Semiconductor film preparation system and preparation method

Abstract

The invention discloses a semiconductor film preparation system and method. The preparation system comprises a micro-arc oxidation device and a control terminal. The micro-arc oxidation device comprises an electrolytic tank, a pulse power supply, a monitoring module and a controller, the electrolytic tank is provided with a stirrer located in the middle and an ultrasonic generator located at the bottom, a constant-temperature cooling module is installed on the side wall of the electrolytic tank, and the monitoring module comprises a conductivity probe, a photometer probe, a conductivity meter and an ultraviolet spectrograph. The conductivity probe is connected with the conductivity meter, the photometer probe is connected with the ultraviolet spectrograph, and the pulse power supply is connected with the electrolytic tank through a wire; the control terminal comprises a control module and a display module. The invention further provides a preparation method of the semiconductor film, reaction conditions and parameters can be automatically detected and regulated, accurate regulation and doping of nanoparticles in the growth process of the semiconductor film are achieved, operation is easy and convenient, controllability and repeatability are high, and the yield and preparation efficiency are improved.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor thin film technology, and in particular to a semiconductor thin film preparation system and preparation method. Background Art

[0002] In the preparation process of semiconductor sensors, the use of metal elements to dope and modify the original transition metal oxide semiconductor surface can further improve the sensing performance. Traditional doping methods such as ion implantation and chemical synthesis have high requirements for cost and process. Micro-arc oxidation uses high voltage and high-temperature plasma discharge to grow oxide films in situ on the metal surface; by adding transition metal nanoparticles to the electrolyte, nanoparticle doping can be achieved while the film is growing, and transient high-temperature sintering and phase change can be achieved during the high-temperature plasma discharge process of micro-arc oxidation.

[0003] The existing micro-arc oxidation device does not monitor and control the process parameters and reaction conditions in real time, and has poor controllability and repeatability, making it unsuitable for the preparation of semiconductor films doped with nanoparticles. During the micro-arc oxidation reaction, parameters such as the electrolyte concentration, nanoparticle composition, and solution temperature change dynamically, and the process complexity is high. These will affect the reaction process and reaction rate, and affect the composition of the final semiconductor film, resulting in unstable film composition, low thickness uniformity, large differences in physical properties, and a high defective rate for the produced semiconductor sensors. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a semiconductor thin film preparation system and preparation method, which can accurately control the micro-arc oxidation reaction, provide more stable reaction conditions, and facilitate the stable growth of nanoparticles and semiconductor thin films.

[0005] On the one hand, an embodiment of the present invention provides a semiconductor thin film preparation system, including a micro-arc oxidation device and a control terminal; the micro-arc oxidation device includes an electrolytic cell, a pulse power supply, a monitoring module and a controller, the electrolytic cell is provided with a stirrer located in the middle position, the electrolytic cell is provided with an ultrasonic generator located at the bottom position, a constant temperature cooling module is installed on the side wall of the electrolytic cell, the monitoring module includes a conductivity probe, a photometer probe, a conductivity meter and an ultraviolet spectrometer, the conductivity probe is connected to the conductivity meter, the photometer probe is connected to the ultraviolet spectrometer, the pulse power supply is connected to the electrolytic cell through a wire, and the controller is electrically connected to the constant temperature cooling module and the monitoring module respectively; the control terminal includes a control module and a display module, the control module is electrically connected to the display module, and the control module is communicatively connected to the controller.

[0006] The embodiments of the present invention have at least the following beneficial effects: The semiconductor film preparation system provided by the present invention includes a micro-arc oxidation device and a control terminal, wherein the micro-arc oxidation device includes an electrolytic cell, a pulse power supply, a monitoring module and a controller; the monitoring module includes a conductivity probe, a photometer probe, a conductivity meter and an ultraviolet spectrometer; and the control terminal includes a control module and a display module. By monitoring the changes of solutes in the electrolyte through the ultraviolet spectrometer and the conductivity meter, the concentration of electrolytes and nanoparticles in the electrolyte can be accurately controlled, and the reaction conditions and reaction parameters can be automatically detected and regulated, thereby reducing the differences caused by the difficulty in controlling the reaction conditions, realizing the precise regulation and doping of nanoparticles in the growth process of the semiconductor film, and ensuring the consistency of the composition structure and performance of the prepared film.

