CN118056920A - Method for carrying out vapor doping in vacuum coating and vapor doping device - Google Patents
Method for carrying out vapor doping in vacuum coating and vapor doping device Download PDFInfo
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- CN118056920A CN118056920A CN202211444275.5A CN202211444275A CN118056920A CN 118056920 A CN118056920 A CN 118056920A CN 202211444275 A CN202211444275 A CN 202211444275A CN 118056920 A CN118056920 A CN 118056920A
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- UPGUYPUREGXCCQ-UHFFFAOYSA-N cerium(3+) indium(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[In+3].[Ce+3] UPGUYPUREGXCCQ-UHFFFAOYSA-N 0.000 description 1
- 238000010205 computational analysis Methods 0.000 description 1
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- UAFICZUDNYNDQU-UHFFFAOYSA-N indium;oxomolybdenum Chemical compound [In].[Mo]=O UAFICZUDNYNDQU-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a method for carrying out vapor doping in vacuum coating and a vapor doping device, which can meet the requirement of tiny vapor flow in vacuum coating, is beneficial to the water pressure stabilization of a vacuum coating chamber and is beneficial to improving the stability of a vacuum coating process needing vapor doping. The method comprises the following steps: placing a water source within a first vacuum chamber and releasing water vapor from the water source; the vacuum coating is performed in a vacuum coating chamber, the vacuum coating chamber is communicated with the first vacuum chamber through a first communication pipe for conveying the water vapor, and a first regulating valve is arranged on the first communication pipe; detecting the water partial pressure in the vacuum coating chamber through a water partial pressure detector to obtain a water partial pressure detection value; the controller adjusts the opening of the first regulating valve according to the comparison result of the water partial pressure detection value and the water partial pressure preset value; the water source is selected from one or more of crystalline hydrate and molecular sieve adsorbed with water vapor.
Description
Technical Field
The invention relates to a vacuum coating technology, in particular to a method for carrying out vapor doping in vacuum coating and a vapor doping device.
Background
In a vacuum coating process, particularly in a process of preparing a semiconductor film by adopting a physical vapor deposition method, MFC (gas mass flow meter) is generally utilized to introduce water vapor generated by taking liquid water as a water source into a process chamber (i.e. a vacuum coating chamber), and the mode is characterized by stable and controllable flow. However, in the actual use process, the inventor finds that the MFC with the measuring range of 10sccm cannot be stably controlled for the flow value less than or equal to 0.5sccm, and the corresponding vacuum degree change cannot be caused by the change of the flow value under the normal condition of equipment, which indicates that the flow of the gas actually entering the vacuum coating chamber is unstable by taking the MFC as a ventilation tool. Because the photoelectric performance of the ITO (indium tin oxide) film is extremely sensitive to the concentration of water vapor, the demand for water vapor is extremely small, for example, the flow rate of water vapor required in some processes is less than 1sccm, and in the existing water vapor doping mode which uses liquid water as a water source and MFC as a ventilation tool, the situation that the flow rate of water vapor is not stably controlled easily occurs, so that the flow rate fluctuation of water vapor is large, and the production stability is affected. In addition, when MFC control is unstable, excessive water vapor can be doped to make deposited films on the cathode baffle plate of the vacuum coating chamber more easily fall off, increase dust in the chamber, and cause pollution of coating products.
Chinese patent CN214736043U discloses a vapor-introducing device of a film plating apparatus, which mainly solves the technical problem that vapor is easy to condense in the transportation process in a pipeline, so that the flow of vapor entering the film plating apparatus cannot be controlled. The device is mainly characterized in that a heat preservation layer, a heating guide wire and a temperature sensor are distributed on the ventilation pipeline, and the temperature difference between the inside and the outside of the ventilation pipeline is controlled in cooperation with a temperature controller on a power supply loop so as to weaken the phenomenon that water vapor condenses on the inner surface of the pipeline; the vent pipe is also provided with a flowmeter and a valve for controlling the flow of the water vapor and the on-off of the pipe. The structure of the vapor device provided by the patent is similar to that of a traditional vapor generator used by vacuum coating equipment, and the problem of water condensation caused by the lewis of the vent pipe of the traditional vapor generator is solved by adjusting the temperature difference between the inside and the outside of the vent pipe by adding a heating and temperature control device on the vent pipe. The water vapor in this patent application is introduced by a gas mass flow meter, and because the water source of a conventional water vapor generator is liquid water, this results in a high vapor pressure of the water in the vent line, and condensed water will appear when the temperature of the inner surface of the line reaches the condensation point of the vapor at that vapor pressure. The device provided by this patent does not solve the problem of how to stably supply water vapor and reduce the influence on the production stability when the flow rate of water vapor is small.
Chinese patent application CN111293192a provides a method for controlling the vapor in a vacuum chamber for preparing TCO films for solar cells. This patent application addresses the problem of poor accuracy of a gas mass flow Meter (MFC) in controlling low flow rates of water vapor. The method is characterized in that a low-temperature condensing pump is arranged in a transition chamber and/or a process chamber of TCO film preparation equipment, and the low-temperature condensing pump is intermittently started or closed so as to adjust the water vapor amount in the transition chamber and/or the process chamber; and a Residual Gas Analyzer (RGA) is installed in the transition chamber and/or the process chamber, and the cryocondensation pump is turned on when the residual gas analyzer detects that the water vapor amount in the chamber is greater than a set value, and is turned off when the water vapor amount is detected to be less than the set value. However, the control mode of the on/off of the cryopump and the response speed may have a certain disturbance on the vacuum degree and the gas concentration of the vacuum chamber, and it is most critical that the cryopump not only adsorbs the water vapor in the vacuum chamber but also adsorbs other types of gases (Ar, O 2、N2) in the chamber after being turned on, which may affect the stability of all process gases, and the patent application does not propose a solution for this.
