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CN117737705B - Film forming method of silicon oxide film - Google Patents

Film forming method of silicon oxide film Download PDF

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CN117737705B
CN117737705B CN202311781167.1A CN202311781167A CN117737705B CN 117737705 B CN117737705 B CN 117737705B CN 202311781167 A CN202311781167 A CN 202311781167A CN 117737705 B CN117737705 B CN 117737705B
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diisopropylamine
oxide film
silicon oxide
purity
vapor deposition
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CN117737705A (en
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毛鸿超
董岐
李禾禾
曲胜伟
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Dalian Hengkun New Material Co ltd
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Abstract

The invention relates to the technical field of silicon materials, and discloses a film forming method of a silicon oxide film, which uses ruthenium loaded molecular sieve catalyst to catalyze diisopropylamine and phenylsilane to carry out reaction and rectification purification, so as to obtain high-purity diisopropylamine silane, wherein the gas phase purity reaches 98.7-99.6%. Then, the silicon oxide film is obtained by taking the silicon oxide film as a silicon source through a plasma chemical vapor deposition method, wherein the content of S i elements and O elements is high, and the content of hetero element C is low and is only 8.92-15.19%. Provides a brand new strategy for preparing the diisopropylamine silane with high purity and the silicon oxide film with high performance.

Description

Film forming method of silicon oxide film
Technical Field
The invention relates to the technical field of silicon materials, in particular to a film forming method of a silicon oxide film.
Background
The silicon compound has unique physical and chemical properties, and can be widely applied to the fields of electrochemical energy, super-hydrophobic materials, microelectronics and the like, and the preparation of the high-purity silicon compound by adopting the novel high-efficiency method is a research hot spot, for example, patent CN115260223B discloses that di (hexamethyldisilazide) calcium or di (hexamethyldisilazide) strontium is used as a chlorine-free catalyst to catalyze the dehydrogenation coupling reaction of monosilane and diisopropylamine to prepare diisopropylamine silane. The silicon oxide film has good wear resistance, insulativity, chemical resistance and light transmittance, is widely applied to the fields of microelectronics, corrosion resistance and the like, the current method for preparing the silicon oxide film mainly takes diisopropylamine silane, hexamethyldisiloxane and the like as silicon sources, and is prepared by a vapor deposition method, an atomic layer deposition method and the like, the patent CN101078109B discloses that an organic aminosilane precursor is used for depositing the silicon oxide film on a substrate by a CVD method, and the purity of the silicon precursor has great influence on the purity and the performance of the silicon oxide film. The invention aims to prepare a silicon oxide film by a plasma chemical vapor deposition method by taking high-purity diisopropylamine silane as a silicon source.
Disclosure of Invention
The silicon oxide film is prepared by taking high-purity diisopropylamine silane as a silicon source through a plasma chemical vapor deposition method.
The technical scheme is that the film forming method of the silicon oxide film comprises the steps of taking high-purity diisopropylamine silane as a silicon source, taking a monocrystalline silicon wafer as a substrate, adopting a dual-power-source plasma chemical vapor deposition device to deposit the silicon oxide film on the monocrystalline silicon wafer substrate, placing the monocrystalline silicon wafer in a vacuum reaction chamber in the vapor deposition device, controlling the vacuum degree of the reaction chamber to be (2-10) multiplied by 10 -4 Pa, introducing oxygen and the high-purity diisopropylamine silane, controlling the microwave power of the vapor deposition device to be 200-250W, and performing vapor deposition to obtain the silicon oxide film.
Further, the flow rate of the introduced oxygen is 300-800mL/h.
Further, the flow rate of the high-purity diisopropylamine silane is 200-600mL/h.
Further, the vapor deposition time is 60-90min.
