Preparation process of n-propyl cyclopentadienyl tris (dimethylamino) zirconium and film-forming preparation method of n-propyl cyclopentadienyl tris (dimethylamino) zirconium
By preparing a composition of n-Pyrylcyclopentadienyltris(dimethylamine)zirconium with materials such as pentamethylcyclopentadienyl, toluene or cycloheptadienyl, the problems of lowering vapor pressure and increasing viscosity during the deposition process are solved, and efficient thin film deposition performance is achieved.
Patent Information
- Application Number
- CN202411617223.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-13
- Publication Date
- 2025-03-04
AI Technical Summary
The existing n-propylcyclopentadienyl tris(dimethylamino)zirconium has reduced vapor pressure and increased viscosity during the deposition process, resulting in contamination of the deposition equipment and affecting the thin film deposition performance.
By preparing a composition of n-Pyrylcyclopentadiene and tetra(dimethylamine)zirconium, a precursor composition is formed with n-propylcyclopentadiene tris(dimethylamine)zirconium, by using materials such as pentamethylcyclopentadiene, toluene or cycloheptadiene to form a precursor composition, thereby reducing the viscosity of the material and improving the film deposition performance.
It effectively reduces the viscosity of the material, improves the film deposition performance of n-propylcyclopentadienyl tris(dimethylamino)zirconium, reduces the pollution of the deposition equipment, and improves the stability of the process.
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Figure CN119552199A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of chemical engineering, and in particular to a preparation process of n-propylcyclopentadienyltri(dimethylamino)zirconium and a preparation method of a film-forming precursor composition. Background Art
[0002] Zirconia film has become an important component of the MIM structure of storage capacitors in dynamic random access memory (DRAM) because of its high dielectric constant. Its manufacturing process uses high-precursor compounds with suitable vapor pressure as raw materials and is achieved through chemical vapor deposition (CVD) or atomic layer deposition (ALD) technology.
[0003] Zirconium tetrachloride, as the simplest inorganic zirconium-containing compound, is used for zirconium oxide thin film deposition. However, it is difficult to use as a precursor due to its solid state at room temperature and its chloride ion corrosiveness. Subsequently, the research on zirconium-containing precursors turned to the field of metal organic precursors, such as alkoxy compounds, alkylamine compounds and cyclopentadienyl compounds. Among these compounds, cyclopentadienyl tris(dimethylamino) zirconium CpZr replaced tetra(methylethylamino) zirconium TEMAZr because of its higher thermal stability and high growth rate and became the mainstream precursor in the process of DRAM deposition of zirconium oxide, and was widely used by semiconductor manufacturers.
[0004] As DRAM manufacturing has higher requirements for aspect ratio, the thermal stability requirements for precursor chemicals have also increased. n-propylcyclopentadienyl tris(dimethylamino)zirconium is the future development direction of zirconium-containing precursors because its n-propyl group participates in coordination during the deposition process, improving reaction stability. However, due to its reduced vapor pressure and increased viscosity, it leads to contamination of deposition equipment during the deposition process. Summary of the invention
[0005] The purpose of the present invention is to provide a preparation process of n-propylcyclopentadienyltri(dimethylamino)zirconium and a preparation method of a film-forming precursor composition to improve its thin film deposition performance.
[0006] The technical solution of the present invention:
[0007] The invention discloses a process for preparing n-propylcyclopentadienyl tris(dimethylamino)zirconium, comprising the following two steps: step 1, preparation of n-propylcyclopentadiene: using bromocyclopentadiene and a mixture of propylmagnesium bromide as raw materials for reaction, filtering out solid impurities after the reaction, and performing reduced pressure distillation to obtain a n-propylcyclopentadiene product; step 2, preparation of n-propylcyclopentadiene tris(dimethylamino)zirconium: using n-propylcyclopentadiene and a tetrakis(dimethylamino)zirconium solution as raw materials for reaction, and performing reduced pressure distillation to obtain n-propylcyclopentadiene tris(dimethylamino)zirconium after the reaction.