Chinese patent application CN104313542B provides a method for preparing an ITO (indium tin oxide) film, which aims to reduce the degree of polycrystallization of the ITO film and solve the problem that crystalline ITO is difficult to etch. The method comprises the following steps: and (3) depositing an ITO film by adopting a magnetron sputtering process, introducing water vapor into the cavity through an MFC in the film deposition process, wherein the water vapor flow is calculated by Q2×T ITO/100000× (1+/-20%) sccm, Q2 is Ar gas flow, T ITO is the thickness of the ITO film, and the water vapor flow value under specific process conditions is calculated by the calculation formula. However, this patent does not address the problems of poor accuracy of MFC in controlling minute flow of water vapor and susceptibility to condensation of liquid water source.
Disclosure of Invention
The invention provides a method for carrying out vapor doping in vacuum coating and a vapor doping device, which can meet the requirement of tiny vapor flow in vacuum coating, is beneficial to the water pressure stabilization of a vacuum coating chamber and is beneficial to improving the stability of a vacuum coating process needing vapor doping.
The invention provides the following technical scheme for achieving the purpose:
the invention provides a method for carrying out vapor doping in vacuum coating, which comprises the following steps:
Placing a water source within a first vacuum chamber and releasing water vapor from the water source; the vacuum coating is performed in a vacuum coating chamber, the vacuum coating chamber is communicated with the first vacuum chamber through a first communication pipe for conveying the water vapor, and a first regulating valve is arranged on the first communication pipe;
Detecting the water partial pressure in the vacuum coating chamber through a water partial pressure detector to obtain a water partial pressure detection value; the controller adjusts the opening of the first regulating valve according to the comparison result of the water partial pressure detection value and the water partial pressure preset value;
the water source is selected from one or more of crystalline hydrate and molecular sieve adsorbed with water vapor.
In some embodiments, the water partial pressure detector is a residual gas analyzer, preferably the residual gas analyzer has a lower detection limit of 1×10 -11 Torr or less for the water partial pressure.
In some embodiments, the first vacuum chamber is connected with a first air pumping system, and the first vacuum chamber can reach a first preset vacuum degree through the first air pumping system; preferably, the first preset vacuum degree is less than or equal to 2E-5Torr;
preferably, the vacuum degree of the first vacuum chamber is controlled to be a first preset vacuum degree before the first vacuum chamber is used for doping the vapor into the vacuum coating chamber.
Preferably, the first vacuum chamber is further provided with a heating element capable of heating the water source.
In some embodiments, the method further comprises:
placing the water source in a storage chamber in advance before the water source is placed in the first vacuum chamber for storage;
Preferably, the storage chamber is connected with a second air extraction system, and the second air extraction system enables the storage chamber to reach a second preset vacuum degree;
preferably, the method further comprises: the water source enables the vacuum degree of the storage chamber to meet a second preset vacuum degree during the storage period in the storage chamber, wherein the second preset vacuum degree is preferably less than or equal to 5E-2Torr;
Preferably, the storage chamber is provided with a water source output port, the water source output port is communicated with a water source receiving port of the first vacuum chamber through a second communicating pipe, and a second regulating valve is arranged on the second communicating pipe; when the water source is required to be conveyed into the first vacuum chamber, the second regulating valve is opened, and the water source stored in the storage chamber is conveyed into the first vacuum chamber through the second communicating pipe.
Preferably, the crystalline hydrate is selected from one or more of CuSO 4·5H2O、CaSO4·2H2O、CH3COONa·3H2 O; the molecular sieve is selected from 3A molecular sieves.
In some embodiments, the quality of the water source disposed within the first vacuum chamber is at least sufficient to meet the water partial pressure requirements of the vacuum coating during the time required for the vacuum coating.
The invention also provides a water vapor doping device for implementing the method described above, the water vapor doping device comprising a first vacuum chamber, a first regulating valve, a first communication pipe, a water partial pressure detector and a controller;
A water source containing area for placing crystalline hydrate and/or molecular sieve absorbing water vapor is arranged in the inner cavity of the first vacuum chamber, the first vacuum chamber is provided with a water vapor outlet, the first communication pipe is used for communicating the water vapor outlet with a vacuum coating chamber of a vacuum coating device, and the first communication pipe is provided with the first regulating valve;
the water partial pressure detector is used for detecting the water partial pressure in the vacuum coating chamber to obtain a water partial pressure detection value, and is preferably a residual gas analyzer;
The controller is respectively in communication connection with the first regulating valve and the water pressure detector, and the controller can regulate the opening of the first regulating valve according to the comparison result of the water pressure detection value and the water pressure preset value.
In some embodiments, the vapor doping apparatus further comprises a first pumping system, the first vacuum chamber being connected to the first pumping system.
Preferably, the first vacuum chamber is further provided with a heating element capable of heating the crystalline hydrate and/or the molecular sieve adsorbed with water vapor which are placed in the first vacuum chamber.
In some embodiments, the vapor doping device further comprises a storage chamber, wherein the storage chamber is provided with a water source output port, the water source output port is communicated with the water source receiving port of the first vacuum chamber through a second communicating pipe, and a second regulating valve is arranged on the second communicating pipe;
preferably, the vapor doping device further comprises a second air pumping system, and the storage chamber is connected with the second air pumping system.
In some embodiments, the vapor doping apparatus further comprises a material transfer mechanism for transferring crystalline hydrate and/or molecular sieves adsorbed with water vapor within the storage chamber to the first vacuum chamber;
preferably, the material conveying mechanism is a mechanical arm.
