CN112813406A - Equipment and method for preparing three-dimensional metal simple substance film on surface of special-shaped piece based on CVD technology - Google Patents
Equipment and method for preparing three-dimensional metal simple substance film on surface of special-shaped piece based on CVD technology Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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Abstract
The invention relates to a device and a method for preparing a three-dimensional metal simple substance film on the surface of a special-shaped piece based on a CVD (chemical vapor deposition) technology. The equipment comprises a reaction chamber cavity, a liquid spraying atomization system, a gas supply system, a vacuum system, a temperature control system, a data acquisition system and a computer control system, wherein the reaction chamber cavity is respectively communicated with the liquid spraying atomization system, the vacuum system and the temperature control system, the gas supply system is respectively communicated with the reaction chamber cavity and the liquid spraying atomization system, the computer control system is connected with the data acquisition system, and the data acquisition system is connected with the reaction chamber cavity, the liquid spraying atomization system, the gas supply system, the vacuum system and the temperature control system. The liquid precursor is conveyed to the top of the volatilization pot along with the inert gas, is gasified and sprayed out, enters the cavity of the reaction chamber under the action of the carrier gas and the reduction protective gas, is sprayed out again, and finally is deposited on the surface of a special-shaped piece on the heating table, so that the three-dimensional metal simple substance film is obtained. The method has the advantages of high deposition rate, wide deposition range, good plating winding performance and the like.
Description
Technical Field
The invention relates to the technical field of thin film materials and chemical vapor deposition, in particular to equipment and a method for preparing a metal simple substance film on the surface of a special-shaped piece based on a CVD (chemical vapor deposition) technology.
Background
The metal film material is more and more widely applied, and the shadow can be found in the fields of aerospace, microelectronic devices, ultra-large scale integrated circuits, even life science and the like. Particularly, in the field of microelectronics, as the structure of electronic components tends to be miniaturized, thinned and lightened, the size of the electronic components also tends to be micron-sized or even nano-sized, and thus, the development of metal thin film materials with better performance is required. The metal thin film material plays a crucial role in this process, which not only facilitates further miniaturization of the device, but also exhibits superior performance over bulk materials.
At present, the preparation method of the metal thin film material mainly includes a Physical Vapor Deposition (PVD) method and a Chemical Vapor Deposition (CVD) method. PVD techniques (such as magnetron sputtering) are widely used due to the advantages of fast film forming speed, but the major disadvantage of the PVD techniques is poor step coverage, i.e. poor capability of covering complex workpieces, and the PVD techniques also have the disadvantages of poor process repeatability, high processing cost, etc. Therefore, the PVD technique is only applicable to a substrate having a regular shape, and is not applicable to a substrate having a complicated shape or a powder. CVD techniques can solve this problem. In contrast to PVD techniques, CVD techniques use one or more compounds containing thin film elements to chemically react in the vapor phase on the substrate surface to form a thin film. Therefore, the CVD technology has good plating winding performance and step coverage, can form uniform and high-quality nano-structure films on substrates with complex shapes, and can easily realize the metallization of grooves and holes.
Disclosure of Invention
One of the objectives of the present invention is to provide an apparatus for preparing a metal film on a surface of a special-shaped member based on a CVD technique, which includes a reaction chamber 25, a liquid spray atomizing system 24, a gas supply system, a vacuum system, a temperature control system, a data acquisition system, and a computer control system. The reaction chamber cavity 25 is respectively communicated with the spray atomizing system 24, the vacuum system and the temperature control system; the gas supply system is respectively communicated with the reaction chamber cavity 25 and the spray liquid atomization system 24; the computer control system is connected with the data acquisition system, and the data acquisition system is connected with the reaction chamber cavity 25, the liquid spraying atomization system 24, the gas supply system, the vacuum system and the temperature control system and is used for monitoring the running state of each subsystem and summarizing the running state to the computer control system.
Further, the reaction chamber cavity 25 includes a current-carrying tube 7 located outside the cavity, and a nozzle 8, a nozzle 9, and a heating stage 10 located inside the cavity, a substrate 11 is disposed on the heating stage 10, and the nozzle 9 of the nozzle 8 is directly opposite to the substrate 11.