Further, the preparation method of the high-purity diisopropylamine silane comprises the steps of introducing argon into a reaction kettle to discharge air, adding a ruthenium-loaded molecular sieve catalyst and diisopropylamine, adding phenylsilane at the temperature of-40 to-50 ℃, then carrying out reaction, filtering materials to remove solids, concentrating to remove the diisopropylamine, rectifying a crude product by a rectifying device, and collecting fractions at 54-56 ℃ under the pressure of 100-120mmHg to obtain the high-purity diisopropylamine silane.
Further, the mass of the ruthenium-supported molecular sieve catalyst and the mass of the diisopropylamine are respectively (8-13)% and (24-35)% of the mass of the phenylsilane.
Further, the reaction temperature is controlled to be 135-170 ℃ and the reaction time is 24-48h.
The preparation method of the ruthenium-loaded molecular sieve catalyst comprises the steps of adding HMCM-22 molecular sieve into a solution of ruthenium nitrosylnitrate, uniformly dispersing, heating, evaporating to remove a solvent, and then placing the solution in an atmosphere furnace for calcination under a nitrogen range to obtain the ruthenium-loaded molecular sieve catalyst.
Further, the mass of ruthenium nitrosylnitrate is (0.05-0.08)% of the mass of HMCM-22 molecular sieve.
Further, the calcination temperature is 400-550 ℃ and the time is 2-3h.
The method has the technical effects that the ruthenium-loaded molecular sieve catalyst is used for catalyzing diisopropylamine and phenylsilane to react and rectifying and purifying, so that the high-purity diisopropylamine silane is obtained, and the gas phase purity reaches 98.7-99.6%. Then, the silicon oxide film is obtained by taking the silicon oxide film as a silicon source through a plasma chemical vapor deposition method, wherein the content of S i elements and O elements is high, and the content of hetero element C is low and is only 8.92-15.19%. Provides a brand new strategy for preparing the diisopropylamine silane with high purity and the silicon oxide film with high performance.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
Example 1
Adding 100 parts by weight of HMCM-22 molecular sieve into an aqueous solution containing 0.05 part by weight of ruthenium nitrosylnitrate, uniformly dispersing, heating and evaporating to remove the solvent, and then placing in an atmosphere furnace, and calcining for 3 hours at 400 ℃ under the nitrogen range to obtain the ruthenium-loaded molecular sieve catalyst.
Introducing argon into a reaction kettle to discharge air, adding 8 parts by weight of ruthenium-loaded molecular sieve catalyst and 28 parts by weight of diisopropylamine, adding 100 parts by weight of phenylsilane at the temperature of-40 ℃, heating the reaction kettle to 170 ℃, reacting for 24 hours, filtering materials to remove solids, concentrating to remove diisopropylamine, rectifying a crude product by a rectifying device, and collecting a fraction at 54 ℃ under the pressure of 100mmHg to obtain the high-purity diisopropylamine silane.
The method comprises the steps of taking high-purity diisopropylamine silane as a silicon source, taking a monocrystalline silicon wafer as a substrate, adopting a double-power-source plasma chemical vapor deposition device to deposit a silicon oxide film on the monocrystalline silicon wafer substrate, placing the monocrystalline silicon wafer in a vacuum reaction chamber in the vapor deposition device, controlling the vacuum degree of the reaction chamber to be 6 multiplied by 10 -4 Pa, introducing oxygen, controlling the flow rate to be 300mL/h, introducing high-purity diisopropylamine silane, controlling the flow rate to be 200mL/h, controlling the microwave power of the vapor deposition device to be 250W, and performing vapor deposition for 60min to obtain the silicon oxide film.
Example 2
Adding 100 parts by weight of HMCM-22 molecular sieve into an aqueous solution containing 0.06 parts by weight of ruthenium nitrosylnitrate, uniformly dispersing, heating and evaporating to remove the solvent, and then placing in an atmosphere furnace, and calcining for 2 hours at 550 ℃ under the nitrogen range to obtain the ruthenium-loaded molecular sieve catalyst.