[0007] According to some embodiments of the present invention, the micro-arc oxidation device also includes a first sampler and a second sampler, and the first sampler and the second sampler are both installed above the electrolytic cell, the first sampler is used to add nanoparticles into the electrolytic cell, and the second sampler is used to add electrolyte into the electrolytic cell.

[0008] According to some embodiments of the present invention, the electrolytic cell is provided with a water inlet valve, and the water inlet valve is installed on the top of the electrolytic cell.

[0009] According to some embodiments of the present invention, the electrolytic cell is provided with a liquid level meter, which is arranged on a side wall of the electrolytic cell, and the liquid level meter is used to detect the liquid position in the electrolytic cell in real time.

[0010] According to some embodiments of the present invention, the electrolytic cell is a barrel-shaped structure and is made of stainless steel.

[0011] In another aspect, an embodiment of the present invention provides a method for preparing a semiconductor thin film, comprising: The substrate surface of the semiconductor sample is ground and polished, the substrate is placed in anhydrous ethanol for ultrasonic cleaning, and air-dried in air; The electrolyte and the nanoparticles are mixed in a preset ratio, stirred until completely dissolved to form a mixed solution, poured into an electrolytic cell, stirred and subjected to ultrasonic treatment to obtain a suspended electrolyte; Connect the semiconductor sample to the wire, with the semiconductor sample as the anode and the electrolytic cell as the cathode, and immerse the substrate in the electrolyte; Set the power supply parameters and the UV-visible light absorption peak intensity, conductivity, and liquid level control threshold in the electrolyte, turn on the pulse power supply to start micro-arc oxidation, and use the constant temperature cooling module and stirrer to keep the electrolyte temperature at the set temperature; After micro-arc oxidation is performed according to the set reaction time, the semiconductor sample is taken out and replaced; Real-time monitoring of electrolyte parameters and automatic replenishment of electrolyte.

[0012] According to some embodiments of the present invention, the substrate of the semiconductor sample is Ti material.

[0013] According to some embodiments of the present invention, the electrolyte includes sodium phosphate and potassium hydroxide, the nanoparticles are niobium oxide nanoparticles, and the electrolyte includes 5-10 g / L sodium phosphate, 0.5-1.5 g / L potassium hydroxide and 3-7 g / L niobium oxide nanoparticles in a mass volume ratio.

[0014] According to some embodiments of the present invention, the power supply parameters include reaction current density, pulse frequency and duty cycle, and the reaction current density is set to 10A / dm 2 , the pulse frequency is set to 400 Hz, and the duty cycle is set to 30%.

[0015] According to some embodiments of the present invention, the set temperature is set to 30-55° C., and the reaction time is set to 3-8 min.

[0016] The electrolyte is prepared according to the formula of 5-10 g / L sodium phosphate, 0.5-1.5 g / L potassium hydroxide and 0.5-1.5 g / L niobium oxide nanoparticles in mass volume ratio. The prepared electrolyte is poured into the electrolytic cell, the constant temperature cooling module, ultrasonic generator and stirrer are turned on, the semiconductor sample is connected through a wire and immersed in a specific area in the electrolyte, the current, frequency, duty cycle and other electrical parameters are adjusted through the pulse power supply, the UV-visible absorption peak intensity, conductivity and liquid level control threshold in the electrolyte are set through the controller, and then the power is turned on to complete the preparation of the nanoparticle-doped semiconductor film.

[0017] The semiconductor thin film preparation method according to the embodiment of the present invention has at least the following beneficial effects: The changes of solutes in the electrolyte are monitored by an ultraviolet spectrometer and a conductivity meter, and the first and second samplers are used to accurately control the concentration of electrolytes and nanoparticles in the electrolyte. The reaction conditions and parameters can be automatically detected and regulated, thereby reducing the differences caused by the difficulty in controlling the reaction conditions, and realizing the precise regulation and doping of nanoparticles in the growth process of semiconductor films, ensuring the consistency of the composition structure and performance of the prepared films. The titanium-niobium alloy is subjected to micro-arc oxidation treatment to produce a semiconductor film with a porous microstructure on its surface, which enhances the charge conduction ability and oxygen ion adsorption ability, further improves the sensing performance, improves the sensitivity, detection range, stability, and anti-interference ability, and is more in line with the needs of industrial automation production in terms of preparation methods. It is suitable for preparing semiconductor films doped with nanoparticles, simplifies the production process of semiconductor sensors, is easy to operate, and has strong controllability and repeatability, and improves the yield rate and preparation efficiency.