The invention also provides vacuum coating equipment which comprises a vacuum coating device and the vapor doping device, wherein the vacuum coating device is provided with a vacuum coating chamber, and the vapor outlet of the first vacuum chamber of the vapor doping device is communicated with the vacuum coating chamber of the vacuum coating device through the first communication pipe.
The technical scheme provided by the invention has the following beneficial effects:
The method provided by the invention does not adopt liquid water as a water source, but adopts crystalline hydrate and/or molecular sieve adsorbed with water vapor as the water source, and the water source can release trace water vapor at a very slow rate, does not generate dew condensation phenomenon, and is easy to realize stable control of water partial pressure when meeting the requirement of micro water partial pressure. In the method, the opening of the first regulating valve is controlled by the controller, and the opening of the first regulating valve is regulated and controlled according to the comparison result of the water partial pressure detection value in the vacuum coating chamber detected by the water partial pressure detector and the preset water partial pressure preset value of the vacuum coating chamber, so that the stability of the water partial pressure in the vacuum coating chamber is guaranteed; moreover, the method of the invention does not influence the pressure of other process gases in the vacuum coating chamber in the process of adjusting the water partial pressure, thereby being beneficial to obtaining good process stability.
Drawings
FIG. 1 is a schematic view showing a vapor doping apparatus according to the present invention disposed on a vacuum coating apparatus in one embodiment.
FIG. 2 is a graph showing the change of vacuum in a vacuum coating chamber with time when copper sulfate pentahydrate is used as a water source in one embodiment.
Part of the reference numerals illustrate: the device comprises a first vacuum chamber 1, a storage chamber 2, a vacuum coating device 3, a vacuum coating chamber 4, a material conveying mechanism 5, a water partial pressure detector 6, a second vacuum pump 7, a molecular pump 71, a mechanical pump 72, a first vacuum pump 8, a molecular pump 81, a mechanical pump 82, an air extractor 9, a molecular pump 91, a mechanical pump 92, a second communicating pipe 10, a second regulating valve 11, a first communicating pipe 12, a first regulating valve 13, a container 14, a water source placing area 15, a first air extracting pipe 16 and a second air extracting pipe 17.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The term "and/or" as may be used herein includes any and all combinations of one or more of the associated listed items.
Where specific experimental steps or conditions are not noted in the examples, they may be performed according to the operations or conditions of the corresponding conventional experimental steps in the art. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In one aspect, the present invention provides a method for performing vapor doping in vacuum coating, and in combination with fig. 1, the method mainly includes:
Placing a water source in the first vacuum chamber 1, and releasing water vapor from the water source in the first vacuum chamber 1;
Vacuum coating is carried out in a vacuum coating chamber 4; the vacuum coating chamber 4 is communicated with the first vacuum chamber 1 through a first communication pipe 12, the first communication pipe 12 is used for conveying water vapor released by a water source in the first vacuum chamber 1, and a first adjusting valve 13 with an adjustable opening is arranged on the first communication pipe 12; the water vapor released by the water source in the first vacuum chamber 1 enters the vacuum coating chamber 4 through the first communication pipe 12;
Detecting the water partial pressure in the vacuum coating chamber 4 by a water partial pressure detector 6 to obtain a water partial pressure detection value; the controller adjusts the opening of the first adjusting valve 13 according to the comparison result of the water partial pressure detection value and the water partial pressure preset value, so that the amount of water vapor entering the vacuum coating chamber 4 from the first vacuum chamber 1 is adjusted, and the water partial pressure in the vacuum coating chamber 4 is maintained at the required water partial pressure preset value;
The water source used is selected from one or more of crystalline hydrate and molecular sieve adsorbed with water vapor.
In the method, liquid water is not used as a water source, but crystal hydrate and/or molecular sieve adsorbed with water vapor are used as water sources, the water sources are greatly different from the liquid water, the water sources (particularly compared with the liquid water) can release trace water vapor at a very slow rate in a vacuum environment, the stable control of the water vapor pressure when meeting the requirement of the micro water vapor pressure is easy to realize, the released water vapor has extremely low vapor pressure in the vacuum environment, the phenomenon of condensation is avoided, and the condensation of the water vapor into liquid drops is avoided. In the method, the opening of the first regulating valve is controlled by the controller, and the opening of the first regulating valve is regulated and controlled according to the comparison result of the water partial pressure detection value in the vacuum coating chamber detected by the water partial pressure detector and the preset water partial pressure preset value of the vacuum coating chamber, so that the stability of the water partial pressure in the vacuum coating chamber is guaranteed; moreover, the method of the invention does not influence the pressure of other process gases in the vacuum coating chamber in the process of adjusting the water partial pressure, thereby being beneficial to obtaining good process stability.
In a preferred embodiment, the water partial pressure detector is a residual gas analyzer (Residual Gas Analyzer: RGA), and the lower limit of detection of the water partial pressure by the residual gas analyzer is preferably 1X 10 -11 Torr or less, for example 1X 10 -11Torr、1×10-12Torr、2×10-12 Torr or the like. The method has the advantages that the crystalline hydrate and/or the molecular sieve adsorbed with the water vapor are/is used as a water source, RGA is adopted instead of MFC, the water partial pressure of the vacuum coating chamber is detected through RGA, the opening of the first regulating valve is regulated by the controller according to the water partial pressure detection value obtained by RGA, the water vapor content in the vacuum coating chamber can be accurately controlled better, the stability of the tiny water partial pressure in the vacuum coating chamber is ensured, the control precision is improved, and the process stability is further improved.
