Preparation of wafer-level two-dimensional In by chemical vapor deposition2Se3Method for making thin film
阅读说明：本技术 一种通过化学气相沉积制备晶圆级二维In2Se3薄膜的方法 (Preparation of wafer-level two-dimensional In by chemical vapor deposition2Se3Method for making thin film ) 是由 冯伟 许弋 杨绪轩 于 2021-06-03 设计创作，主要内容包括：一种通过化学气相沉积制备晶圆级二维In-2Se-3薄膜的方法；属于晶圆级二维半导体材料薄膜制备领域。本发明要解决现有机械剥离法制备获得的二维In-2Se-3尺寸过小且难以控制,以及脉冲激光沉积制备成本过高、性能较差的技术问题。本发明的方法：一、配置硝酸铟溶液,过滤；二、量取步骤一所得溶液,高速旋涂于晶圆级尺寸的基底上,进行加热除杂后再受热分解,得到氧化铟薄膜,再对氧化铟薄膜进行高温退火处理；三、对氧化铟薄膜置于CVD炉中进行原位硒化处理,得到大尺寸二维In-2Se-3薄膜。本发明合成得到的二维In-2Se-3薄膜尺寸大、均匀度好、表面清洁,用于制作大面积、集成化电子和光电器件。(Preparation of wafer-level two-dimensional In by chemical vapor deposition 2 Se 3 A method of forming a film; belonging to the field of wafer-level two-dimensional semiconductor material film preparation. The invention aims to solve the problem that the two-dimensional In prepared by the existing mechanical stripping method 2 Se 3 The size is too small and difficult to control, and the preparation cost of the pulse laser deposition is too high and the performance is poorer. The method comprises the following steps: firstly, preparing an indium nitrate solution and filtering; secondly, measuring the solution obtained in the first step, spin-coating the solution on a substrate with a wafer level size at a high speed, heating the substrate to remove impurities, then performing thermal decomposition on the substrate to obtain an indium oxide film, and performing high-temperature annealing treatment on the indium oxide film; thirdly, placing the indium oxide film In a CVD furnace for In-situ selenization treatment to obtain large-size two-dimensional In 2 Se 3 A film. Two-dimensional In synthesized by the invention 2 Se 3 The film has large size, good uniformity and clean surface, and can be used for manufacturing large-area and integrated electronic and photoelectric devices.)
1. Preparation of wafer-level two-dimensional In by chemical vapor deposition2Se3A method for manufacturing a thin film, comprising the steps of,the method is characterized by comprising the following steps:
step one, adding indium nitrate into an organic solvent, heating while stirring, and then filtering;
secondly, measuring the solution obtained in the first step, spin-coating the solution on a substrate with a wafer-level size at a high speed, heating the substrate to remove impurities, then performing thermal decomposition on the substrate to obtain an indium oxide film, and performing high-temperature annealing treatment on the indium oxide film;
step three, placing the film obtained In the step two In a CVD furnace for high-temperature selenization In the atmosphere of argon and hydrogen to obtain large-size two-dimensional In2Se3A film.
2. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method for preparing the thin film is characterized in that the organic solvent in the step one is ethylene glycol monomethyl ether, and the concentration of the indium nitrate solution in the step one is 0.1-0.5 mol/ml.
3. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method for preparing the film is characterized in that in the step one, the solution is heated at 70-80 ℃, the stirring speed is 400-1200 rpm, and the heating and stirring time is 8-20 h.
4. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method of the membrane is characterized in that the filtration in the step one is micron-scale filtration.
5. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method for preparing the film is characterized in that 30-500 mul of the solution obtained in the first step is measured in the second step.
6. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3Method of producing filmThe method is characterized in that the rotating speed of the high-speed spin coating in the second step is 2000 rpm-6000 rpm, and the time of the high-speed spin coating in the second step is 60 s.
7. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method for removing the film is characterized in that the heating impurity removal in the step two is carried out according to the following operations: heating to 100 deg.C within 7min and maintaining for 5 min; heating to 130 deg.C within 3min and maintaining for 60 min; then heating to 300 ℃ within 15 min; in the second step, the thermal decomposition temperature is 300 ℃, and the thermal decomposition time is 60-120 min.
8. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method for preparing the film is characterized in that the high-temperature annealing temperature in the step two is 500 ℃, and the high-temperature annealing time is 60-120 min.
9. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method for preparing the thin film is characterized in that the ratio of argon to hydrogen atmosphere in the third step is (4-1): 1, the argon flux is 20-40 sccm, the hydrogen flux is 5-20 sccm, the argon service time in the third step is the whole process time from heating to cooling, the hydrogen service time is from heating to high-temperature reaction ending, and the specific time is 40-140 min.
10. Preparation of wafer-level two-dimensional In by chemical vapor deposition according to claim 12Se3The method for preparing the film is characterized in that the high-temperature selenizing temperature in the third step is 630-700 ℃, the corresponding selenium powder heating temperature is 180-220 ℃, and the reaction time is 10-90 min.
Technical Field
The invention belongs to the field of wafer-level two-dimensional semiconductor film preparation; in particular to a method for preparing wafer-level two-dimensional In by chemical vapor deposition2Se3A method of making a thin film.
Background
The 2010 Nobel Physics winning owner Andre Geim and Konstantin Novoseov obtain single-layer graphene by stripping graphite through adhesive tapes, and show excellent carrier mobility (2 x 10)5cm2V-1s-1) Thereby opening up the research field of two-dimensional materials. However, the intrinsic zero band gap of graphene cannot be used as a channel material of a high-performance field effect transistor and a photoelectric detector, so that other graphene materials are preferred objects of relevant researches. In2Se3The material is a III-VI semiconductor material, has a layered structure and a smaller direct band gap energy band, has good light responsiveness and light absorptivity for visible light and near infrared light, has excellent electron mobility and stability, and is a popular material in current research.
However, two-dimensional In for large area is currently concerned2Se3The field of film preparation is less reported. At the earliest, the Xin Tao and Yi Gu of Washington State university In 2013 firstly obtained two-dimensional In by mechanical peeling2Se3The method can obtain the film with high quality but low yield, and the obtained film has small size (micron-sized) and difficult shape and size reproduction, thereby being not beneficial to large-scale production. Then, people adopt a pulsed laser deposition method to obtain two-dimensional In with wafer level size2Se3However, the thin film has problems of expensive equipment, fine crystal grains, excessive cost of raw materials required for production, complex operation flow and the like, so that the large-area two-dimensional In2Se3The synthesis of thin films remains a problem.
Disclosure of Invention
The invention aims to solve the problem of two-dimensional In obtained by the existing mechanical stripping2Se3The problems of low film yield, small size and difficult control, and the technical problems of high cost of pulse laser deposition and difficult large-scale production and application, and provides a method for preparing wafer-level two-dimensional In by chemical vapor deposition2Se3A method of making a thin film.
To solve the above problems, the present invention provides a method for chemical vapor depositionVolume preparation of wafer-level two-dimensional In2Se3The method of the film is carried out according to the following steps:
step one, adding a certain amount of massive indium nitrate solid into an organic solvent to prepare an indium nitrate solution with a certain concentration, heating and stirring the solution for enough time, and then filtering the solution;
step two, taking the solution obtained In the step one according to a certain amount, spin-coating the solution on a substrate with a wafer-level size at a high speed to obtain an indium nitrate film, heating the indium nitrate film to remove impurities, and then thermally decomposing the indium nitrate film to obtain indium oxide (In)2O3Oxide semiconductor material) film, and performing high-temperature annealing treatment on the indium oxide film;
step three, placing the film obtained In the step two In a CVD furnace for high-temperature selenization In the atmosphere of argon and hydrogen to obtain large-size two-dimensional In2Se3A film.
Further defined, in the first step, the organic solvent is ethylene glycol methyl ether (2-Me).
Further defined, In step one, the bulk indium nitrate solid is indium nitrate hydrate (In (NO)3)3·xH2O)。
Further, the concentration of the indium nitrate solution prepared in the step one is 0.1mol/ml to 0.5 mol/ml.
Further limiting, in the step one, the heating temperature of the solution is 70-80 ℃, the stirring speed is 400-1200 rpm, and the heating and stirring time is 8-20 h.
Further limiting, in the step one, filtering is performed by adopting a PVDF micron-sized filter head.
Further limiting, in the second step, 20-500 mul of the solution obtained in the first step is measured.
Further, in the second step, the substrate is silicon chip, natural mica or fluorine crystal mica.
Further, the rotation speed of the high-speed spin coating in the second step is 2000rpm to 6000rpm, and the time is 60 s.