[0018] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which: Figure 1 A schematic structural diagram of a micro-arc oxidation device of a semiconductor thin film preparation system according to an embodiment of the present invention; Figure 2 A module diagram of a micro-arc oxidation device of a semiconductor thin film preparation system according to an embodiment of the present invention; Figure 3 A schematic diagram of the structure of a semiconductor thin film preparation system according to an embodiment of the present invention; Figure 4 A flowchart of a method for preparing a semiconductor thin film according to an embodiment of the present invention; Figure 5 is a detailed flow chart of a method for preparing a semiconductor thin film according to an embodiment of the present invention; Figure 6 A comparison diagram of the change in the atomic ratio of Nb element in the semiconductor thin film obtained after multiple consecutive preparations according to an embodiment of the present invention; Figure 7 This is a comparison chart of the average thickness change of the semiconductor thin films obtained after multiple consecutive preparations according to an embodiment of the present invention.

[0020] Reference numerals: Electrolytic cell 100, agitator 110, ultrasonic generator 120, constant temperature cooling module 130, water inlet valve 140, liquid level meter 150, first sample adder 160, second sample adder 170, pulse power supply 200, monitoring module 300, conductivity probe 310, photometer probe 320, conductivity meter 330, ultraviolet spectrometer 340, sound and light alarm 350, controller 400, semiconductor sample 500, control terminal 600, control module 610, display module 620. DETAILED DESCRIPTION

[0021] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and cannot be understood as limiting the present invention.

[0022] In the description of the present invention, it should be understood that descriptions involving orientations, such as up, down, front, back, left, right, etc., and orientations or positional relationships indicated are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0023] In the description of the present invention, "several" means one or more, "multiple" means more than two, greater than, less than, and exceeding are understood as not including the number itself, and "above", "below", and "within" are understood as including the number itself. If there is a description of "first", "second", etc., it is only used for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.

[0024] In the description of the present invention, unless otherwise clearly defined, words such as “set”, “install”, “connect” and “connected” should be understood in a broad sense, and technicians in the relevant technical field can reasonably determine the specific meanings of the above words in the present invention based on the specific content of the technical solution.

[0025] A series of hydrogen safety accidents, such as explosions at hydrogen refueling stations, have sounded the alarm for the hydrogen energy industry, indicating that hydrogen safety issues have become one of the key bottlenecks restricting the commercial development of hydrogen energy. The hazardous chemical properties of hydrogen require real-time monitoring of hydrogen leakage and hydrogen concentration during the production, storage and transportation of hydrogen. At present, hydrogen sensing is mainly achieved through the detection of optical, electrochemical, mechanical and electrical signals; among them, chemical resistance hydrogen sensors that convert hydrogen chemical signals into electrical signals have advantages such as high efficiency detection performance, low manufacturing cost, simple signal mechanism and good portability.

[0026] Semiconductor metal oxide materials, such as titanium dioxide, tin dioxide, zinc oxide, etc., can be used as hydrogen-sensitive material components in hydrogen sensor chips due to their low manufacturing cost, good detection activity and stability in harsh environments. 2 Titanium dioxide is a broadband n-type semiconductor material with unique electro-optical and catalytic activity, and is widely used in electrochemistry, photocatalysis, etc. Semiconductor metal oxide materials represented by titanium dioxide have two main signal mechanisms in hydrogen sensing. One is the oxygen vacancy mechanism. When hydrogen molecules come into contact with titanium dioxide, the surface of titanium dioxide is reduced, resulting in a metallization effect and the generation of oxygen vacancies, thereby reducing its surface resistance; the other is the ion adsorption mechanism. Hydrogen molecules react with oxygen ions chemically adsorbed on the depletion layer of the titanium dioxide surface, resulting in electron transfer and the generation of water molecules, thereby reducing the surface resistance.