[0008] Preferably, the propylmagnesium bromide mixture is a mixed solution of propylmagnesium bromide and tetrahydrofuran, the concentration of tetrahydrofuran in the mixed solution is 2 mol / L, and the balance is n-propylmagnesium bromide;
[0009] The molar ratio of bromocyclopentadiene to n-propylmagnesium bromide is 0.5 to 2:1;
[0010] Step 1: The reaction time is 14-18 hours and the reaction temperature is -30 to 50°C;
[0011] The pressure of reduced pressure distillation is -0.095MPa and the temperature is 70~100℃.
[0012] Preferably, the tetrakis(dimethylamino)zirconium solution is a toluene solution of tetrakis(dimethylamino)zirconium, and the mass concentration of tetrakis(dimethylamino)zirconium is 5% to 10%;
[0013] The molar ratio of tetrakis(dimethylamino)zirconium to n-propylcyclopentadiene is 0.8 to 1.5:1;
[0014] The reaction time of step 2 is 8 to 20 hours, and the reaction temperature is -20 to 80°C;
[0015] The pressure of reduced pressure distillation is 10-200 Pa and the temperature is 70-80°C.
[0016] Preferably, in step 1, the molar ratio of cyclopentadiene to n-propylmagnesium bromide is 1.2:1; and the reaction temperature is -10 to 25°C.
[0017] Preferably, in step 2, the molar ratio of tetrakis(dimethylamino)zirconium to n-propylcyclopentadiene is 1:1.
[0018] A method for preparing a film-forming precursor composition comprises: using n-propylcyclopentadienyltri(dimethylamino)zirconium prepared by a n-propylcyclopentadienyltri(dimethylamino)zirconium preparation process, and forming a precursor composition with n-propylcyclopentadienyltri(dimethylamino)zirconium and pentamethylcyclopentadiene, toluene or cycloheptadiene, wherein the mass content of n-propylcyclopentadienyltri(dimethylamino)zirconium in the precursor composition is 10% to 90%.
[0019] Preferably, the precursor composition forms an oxide film, a nitride film or a nitride oxide film, and the film deposition method is chemical vapor deposition or atomic layer deposition.
[0020] Preferably, the chemical vapor deposition is free chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition or plasma enhanced cyclic chemical vapor deposition;
[0021] The atomic layer deposition is plasma enhanced atomic layer deposition.
[0022] Preferably, the method comprises the following steps:
[0023] S1. placing one or more substrates into a reaction chamber;
[0024] S2, introducing the precursor composition into a reaction chamber through a carrier gas, wherein the temperature of the reaction chamber is 50-110° C., and the carrier gas is nitrogen, argon, helium or neon or a mixture thereof;
[0025] S3, the precursor composition reacts with the substrate surface in the reaction chamber to form a thin film;
[0026] S4, introducing one or both of an oxygen source and a nitrogen source into the reaction chamber, or introducing into the reaction chamber via a carrier gas, wherein the carrier gas is nitrogen, argon, helium or neon and a mixture thereof;
[0027] S5, one or both of the oxygen source and the nitrogen source react with the organic groups remaining on the surface of the substrate to form a complete oxide film, nitride film or oxynitride film.
[0028] Preferably, the oxygen source includes oxygen, ozone and water.
[0029] Nitrogen sources include ammonia, nitrous oxide, nitric oxide and nitrogen dioxide.
[0030] The substrate is single crystal silicon or polycrystalline silicon.
[0031] Beneficial effects of the present invention:
[0032] 1) Using cyclopentadiene and propylmagnesium bromide as raw materials to prepare n-propylcyclopentadiene, the raw material sources are wide, the cost is low, and the reaction safety is high.
[0033] 2) Using materials such as pentamethylcyclopentadiene, toluene, cycloheptadiene and n-propylcyclopentadienyl tris(dimethylamino)zirconium to form a precursor composition can reduce the viscosity of the material and improve its thin film deposition performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] Figure 1 This is a TEM electron microscope image of the sediment of the present invention. DETAILED DESCRIPTION
[0035] Step 1, preparation of n-propyl cyclopentadiene: prepared from brominated cyclopentadiene and propyl magnesium bromide as raw materials. The molar ratio of brominated cyclopentadiene to n-propyl magnesium bromide is 0.5-2:1, preferably 1.2:1. Propyl magnesium bromide uses a 2.0M tetrahydrofuran solution. The reaction temperature is -30-50°C, preferably -10-25°C. After the reaction is completed, the solid impurities are removed by filtration, and the pure n-propyl cyclopentadiene product is obtained by reduced pressure distillation.