Further, the first vacuum chamber 1 is connected with a first air pumping system, and the first vacuum chamber 1 can reach a first preset vacuum degree through the first air pumping system. The first air extraction system may specifically include a first vacuum pump 8 and a first air extraction pipe 16, where the first vacuum pump 8 is connected to the first vacuum chamber 1 through the first air extraction pipe 16, and the first vacuum chamber 1 can reach a desired target vacuum degree, that is, a first preset vacuum degree, by performing vacuum extraction through the first vacuum pump 8. The first vacuum pump 8 may specifically be a mechanical pump 82 and a molecular pump 81 connected in series, the molecular pump 81 being directly connected to the first vacuum chamber 1.
In some embodiments, the first vacuum chamber 1 may further be provided with a heating element (not shown) capable of heating the water source disposed in the first vacuum chamber 1, so that when a larger water partial pressure is required, the heating element heats the water source (for example, the water source can be heated in a range of less than or equal to 100 ℃), and the release rate of water vapor can be increased, so as to meet the vacuum coating process requirement of the higher water partial pressure. The heating element may be, for example, an electric heating wire, an infrared lamp, or the like, and the installation position of the heating element is not particularly limited as long as the heating element can perform the function of heating the water source. Specifically, for example, a heating wire can be arranged in a water source accommodating area for placing a water source in the first vacuum chamber, and a heat homogenizing plate made of copper, graphite or stainless steel can be covered on the heating wire; for example, an infrared lamp may be provided above the water source receiving area to perform radiant heating.
In a preferred embodiment, the method further comprises: the water source is previously stored in the storage chamber 2 before being placed in the first vacuum chamber 1. Preferably, the storage chamber 2 is also a vacuum chamber, the storage chamber 2 is connected with a second air extraction system, the storage chamber 2 is enabled to reach a second preset vacuum degree through the second air extraction system, the second air extraction system specifically can comprise a second vacuum pump 7 and a second air extraction pipe 17, the second vacuum pump 7 is connected with the storage chamber 2 through the second air extraction pipe 17, and the storage chamber 2 can reach a required target vacuum degree, namely the second preset vacuum degree through vacuumizing of the second vacuum pump 7. The second vacuum pump 7 may specifically be a mechanical pump 72 and a molecular pump 71 connected in series, the molecular pump 71 being directly connected to the reservoir 2. In a preferred embodiment, in the method of the present invention, the vacuum degree of the storage chamber 2 satisfies a second preset vacuum degree during the storage of the water source in the storage chamber 2, the second preset vacuum degree is preferably less than or equal to 5E-2Torr, and the water source is stored under the preferred second preset vacuum degree, so that the release of water vapor in the water source during the storage period is reduced, and the water vapor loss is reduced. Further specifically, the storage chamber 2 is provided with a water source outlet (not shown in the figure), the first vacuum chamber 1 is provided with a water source receiving port (not shown in the figure), the water source outlet is communicated with the water source receiving port of the first vacuum chamber 1 through the second communicating pipe 10, and the second communicating pipe 10 is provided with the second regulating valve 11. In some embodiments, a plurality of water sources can be placed in the storage chamber 2 in advance, and each water source at least meets the quality of the water source required by the corresponding vacuum coating process; therefore, when the water source in the first vacuum chamber 1 can not release the water vapor meeting the requirement any more when the multiple vacuum coating processes are performed, the water source of the storage chamber 2 can be supplemented into the first vacuum chamber 1 through the second communicating pipe 10 by opening the second regulating valve 11, so that the water source does not need to be frequently supplemented from the outside, and the vacuum environment does not need to be frequently broken. More specifically, the water source in the storage chamber 2 is transferred to the first vacuum chamber 1 through the material transfer mechanism 5, and the material transfer mechanism 5 may be, for example, a mechanical arm; the mechanical arm can be a corresponding mechanical arm with grabbing and material transferring functions which are conventional in the prior art, and the mechanical arm can be arranged in a conventional manner in the field, so that the grabbing part of the mechanical arm can be ensured to move among the storage chamber, the second communicating pipe and the first vacuum chamber; the mechanical arm is driven by an external power device; preferably, the mechanical arm is sealed at the position where the mechanical arm is connected with the storage chamber or the first vacuum chamber. Specifically, a water source placing area (or water source accommodating area) 15 for placing a water source, which may specifically be a water source placing table, may be provided in the storage chamber 2 and the first vacuum chamber 1. In a specific embodiment, when the water source in the storage chamber 2 needs to be sent to the first vacuum chamber 1, the second regulating valve 11 is opened, the grabbing part of the mechanical arm grabs the container 14 containing the water source in the storage chamber and sends the container to the water source placing table of the first vacuum chamber 1, and then the grabbing part of the mechanical arm returns to the storage chamber 2, and the second regulating valve 11 is closed, so that the water source conveying operation is completed.
Specifically, a water source is placed in the first vacuum chamber 1 or the storage chamber 2 in a form of being accommodated in a container 14 (e.g., a reagent vessel), which may be a container of a nonmetallic material such as a beaker or ceramic.
Preferably, the vacuum degree of the first vacuum chamber 1 is controlled to be a first preset vacuum degree before the first vacuum chamber 1 is doped with the water vapor into the vacuum coating chamber 4. In some embodiments, when the storage chamber 2 is not present, after the water source is directly obtained from the outside without passing through the storage chamber 2 and put into the first vacuum chamber 1, the first vacuum chamber 1 is pumped by the first pumping system to reach the first preset vacuum degree; when the storage chamber 2 is arranged, before a water source in the storage chamber 2 is transmitted to the first vacuum chamber 1, the first vacuum chamber 1 is pumped by a first pumping system to reach a first preset vacuum degree; by adopting the preferable mode, the impurity gas can be removed as much as possible, and the diffusion amount of the impurity gas into the vacuum coating chamber 4 during the subsequent vacuum coating can be reduced. In actual production, whether to perform the above operation can also be selected according to the process requirements or the product requirements. In some embodiments, the first predetermined vacuum is, for example, 2E-5Torr.