[0027] Constructing special-shaped structures in semiconductor materials can adjust the junction barrier height and produce accumulation layers, thereby improving the signal response and selectivity of semiconductor materials in gas sensing. Doping titanium dioxide with transition metal elements (such as cobalt, nickel, chromium, tantalum, niobium, etc.) can adjust its band structure and carrier density, thereby further improving the performance of titanium dioxide-based hydrogen sensors. Nb (niobium)-doped Ti0 2 It is a material used in conductive films. 2 Nb doping is performed, and the 4d valence electron structure of Nb element can be 2 The energy band of Ti0 is introduced with a new occupied state, thereby changing 2 The electronic structure of Nb-doped Ti0 2 (NTO) is a sensitive sensing material with good application potential, and in-depth research and clarification of Ti0 2 The hydrogen-sensitive mechanism and the related Nb element doping enhancement mechanism are the key to further developing the application of NTO in the field of hydrogen sensing.

[0028] Micro-arc oxidation is a thin film preparation method developed on the basis of anodic oxidation. Non-ferrous metals or alloys such as titanium and aluminum are placed in a specific electrolyte, and a small spark discharge is generated on the metal surface by applying a high voltage. Under the combined action of high-temperature sintering, plasma chemistry and electrochemistry, a porous oxide ceramic composite film mainly composed of matrix oxide is grown in situ on the surface of the material. The ceramic film prepared by micro-arc oxidation is firmly bonded to the matrix and has good durability, corrosion resistance and high temperature impact resistance. The porous micro-nano structure on the surface of the film has excellent specific surface area characteristics and is a good sensing and catalytic interface. Compared with other thin film preparation methods, micro-arc oxidation technology has a simple process, and the reaction system mostly uses a weak alkaline electrolyte solution. No harmful substances are introduced or produced during the process, and no environmental pollution is caused. The deposition efficiency is high, the preparation process is controllable, and it is easy to control the composition structure of the film through process optimization and component doping. Therefore, micro-arc oxidation is a thin film preparation method with industrial application prospects, which can greatly reduce the manufacturing cost and process difficulty of hydrogen sensor chips. By subjecting the titanium-niobium alloy to micro-arc oxidation treatment, a semiconductor film with a porous microstructure is prepared on its surface, thereby further improving the hydrogen sensing performance.

[0029] The technical solution of the present invention is described in detail below through the accompanying drawings and specific embodiments.

[0030] Please refer to Figures 1 to 3 This embodiment discloses a semiconductor thin film preparation system, including a micro-arc oxidation device and a control terminal 600. The micro-arc oxidation device includes an electrolytic cell 100, a pulse power supply 200, a monitoring module 300 and a controller 400. The electrolytic cell 100 is provided with a stirrer 110 located in the middle position, the electrolytic cell 100 is provided with an ultrasonic generator 120 located at the bottom position, and a constant temperature cooling module 130 is installed on the side wall of the electrolytic cell 100. The monitoring module 300 includes a conductivity probe 310, a photometer probe 320, a conductivity meter 330 and an ultraviolet spectrometer 340. The conductivity probe 310 is connected to the conductivity meter 330, the photometer probe 320 is connected to the ultraviolet spectrometer 340, the pulse power supply 200 is connected to the electrolytic cell 100 through a wire, and the controller 400 is electrically connected to the constant temperature cooling module 130 and the monitoring module 300 respectively; the control terminal 600 includes a control module 610 and a display module 620, the control module 610 is electrically connected to the display module 620, and the control module 610 is communicatively connected to the controller 400. By monitoring the changes in solutes in the electrolyte through the ultraviolet spectrometer 340 and the conductivity meter 330, the concentrations of electrolytes and nanoparticles in the electrolyte can be accurately controlled. The reaction conditions and parameters can be automatically detected and regulated, thereby reducing the differences caused by the difficulty in controlling the reaction conditions, and achieving precise control and doping of nanoparticles during the growth of semiconductor films, ensuring the consistency of the composition structure and performance of the prepared films.

[0031] Please refer to Figure 3 The micro-arc oxidation device further includes a first sampler 160 and a second sampler 170, both of which are installed above the electrolytic cell 100. The first sampler 160 is used to add nanoparticles to the electrolytic cell 100, and the second sampler 170 is used to add electrolyte to the electrolytic cell 100. The electrolyte includes sodium phosphate and potassium hydroxide, and the nanoparticles are niobium oxide nanoparticles. The controller 400 controls the first sampler 160 and the second sampler 170 to automatically add nanoparticles and electrolyte.