Introducing argon into a reaction kettle to discharge air, adding 13 parts by weight of ruthenium-loaded molecular sieve catalyst and 35 parts by weight of diisopropylamine, adding 100 parts by weight of phenylsilane at the temperature of-50 ℃, heating the reaction kettle to 135 ℃, reacting for 48 hours, filtering materials to remove solids, concentrating to remove diisopropylamine, rectifying a crude product by a rectifying device, and collecting a fraction at 56 ℃ under the pressure of 120mmHg to obtain the high-purity diisopropylamine silane.
The method comprises the steps of taking high-purity diisopropylamine silane as a silicon source, taking a monocrystalline silicon wafer as a substrate, adopting a double-power-source plasma chemical vapor deposition device to deposit a silicon oxide film on the monocrystalline silicon wafer substrate, placing the monocrystalline silicon wafer in a vacuum reaction chamber in the vapor deposition device, controlling the vacuum degree of the reaction chamber to be 10 multiplied by 10 -4 Pa, introducing oxygen, controlling the flow rate to be 600mL/h, introducing high-purity diisopropylamine silane, controlling the flow rate to be 400mL/h, controlling the microwave power of the vapor deposition device to be 250W, and performing vapor deposition for 90min to obtain the silicon oxide film.
Example 3
Adding 100 parts by weight of HMCM-22 molecular sieve into an aqueous solution containing 0.06 parts by weight of ruthenium nitrosylnitrate, uniformly dispersing, heating and evaporating to remove the solvent, and then placing in an atmosphere furnace, and calcining for 3 hours at 550 ℃ under the nitrogen range to obtain the ruthenium-loaded molecular sieve catalyst.
Introducing argon into a reaction kettle to discharge air, adding 13 parts by weight of ruthenium-loaded molecular sieve catalyst and 24 parts by weight of diisopropylamine, adding 100 parts by weight of phenylsilane at the temperature of-40 ℃, heating the reaction kettle to 150 ℃, reacting for 36 hours, filtering materials to remove solids, concentrating to remove diisopropylamine, rectifying a crude product by a rectifying device, and collecting a fraction at 54 ℃ under the pressure of 100mmHg to obtain the high-purity diisopropylamine silane.
The method comprises the steps of taking high-purity diisopropylamine silane as a silicon source, taking a monocrystalline silicon wafer as a substrate, adopting a double-power-source plasma chemical vapor deposition device to deposit a silicon oxide film on the monocrystalline silicon wafer substrate, placing the monocrystalline silicon wafer in a vacuum reaction chamber in the vapor deposition device, controlling the vacuum degree of the reaction chamber to be 2X 10 -4 Pa, introducing oxygen, controlling the flow rate to be 800mL/h, introducing high-purity diisopropylamine silane, controlling the flow rate to be 600mL/h, controlling the microwave power of the vapor deposition device to be 200W, and performing vapor deposition for 90min to obtain the silicon oxide film.
Example 4
100 Parts by weight of HMCM-22 molecular sieve is added into an aqueous solution containing 0.08 parts by weight of ruthenium nitrosylnitrate, the mixture is uniformly dispersed, the solvent is removed by heating evaporation, and then the mixture is placed in an atmosphere furnace and calcined for 3 hours at a temperature of 500 ℃ in a nitrogen range, so that the ruthenium-loaded molecular sieve catalyst is obtained.
Introducing argon into a reaction kettle to discharge air, adding 12 parts by weight of ruthenium-loaded molecular sieve catalyst and 35 parts by weight of diisopropylamine, adding 100 parts by weight of phenylsilane at the temperature of-50 ℃, heating the reaction kettle to 150 ℃, reacting for 36 hours, filtering the materials to remove solids, concentrating to remove diisopropylamine, rectifying the crude product by a rectifying device, and collecting fractions at 56 ℃ under the pressure of 120mmHg to obtain the high-purity diisopropylamine silane.