Preferably, the crystalline hydrate as the water source satisfies the following conditions: 1. no other volatile components except crystal water in a vacuum environment; 2. non-high-risk chemicals (i.e., non-toxic and harmless), easy to store, and not easy to deliquesce in the air. Preferably, in the method of the invention, the crystal hydrate used as a water source is one or more of CuSO 4·5H2O、CaSO4·2H2O、CH3COONa·3H2 O (sodium acetate trihydrate) and other crystals, and preferably, calcium chloride dihydrate is not used as the water source; the method of the invention adopts the preferable crystal hydrate as a water source, can more stably meet the requirement of tiny steam flow in vacuum coating, and can obtain better stability of the vacuum coating process needing to be doped with steam. In the method, the crystalline hydrate is used as a water source, the crystalline hydrate can be weathered to a certain extent after being dehydrated in a vacuum environment, and powder formed by the weathering can be recycled after being recrystallized in distilled water, so that the waste and discharge of chemicals are avoided.
Preferably, the molecular sieve used as a water source is a molecular sieve for selectively adsorbing water vapor, preferably a 3A molecular sieve, wherein the effective pore diameter of the 3A molecular sieve is about 3 angstroms, and the molecular sieve mainly adsorbs water vapor, has no adsorption effect on other molecules with diameters larger than 3 angstroms, and can ensure that the gas released by the molecular sieve is pure water vapor. The molecular sieve is used as a water source, and can be regenerated by heating so as to be reused. Illustratively, the 3A molecular sieve may be subjected to a water vapor adsorption operation using the following steps: 1. regenerating the 3A molecular sieve to remove water molecules adsorbed in the molecular sieve; 2. at room temperature, the molecular sieve is subjected to steam adsorption in an environment with the humidity of 70-80, so that the inside of the molecular sieve adsorbs steam; after the above operation is completed, the 3A molecular sieve with adsorbed water vapor is obtained and used as a water source.
In some embodiments, the method of the present invention specifically comprises the steps of:
S1: determining the mass M of the water source required to maintain the water partial pressure preset value of the vacuum coating chamber 4 within the time required for satisfying the vacuum coating (for example, the time required for sputtering deposition);
S2: placing at least one water source with the mass M in the storage chamber 2, starting a second air pumping system, and maintaining the vacuum degree of the storage chamber 2 at a second preset vacuum degree, preferably within the range of less than or equal to 5E-2Torr;
S3: opening a second regulating valve 11, and conveying a water source of the mass M from the storage chamber 2 into the first vacuum chamber 1 through the material conveying mechanism 5; preferably, the vacuum degree of the first vacuum chamber 1 is controlled to be a first preset vacuum degree (preferably less than or equal to 2E-5 Torr) before the first vacuum chamber 1 is doped with steam into the vacuum coating chamber 4;
S4: the water partial pressure detector 6 (RGA) is started to detect the water partial pressure in the vacuum coating chamber 4, and the controller adjusts the opening of the first regulating valve 13 according to the comparison result of the water partial pressure detection value obtained by the RGA and the water partial pressure preset value so as to maintain the water partial pressure in the vacuum coating chamber 4 at the water partial pressure preset value.
S5: and when the water partial pressure in the vacuum coating chamber 4 is maintained at the preset water partial pressure value, vacuum coating is carried out.
In some embodiments, the mass M of the water source required to maintain the predetermined water partial pressure of the vacuum coating chamber for the time required to satisfy the vacuum coating mentioned in step S1 may be determined by the steps of:
S1-1: determining the time taken for vacuum coating and the desired water partial pressure preset value in the vacuum coating chamber 4 equipped with the air extracting device 9;
S1-2: placing a water source with the mass X in the first vacuum chamber 1, keeping the first regulating valve 13 fully open, simultaneously starting the air extractor 9 of the vacuum coating chamber 4 to continuously extract air, and monitoring the real-time water partial pressure in the vacuum coating chamber 4;
S1-3: and obtaining the duration time when the real-time water partial pressure is larger than or equal to (preferably larger than) the water partial pressure preset value, and considering the mass M as the mass X when the duration time is larger than or equal to (preferably larger than) the time required to be spent by the vacuum coating.
The preset parameters such as the preset water partial pressure value can be set correspondingly according to different requirements of the vacuum coating process or target products. The specific process operation of the vacuum coating can be determined according to the specific vacuum coating process requirement, and can be performed by adopting the vacuum coating operation conventional in the art, which is not described in detail.
The method can well meet the requirement of the moisture pressure (for example, the moisture pressure is generally between 10 -6 Torr and 10 -8 Torr) in the sputtering deposition process of the TCO film (transparent conductive film), can realize more direct and accurate control of the moisture pressure, particularly the tiny moisture pressure, and is beneficial to improving the process stability. TCO films such as, but not limited to, indium tin oxide, indium cerium oxide, indium molybdenum oxide, aluminum doped zinc oxide, and the like.
The "vacuum coating" referred to in the present invention may be a physical vapor deposition coating.
The second aspect of the invention also provides a water vapour doping apparatus for carrying out the method described above. Referring to fig. 1, the vapor doping apparatus mainly includes a first vacuum chamber 1, a first regulating valve 13, a first communication pipe 12, a partial pressure detector 6, and a controller (not shown).