[0032] Please refer to Figure 3 The electrolytic cell 100 is provided with a water inlet valve 140, which is installed on the top of the electrolytic cell 100. The electrolytic cell 100 is provided with a liquid level meter 150, which is arranged on the side wall of the electrolytic cell 100, and the liquid level meter 150 is used to detect the liquid position in the electrolytic cell 100 in real time.

[0033] Please refer to Figure 3 The electrolytic cell 100 is a barrel-shaped structure and is made of stainless steel material to improve the load capacity and corrosion resistance and extend the service life.

[0034] Please refer to Figure 3 The monitoring module 300 further includes an audible and visual alarm 350, which is electrically connected to the controller 400. When the electrolyte is added to the electrolytic cell 100, if there is no water in the water inlet valve 140, the first sampler 160 cannot add nanoparticles, or the second sampler 170 cannot add electrolyte, the audible and visual alarm 350 will sound an audible and visual alarm to remind the operator.

[0035] See also Figure 4 This embodiment also provides a method for preparing a semiconductor thin film using the semiconductor thin film preparation system, which mainly includes steps S101 to S106: S101, grinding and polishing the substrate surface of the semiconductor sample 500, placing the semiconductor sample 500 in anhydrous ethanol for ultrasonic cleaning, and air-drying in air. Exemplarily, the semiconductor sample 500 is a hydrogen sensor chip.

[0036] S102, mixing the electrolyte and the nanoparticles according to a preset ratio, stirring until completely dissolved to form a mixed solution, pouring the mixed solution into the electrolytic cell 100, stirring and performing ultrasonic treatment to obtain a suspended electrolyte. Specifically, the electrolyte includes sodium phosphate and potassium hydroxide, and the nanoparticles are niobium oxide nanoparticles; the electrolyte includes 5-10 g / L sodium phosphate, 0.5-1.5 g / L potassium hydroxide, and 3-7 g / L niobium oxide nanoparticles in terms of mass volume ratio.

[0037] S103, the semiconductor sample 500 is connected to the wire, the semiconductor sample 500 is used as the anode, the electrolytic cell 100 is used as the cathode, and the semiconductor sample 500 is immersed in the electrolyte. The positive electrode of the pulse power supply 200 is connected to the semiconductor sample 500, and the negative electrode of the pulse power supply 200 is connected to the electrolytic cell 100, thereby forming a discharge path.

[0038] S104, setting power supply parameters and the ultraviolet visible light absorption peak intensity, conductivity, and liquid level control threshold in the electrolyte, turning on the pulse power supply 200 to start micro-arc oxidation, and using the constant temperature cooling module 130 and the agitator 110 to keep the electrolyte temperature at the set temperature. Specifically, the reaction current density is set to 10A / dm2, the pulse frequency is set to 400Hz, and the duty cycle is set to 30%; the set temperature is 30~55℃, for example, the temperature is set to 30℃, 35℃, 40℃, 45℃, 50℃ or 55℃.

[0039] S105, after the micro-arc oxidation is performed according to the set reaction time, the semiconductor sample 500 is taken out and replaced. Specifically, the reaction time is set to 3 to 8 minutes, for example, 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, 5 minutes, 5.5 minutes, 6 minutes, 7 minutes or 8 minutes.

[0040] S106, real-time monitoring of electrolyte parameters, and automatic replenishment of electrolyte.

[0041] See also Figure 5 , provides a detailed schematic diagram of a method for preparing a semiconductor thin film according to an embodiment of the present application. Figure 5 As shown, the preparation method of the embodiment of the present application may include the following steps: S201. Prepare an electrolyte by using a formula of 5-10 g / L sodium phosphate, 0.5-1.5 g / L potassium hydroxide and 3-7 g / L niobium oxide nanoparticles according to a mass volume ratio.

[0042] S202, substrate pretreatment, using different types of sandpaper to polish the substrate surface of the semiconductor sample 500 step by step, and put the semiconductor sample 500 into anhydrous ethanol for ultrasonic cleaning, and air-dry in the air. The substrate of the semiconductor sample 500 is Ti material.

[0043] S203, setting reaction parameters, power supply parameters, UV-visible light absorption peak intensity, conductivity, and liquid level control threshold. Input reaction parameters on the display module 620 and transmit them to the controller 400 through the control module 610, thereby remotely controlling the semiconductor film preparation process. Among them, the reaction current density is set to 10A / dm2, the pulse frequency is set to 400Hz, and the duty cycle is set to 30%.