Further limiting, the heating and impurity removal in the second step are carried out according to the following operations: heating to 100 deg.C within 7min and maintaining for 5 min; heating to 130 deg.C within 3min and maintaining for 60 min; the temperature was then raised to 300 ℃ over a period of 15 min.
Further limiting, the temperature of the thermal decomposition in the step two is 300 ℃, and the heating time is 60-120 min.
Further limiting, the high-temperature annealing temperature in the step two is 500 ℃, and the heating time is 60-120 min.
Further, in the third step, the ratio of argon to hydrogen atmosphere is (4-1): 1, specifically, the flux of argon (Ar) is 20 sccm-40 sccm, and the flux of hydrogen is 5 sccm-20 sccm.
And further limiting, in the third step, the argon gas using time is the whole process time from heating to cooling, the hydrogen gas using time is from heating to high-temperature reaction ending, and the specific time is 40-140 min.
Further limiting, in the third step, the high-temperature selenization temperature is 630-700 ℃, the corresponding selenium powder heating temperature is 180-220 ℃, and the reaction time is 10-90 min.
In the first step of the invention, the blocky indium nitrate hydrate is a milky white solid, is weighed and twisted into powder to be dissolved in ethylene glycol monomethyl ether, and is heated and stirred for a long time to be a light yellow or colorless transparent solution. In step two, the spin-coated sample is thermally decomposed and water (H) is removed at a temperature of 100 ℃2O), removing ethylene glycol monomethyl ether (2-Me) at the temperature of 130 ℃, thermally decomposing at the temperature of 300 ℃, obtaining a light yellow indium oxide film on a silicon chip, and obtaining a colorless transparent indium oxide film on mica and fluorophlogopite, wherein the specific chemical reactions are as follows:
100℃：In(NO3)3·xH2O→In(NO3)3·(x-1)H2O+H2O
300℃：In(NO3)3→In2O3+3NO2
in the fourth step of the invention, the indium oxide film is selenized at a high temperature of 630-700 ℃ under the mixed atmosphere of argon and hydrogen, and after the reaction is finished, the temperature is reduced to room temperature, and then the large-size two-dimensional In film is obtained2Se3A film, wherein the specific chemical reactions that occur are as follows:
In2O3+3H2+3Se→In2Se3+3H2O
compared with the prior art, the invention has the following beneficial effects:
the invention adopts a chemical vapor deposition method to prepare two-dimensional In with the thickness of several nanometers to dozens of nanometers on a wafer-level substrate2Se3A film. The method has good repeatability, and two-dimensional In is obtained2Se3The film quality is high. Can be used for making two-dimensional In2Se3The photoelectric detector array plays a good reference role in the preparation of other large-size two-dimensional material films, and has the following specific advantages:
1. two-dimensional In production relative to conventional mechanical stripping2Se3Method of thin film, two-dimensional In prepared by the invention2Se3The film has extremely large size, can reach the wafer level size, has high quality, uniform components and clean surface, and can be used for preparing two-dimensional In2Se3An array of photodetectors.
2. The method has the advantages of few process flows, simple operation, low cost of required equipment, good safety and high repeatability, and is suitable for industrial production.
3. In with different thicknesses is prepared and obtained by strictly controlling the spin-coating rotating speed of the indium nitrate film2O3And two-dimensional In2Se3The film thickness can range from a few nanometers to tens of nanometers.
4. Two-dimensional In finally obtained by the invention2Se3High film uniformity, and two-dimensional In-based2Se3Thin films provide a good foundation for the construction of electronic devices and photodetectors.
Drawings
FIG. 1 shows a large-sized two-dimensional In obtained In example 12Se3A photograph of the film;
FIG. 2 shows a large-sized two-dimensional In obtained In example 12Se3Raman Shift (Raman Shift) profile of the film.