Wherein, a water source accommodating area 15 for placing a water source (specifically, crystalline hydrate and/or molecular sieve adsorbed with water vapor) is arranged in the inner cavity of the first vacuum chamber 1, the first vacuum chamber 1 is provided with a water vapor outlet (shown in the figure), a first communication pipe 12 is used for communicating the water vapor outlet of the first vacuum chamber 1 with the vacuum coating chamber 4 of the vacuum coating device 3, and a first regulating valve 13 is arranged on the first communication pipe 12.
The partial pressure detector 6 is used for detecting the partial pressure of water in the vacuum coating chamber to obtain a partial pressure detection value, and is preferably a Residual Gas Analyzer (RGA).
The controller is respectively in communication connection with the first regulating valve 13 and the water pressure detector 6, and can regulate the opening of the first regulating valve 13 according to the comparison result of the water pressure detection value and the water pressure preset value, so as to regulate the amount of water vapor entering the vacuum coating chamber 4 from the first vacuum chamber 1 through the first communication pipe 12, and further maintain the water pressure in the vacuum coating chamber 4 at the required water pressure preset value. The controller used may be one conventionally known in the art having corresponding computational analysis and control functions, such as a pneumatic controller or the like.
Further, the vapor doping device further comprises a first air pumping system, and the first vacuum chamber 1 is connected with the first air pumping system. The first air extraction system specifically comprises a first vacuum pump 8 and a first air extraction pipe 16, wherein the first vacuum pump 8 is connected with the first vacuum chamber 1 through the first air extraction pipe 16, and the first vacuum chamber 1 can reach a required target vacuum degree, such as a first preset vacuum degree, by vacuumizing the first vacuum pump 8. The first vacuum pump 8 may specifically be a mechanical pump 82 and a molecular pump 81 connected in series, the molecular pump 81 being directly connected to the first vacuum chamber 1.
Further, the first vacuum chamber 1 may be provided with a heating element capable of heating a water source placed in the first vacuum chamber. The heating element may be, for example, an electric heating wire or an infrared lamp, and the installation position of the heating element is not particularly limited, so long as the heating effect on the water source can be achieved, and the description of the heating element may refer to the foregoing description, and will not be repeated herein.
Further, the vapor doping apparatus further comprises a storage chamber 2, the storage chamber 2 is provided with a water source output port (not shown in the figure), the water source output port is communicated with a water source receiving port (not shown in the figure) of the first vacuum chamber 1 through a second communicating pipe 10, and the second communicating pipe 10 is provided with a second regulating valve 11. When it is desired to transfer the water source in the reservoir 2 to the first vacuum chamber 1, the second regulating valve 11 is opened. Further, the vapor doping device further comprises a second air extraction system, and the storage chamber 2 is connected with the second air extraction system; specifically, the second air pumping system includes a second vacuum pump 7 and a second air pumping pipe 17, the second vacuum pump 7 is connected with the storage chamber 2 through the second air pumping pipe 17, and the storage chamber 2 can reach a required target vacuum degree, for example, a second preset vacuum degree, by pumping vacuum through the second vacuum pump 7. The second vacuum pump 7 may specifically be a mechanical pump 72 and a molecular pump 71 connected in series, the molecular pump 71 being directly connected to the reservoir 2.
Further, the vapor doping apparatus further includes a material conveying mechanism 5 for conveying the water source in the storage chamber 2 to the first vacuum chamber 1, such as, but not limited to, a mechanical arm, etc., and the description of the material conveying mechanism may refer to the foregoing description and will not be repeated herein.
Specifically, the first regulating valve 13 may be a gate valve, a butterfly valve, or the like, and the second regulating valve 11 may be a gate valve, or the like.
The invention also provides vacuum coating equipment, which comprises a vacuum coating device 3 and the vapor doping device, as shown in fig. 1, wherein the vacuum coating device 3 is provided with a vacuum coating chamber 4, and a vapor outlet of a first vacuum chamber 1 of the vapor doping device is communicated with the vacuum coating chamber 4 of the vacuum coating device 3 through a first communication pipe 12. The specific description of the vapor doping apparatus is referred to above, and will not be repeated here. One of the main improvements of the present invention is to provide a vapor doping device on the basis of a vacuum coating device, and the vacuum coating device may be a corresponding device capable of realizing vacuum coating requirements in the art, for example, a conventional vacuum coating device existing in the art, which will not be described in detail. The vacuum coating apparatus is provided with a suction device 9, and specifically includes, for example, a molecular pump 91 communicating with the vacuum coating chamber 4, and a mechanical pump 92 connected in series with the molecular pump 91.
The method of the invention is illustrated by means of specific examples.
Example 1:
In the embodiment, the crystalline hydrate CuSO 4·5H2 O is used as a water source, a magnetron sputtering method is adopted to deposit a 120nm ITO film on a glass substrate, the required water partial pressure preset value in a vacuum coating chamber is 5E-7Torr, and the sputtering deposition time is 45min. And testing the surface resistance of the ITO film by adopting a four-probe resistance tester. The structure of the vapor doping apparatus is described above with reference to fig. 1, and will not be described again here. Wherein, the water partial pressure detector is a residual gas analyzer (RGA of HIDEN ANALYTICAL is adopted, and the detection limit is not less than 2X 10 -12 Torr). The first regulating valve 13 is a butterfly valve with an adjustable opening, and the second regulating valve 11 is a gate valve. The first vacuum pump 8 is a molecular pump 81 and a mechanical pump 82 connected in series, and the second vacuum pump 7 is a molecular pump 71 and a mechanical pump 72 connected in series. The vacuum coating apparatus 3 is provided with an air extracting device 9 which specifically comprises a molecular pump 91 and a mechanical pump 92 connected in series, wherein the molecular pump 91 is connected with the vacuum coating chamber 4.