[0044] S204, pouring the electrolyte, pouring the pre-configured electrolyte into the electrolytic cell, turning on the constant temperature cooling module 130, the ultrasonic generator 120 and the stirrer 110, stirring with the stirrer 110 and performing ultrasonic treatment with the ultrasonic generator 120 to obtain a suspended electrolyte.

[0045] S205, placing the semiconductor sample, connecting the semiconductor sample 500 through a wire and immersing it in the electrolyte.

[0046] S206, micro-arc oxidation, turn on the pulse power supply 200 to start micro-arc oxidation, and proceed according to the set reaction time. Specifically, the pulse power supply 200 is a DC pulse power supply, and the constant temperature cooling module 130 and the stirrer 110 are used to keep the electrolyte temperature at the set temperature; the set temperature is 55°C, and the reaction time is set to 5 minutes.

[0047] S207, monitor the reaction process, monitor the electrolyte parameters in real time, and automatically replenish or update the electrolyte by controlling the water inlet valve 140, the first sampler 160 and the second sampler 170 through the controller 400. The signal collected by the liquid level meter 150 is processed by the controller 400 to switch the water inlet valve 140, the signal collected by the conductivity meter 330 is processed by the controller 400 to control the operation of the first sampler 160, and the signal collected by the ultraviolet spectrometer 340 is processed by the controller 400 to control the operation of the second sampler 170.

[0048] S208, replace the semiconductor sample. After completing the micro-arc oxidation, take out the semiconductor sample 500 and replace it.

[0049] For better explanation, the semiconductor film preparation and preparation method provided in the embodiment of the present invention and the existing micro-arc oxidation device in the comparative example are used to prepare semiconductor films multiple times; then the composition structure of the prepared semiconductor films is analyzed and compared. Both are also based on the mass volume ratio, using a formula of 7g / L sodium phosphate, 1g / L potassium hydroxide and 5g / L niobium oxide nanoparticles to prepare the electrolyte; the reaction current density is set to 10A / dm2, the pulse frequency is set to 400Hz, and the duty cycle is set to 30%; the set temperature is 55℃, and the reaction time is set to 5min.

[0050] Please refer to Figure 6 After 5 consecutive preparations, the atomic ratio of the Nb element in the semiconductor film prepared by using the preparation system and preparation method provided by the embodiment of the present invention is basically stable; while the atomic ratio of the Nb element in the semiconductor film prepared by using the existing micro-arc oxidation device in the comparative example continues to decrease.

[0051] Please refer to Figure 7After 5 consecutive preparations, the average thickness of the semiconductor sample 500 is stable when the preparation system and preparation method of the embodiment of the present invention are used; while the thickness deviation of the semiconductor film prepared by the existing micro-arc oxidation device in the comparative example is large, with large fluctuations and a high defective rate.

[0052] These indicate that the semiconductor thin film preparation system and preparation method provided in the embodiments of the present invention can provide more stable reaction conditions, which is conducive to the stable doping of nanoparticles and thin film growth; and can prepare high-quality, low-cost, large-area, uniform-thickness semiconductor films, thereby providing favorable support for the research and production of semiconductor thin film materials.

[0053] The conductor film preparation system and preparation method provided by the embodiment of the present invention monitors the change of solute in the electrolyte by ultraviolet spectrometer 340 and conductivity meter 330, and uses the first sampler 160 and the second sampler 170 to achieve precise control of the concentration of electrolyte and nanoparticles in the electrolyte, and can automatically detect and control the reaction conditions and reaction parameters, thereby reducing the difference caused by the difficulty in controlling the reaction conditions, and achieving precise control and doping of nanoparticles in the growth process of semiconductor film, ensuring the consistency of the composition structure and performance of the prepared film. Micro-arc oxidation treatment is performed on titanium-niobium alloy to prepare a semiconductor film with a porous microstructure on its surface, and Nb-doped Ti0 2 Conductive film materials enhance charge conduction and oxygen ion adsorption capabilities, further improving their performance; high thickness uniformity, improved sensitivity, detection range, stability, and anti-interference capabilities, and the preparation method is more in line with the needs of industrial automation production. It is suitable for preparing semiconductor films doped with nanoparticles, simplifying the production process of semiconductor sensors, and is easy to operate, controllable, and repeatable, achieving the goals of low cost, high efficiency, and repeatability, thereby improving the yield rate. By adjusting the power supply parameters, the performance of the semiconductor sensor chip can be controlled, and the prepared semiconductor sensor chip has the characteristics of large specific surface area, high response sensitivity, and low cost.

