Stress control method of SiO2 layer based on silicon-containing polymer

Abstract

The present invention relates to a method for regulating stress in a SiO2 layer based on a silicon-containing polymer, and belongs to the technical field of silicon-containing polymers. In the method of the present invention, a boron-containing compound is used to modify the silicon-containing polymer. The modified silicon-containing polymer can avoid common defects such as pores and micro-phase separation during thermal annealing, thereby increasing the density of the dielectric layer, reducing the stress of the SiO2 layer, and improving its electrical performance and reliability. The process of the present invention is simple and easy to scale up. The method of the present invention can freely regulate the stress of the SiO2 layer over a wide range. The SiO2 layer prepared in the present invention can provide higher performance in microelectronic devices and has good application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of silicon-containing polymers, and in particular to a method for regulating stress of a SiO2 layer based on silicon-containing polymers. Background Art

[0002] In electronic devices, SiO2 dielectric layers serve as key materials for insulation, isolation, protection, and device performance enhancement, ensuring that different functional layers are independent of each other and preventing crosstalk and electron migration. However, during the conversion of silicon-containing polymers into SiO2 layers, volume shrinkage occurs, leading to stress generation. Appropriate stress helps enhance the structural stability of the dielectric layer, but excessive stress can lead to decreased device performance and reliability, and even cause device failure. Typically, excessive tensile or compressive stress can cause the dielectric layer to crack or peel, destroying its isolation function and even causing device failure. Therefore, during the design and manufacturing process of the SiO2 layer, it is necessary to control the generation of stress, select appropriate materials and structures, and optimize the film formation process to ensure the high performance and reliability of the SiO2 layer.

[0003] Furthermore, in certain application scenarios, introducing stress into dielectric layers can, through precise control, synergistically optimize the mechanical, electrical, optical, and thermal properties of the material. Compressive stress can reconfigure lattice symmetry to improve carrier transport efficiency, while gradient stress can induce band bending to enhance photogenerated carrier separation. Therefore, achieving stress control in dielectric layers is of great significance. However, existing methods do not enable free regulation of stress. Summary of the Invention

[0004] In view of the above analysis, the present invention aims to provide a method for regulating stress of SiO2 layer based on silicon-containing polymers, so as to solve at least one of the problems that the existing methods cannot achieve free regulation of stress of SiO2 layer in a wide range, and the prepared microelectronic devices have low performance and poor reliability.

[0005] In a first aspect, the present invention provides a method for regulating stress in a SiO2 layer based on a silicon-containing polymer, comprising the following steps:

[0006] (1) Under an inert atmosphere, reacting a boron-containing compound and a silicon-containing polymer solution to obtain a boron-modified silicon-containing polymer precursor;

[0007] (2) Adding a catalyst to the boron-modified silicon-containing polymer precursor, mixing, coating a film on a substrate, baking, and thermally annealing to obtain the SiO2 layer.

[0008] Furthermore, in step (1), the structural formula of the silicon-containing polymer is as follows:

[0009] ;

[0010] Wherein, R1, R2, and R3 are independently selected from one of H, halogen, C1-C6 aliphatic hydrocarbons and their derivatives, C6-C12 aromatic hydrocarbons and their derivatives, and the value of n is 20-1000.

[0011] Furthermore, the weight average molecular weight Mw of the silicon-containing polymer is 2000-50000 g / mol, and the PDI is 2-10.

[0012] Furthermore, in step (1), the boron-containing compound includes one or more of boric acid, sodium borate, borane complex, trimethyl borate, triborane, tetraborane, boron tetrafluoride, boron trifluoride, boron chloride, boron trichloride, boron dichloride, boron fluoride, sodium borohydride, perboric acid, phenylboric acid, and triphenylboron.

[0013] Furthermore, in step (1), the mass fraction of the silicon-containing polymer in the silicon-containing polymer solution is 1 to 100%.

[0014] Furthermore, in step (1), the reaction is specifically as follows: the silicon-containing polymer solution and the boron-containing compound are thoroughly stirred and mixed until no bubbles are generated, then heated to react until bubbles are generated again in the solution, and then stirred to obtain a boron-modified silicon-containing polymer precursor.

[0015] Furthermore, the heating reaction temperature is 30-120° C., and the stirring time is 0.1-24 h.