The method comprises the steps of taking high-purity diisopropylamine silane as a silicon source, taking a monocrystalline silicon wafer as a substrate, adopting a double-power-source plasma chemical vapor deposition device to deposit a silicon oxide film on the monocrystalline silicon wafer substrate, placing the monocrystalline silicon wafer in a vacuum reaction chamber in the vapor deposition device, controlling the vacuum degree of the reaction chamber to be 10 multiplied by 10 -4 Pa, introducing oxygen, controlling the flow rate to be 500mL/h, introducing high-purity diisopropylamine silane, controlling the flow rate to be 400mL/h, controlling the microwave power of the vapor deposition device to be 250W, and performing vapor deposition for 60min to obtain the silicon oxide film.
Comparative example 1
Introducing argon into a reaction kettle to discharge air, adding 0.004 part of ruthenium nitrosylnitrate, 8 parts of HMCM-22 and 28 parts of diisopropylamine, adding 100 parts of phenylsilane at the temperature of minus 40 ℃, heating the reaction kettle to 170 ℃, reacting for 24 hours, filtering materials to remove solids, concentrating to remove diisopropylamine, rectifying a crude product by a rectifying device, and collecting a fraction at 54 ℃ under the pressure of 100mmHg to obtain the high-purity diisopropylamine silane.
The method comprises the steps of taking high-purity diisopropylamine silane as a silicon source, taking a monocrystalline silicon wafer as a substrate, adopting a double-power-source plasma chemical vapor deposition device to deposit a silicon oxide film on the monocrystalline silicon wafer substrate, placing the monocrystalline silicon wafer in a vacuum reaction chamber in the vapor deposition device, controlling the vacuum degree of the reaction chamber to be 6 multiplied by 10 -4 Pa, introducing oxygen, controlling the flow rate to be 300mL/h, introducing high-purity diisopropylamine silane, controlling the flow rate to be 200mL/h, controlling the microwave power of the vapor deposition device to be 250W, and performing vapor deposition for 60min to obtain the silicon oxide film.
The gas phase purity of diisopropylamine silane was tested using a gas chromatograph.
TABLE 1 diisopropylamine silane gas phase purity test
Examples 1 to 4 use ruthenium-supported molecular sieve catalyst as catalyst to catalyze the reaction of diisopropylamine and phenylsilane to obtain high-purity diisopropylamine silane, and the gas phase purity reaches 98.7-99.6%. Provides convenience for the subsequent preparation of high-performance silicon oxide films.
In the comparative example 1, ruthenium nitrosylnitrate and HMCM-22 molecular sieve are used as synergistic catalysts, so that the catalyst does not have a good catalytic effect, the reaction system is relatively complex, and the gas phase purity of diisopropylamine silane is only 86.8%.
The silicon oxide film was subjected to elemental analysis using an XPS photoelectron spectrometer.
TABLE 2 elemental analysis of silicon oxide films
Example 1 Example 2 Example 3 Example 4 Comparative example 1
Si element (%) 23.13 22.93 21.14 23.05 32.18
O element (%) 67.95 64.94 63.67 66.41 11.12
C element (%) 8.92 12.13 15.19 10.54 56.70
Examples 1 to 4 use diisopropylamine silane with high purity as silicone oil, and the silicon oxide film obtained by the ion-based chemical vapor deposition method has high content of Si element and O element, and low content of hetero element C, which is only 8.92 to 15.19%.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (4)