Further, the spray liquid atomization system 24 comprises a liquid precursor material tank 1, a liquid extraction switch 2, an atomizer 3, an evaporator 5 and a volatilization tank 6, wherein the liquid precursor material tank 1 is sequentially communicated with the liquid extraction switch 2, the atomizer 3 and the volatilization tank 6 through pipelines, a nozzle of the atomizer 3 is positioned at the top of the volatilization tank 6, and the evaporator 5 is positioned inside the volatilization tank 6; after the liquid extraction switch 2 is turned on, liquid in the liquid precursor raw material tank is pumped to the sprayer 3 to be sprayed out, the sprayer 4 is heated by the evaporator 5 in the falling process, the gasified precursor enters the reaction chamber cavity 25 along with the carrier gas to be sprayed out, and a three-dimensional metal simple substance film is formed on the substrate 11 in a deposition mode.
Further, the gas supply system includes an inert gas cylinder 16(He gas), a current-carrying gas cylinder 17(Ar gas), a reduction protection gas cylinder 18(H gas)2Or O2Gas). The inert gas cylinder 16 is communicated with the liquid precursor raw material tank 1 of the liquid spraying atomization system 24 through a pipeline and is used for preventing the liquid precursor from being oxidized and deteriorated and pressing the liquid precursor into the pipeline; the current-carrying gas cylinder 17 is communicated with the volatilization tank 6 of the liquid spray atomization system 24 through a pipeline and is used for carrying precursors (driving materials) to enter a reaction chamber cavity 25 together; the reduction protection gas cylinder 18 is communicated with the current-carrying pipe 7 outside the reaction chamber cavity 25 through a pipeline, and is used for preventing the metal simple substance film from being oxidized in the deposition process and protecting the CVD from being smoothly carried out.
Further, the vacuum system comprises a deflation valve 13, a butterfly valve 14 and a vacuum pump 15. The vacuum pump 15 and the butterfly valve 14 are communicated with the reaction chamber cavity 25 through pipelines, and the air release valve 13 is arranged on the reaction chamber cavity 25 and communicated with the interior of the cavity.
Further, the temperature control system comprises a heating element and a circulating cooling water system. The circulating water system comprises a cooling element, a cooling water pipe and a water chiller, wherein the cooling element and the water chiller are connected through the cooling water pipe, and circulating cooling water flows through a water inlet and a water outlet of the cooling element connected with the heating element and the reaction chamber cavity through pipelines and is used for regulating and controlling the internal temperature of the reaction chamber cavity 25.
Further, the data acquisition system comprises a vacuum gauge 12, a flow meter 19, an infrared thermometer 20 and a data acquisition instrument 22. The vacuum gauge 12 and the infrared thermometer 20 are both communicated with the interior of the reaction chamber cavity 25, and are respectively used for monitoring the vacuum degree and the temperature in the cavity and transmitting the vacuum degree and the temperature to the computer control system through the data acquisition instrument 22; the flow meter 19 is connected with the gas and liquid conveying pipelines respectively and used for measuring the real-time flow of the gas and the liquid.
Another object of the present invention is to provide a method for preparing a three-dimensional elemental metal film on the surface of a special-shaped piece by using the above apparatus, which comprises the following steps: (a) preparing a liquid precursor by using a metal organic compound and a solvent; (b) injecting a liquid precursor into a liquid precursor raw material tank 1, cleaning a special-shaped piece to be processed, placing the special-shaped piece on a heating table 10, starting equipment, setting deposition parameters, and carrying out CVD reaction.
Further, the metal organic compound is specifically a beta-diketone metal organic compound, including copper bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), diisopropoxybis (2,2,6, 6-tetramethyl-3, 5-heptanedionate titanium), iridium acetylacetonate, and the like; the solvent is selected from organic solutions with high solubility, low toxicity and good volatility to metal organic matters, and comprises tetrahydrofuran, absolute ethyl alcohol and the like; the metal simple substance film comprises other metals except alkali metal and radioactive metal, including copper, titanium, iridium and the like.
Further, the ratio of the metal organic compound to the solvent in the liquid precursor is 1g: 50-500 mL.