[0016] Furthermore, in step (1), the molar ratio of the Si element in the silicon-containing polymer to the B element in the boron compound is 0.5:1 to 20:1.

[0017] Furthermore, the mass fraction of the catalyst in the boron-modified silicon-containing polymer precursor is 0-1%.

[0018] In a second aspect, the present invention provides a microelectronic device comprising a SiO2 layer obtained in the application.

[0019] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0020] In the present invention, boron-containing compounds are used to modify silicon-containing polymers. The modified silicon-containing polymers can avoid common defects such as pores and micro-phase separation during thermal annealing, improve the density of the dielectric layer, reduce the stress of the SiO2 layer, and improve its electrical performance and reliability. The application process of the present invention is simple and easy to mass produce. The method of the present invention can freely regulate the stress of the SiO2 layer over a wide range. The SiO2 layer prepared in the present invention can provide higher performance in microelectronic devices and has good application prospects.

[0021] 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

[0022] 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.

[0023] Figure 1 This is an infrared spectrum of the boron-modified silicon-containing polymer precursor prepared in Example 1 of the present invention;

[0024] Figure 2 This is an electron microscope image of a trench structure filled with the method of Example 3 of the present invention;

[0025] Figure 3 The electron microscope image of the groove structure after filling using the method of comparative example 1 of the present invention is as follows: DETAILED DESCRIPTION

[0026] 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.

[0027] A specific embodiment of the present invention discloses a method for regulating stress in a SiO2 layer based on a silicon-containing polymer, comprising the following steps:

[0028] (1) Under an inert atmosphere, reacting a boron-containing compound and a silicon-containing polymer solution to obtain a boron-modified silicon-containing polymer precursor;

[0029] (2) Adding a catalyst to the boron-modified silicon-containing polymer precursor, mixing, coating a film on a substrate, baking, and thermally annealing to obtain the SiO2 layer.

[0030] Compared with the prior art, the present invention uses boron-containing compounds to modify silicon-containing polymers. The modified silicon-containing polymers can avoid common defects such as pores and micro-phase separation during thermal annealing, improve the density of the dielectric layer, reduce the stress of the SiO2 layer, and improve its electrical performance and reliability. The process of the present invention is simple and easy to mass produce. The method of the present invention can freely regulate the stress of the SiO2 layer over a wide range. The SiO2 layer prepared in the present invention can provide higher performance and longer service life in microelectronic devices, and has good application prospects.

[0031] Specifically, in step (1), the structural formula of the silicon-containing polymer is as follows:

[0032] ;

[0033] Wherein, R1, R2, and R3 are independently selected from one of H, halogen, C1-C6 aliphatic hydrocarbons and their derivatives, C6-C12 aromatic hydrocarbons and their derivatives, and the value of n is 20-1000, for example, 100, 200, 300, 400, 500, 600, 700, 800, 900.

[0034] It should be noted that the silicon-containing polymers of the present invention are all commercially available raw materials or prepared using existing methods.

[0035] Preferably, the weight average molecular weight Mw of the silicon-containing polymer is 2000~50000 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 PDI is 2~10, for example, 3, 4, 5, 6, 7, 8, 9.

[0036] Specifically, the boron-containing compound includes one or more of boric acid, sodium borate, borane complex, trimethyl borate, triborane, tetraborane, boron tetrafluoride, boron trifluoride, boron chloride, boron trichloride, boron dichloride, boron fluoride, sodium borohydride, perboric acid, phenylboric acid, and triphenylboron.

[0037] Preferably, the borane complex comprises a dimethyl sulfide complex of borane.

[0038] Specifically, in step (1), the inert atmosphere includes nitrogen and / or argon.

[0039] Specifically, in step (1), the mass fraction of the silicon-containing polymer in the silicon-containing polymer solution is 1 to 100%, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.

[0040] Preferably, the solvent in the silicon-containing polymer solution is one or more of aromatic compounds, saturated hydrocarbon compounds, chlorinated solvents, esters, and ketones.