[0036] Step 2, preparation of n-propylcyclopentadiene tris(dimethylamino)zirconium: n-propylcyclopentadiene and tetrakis(dimethylamino)zirconium are used as raw materials. The molar ratio of tetrakis(dimethylamino)zirconium to n-propylcyclopentadiene is 0.8 to 1.5:1, preferably 1:1. The reaction temperature is -20 to 80°C. After the reaction is completed, the pure n-propylcyclopentadiene tris(dimethylamino)zirconium is obtained by vacuum distillation.
[0037] The preparation method of the film-forming precursor composition is as follows: n-propylcyclopentadiene tris(dimethylamino)zirconium is fully mixed with pentamethylcyclopentadiene, toluene or cycloheptadiene to form a precursor composition, wherein the mass ratio of n-propylcyclopentadiene tris(dimethylamino)zirconium in the precursor composition is 10% to 90%.
[0038] Film forming process: the precursor composition is used to form an oxide film / nitride film / nitride oxide film; the film deposition method is chemical vapor deposition CVD / atomic layer deposition ALD.
[0039] The deposition process includes the following steps:
[0040] S1. providing one or more surfaces of the substrate to a reaction chamber;
[0041] S2, introducing the precursor composition into the reaction chamber through a carrier gas, the temperature of the pre-reaction chamber is 50-110° C., and the carrier gas is nitrogen / argon / helium / neon or a mixture thereof;
[0042] S3, the precursor composition reacts with the substrate surface in the reaction chamber to form a thin film;
[0043] S4, introducing an oxygen / nitrogen source into the chamber or introducing the oxygen / nitrogen source into the chamber through a carrier gas, wherein the oxygen / nitrogen source includes oxygen / ozone / water / ammonia / nitrous oxide / nitric oxide / nitrogen dioxide, and the carrier gas is nitrogen / argon / helium / neon or a mixture thereof;
[0044] S5. The oxygen / nitrogen source reacts with the organic groups remaining on the surface of the substrate to form a complete oxide / nitride film.
[0045] Example of preparation process of n-propylcyclopentadienyl tris(dimethylamino)zirconium
[0046] Preparation Example 1 of n-propylcyclopentadienyltri(dimethylamino)zirconium
[0047] Step 1, preparation of n-propylcyclopentadiene: 17.6 g of bromocyclopentadiene and 50 mL of 2.0 M n-propylmagnesium bromide solution (tetrahydrofuran solvent) were mixed in a 250 mL flask at -10°C and reacted for 16 hours at this temperature. After the reaction was completed, solid impurities were removed by filtration, and 9.20 g of pure n-propylcyclopentadiene liquid product was obtained by vacuum distillation with a yield of 85.2%.
[0048] Step 2, preparation of n-propylcyclopentadiene tris(dimethylamino)zirconium: 20.0 g of tetrakis(dimethylamino)zirconium solid was dissolved in 200 g of toluene solvent, and 8.0 g of n-propylcyclopentadiene was added. The reaction temperature was 80° C. After the reaction was completed, the mixture was heated to 80° C. and distilled under reduced pressure at 100 Pa to obtain 19.60 g of light yellow n-propylcyclopentadiene tris(dimethylamino)zirconium liquid, with a yield of 80%.
[0049] Preparation Example 2 of n-propylcyclopentadienyltri(dimethylamino)zirconium
[0050] Step 1, preparation of n-propylcyclopentadiene: 17.6 g of bromocyclopentadiene and 50 mL of 2.0 M n-propylmagnesium bromide solution (tetrahydrofuran solvent) were mixed in a 250 mL flask at 25° C. and reacted at this temperature for 20 hours. After the reaction was completed, solid impurities were removed by filtration, and 7.6 g of pure n-propylcyclopentadiene liquid product was obtained by vacuum distillation with a yield of 70.3%.