[0054] The embodiments of the present invention are described in detail above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. A semiconductor thin film preparation system, characterized in that: include: A micro-arc oxidation device, the micro-arc oxidation device comprising an electrolytic cell, a pulse power supply, a monitoring module and a controller, the electrolytic cell being provided with a stirrer located in the middle, the electrolytic cell being provided with an ultrasonic generator located in the bottom, a constant temperature cooling module being installed on the side wall of the electrolytic cell, the monitoring module comprising a conductivity probe, a photometer probe, a conductivity meter and an ultraviolet spectrometer, the conductivity probe being connected to the conductivity meter, the photometer probe being connected to the ultraviolet spectrometer, the pulse power supply being connected to the electrolytic cell via a wire, and the controller being electrically connected to the constant temperature cooling module and the monitoring module respectively; The control terminal comprises a control module and a display module, wherein the control module is electrically connected to the display module, and the control module is communicatively connected to the controller.

2. The semiconductor thin film preparation system according to claim 1, characterized in that: The micro-arc oxidation device also includes a first sampler and a second sampler, both of which are installed above the electrolytic cell. The first sampler is used to add nanoparticles to the electrolytic cell, and the second sampler is used to add electrolytes to the electrolytic cell.

3. The semiconductor thin film preparation system according to claim 2, characterized in that: The electrolytic cell is provided with a water inlet valve, and the water inlet valve is installed on the top of the electrolytic cell.

4. The semiconductor thin film preparation system according to claim 1, characterized in that: The electrolytic cell is provided with a liquid level meter, which is arranged on the side wall of the electrolytic cell and is used to detect the liquid position in the electrolytic cell in real time.

5. The semiconductor thin film preparation system according to claim 1, characterized in that: The electrolytic cell is a barrel-shaped structure and is made of stainless steel.

6. A method for preparing a semiconductor thin film, characterized in that: A semiconductor thin film preparation system according to any one of claims 1 to 5, comprising: The substrate surface of the semiconductor sample is ground and polished, the semiconductor sample is placed in anhydrous ethanol for ultrasonic cleaning, and then air-dried in air; The electrolyte and the nanoparticles are mixed in a preset ratio, stirred until completely dissolved to form a mixed solution, poured into an electrolytic cell, stirred and subjected to ultrasonic treatment to obtain a suspended electrolyte; Connect the semiconductor sample to the wire, with the semiconductor sample as the anode and the electrolytic cell as the cathode, and immerse the semiconductor sample in the electrolyte; Set the power supply parameters and the UV-visible light absorption peak intensity, conductivity, and liquid level control threshold in the electrolyte, turn on the pulse power supply to start micro-arc oxidation, and use the constant temperature cooling module and stirrer to keep the electrolyte temperature at the set temperature; After micro-arc oxidation is performed according to the set reaction time, the semiconductor sample is taken out and replaced; Real-time monitoring of electrolyte parameters and automatic replenishment of electrolyte.

7. The method for preparing a semiconductor thin film according to claim 6, characterized in that: The substrate of the semiconductor sample is Ti material.

8. The method for preparing a semiconductor thin film according to claim 6, characterized in that: The electrolyte comprises sodium phosphate and potassium hydroxide, the nanoparticles are niobium oxide nanoparticles, and the electrolyte comprises 5-10 g / L sodium phosphate, 0.5-1.5 g / L potassium hydroxide and 3-7 g / L niobium oxide nanoparticles in terms of mass volume ratio.

9. The method for preparing a semiconductor thin film according to claim 7, characterized in that: The power supply parameters include reaction current density, pulse frequency and duty cycle. The reaction current density is set to 10A / dm 2 , the pulse frequency is set to 400 Hz, and the duty cycle is set to 30%.

10. The method for preparing a semiconductor thin film according to claim 9, characterized in that: The set temperature is set to 30-55°C, and the reaction time is set to 3-8min.

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