[0041] More preferably, the aromatic compound includes one or more of benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, and triethylbenzene;

[0042] The saturated hydrocarbon compound includes one or more of cyclohexane, decahydronaphthalene, dipentene, n-pentane, isopentane, n-hexane, isohexane, isoheptane, n-heptane, n-octane, isooctane, n-nonane, isononane, n-decane, ethylcyclohexane, methylcyclohexane, cyclohexane, and p-menthane;

[0043] The chlorinated solvent includes one or more of chloroform, carbon tetrachloride, and ethylene dichloride;

[0044] The ester includes one or more of n-butyl acetate, n-pentyl acetate, isoamyl acetate, and ethyl acetate;

[0045] The ketone includes methyl isobutyl ketone and / or cyclohexanone.

[0046] Specifically, in step (1), the reaction is as follows: the silicon-containing polymer solution and the boron-containing compound are thoroughly stirred and mixed until no bubbles are generated, then heated to react until bubbles are generated again in the solution, and then stirred to obtain a boron-modified silicon-containing polymer precursor.

[0047] Preferably, the temperature of the heating reaction is 30~120℃, for example, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, and the stirring time is 0.1~24h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h.

[0048] Specifically, in step (1), the molar ratio of the Si element in the silicon-containing polymer to the B element in the boron compound is 0.5:1~20:1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, and 19:1.

[0049] It should be noted that different mixing ratios of boron-containing compounds and silicon-containing polymers will have a significant impact on the properties of the resulting boron-modified silicon-containing polymer precursor, especially the stress performance of the SiO2 layer. As the mixing ratio changes, the stress of the resulting SiO2 layer will also change.

[0050] Specifically, in step (2), the catalyst is a metal catalyst and / or an amine catalyst.

[0051] Preferably, the metal catalyst is an organotin catalyst and / or a palladium catalyst;

[0052] More preferably, the organotin catalyst is one or more of dibutyltin dilaurate, triphenyltin, and stannous octoate;

[0053] The palladium catalyst is one or more of carbon / palladium, palladium propionate and palladium chloride.

[0054] Preferably, the amine catalyst is one or more of aliphatic amine, alicyclic amine, alcohol amine and aromatic amine.

[0055] More preferably, the fatty amine includes one or more of diethylamine, triethylamine and triethylenetetramine;

[0056] The alicyclic amine includes one or more of triethylenediamine, piperazine, piperidine, and morpholine;

[0057] The alcoholamine includes one or more of N,N'-diethylethanolamine, N,N'-dimethylethanolamine, and diisopropanolamine;

[0058] The aromatic amines include one or more of aniline, benzidine, o-phenylenediamine and N,N'-dimethylaniline.

[0059] Specifically, the mass fraction of the catalyst in the boron-modified silicon-containing polymer precursor is 0-1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%.

[0060] Specifically, in step (2), the substrate is a silicon wafer or a glass wafer.

[0061] It should be noted that the bottom surface needs to be pre-treated before coating. Specifically, cleaning, drying and other treatment processes can be selected according to the properties of the material to improve the adhesion of the SiO2 layer.

[0062] Preferably, the coating is selected as a spin coating process, and the spin coating speed is set at 100~12000rpm, for example, 1000rpm, 2000rpm, 3000rpm, 4000rpm, 5000rpm, 6000rpm, 7000rpm, 8000rpm, 9000rpm, 10000rpm, 11000rpm, and the spin coating time is 5~120s, for example, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s.

[0063] It should be noted that the uniformity and appropriate thickness of the film can be ensured at the above-mentioned spin coating speed, and the film can be formed within the above-mentioned spin coating time without causing the solution to evaporate too quickly or become uneven due to too long a spin coating time.

[0064] Specifically, in step (2), the baking temperature is 30-200°C, for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and the baking time is 1-60 min, for example, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min. The purpose of this step is to remove the solvent and prevent the solvent from volatilizing during the subsequent conversion process and affecting the densification and uniformity of the dielectric layer. If the temperature is too low, the solvent will be difficult to volatilize, resulting in defects in the subsequent curing process. If the temperature is too high, it may cause premature conversion of the silicone polymer, affecting the subsequent density.