Furthermore, the flow rate of the liquid precursor in the CVD process is 0.5-10g/min, the flow rate of carrier gas is not more than 10000sccm, the flow rate of reduction protective gas is not more than 1000sccm, the gas pressure in the inert gas cylinder 16 is not more than 1MPa, the pressure in the reaction chamber cavity is controlled to be 50-5000Pa, the deposition time is controlled to be 10-5000min, and the deposition temperature is controlled to be 400-. The temperature in the volatilization pot is set according to the melting point of the selected metal organic compound, and is generally 2-30 ℃ higher than the melting point of the selected metal organic compound.
The invention improves the existing CVD deposition equipment, replaces the traditional bubbling method liquid supply system with a newly developed liquid spray atomization liquid supply system, and ensures that liquid drops formed by a liquid precursor are more uniform and fine (the particle size of raw material particles is smaller and the form is more uniform and consistent) through two times of spraying treatment, so that the performance of the deposited three-dimensional metal simple substance film is more excellent. In addition, the invention also improves the formula and the liquid supply mode of the liquid precursor, and the participation of the high-pressure inert gas can not only prevent the liquid precursor from deteriorating, but also ensure the stability of the liquid material delivery, and is also helpful to reduce the first liquid spraying/atomizing resistance and enhance the liquid spraying/atomizing effect.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the PVD technology, the metal organic precursor adopted by the CVD technology is in a gas phase state in a reaction chamber cavity, and is cracked at the reaction temperature and moves along with molecular heat, so that a uniform and compact metal simple substance film can be deposited on the surface of a special-shaped piece with a complex shape;
(2) the method has the advantages of high deposition rate, wide film deposition range, good plating winding performance and the like, can be carried out on large-size base materials (substrates) or multiple base materials (multiple substrates), and in addition, the higher deposition temperature greatly improves the crystal integrity of metal crystals;
(3) compared with a bubbling method conveying system generally adopted by the traditional CVD technology, the liquid spraying atomizing liquid supply system has the advantages of constant liquid supply amount, stable liquid supply flow rate and the like, so that the liquid precursor can uniformly reach a base material and form a high-quality film;
(4) the invention uses halogen-free metal organic compound as precursor, avoids generating corrosive gas similar to hydrogen chloride and the like in the deposition process and the damage to equipment, does not need expensive tail gas treatment device and vacuum equipment, has environment-friendly whole deposition production process, and can be widely applied to large-scale industrial production.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is an XRD pattern of a copper metal thin film obtained in example 1 of the present invention;
FIG. 3 is a macroscopic view of the titanium metal film obtained in example 2;
fig. 4 is a macroscopic surface view of the iridium metal film produced on the surface of the profile member in example 3 of the present invention.
The method comprises the following steps of 1-a liquid precursor raw material tank, 2-a liquid extraction switch, 3-a sprayer, 4-spraying, 5-an evaporator, 6-a volatilization tank, 7-a current-carrying pipe, 8-a spray pipe, 9-a nozzle, 10-a heating table, 11-a substrate, 12-a vacuum gauge, 13-a vent valve, 14-a butterfly valve, 15-a vacuum pump, 16-an inert gas cylinder, 17-a current-carrying gas cylinder, 18-a reduction protection gas cylinder, 19-a flow meter, 20-an infrared thermometer, 21-a cable, 22-a data acquisition instrument, 23-a computer, 24-a liquid spray atomization system and 25-a reaction chamber cavity.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following description is further provided with reference to the accompanying drawings and specific examples.