[0051] Step 2, preparation of n-propylcyclopentadiene tris(dimethylamino)zirconium: 20.0 g of tetrakis(dimethylamino)zirconium solid was dissolved in 340 g of toluene solvent, and 7.0 g of n-propylcyclopentadiene was added. The reaction temperature was 80° C. After the reaction was completed, the mixture was heated to 70-80° C. and distilled under reduced pressure at 100 Pa to obtain 10.7 g of light yellow n-propylcyclopentadiene tris(dimethylamino)zirconium liquid, with a yield of 49.8%.
[0052] Preparation Example 3 of n-propylcyclopentadienyltri(dimethylamino)zirconium
[0053] Step 1, preparation of n-propylcyclopentadiene: 17.6 g of bromocyclopentadiene and 50 mL of 2.0 M n-propylmagnesium bromide solution (tetrahydrofuran solvent) were mixed in a 250 mL flask at 0°C and reacted at this temperature for 20 hours. After the reaction was completed, solid impurities were removed by filtration, and 8.1 g of pure n-propylcyclopentadiene liquid product was obtained by vacuum distillation with a yield of 75.0%.
[0054] Step 2, preparation of n-propylcyclopentadiene tris(dimethylamino)zirconium: 20.0 g of tetrakis(dimethylamino)zirconium solid was dissolved in 170 g of toluene solvent, and 7.0 g of n-propylcyclopentadiene was added. The reaction temperature was 40° C. After the reaction was completed, the mixture was heated to 70-80° C. and distilled under reduced pressure at 100 Pa to obtain 8.18 g of light yellow n-propylcyclopentadiene tris(dimethylamino)zirconium liquid, with a yield of 33.1%.
[0055] Preparation Example 4 of n-propylcyclopentadienyltri(dimethylamino)zirconium
[0056] Step 1, preparation of n-propylcyclopentadiene: 162.0 g of bromocyclopentadiene and 500 mL of 2.0 M n-propylmagnesium bromide solution (tetrahydrofuran solvent) were mixed in a 1 L flask at -10°C and reacted at this temperature for 20 hours. After the reaction was completed, solid impurities were removed by filtration, and 84.5 g of pure n-propylcyclopentadiene liquid product was obtained by vacuum distillation with a yield of 78.2%.
[0057] Step 2, preparation of n-propylcyclopentadiene tris(dimethylamino)zirconium: 200.0 g of tetrakis(dimethylamino)zirconium solid was dissolved in 2 kg of toluene solvent, and 80.0 g of n-propylcyclopentadiene was added. The reaction temperature was 60° C. After the reaction was completed, the mixture was heated to 70-80° C. and distilled under reduced pressure at 100 Pa to obtain 164.1 g of light yellow n-propylcyclopentadiene tris(dimethylamino)zirconium liquid, with a yield of 66.8%.
[0058] Film Formation Preparation Method Example
[0059] Film Forming Example 1
[0060] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0061] The deposition process includes the following steps:
[0062] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0063] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: pentamethylcyclopentadiene = 10%:90%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The temperature of the reaction chamber is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0064] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0065] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0066] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0067] (6) Repeat the above operation to form 100 layers of zirconium oxide film. The TEM electron microscope image of the deposit is as follows: Figure 1 As shown, the test GPC is
[0068] Film Forming Example 2
[0069] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0070] The deposition process includes the following steps:
[0071] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0072] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: pentamethylcyclopentadiene = 30%:70%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The temperature of the reaction chamber is 110° C., and the carrier gas is argon and helium. The gas is ventilated for 5 seconds.