Detailed Description
Example 1: in this embodiment, a method for preparing wafer-level two-dimensional In by chemical vapor deposition2Se3The method of the film is carried out according to the following steps:
step one, indium nitrate hydrate (In (NO)3)3·xH2O) is used as a solute, ethylene glycol monomethyl ether (2-Me) is used as a solvent, 0.2mol/L indium nitrate solution is prepared, placed on a magnetic heating stirrer and heated and stirred for 12 hours at the rotating speed of 75 ℃ and 900 rpm. Filtering the solution after heating and stirring by using a PVDF micron-sized filter head;
step two, sucking 30 mul of solution each time by a liquid-transfering gun and uniformly spin-coating the solution on 1 multiplied by 1cm by a method of spin-coating in a shape of Chinese character' hui2Spin-coating the square silicon wafer for 60s at the rotating speed of 5000rpm by using a spin coater; placing the spin-coated silicon wafer on a quartz wafer, placing the quartz wafer into a quartz tube, and carrying out heat treatment according to the following steps to obtain an indium oxide film: (1) heating to 100 deg.C within 7min and maintaining for 5 min; (2) heating to 130 deg.C within 3min and maintaining for 60 min; (3) heating to 300 deg.C within 15min, maintaining for 120min, and cooling to room temperature; (4) heating to 500 deg.C within 35min, maintaining for 60min, and cooling to room temperature;
thirdly, placing the indium oxide film prepared in the second step on a quartz plate, placing the quartz plate in a lower air inlet temperature area of a quartz tube of a double-area heating CVD furnace, weighing 200mg of selenium powder, placing the selenium powder in a quartz boat, and placing the quartz boat in an upper air inlet temperature area of the quartz tube; sealing the quartz tube, and introducing high-purity argon gas of 300sccm into the quartz tube for 30 min; argon flux was changed to 20sccm while introducing 5sccm hydrogen and the quartz tube was heated simultaneously for two hot zones as follows: keeping the hot zone of the air inlet at the room temperature for 32min, then heating to 200 ℃ within 14min, keeping the temperature for 50min, and then reducing the temperature to the room temperature; the lower tuyere heat area is heated to 680 ℃ within 46min and kept for 50 min; after the heating time is over, the hydrogen valve is closed, and argon is introduced at 20sccm until the quartz tube is cooled to room temperature.
As can be seen from FIG. 1, the film size is extremely large, reaching the wafer level size; as can be seen from FIG. 2, the Raman characteristic peak of the thin film is sharp, and the two-dimensional In is reported In the characteristic peak position and related literature2Se3The crystals are consistent with each other and the crystal quality is good,indicating that the film has high quality and uniform components.
Example 2: in this embodiment, a method for preparing wafer-level two-dimensional In by chemical vapor deposition2Se3The method of the film is carried out according to the following steps:
step one, indium nitrate hydrate (In (NO)3)3·xH2O) is used as a solute, ethylene glycol monomethyl ether (2-Me) is used as a solvent, 0.2mol/L indium nitrate solution is prepared, placed on a magnetic heating stirrer and heated and stirred for 12 hours at the rotating speed of 75 ℃ and 900 rpm. Filtering the solution after heating and stirring by using a PVDF micron-sized filter head;
step two, sucking 50 mul of solution each time by a liquid-transfering gun and uniformly spin-coating the solution on 2 multiplied by 2cm by a method of spin-coating in a shape of Chinese character' hui2Spin-coating the square natural mica with a spin coater at 5000rpm for 60 s; placing the mica sheet after spin coating on a quartz plate, placing the quartz plate into a quartz tube, and carrying out heat treatment according to the following steps to obtain the indium oxide film: (1) heating to 100 deg.C within 7min and maintaining for 5 min; (2) heating to 130 deg.C within 3min and maintaining for 60 min; (3) heating to 300 deg.C within 15min, maintaining for 120min, and cooling to room temperature; (4) heating to 500 deg.C within 35min, maintaining for 60min, and cooling to room temperature;
thirdly, placing the indium oxide film prepared in the second step on a quartz plate, placing the quartz plate in a lower air inlet temperature area of a quartz tube of a double-area heating CVD furnace, weighing 200mg of selenium powder, placing the selenium powder in a quartz boat, and placing the quartz boat in an upper air inlet temperature area of the quartz tube; sealing the quartz tube, and introducing high-purity argon gas of 300sccm into the quartz tube for 30 min; argon flux was changed to 20sccm while introducing 5sccm hydrogen and the quartz tube was heated simultaneously for two hot zones as follows: keeping the hot zone of the air inlet at the room temperature for 32min, then heating to 200 ℃ within 14min, keeping the temperature for 50min, and then reducing the temperature to the room temperature; the lower tuyere heat area is heated to 680 ℃ within 46min and kept for 50 min; after the heating time is over, the hydrogen valve is closed, and argon is introduced at 20sccm until the quartz tube is cooled to room temperature.
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