The CVD equipment shown in fig. 1 mainly comprises a liquid precursor raw material tank 1, a volatilization tank 6, a release valve 13, a butterfly valve 14, a vacuum pump 15, an inert gas cylinder 16, a current-carrying gas cylinder 17, a reduction protection gas cylinder 18, a data acquisition instrument 22, a computer 23, a flow meter 19 and a reaction chamber cavity 25. The liquid precursor is filled in the liquid precursor raw material tank 1, and two pipelines are arranged on the tank body. One pipeline is communicated with the liquid extraction switch 2, the flowmeter and the volatilization tank 6 and is used for supplying liquid precursors; the other pipeline is connected with a flowmeter and an inert gas cylinder 16 and is used for charging gas into the tank to protect the liquid precursor. The evaporator 5 is arranged in the volatilization tank 6, the top and the bottom are respectively provided with a current-carrying gas inlet, a liquid precursor inlet and a precursor (material) outlet, and the top and the bottom are respectively communicated with a current-carrying gas cylinder 17 (the middle of which is provided with a flowmeter), the liquid precursor material tank 1 and the current-carrying pipe 7 through pipelines. The current-carrying pipe is equivalent to a tee joint and is respectively communicated with the reduction protection gas cylinder 18 and the spray pipe 8 in the reaction chamber cavity 25. The nozzle 8 is arranged at the top of the reaction chamber cavity, and the tail end of the nozzle is provided with a nozzle 9. A heating table 10 is arranged in the middle of the inner part of the reaction chamber cavity 25, a substrate 11 (the substrate 11 can be a special-shaped piece to be processed) is arranged on the heating table 10, and the nozzle 9 is suspended to be opposite to the substrate 11. Besides the current-carrying pipe 7, the surface of the reaction chamber cavity 25 is also provided with a circulating cooling water inlet and outlet, cooling water enters a cooling element in the reaction chamber cavity, the temperature of the reaction chamber cavity (or circulating water flows into and out of a hollow interlayer of the reaction chamber cavity after being heated by a heating element) is reduced, so that the internal temperature of the cavity is regulated and controlled, and the internal temperature of the cavity is monitored in real time by an infrared thermometer 20 fixed on the cavity. The bottom and the side of the reaction chamber cavity 25 are respectively provided with an air pumping port, an air release valve 13 and a vacuum gauge 12, and the vacuum pump 15 and the butterfly valve 14 are respectively connected with the air pumping port through pipelines. The flow meter 19, the infrared thermometer 20, the vacuum gauge 12, the liquid extraction switch 2 and other monitoring control devices are connected with the data acquisition instrument 22 through leads, and the collected data are transmitted to the computer 23. The respective gas, liquid streams flow towards the arrows in fig. 1.
Example 1
The specific process for preparing the metal copper simple substance film on the surface of the substrate by using the equipment is as follows:
(1) copper (Cu (DPM)) bis (2,2,6, 6-tetramethyl-3, 5-heptanedione was converted into copper (1 g:150 mL)2) Is added to tetrahydrofuran (C)4H8O, THF), stirred to completely dissolve it, to obtain a liquid precursor. And injecting the prepared liquid precursor into a liquid precursor raw material tank for later use.
(2) The inspection ensures that the whole set of equipment is operating normally. An aluminum nitride (AlN) polycrystalline substrate having a size of 15mm × 9mm × 1mm was previously cleaned with an ethanol solution having a volume fraction of 95%, and then placed on a heating stage. Starting the whole set of equipment and setting relevant parameters, filling He gas into the liquid precursor raw material tank by using the inert gas cylinder to prevent the He gas from deteriorating, then opening circulating cooling water, a heating element, a computer system, a data acquisition unit, a vacuum pump, a heating table and a required gas cylinder main valve, closing a cavity, and setting relevant deposition parameters on the computer system. To be reversedChemical vapor deposition was started when the pressure and temperature inside the chamber were stabilized at 800Pa and 400 c, respectively (at which levels during the reaction). The computer automatically turns on the current-carrying gas pipeline sub-switch, the reduction protection gas pipeline sub-switch and the liquid-extracting switch according to the program, the liquid precursor is conveyed to the sprayer at the liquid supply speed of 1.5g/min to be sprayed out, and the spray is gasified by the evaporator and then flows in the current-carrying gas (Ar, the flow rate is 1000sccm) and the reduction protection gas (H)2And the flow rate is 1000sccm), enters the cavity of the reaction chamber through the current-carrying pipe, is sprayed out again, is deposited on the surface of the substrate, and obtains the copper simple substance film after about 30 min.
The deposition temperature is changed under the same condition, and the copper simple substance film with better quality can be obtained by carrying out experiments at 500 ℃, 600 ℃, 700 ℃, 800 ℃ and 900 ℃.
XRD analysis and test are carried out on the copper simple substance film with the deposition temperature of 800 ℃, and the result is shown in figure 2. Fig. 2 shows that Cu thin films having (111), (200) and (220) orientations were prepared at 800 ℃, in which the Cu diffraction peak shape of the (111) orientation was the preferred orientation and the (111) orientation was sharp and narrow, indicating that the crystallinity of the (111) oriented crystal grains was good. In addition, the Cu thin film having a preferred orientation of (111) is also an important factor in its high electromigration resistance.