[0073] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0074] (4) introducing the prepared nitric oxide into the reaction chamber through argon and helium, and ventilating for 5S;
[0075] (5) Nitric oxide reacts with residual organic groups on the surface to form a complete nitride film at a reaction temperature of 350°C;
[0076] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0077] Film Forming Example 3
[0078] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0079] The deposition process includes the following steps:
[0080] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0081] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: pentamethylcyclopentadiene = 60%:40%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The temperature of the reaction chamber is 50° C., the carrier gas is nitrogen, and the ventilation is continued for 5 seconds;
[0082] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0083] (4) introducing the prepared ozone and ammonia into the reaction chamber via nitrogen and ventilating for 5 seconds;
[0084] (5) Ozone and ammonia react with the organic groups remaining on the surface to form a complete nitrogen oxide film at a reaction temperature of 350°C;
[0085] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0086] Film Forming Example 4
[0087] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0088] The deposition process includes the following steps:
[0089] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0090] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: pentamethylcyclopentadiene = 90%:10%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The temperature of the reaction chamber is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0091] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0092] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0093] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0094] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0095] Film Forming Example 5
[0096] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0097] The deposition process includes the following steps:
[0098] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0099] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: cycloheptadiene = 10%:90%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The temperature of the reaction chamber is 100° C., and the carrier gas is an argon mixed gas. The gas is ventilated for 5 seconds.
[0100] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0101] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0102] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0103] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0104] Film Forming Example 6
[0105] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0106] The deposition process includes the following steps:
[0107] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0108] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium:cycloheptadiene=30%:70%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The reaction chamber temperature is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0109] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0110] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0111] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0112] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0113] Examples 4-15 are the GPC (growth per cycle) values of zirconium oxide films deposited using three precursor compositions. From the table, it can be seen that the deposition thickness of the three precursor compositions is stable at high temperatures, among which cycloheptadiene has the best deposition stability.
[0114] Film Forming Example 7
[0115] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0116] The deposition process includes the following steps:
[0117] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0118] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium:cycloheptadiene=60%:40%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The reaction chamber temperature is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0119] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0120] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0121] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0122] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0123] Film Forming Example 8
[0124] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0125] The deposition process includes the following steps:
[0126] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0127] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium:cycloheptadiene=90%:10%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The temperature of the reaction chamber is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0128] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0129] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0130] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0131] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0132] Film Forming Example 9
[0133] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0134] The deposition process includes the following steps:
[0135] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0136] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: toluene = 10%:90%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The reaction chamber temperature is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0137] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0138] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0139] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0140] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0141] Film Forming Example 10
[0142] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0143] The deposition process includes the following steps:
[0144] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0145] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: toluene = 30%:70%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The reaction chamber temperature is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0146] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0147] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0148] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0149] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0150] Film Forming Example 11
[0151] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0152] The deposition process includes the following steps:
[0153] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0154] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: toluene = 60%:40%) was vaporized, it was introduced into the reaction chamber through a carrier gas. The reaction chamber temperature was 100° C., the carrier gas was argon, and the gas was ventilated for 5 seconds;
[0155] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0156] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0157] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0158] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0159] Film Forming Example 12
[0160] The above products are mixed with corresponding solvents in a certain proportion to form a precursor composition, see Table 1.
[0161] The deposition process includes the following steps:
[0162] (1) Providing a polycrystalline silicon (111) substrate into a reaction chamber;
[0163] (2) After the precursor composition (n-propylcyclopentadiene tris(dimethylamino)zirconium: toluene = 90%:10%) is vaporized, it is introduced into the reaction chamber through a carrier gas. The reaction chamber temperature is 100° C., the carrier gas is argon, and the gas is ventilated for 5 seconds;
[0164] (3) the precursor composition reacts with the substrate surface in the reaction chamber at a reaction temperature of 350° C.
[0165] (4) introducing the prepared ozone into the reaction chamber via argon gas and ventilating for 5 seconds;
[0166] (5) Ozone reacts with residual organic groups on the surface to form a complete oxide film at a reaction temperature of 350°C;
[0167] (6) Repeat the above operation to form 100 layers of zirconium oxide film, and test GPC:
[0168] Film forming examples 1-12 are the GPC (growth per cycle) values of zirconium oxide thin films deposited by the three precursor compositions. From the table, it can be seen that the deposition thickness of the three precursor compositions is stable at high temperature, among which cycloheptadiene has the best deposition stability.