[0065] Specifically, in step (2), the temperature of the thermal annealing treatment is 100~1000℃, for example, 200℃, 300℃, 400℃, 500℃, 600℃, 700℃, 800℃, 900℃, the heating rate is 1~20℃ / min, for example, 2℃ / min, 4℃ / min, 6℃ / min, 8℃ / min, 10℃ / min, 12℃ / min, 14℃ / min, 16℃ / min, 18℃ / min, and the total time of the thermal annealing treatment is 5~300min, for example, 30min, 60min, 90min, 120min, 150min, 180min, 210min, 240min, 270min.

[0066] Preferably, in step (2), the thermal annealing treatment further includes a constant temperature zone.

[0067] The holding time of the constant temperature zone is 1 to 80 minutes, for example, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, or 70 minutes.

[0068] It should be noted that the constant temperature zone refers to the period of time during which the target temperature is maintained after the temperature is heated to the target temperature during the thermal annealing process.

[0069] Preferably, in step (2), the atmosphere in the thermal annealing treatment is one or more of oxygen, air, nitrogen and water vapor.

[0070] In another specific embodiment of the present invention, a microelectronic device is disclosed, comprising a SiO2 layer obtained by the above method.

[0071] Preferably, the microelectronic device includes one of a memristor, a transistor, and a solar cell.

[0072] The technical solution of the present invention is further explained below in conjunction with specific embodiments.

[0073] Example 1

[0074] The SiO2 layer stress control method based on the silicon-containing polymer of this embodiment includes the following steps:

[0075] (1) Under nitrogen atmosphere, a dimethyl sulfide complex of borane and a 10% by mass n-butyl ether solution of a silicon-containing polymer were mixed at a silicon-boron molar ratio of 20:1, and stirred at room temperature for 30 minutes. The structure of the silicon-containing polymer was such that R1, R2, and R3 were all H atoms. After the solution was free of bubbles, it was heated at 50°C. When bubbles were generated again, the solution was stirred for 1 hour to obtain a boron-modified silicon-containing polymer precursor.

[0076] Among them, the weight average molecular weight of perhydropolysiloxane is 4500 g / mol and the PDI is 5.5;

[0077] (2) Add 0.1% by mass of dibutyltin dilaurate as a catalyst to the boron-modified silicon-containing polymer precursor, mix thoroughly, and then spin-coat on a silicon wafer at a spin-coating speed of 1000 rpm for 60 seconds. After heating and baking at 120°C for 5 minutes to volatilize the solvent, transfer to a high-temperature furnace and heat at a rate of 10°C / min to 600°C, and keep warm for 2 hours to obtain the SiO2 layer.

[0078] The infrared spectrum of the boron-modified silicon-containing polymer precursor prepared in this example is as follows: Figure 1 As shown, 1375cm -1 The characteristic absorption peak of BN is shown in Fig.

[0079] Example 2

[0080] The stress control method of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (1), the dimethyl sulfide complex of borane and a 10% by mass n-butyl ether solution of silicon-containing polymer are mixed at a silicon-boron element molar ratio of 10:1, heated at 30°C, and stirred for 24 hours;

[0081] In step (2), the mass fraction of the catalyst is 1%.

[0082] Example 3

[0083] The stress control method of the SiO2 layer based on the silicon-containing polymer of this embodiment is the same as that of Example 1, except that, in step (1), the dimethyl sulfide complex of borane and the n-butyl ether solution of the silicon-containing polymer with a mass fraction of 10% are mixed at a silicon-boron element molar ratio of 5:1, heated at 120°C, and stirred for 1 minute;

[0084] In step (2), the catalyst is N,N'-dimethylethanolamine.

[0085] Example 4

[0086] The stress control method of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (1), the dimethyl sulfide complex of borane and a 1% by mass n-butyl ether solution of silicon-containing polymer are mixed at a silicon-boron element molar ratio of 2:1;

[0087] In step (2), no catalyst is added.

[0088] Example 5

[0089] The stress control method of the SiO2 layer based on the silicon-containing polymer of this embodiment is the same as that of Example 1, except that, in step (1), the dimethyl sulfide complex of borane and the n-butyl ether solution of the silicon-containing polymer with a mass fraction of 10% are mixed at a silicon-boron element molar ratio of 1:1.

[0090] Example 6

[0091] The stress control method of the SiO2 layer based on the silicon-containing polymer of this embodiment is the same as that of Example 1, except that, in step (1), the dimethyl sulfide complex of borane and the n-butyl ether solution of the silicon-containing polymer with a mass fraction of 10% are mixed at a silicon-boron element molar ratio of 0.5:1.

