, except that it is heated at 110 °C for 10 h.

[0060] Test Example 1 The basic structural characterizations of the silicon-containing polymer solutions prepared in Examples 1-8 and Comparative Examples 1-3 were tested respectively, and the results are shown in Table 1.

[0061] The test method for the basic structure of the silicon-containing polymer in the present invention is as follows: (1) The molecular weight of the product was measured 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; (2) The 1H NMR, 29Si NMR and two-dimensional spectra of the product were measured using a nuclear magnetic resonance spectrometer (Bruker AV 600). The deuterated reagent selected was deuterated chloroform, and the relaxation reagent selected was chromium acetylacetonate; (3)The relative contents of Si, N, and O elements in the product were analyzed by X-ray photoelectron spectroscopy (XPS, VG Scientific). During the test, 300W Al Ka excitation was used, and the base pressure was 3×10 -9 mbar. First, the solvent in the silicon-containing polymer solution was removed by vacuum distillation, and then it was transferred into a glove box. To prevent oxidation, a special airtight container was used to transfer the sample from the glove box to the XPS tester, and N2 protection was provided throughout the process.

[0062]

[0063] Test Example 2 The properties of the silicon-containing polymer solutions prepared in Examples 1-8 and Comparative Examples 1-3 were tested respectively. As shown in Table 2, the specific test methods are as follows: (1)0.5 mL of the silicon-containing polymer solutions prepared in Examples 1-8 and Comparative Examples 1-3 were respectively spin-coated on 4-inch silicon wafers to form silicon-containing polymer films, where the spin-coating speed was 1000 rpm / s and the time was 30 s; the silicon wafers were transferred to a hot plate at 150 °C and baked for 3 min to volatilize the solvent. The thickness of the film after baking was measured by an ellipsometer (M-2000V, J. A. Woollam), and the radius of curvature R1 of the film was measured by a thin film stress meter (Toho FLX-2320-S); then the silicon wafers were transferred into a high-temperature furnace and annealed at 600 °C under high-temperature and humid conditions for 2 h to form a SiO2 film, and then the thickness and radius of curvature R2 of the film were measured again. According to the thickness and curvature changes of the film before and after annealing, the shrinkage rate and internal stress during the material conversion process were calculated.

[0064] Shrinkage rate = (thickness before conversion - thickness after conversion) / thickness before conversion × 100%; Internal stress test formula,

[0065] where σ is the average stress of the dielectric layer (Pa); E / (1 - ν) is the biaxial elastic modulus of the substrate. For a 100-crystalline silicon wafer, its value is 1.805×10 11 Pa; h is the substrate thickness (m); T is the dielectric layer thickness (m); R is the radius of curvature (m).

[0066] Wet etching rate: The SiO2 film prepared by conversion through the above method was placed in a 1v% hydrofluoric acid solvent, and its thickness change was measured every once in a while, and its etching rate was calculated.

[0067] Nanogroove filling property: The same as the above spin coating and conversion process, but the substrate is replaced with a silicon structure wafer (groove wafer). The groove size is 50 nm wide and 250 nm deep. After the conversion is completed, the cross-sectional state is observed by SEM.

[0068] Among them, the SEM photo of filling the groove structure with the silicon-containing polymer solution prepared in Example 1 is as Figure 5 shown. There are no defects such as voids and cracks in the filling result. The SEM photo of filling the groove structure with the solution of the silicon polymer prepared in Comparative Example 1 is as Figure 6 shown. There are obvious cracking problems on the filled surface layer.

[0069]

[0070] As can be seen from Table 2 above, using the silicon-containing polymers prepared in Examples 1 to 8 for filling the groove structure can achieve uniform and defect-free filling. At the same time, compared with Comparative Examples 1-3, it has lower shrinkage rate, internal stress and wet etching rate.

[0071] In the method of the present invention, the shrinkage rate of the formed SiO2 is 16.8-18.2%, the internal stress is 120-165 Mpa, and the wet etching rate is 12.0-15.4%.

[0072] As mentioned above, only the specific preferred embodiments of the present invention are described. However, the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. Application of a silicon-containing polymer in filling a nano-groove structure, characterized in that, 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, ; Among them, 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.

2. The application of a silicon-containing polymer in filling a nano-groove structure according to claim 1, characterized in that The number-average molecular weight Mn of the silicon-containing polymer is 800 - 20000 g / mol, the weight-average molecular weight Mw is 1000 - 50000 g / mol, and the molecular weight distribution PDI is 2 - 8.

3. The application of a silicon-containing polymer in the filling of a nano-groove structure according to claim 1, wherein The characteristic structural unit of the silicon-containing polymer satisfies the following relational expression: 0.2 ≤ SiH3 / SiH m , 0.7 ≤ NH x / SiH3 ≤ 3; Among them, SiH3 represents the integral area of the characteristic peak corresponding to SiH3 in the 1H NMR spectrum of the silicon-containing polymer, and the peak position is at 4.34 ppm; SiH m represents the total integrated area of the characteristic peaks corresponding to SiH, SiH2, and SiH3 in the 1H NMR spectrum of the silicon-containing polymer, and the peak positions are at 4.2 - 5.3 ppm; NH x represents the integral area corresponding to the N-H and NH2 groups in the 1H NMR spectrum of the silicon-containing polymer, and the integration range is 1.0 - 2.0 ppm.

4. Use of a silicon-containing polymer according to claim 1 in filling a nano-groove structure, characterized in that, The characteristic structural unit of the silicon-containing polymer satisfies the following relational expression: 0.3 ≤ N / NH n ≤ 0.7, where N represents the number of N atoms in the silicon-containing polymer that are all three-bonded to Si atoms, and NH n represents the number of N atoms in the silicon-containing polymer that have H atoms on the N.

5. Use of a silicon-containing polymer according to any one of claims 1-4 in filling a nano-groove structure, characterized in that The specific application includes the following steps: (1) Prepare the silicon-containing polymer; (2) Add a catalyst to the silicon-containing polymer, coat it on a substrate with a nano-groove structure, bake until the solvent completely evaporates, and then perform high-temperature annealing treatment.

6. The application of a silicon-containing polymer in filling a nano-groove structure according to claim 5, wherein 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, an ammonolysis condensation reaction is carried out, and then a further post-polymerization treatment is carried out to obtain the silicon-containing polymer.

7. Use of a silicon-containing polymer in filling a nano-groove structure according to claim 5, characterized in that, The temperature of the post-polymerization treatment is 50°C - 100°C, and the time is 5 - 10 h.

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

9. A silicon-containing polymer, characterized in that, 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, ; Among them, 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.

10. A method for preparing the silicon-containing polymer according to claim 9, characterized in that, Including: Under an inert gas, a solvent, a chlorosilane, and an amine compound are sequentially added to a reaction vessel, an ammonolysis condensation reaction is carried out, and then a further post-polymerization treatment is carried out to obtain the silicon-containing polymer.

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