The experimental procedure was as follows:
1): determining the mass M of a water source required for maintaining the water partial pressure preset value of the vacuum coating chamber in the sputtering deposition time of the vacuum coating:
Weighing a certain mass of copper sulfate pentahydrate by an analytical balance, and placing the copper sulfate pentahydrate in a beaker;
M1＝MCuSO4·5H2O＝3.2937g
M2＝MCuSO4·5H2O+ Beaker ＝11.8073g
Firstly, placing the beaker into a storage chamber, and pumping air by a second vacuum pump until the vacuum degree is 5E-4Torr; pumping the first vacuum chamber to a vacuum degree of 2E-5Torr by using a first vacuum pump; the gate valve (i.e., the second regulator valve) was then opened, and the beaker with CuSO 4·5H2 O was transferred to the first vacuum chamber with a robotic arm, closing the gate valve. When the air pressure of the vacuum coating chamber reaches 4E-8Torr (the vacuum is background vacuum), the first regulating valve is completely opened, and the vacuum coating chamber is continuously pumped by the pumping device 9; the change rule of the air pressure of the vacuum coating chamber along with the release of crystal water in the copper sulfate pentahydrate is observed and recorded in real time, and the obtained curve is shown in figure 2.
As can be seen from FIG. 2, after the first regulating valve is opened, the air pressure of the vacuum coating chamber is rapidly increased from 4E-8Torr (background vacuum) to 1.3E-5Torr, the change of the air pressure in the coating equipment is continuously observed, the air pressure in the vacuum coating chamber is continuously reduced due to the continuous reduction of the release rate of crystal water in anhydrous copper sulfate along with time, the air pressure in the vacuum coating chamber is reduced to about 5E-8Torr after the vacuum coating chamber is continuously pumped for 140 hours (the air pressure is measured by a high vacuum gauge), and the air pressure is close to the background vacuum of the vacuum coating chamber (reaches the same order of magnitude), so that the influence of the amount of water vapor released by crystal hydrate on the vacuum degree is very small and almost negligible. The beaker was then removed and weighed with an analytical balance:
M3＝MCuSO4·5H2O+ Beaker ＝10.7565g
the total released crystallization water mass was:
△M＝M2-M3＝1.0508g
Assuming the final copper sulfate chemical formula is CuSO 4·xH2 O, using the above data, x.apprxeq.0.6 can be calculated, so that 3.2937g of CuSO 4·5H2 O is converted into CuSO 4·0.6H2 O after 140 hours of pumping, 1.0508g of crystal water is released, and thus it can be seen that the release rate of water vapor is extremely trace and gentle in 140 hours. From the air pressure change curve of the vacuum coating chamber in fig. 2, the air pressure in the vacuum coating chamber is subtracted with background vacuum to obtain the water partial pressure, and the duration time of the water partial pressure is far longer than the sputtering deposition time (45 min) of the vacuum coating when the water partial pressure is larger than the preset value (namely 5E-7 Torr), so that the water vapor release amount brought by 3.2937g of copper sulfate pentahydrate can completely meet the process requirement of the coating equipment for depositing the ITO film, and the quality M of a water source is determined to be 3.2937g.
2) One part by mass M (3.2937 g) of CuSO4.5H2O crystals contained in a beaker is placed in a storage chamber (a plurality of parts by mass M of CuSO4.5H2O crystals can be placed in the storage chamber according to requirements), a second vacuum pump is started, and the vacuum degree is 5E-4Torr. The first vacuum chamber was evacuated to a vacuum level of 2E-5Torr using a first vacuum pump.
3) The gate valve (i.e., the second regulating valve) was opened, and the beaker containing the mass M of CuSO 4·5H2 O was transferred into the first vacuum chamber with a robot, and the gate valve was closed.
4) And (3) starting the RGA, detecting the water partial pressure in the vacuum coating chamber, and regulating the opening of the first regulating valve by the controller according to the comparison result of the water partial pressure detection value obtained by the RGA and a water partial pressure preset value (5E-7 Torr in the embodiment), namely increasing the opening of the first regulating valve when the water partial pressure detection value is lower than the water partial pressure preset value, and otherwise, reducing the opening of the first regulating valve.
5) When the water partial pressure In the vacuum coating chamber is kept at a water partial pressure preset value and does not fluctuate, vacuum coating is carried out, specifically, the target material is indium tin oxide (In 2O3:SnO2 =95:5wt%), ar with the flow of 20sccm is introduced into the vacuum coating chamber, the power supply power is set to be 50W, the vacuum coating chamber is continuously pumped by an air pumping device 9 In the vacuum film process, the total air pressure In the vacuum coating chamber is kept at 3mTorr, and the sputtering deposition time is 45 minutes.
After the preparation of the ITO film, the thickness of the film was measured by a step tester, and the surface resistance value of the ITO film was measured by four probes, with the results of 125nm and 125nm, respectivelyThe resistivity is 2.95E-4Ω.cm.
Vacuum coating is performed according to the step 5), except that no steam is introduced into the vacuum coating chamber, and the surface resistance of the ITO film is raised to
Example 2
Referring to steps 2) to 5) of example 1, the tests (corresponding to experiments 1# -4# in table 1 below, respectively) were repeated 4 times, and the area resistance, film thickness and resistivity of the obtained ITO thin film are shown in table 1 below.