[0092] Example 7

[0093] The method for controlling stress of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (1), the dimethyl sulfide complex of borane is replaced by boron trichloride.

[0094] Example 8

[0095] The method for controlling stress of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (1), the dimethyl sulfide complex of borane is replaced by trimethyl borate.

[0096] Example 9

[0097] The method for controlling stress of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (1), the dimethyl sulfide complex of borane is replaced by triborane.

[0098] Example 10

[0099] The stress control method of the SiO2 layer based on the silicon-containing polymer in this embodiment is the same as that in Example 1, except that in step (1), the silicon-containing polymer is replaced by a silicon-containing polymer in which R1 is a methyl group, R2 and R3 are hydrogen atoms, and the weight-average molecular weight is 3300 g / mol and the PDI is 4.5.

[0100] Example 11

[0101] The SiO2 layer stress control method based on the silicon-containing polymer in this embodiment is the same as that in Example 1, except that the silicon-containing polymer is replaced by a silicon-containing polymer in which R1 is a vinyl group, R2 is a methyl group, and R3 is a hydrogen atom, and the weight-average molecular weight is 4200 and the PDI is 3.9.

[0102] Example 12

[0103] The method for controlling stress of a SiO2 layer based on a silicon-containing polymer in this embodiment is the same as that in Example 1, except that n-butyl ether is replaced by ethyl acetate.

[0104] Example 13

[0105] The method for controlling stress of a SiO2 layer based on a silicon-containing polymer in this embodiment is the same as that in Example 1, except that n-butyl ether is replaced by toluene.

[0106] Example 14

[0107] The stress control method of the SiO2 layer based on the silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (2), the SiO2 layer is obtained by transferring the SiO2 layer to a high-temperature furnace and heating the temperature at a rate of 10°C / min to 800°C and keeping the temperature for 2 hours.

[0108] Comparative Example 1

[0109] The method for controlling stress of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (1), the dimethyl sulfide complex of borane is not added.

[0110] Comparative Example 2

[0111] The method for controlling stress of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 10, except that, in step (1), the dimethyl sulfide complex of borane is not added.

[0112] Comparative Example 3

[0113] The method for controlling stress of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 11, except that, in step (1), the dimethyl sulfide complex of borane is not added.

[0114] Comparative Example 4

[0115] The stress control method of the SiO2 layer based on the silicon-containing polymer of this embodiment is the same as that of Example 1, except that, in step (1), the dimethyl sulfide complex of borane and the n-butyl ether solution of perhydropolysilazane with a mass fraction of 10% are mixed at a silicon-boron element molar ratio of 30:1.

[0116] Comparative Example 5

[0117] The stress control method of SiO2 layer based on silicon-containing polymer in this embodiment is the same as that in Example 1, except that, in step (1), the heating reaction temperature is 20°C and the stirring time is 48 hours.

[0118] Test Example 1

[0119] The thickness of the films before annealing in step (2) of Examples 1-14 and Comparative Examples 1-5 was measured using an ellipsometer (M-2000V, JA Woollam), and their curvature radius R1 was measured using a thin film stress meter (Toho FLX-2320-S). The thickness and curvature radius R2 of the SiO2 layer formed after annealing were again measured. Based on the changes in film thickness and curvature before and after annealing, the shrinkage rate and stress during the film conversion process were calculated. The results are shown in Table 1.

[0120] Shrinkage rate = (thickness before annealing - thickness after annealing) / thickness before annealing × 100%;

[0121] The stress calculation formula is as follows:

[0122] ;

[0123] 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).

[0124] ;

[0125] Note: In Table 1, negative values ​​represent compressive stress and positive values ​​represent tensile stress.