[0169] Table 1
[0170]
[0171]
Claims
1. A process for preparing n-propylcyclopentadienyl tris(dimethylamino)zirconium, characterized in that: It includes the following two steps: Step 1, preparation of n-propylcyclopentadiene: reacting a mixture of bromocyclopentadiene and n-propylmagnesium bromide as raw materials, filtering out solid impurities after the reaction, and performing reduced pressure distillation to obtain the n-propylcyclopentadiene product; Step 2, preparation of n-propylcyclopentadiene tris(dimethylamino)zirconium; reacting n-propylcyclopentadiene and tetrakis(dimethylamino)zirconium solution as raw materials, and after the reaction, performing reduced pressure distillation to obtain n-propylcyclopentadiene tris(dimethylamino)zirconium.
2. The process for preparing n-propylcyclopentadienyl tris(dimethylamino)zirconium according to claim 1, characterized in that: The n-propyl magnesium bromide mixture is a mixed solution of n-propyl magnesium bromide and tetrahydrofuran, wherein the concentration of tetrahydrofuran in the mixed solution is 2 mol / L, and the remainder is n-propyl magnesium bromide; The molar ratio of bromocyclopentadiene to n-propylmagnesium bromide is 0.5 to 2:1; Step 1: The reaction time is 14-18 hours and the reaction temperature is -30 to 50°C; The pressure of reduced pressure distillation is -0.095MPa and the temperature is 70~100℃.
3. The process for preparing n-propylcyclopentadienyl tris(dimethylamino)zirconium according to claim 1, characterized in that: The tetrakis(dimethylamino)zirconium solution is a toluene solution of tetrakis(dimethylamino)zirconium, and the mass concentration of tetrakis(dimethylamino)zirconium is 5% to 10%; The molar ratio of tetrakis(dimethylamino)zirconium to n-propylcyclopentadiene is 0.8 to 1.5:1; The reaction time of step 2 is 8 to 20 hours, and the reaction temperature is -20 to 80°C; The pressure of reduced pressure distillation is 10-200 Pa and the temperature is 70-80°C.
4. The process for preparing n-propylcyclopentadienyl tris(dimethylamino)zirconium according to claim 1, characterized in that: In step 1, the molar ratio of bromocyclopentadiene to n-propylmagnesium bromide is 1.2:1; and the reaction temperature is -10 to 25°C.
5. The process for preparing n-propylcyclopentadienyl tris(dimethylamino)zirconium according to claim 1, characterized in that: In step 2, the molar ratio of tetrakis(dimethylamino)zirconium to n-propylcyclopentadiene is 1:
1.
6. A film preparation method, using the n-propylcyclopentadienyltri(dimethylamino)zirconium prepared by the n-propylcyclopentadienyltri(dimethylamino)zirconium preparation process described in claim 1, characterized in that: The precursor composition is formed by using n-propylcyclopentadiene tris(dimethylamino)zirconium and pentamethylcyclopentadiene, toluene or cycloheptadiene. The mass content of n-propylcyclopentadiene tris(dimethylamino)zirconium in the precursor composition is 10% to 90%.
7. The film forming method according to claim 6, characterized in that: The precursor composition forms an oxide film, a nitride film or a nitride oxide film, and the film deposition method is chemical vapor deposition or atomic layer deposition.
8. The film forming method according to claim 7, characterized in that: The chemical vapor deposition is free chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition or plasma enhanced cyclic chemical vapor deposition; The atomic layer deposition is plasma enhanced atomic layer deposition.
9. The film forming method according to claim 8, characterized in that: The steps include: S1. placing one or more substrates into a reaction chamber; S2, introducing the precursor composition into the reaction chamber through a carrier gas, the temperature of the reaction chamber is 50-110° C., and the carrier gas is nitrogen, argon, helium or neon and a mixed gas thereof; S3, the precursor composition reacts with the substrate surface in the reaction chamber to form a thin film; S4, introducing one or both of an oxygen source and a nitrogen source into the reaction chamber, or introducing into the reaction chamber via a carrier gas, wherein the carrier gas is nitrogen, argon, helium or neon or a mixture thereof; S5, one or both of the oxygen source and the nitrogen source react with the organic groups remaining on the surface of the substrate to form a complete oxide film, nitride film or oxynitride film.
10. The film forming method according to claim 9, characterized in that: The oxygen source includes oxygen, ozone and water; Nitrogen sources include ammonia, nitrous oxide, nitric oxide, and nitrogen dioxide; The substrate is polycrystalline silicon.