Example 2
(1) Diisopropoxybis (2,2,6, 6-tetramethyl-3, 5-heptanedioic acid) titanium (Ti (O-iPr) in a ratio of 1g:150mL2(DPM)2) Is added to tetrahydrofuran (C)4H8O, THF), stirred to completely dissolve it, to obtain a liquid precursor. And injecting the prepared liquid precursor into a liquid precursor raw material tank for later use.
(2) The inspection ensures that the whole set of equipment is operating normally. An aluminum nitride (AlN) polycrystalline substrate having a size of 7mm × 8mm × 1mm was previously cleaned with an ethanol solution having a volume fraction of 95%, and then placed on a heating stage. With reference to the operating method of example 1, the corresponding deposition process parameters were set: the flow rate of the liquid supply is 1.5g/min, Ar and H2The flow rate is 1000sccm and 50sccm respectively, the deposition temperature is 400 ℃, the total pressure in the reaction chamber cavity is maintained at 800Pa, and the deposition time is 30 min. Titanium sheet produced in this exampleThe film is shown in fig. 3, and it can be seen from fig. 3 that the film has a distinct titanium metallic luster.
The deposition temperature is changed under the same condition, and the titanium elementary substance film with better quality can be obtained by carrying out experiments at 450 ℃, 500 ℃, 550 ℃ and 600 ℃.
Example 3
(1) Iridium acetylacetonate (Ir (acac) in a proportion of 1g:150mL3) Is added to tetrahydrofuran (C)4H8O, THF), stirred to completely dissolve it, to obtain a liquid precursor. And injecting the prepared liquid precursor into a liquid precursor raw material tank for later use.
(2) The inspection ensures that the whole set of equipment is operating normally. The shaped piece to be processed having a size of 7mm × 8mm × 1mm was washed clean in advance with an ethanol solution having a volume fraction of 95%, and then placed on a heating stage. With reference to the operating method of example 1, the corresponding deposition process parameters were set: the flow rate of the liquid supply is 1.0g/min, Ar and O2The flow rate is 1500sccm and 10sccm respectively, the deposition temperature is 550 ℃, the total pressure in the reaction chamber cavity is maintained at 800Pa, and the deposition time is 30 min. As shown in FIG. 4, the three-dimensional metallic simple substance iridium film prepared by the embodiment has obvious iridium metal luster, and the grooves and the tubes of the special-shaped piece are covered by the film, so that the plating property is good.
Claims (10)
1. An apparatus for preparing a metal simple substance film on the surface of a special-shaped piece based on a CVD technology is characterized in that: the equipment comprises a reaction chamber cavity (25), a spray atomizing system (24), a gas supply system, a vacuum system, a temperature control system, a data acquisition system and a computer control system; the reaction chamber cavity (25) is respectively communicated with the spray atomizing system (24), the vacuum system and the temperature control system; the gas supply system is respectively communicated with the reaction chamber cavity (25) and the spray liquid atomization system (24); the computer control system is connected with the data acquisition system, and the data acquisition system is connected with the reaction chamber cavity (25), the spray atomizing system (24), the gas supply system, the vacuum system and the temperature control system and is used for monitoring the running state of each subsystem and summarizing the running state to the computer control system.
2. The apparatus of claim 1, wherein: the reaction chamber cavity (25) comprises a current-carrying pipe (7) positioned outside the cavity, and a spray pipe (8), a nozzle (9) and a heating table (10) positioned inside the cavity, wherein a substrate (11) is arranged on the heating table (10), and the nozzle (9) of the spray pipe (8) is right opposite to the substrate (11).
3. The apparatus of claim 1, wherein: the liquid spraying atomization system (24) comprises a liquid precursor raw material tank (1), a liquid extraction switch (2), an atomizer (3), an evaporator (5) and a volatilization tank (6), wherein the liquid precursor raw material tank (1) is sequentially communicated with the liquid extraction switch (2), the atomizer (3) and the volatilization tank (6) through pipelines, a nozzle of the atomizer (3) is positioned at the top of the volatilization tank (6), and the evaporator (5) is positioned inside the volatilization tank (6); after the liquid extraction switch (2) is opened, liquid in the liquid precursor raw material tank is pumped to the sprayer (3) to be sprayed out, the sprayer (4) is heated by the evaporator (5) in the falling process, the gasified precursor enters the reaction chamber cavity (25) along with the carrier gas to be sprayed out, and a three-dimensional metal simple substance film is deposited on the substrate (11).