[0126] Comparing Comparative Example 1 with Example 1, Comparative Example 2 with Example 10, and Comparative Example 3 with Example 11, the stress of the SiO2 layer obtained without B doping is tensile stress. As can be seen from the comparison of Examples 1-6, as the B doping amount increases, that is, the Si / B ratio decreases, the stress of the SiO2 layer decreases, and the stress of the SiO2 layer is freely regulated. In addition, Example 3 shows that after the Si / B ratio is less than 5, the stress state of the dielectric layer changes from tensile stress to compressive stress, and the stress increases as the Si / B ratio decreases. In addition, it can be seen from the Examples and Comparative Examples that the type of solvent, holding temperature, and reaction conditions have a certain influence on the shrinkage rate and stress of the dielectric layer. Overall, a larger shrinkage rate will show tensile stress, and a smaller shrinkage rate may show compressive stress.

[0127] The shrinkage rate of the SiO2 layer prepared by the present invention is 14.5-18.9%, and the stress is -29.7-66.3 MPa.

[0128] Test Example 2

[0129] The methods of Example 3 and Comparative Example 1 were respectively applied to the trench structure filling. The trench structure filled was 500nm deep, 100nm wide, and 200nm periodic. The specific filling process was as follows: the boron-modified silicon-containing polymer precursor prepared in Example 3 and Comparative Example 1 was spin-coated on the trench wafer (silicon wafer), and then the baking and high-temperature annealing steps as described in Example 3 were performed in sequence to complete the filling of the trench structure. The filling effect of Example 3 is as follows: Figure 2 As shown in Figure 1, due to the low stress, there is no obvious separation, pores and other defects in the filling layer. Figure 3 As shown in Figure 3, there is an obvious interface separation phenomenon, which is caused by the excessively high stress.

[0130] The present invention carried out the above test on other embodiments and comparative examples, and the results were basically the same. Due to limited space, they are not listed one by one.

[0131] 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. A method for regulating stress in a SiO2 layer based on a silicon-containing polymer, characterized in that: The steps include: (1) reacting a solution of a boron-containing compound and a silicon-containing polymer under an inert atmosphere to obtain a boron-modified silicon-containing polymer precursor, wherein the molar ratio of the Si element in the silicon-containing polymer to the B element in the boron-containing compound is 0.5:1 to 20:1; (2) adding a catalyst to the boron-modified silicon-containing polymer precursor, mixing, coating a film on a substrate, baking, and thermally annealing to obtain the SiO2 layer; Wherein, in step (2), the catalyst is a metal catalyst and / or an amine catalyst.

2. The method for controlling stress of SiO2 layer based on silicon-containing polymer according to claim 1, characterized in that: In step (1), the structural formula of the silicon-containing polymer is as follows: ； Wherein, R1, R2, and R3 are independently selected from one of H, halogen, C1-C6 aliphatic hydrocarbon, and C6-C12 aromatic hydrocarbon, and the value of n is 20-1000.

3. The method for controlling stress of SiO2 layer based on silicon-containing polymer according to claim 2, characterized in that: The weight average molecular weight Mw of the silicon-containing polymer is 2000-50000 g / mol, and the PDI is 2-10.

4. The method for controlling stress in a SiO2 layer based on a silicon-containing polymer according to any one of claims 1 to 3, wherein: In step (1), the boron-containing compound includes one or more of boric acid, sodium borate, borane complex, trimethyl borate, triborane, tetraborane, boron tetrafluoride, boron trifluoride, boron chloride, boron trichloride, boron dichloride, boron fluoride, sodium borohydride, perboric acid, phenylboric acid, and triphenylboron.

5. The method for controlling stress in a SiO2 layer based on a silicon-containing polymer according to any one of claims 1 to 3, wherein: In step (1), the mass fraction of the silicon-containing polymer in the silicon-containing polymer solution is 1 to 100%.

6. The method for controlling stress of SiO2 layer based on silicon-containing polymer according to claim 1, characterized in that: In step (1), the reaction is specifically as follows: the silicon-containing polymer solution and the boron-containing compound are fully stirred and mixed until no bubbles are generated, then heated to react until bubbles are generated again in the solution, and then stirred to obtain a boron-modified silicon-containing polymer precursor.

7. The method for controlling stress of SiO2 layer based on silicon-containing polymer according to claim 6, characterized in that: The heating reaction temperature is 30~120℃, and the stirring time is 0.1~24h.

8. The method for controlling stress of SiO2 layer based on silicon-containing polymer according to claim 1, characterized in that: In step (2), the mass fraction of the catalyst in the boron-modified silicon-containing polymer precursor is 0-1%.

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