1.一种硅氧化物膜的成膜方法，其特征在于，所述成膜方法为：以高纯度二异丙胺硅烷作为硅源，单晶硅片作为衬底，采用双功率源等离子体化学气相沉积设备，在单晶硅片衬底上进行沉积硅氧化物膜；将单晶硅片置于气相沉积设备中的真空反应室中，控制反应室真空度为2×10-4Pa-10×10-4Pa；通入氧气和高纯二异丙胺硅烷，并控制气相沉积设备的微波功率为200-250W，进行气相沉积，得到硅氧化物膜，其中，硅氧化物膜中元素C的含量为8.92%-15.19%；1. A method for forming a silicon oxide film, characterized in that the method comprises: using high-purity diisopropylamine silane as a silicon source and a single crystal silicon wafer as a substrate, and using a dual-power source plasma chemical vapor deposition device to deposit a silicon oxide film on the single crystal silicon wafer substrate; placing the single crystal silicon wafer in a vacuum reaction chamber in the vapor deposition device, and controlling the vacuum degree of the reaction chamber to be 2×10 -4 Pa-10×10 -4 Pa; introducing oxygen and high-purity diisopropylamine silane, and controlling the microwave power of the vapor deposition device to be 200-250W, and performing vapor deposition to obtain a silicon oxide film, wherein the content of element C in the silicon oxide film is 8.92%-15.19%; 其中，所述通入氧气的流速为300-800mL/h；Wherein, the flow rate of the oxygen introduced is 300-800 mL/h; 所述通入高纯二异丙胺硅烷的流速为200-600mL/h；The flow rate of high-purity diisopropylamine silane is 200-600 mL/h; 所述气相沉积的时间为60-90min；The vapor deposition time is 60-90 min; 所述高纯二异丙胺硅烷的制备方法为：向反应釜中通入氩气排出空气，加入钌负载分子筛催化剂、二异丙胺，在-40至-50℃的温度下加入苯硅烷，然后进行反应，将物料过滤除去固体，浓缩除去二异丙胺，粗产物通过精馏装置进行精馏，100-120 mmHg的压力下，收集54-56℃的馏分，得到高纯度二异丙胺硅烷，其中，所述钌负载分子筛催化剂的质量是苯硅烷质量的8%-13%，所述二异丙胺的质量是苯硅烷质量的24%-35%，所述反应的温度控制为135-170℃，反应时间为24-48h，所述高纯二异丙胺硅烷的气相纯度达到98.7%-99.6%。The preparation method of the high-purity diisopropylamine silane is as follows: introducing argon gas into a reaction kettle to exhaust air, adding a ruthenium-loaded molecular sieve catalyst and diisopropylamine, adding phenylsilane at a temperature of -40 to -50°C, then reacting, filtering the material to remove solids, concentrating to remove diisopropylamine, and distilling the crude product through a distillation device. Under a pressure of 100-120 mmHg, a fraction of 54-56°C is collected to obtain high-purity diisopropylamine silane, wherein the mass of the ruthenium-loaded molecular sieve catalyst is 8%-13% of the mass of phenylsilane, the mass of the diisopropylamine is 24%-35% of the mass of phenylsilane, the reaction temperature is controlled at 135-170°C, the reaction time is 24-48h, and the gas phase purity of the high-purity diisopropylamine silane reaches 98.7%-99.6%. 2.根据权利要求1所述的硅氧化物膜的成膜方法，其特征在于，所述钌负载分子筛催化剂的制备方法为：将HMCM-22分子筛加入到亚硝酰硝酸钌的溶液中，分散均匀，加热蒸发除去溶剂，然后置于气氛炉中，氮气范围下进行煅烧，得到钌负载分子筛催化剂。2. The film-forming method of silicon oxide film according to claim 1 is characterized in that the preparation method of the ruthenium-loaded molecular sieve catalyst is: adding HMCM-22 molecular sieve to a solution of ruthenium nitrosyl nitrate, dispersing it evenly, heating and evaporating it to remove the solvent, and then placing it in an atmosphere furnace and calcining it under a nitrogen range to obtain a ruthenium-loaded molecular sieve catalyst. 3.根据权利要求2所述的硅氧化物膜的成膜方法，其特征在于，所述亚硝酰硝酸钌的质量是HMCM-22分子筛质量的0.05%-0.08%。3 . The method for forming a silicon oxide film according to claim 2 , wherein the mass of the ruthenium nitrosyl nitrate is 0.05%-0.08% of the mass of the HMCM-22 molecular sieve. 4.根据权利要求2所述的硅氧化物膜的成膜方法，其特征在于，所述煅烧温度为400-550℃，时间为2-3h。4 . The method for forming a silicon oxide film according to claim 2 , wherein the calcination temperature is 400-550° C. and the calcination time is 2-3 hours.
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