TABLE 1
| Experiment number | Surface resistance/Ω/≡ | Film thickness/nm | Resistivity/Ω cm |
| 1# | 24.57 | 124 | 3.05E-4 |
| 2# | 23.31 | 129 | 3.01E-4 |
| 3# | 23.24 | 129 | 3.00E-4 |
| 4# | 23.25 | 128 | 2.98E-4 |
As can be seen from the experimental results of example 1 and example 2, the surface resistance, the film thickness value and the resistivity of the obtained ITO thin film have excellent repeatability through multiple experiments under the same process conditions, and excellent process stability can be obtained under the minute water partial pressure requirement. Therefore, by adopting the method provided by the invention, trace water vapor meeting the micro water vapor pressure requirement can be doped into the vacuum coating, the water vapor pressure stability of the vacuum coating chamber can be ensured, and the stability of the vacuum coating process needing to be doped with the water vapor is improved.
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (11)
1. A method of vapor doping in a vacuum coating, the method comprising:
Placing a water source within a first vacuum chamber and releasing water vapor from the water source; the vacuum coating is performed in a vacuum coating chamber, the vacuum coating chamber is communicated with the first vacuum chamber through a first communication pipe for conveying the water vapor, and a first regulating valve is arranged on the first communication pipe;
Detecting the water partial pressure in the vacuum coating chamber through a water partial pressure detector to obtain a water partial pressure detection value; the controller adjusts the opening of the first regulating valve according to the comparison result of the water partial pressure detection value and the water partial pressure preset value;
the water source is selected from one or more of crystalline hydrate and molecular sieve adsorbed with water vapor.
2. The method according to claim 1, wherein the water partial pressure detector is a residual gas analyzer, preferably the residual gas analyzer has a lower detection limit of 1 x 10 -11 Torr or less for the water partial pressure.
3. The method of claim 1, wherein the first vacuum chamber is connected to a first pumping system by which the first vacuum chamber can be brought to a first predetermined vacuum level; preferably, the first preset vacuum degree is less than or equal to 2E-5Torr;
preferably, the vacuum degree of the first vacuum chamber is controlled to be a first preset vacuum degree before the first vacuum chamber is used for doping the vapor into the vacuum coating chamber.
Preferably, the first vacuum chamber is further provided with a heating element capable of heating the water source.
4. A method according to claim 3, characterized in that the method further comprises:
placing the water source in a storage chamber in advance before the water source is placed in the first vacuum chamber for storage;
Preferably, the storage chamber is connected with a second air extraction system, and the second air extraction system enables the storage chamber to reach a second preset vacuum degree;
preferably, the method further comprises: the water source enables the vacuum degree of the storage chamber to meet a second preset vacuum degree during the storage period in the storage chamber, wherein the second preset vacuum degree is preferably less than or equal to 5E-2Torr;
Preferably, the storage chamber is provided with a water source output port, the water source output port is communicated with a water source receiving port of the first vacuum chamber through a second communicating pipe, and a second regulating valve is arranged on the second communicating pipe; when the water source is required to be conveyed into the first vacuum chamber, the second regulating valve is opened, and the water source stored in the storage chamber is conveyed into the first vacuum chamber through the second communicating pipe.
5. A method according to any one of claims 1 to 3, wherein the crystalline hydrate is selected from one or more of CuSO 4·5H2O、CaSO4·2H2O、CH3COONa·3H2 O; the molecular sieve is selected from 3A molecular sieves.
6. A method according to any one of claim 1 to 3, wherein,
The quality of the water source placed in the first vacuum chamber is at least sufficient to meet the water partial pressure requirement of the vacuum coating during the time required for the vacuum coating.
7. A water vapor doping apparatus for carrying out the method of any one of claims 1-6, wherein the water vapor doping apparatus comprises a first vacuum chamber, a first regulator valve, a first communication tube, a water partial pressure detector, and a controller;
A water source containing area for placing crystalline hydrate and/or molecular sieve absorbing water vapor is arranged in the inner cavity of the first vacuum chamber, the first vacuum chamber is provided with a water vapor outlet, the first communication pipe is used for communicating the water vapor outlet with a vacuum coating chamber of a vacuum coating device, and the first communication pipe is provided with the first regulating valve;
the water partial pressure detector is used for detecting the water partial pressure in the vacuum coating chamber to obtain a water partial pressure detection value, and is preferably a residual gas analyzer;
The controller is respectively in communication connection with the first regulating valve and the water pressure detector, and the controller can regulate the opening of the first regulating valve according to the comparison result of the water pressure detection value and the water pressure preset value.
8. The vapor doping apparatus of claim 7, further comprising a first pumping system, wherein the first vacuum chamber is connected to the first pumping system;
Preferably, the first vacuum chamber is further provided with a heating element capable of heating the crystalline hydrate and/or the molecular sieve adsorbed with water vapor placed in the first vacuum chamber.
9. The vapor doping apparatus of claim 7, further comprising a storage chamber, wherein the storage chamber is provided with a water source output port, the water source output port is communicated with a water source receiving port of the first vacuum chamber through a second communicating pipe, and a second regulating valve is arranged on the second communicating pipe;
preferably, the vapor doping device further comprises a second air pumping system, and the storage chamber is connected with the second air pumping system.
10. The water vapor doping apparatus of claim 9, further comprising a material transfer mechanism for transferring crystalline hydrate and/or molecular sieves adsorbed with water vapor within the storage chamber to the first vacuum chamber;
preferably, the material conveying mechanism is a mechanical arm.
11. A vacuum coating apparatus, characterized in that the vacuum coating apparatus comprises a vacuum coating device and a water vapor doping device according to any one of claims 7-10, the vacuum coating device is provided with a vacuum coating chamber, and the water vapor outlet of the first vacuum chamber of the water vapor doping device is communicated with the vacuum coating chamber of the vacuum coating device through the first communication pipe.
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