4. The apparatus of claim 1, wherein: the gas supply system comprises an inert gas cylinder (16), a current-carrying gas cylinder (17) and a reduction protection gas cylinder (18); the inert gas cylinder (16) is communicated with a liquid precursor raw material tank (1) of the liquid spraying atomization system (24) through a pipeline and is used for preventing the liquid precursor from being oxidized and deteriorated and pressing the liquid precursor into the pipeline; the current-carrying gas cylinder (17) is communicated with a volatilization tank (6) of a liquid spray atomization system (24) through a pipeline and is used for carrying a precursor to enter a reaction chamber cavity (25) together; the reduction protection gas cylinder (18) is communicated with a current-carrying pipe (7) outside the reaction chamber cavity (25) through a pipeline and is used for preventing the oxidation of the metal simple substance film in the deposition process.
5. The apparatus of claim 1, wherein: the vacuum system comprises a deflation valve (13), a butterfly valve (14) and a vacuum pump (15); the vacuum pump (15) and the butterfly valve (14) are communicated with the reaction chamber cavity (25) through pipelines, and the air release valve (13) is arranged on the reaction chamber cavity (25) and communicated with the interior of the cavity.
6. The apparatus of claim 1, wherein: the temperature control system comprises a heating element and a circulating cooling water system; the circulating water system comprises a cooling element, a cooling water pipe and a water chiller, wherein the cooling element and the water chiller are connected through the cooling water pipe; circulating cooling water flows through a cooling element water inlet and a cooling element water outlet which are connected with the heating element and the reaction chamber cavity through pipelines and is used for regulating and controlling the internal temperature of the reaction chamber cavity (25).
7. The apparatus of claim 1, wherein: the data acquisition system comprises a vacuum gauge (12), a flowmeter (19), an infrared thermometer (20) and a data acquisition instrument (22); the vacuum gauge (12) and the infrared thermometer (20) are communicated with the interior of the reaction chamber cavity (25), are respectively used for monitoring the vacuum degree and the temperature in the cavity and are transmitted to the computer control system through the data acquisition instrument (22); the flow meter (19) is respectively connected with the gas and liquid conveying pipelines and is used for measuring the real-time flow of the gas and the liquid.
8. Method for producing a three-dimensional elementary metal film on the surface of a profiled element using a device according to any one of claims 1 to 7, characterized in that it comprises the following steps: (a) preparing a liquid precursor by using a metal organic compound and a solvent; (b) injecting a liquid precursor into a liquid precursor raw material tank (1), cleaning a special-shaped piece to be processed, placing the special-shaped piece on a heating table (10), starting equipment, setting deposition parameters, and carrying out CVD reaction.
9. The method of claim 8, wherein: the metal organic compound is a beta-diketone metal organic source and comprises copper bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), diisopropoxybis (2,2,6, 6-tetramethyl-3, 5-heptanedionate titanium) and iridium acetylacetonate; the solvent is selected from organic solvents with higher solubility, volatility and low toxicity to metal organic compounds, and comprises tetrahydrofuran and absolute ethyl alcohol; the metal simple substance film is selected from at least one of copper, titanium and iridium; the proportion of the metal organic compound to the solvent in the liquid precursor is 1g: 50-500 mL.
10. The method of claim 8, wherein: in the CVD process, the flow rate of the liquid precursor is 0.5-10g/min, the flow rate of the carrier gas is not more than 10000sccm, the flow rate of the reduction protective gas is not more than 1000sccm, the pressure of the inert gas is not more than 1MPa, the pressure in the cavity of the reaction chamber is controlled to be 50-5000Pa, the deposition time is controlled to be 10-5000min, the deposition temperature is controlled to be 400-1200 ℃, and the temperature in the volatilization tank is 2-30 ℃ higher than the melting point of the metal organic compound.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913787A (en) * | 2021-10-15 | 2022-01-11 | 浙江生波智能装备有限公司 | Novel film preparation process and vacuum coating equipment |
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| CN112813406B (en) | 2023-07-14 |
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