CN111977642B - Soaking and spraying etching method and equipment - Google Patents
Soaking and spraying etching method and equipment Download PDFInfo
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- CN111977642B CN111977642B CN201910429642.6A CN201910429642A CN111977642B CN 111977642 B CN111977642 B CN 111977642B CN 201910429642 A CN201910429642 A CN 201910429642A CN 111977642 B CN111977642 B CN 111977642B
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Abstract
The invention provides a soaking spraying etching method and a soaking spraying etching device, wherein the soaking spraying etching method comprises the following steps: covering a protective film on one surface of a substrate on which graphene grows, wherein the surface of the substrate is provided with a graphene film which needs to be retained; and then adding the graphene oxide into flowing etching liquid medicine to etch the substrate to form a protective film/graphene. The soaking and spraying etching equipment comprises an etching device, a liquid distribution device, a liquid outlet pipe and a liquid supplementing pipe, wherein the etching device comprises an etching groove, the liquid distribution device comprises a liquid distribution groove, the liquid outlet pipe is communicated with the bottom of the etching groove and the bottom of the liquid distribution groove and used for enabling liquid medicine to flow from the bottom of the etching groove to the bottom of the liquid distribution groove, and the liquid supplementing pipe is communicated with the etching device and the liquid distribution device and used for enabling the liquid medicine to flow from the liquid distribution device to the etching device. The method and the equipment provided by the invention can balance the etching rate of the substrate and ensure the uniformity and the yield of the sheet resistance of the graphene.
Description
Technical Field
The invention belongs to the field of graphene substrate etching engineering, and relates to a process method for optimizing and improving an etching metal substrate.
Background
At present, the production of graphene film adopts the mode of soaking the sculpture perpendicularly, and the multi-disc product is placed in the tool simultaneously, then at the inslot sculpture metal substrate that only inner loop and single export flow, because the inslot liquid medicine flow is inhomogeneous, the liquid medicine that adds mixes with the inslot liquid medicine and can produce the proportion difference slowly and inslot liquid medicine component from the top down, leads to the etching rate of copper foil to appear the difference, and the product resistance is not of uniform size.
Due to the instability of the resistance of the product caused in the process of etching the copper foil, various problems can be encountered in the subsequent production of the product, such as infrared yield and the like. Therefore, the process of etching the metal substrate needs to be optimized, so that the etching rate of the copper foil in the etching groove is uniform, and the problems of uneven flow of liquid medicine in the groove, slow mixing of added liquid medicine and liquid medicine in the groove and difference of specific gravity of liquid medicine components in the prior art need to be solved.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
Aiming at one or more problems in the prior art, the invention aims to change the traditional centralized vertical etching mode into soaking and spraying etching, so that the uniformly mixed liquid medicine can reach the surface of each product metal substrate at a constant speed, and the substrate copper can be stably and uniformly etched. In order to achieve the above object, the present invention provides a method for immersion spray etching, comprising:
covering a protective film on one surface of a substrate on which graphene grows, wherein the surface of the substrate is provided with a graphene film which needs to be retained;
and then adding the graphene oxide into flowing etching liquid medicine to etch the substrate to form a protective film/graphene.
According to one aspect of the invention, the method for etching the substrate by adding the etching solution into the flowing etching solution comprises the following steps: and soaking the graphene/substrate covered with the protective film in etching liquid medicine, and spraying the etching liquid medicine on the surface of the substrate on which the graphene grows. The graphene/substrate covered with the protective film is added into flowing etching liquid medicine to etch the substrate, so that the concentration of the liquid medicine on the surface of the metal substrate can be kept in a relatively stable range, and the etching rate of the metal substrate is uniform.
According to one aspect of the invention, the substrate is a metal substrate.
Preferably, the metal substrate is a copper substrate, a nickel substrate, or a copper-nickel alloy substrate.
According to one aspect of the invention, the etching solution is a hydrochloric acid/hydrogen peroxide solution.
Preferably, the HCL content in the hydrochloric acid/hydrogen peroxide solution is 35-50g/L, H 2 O 2 The content of (A) is 0.7-0.95M.
Further preferably, the temperature of the etching liquid medicine is controlled to be 20-25 ℃. The temperature of the liquid medicine is controlled to stabilize the etching rate, so that the etching rate is not too fast or too slow, and the uniformity and stability of the etching process are ensured.
Preferably, the pressure of the sprayed etching solutionIs 1-1.5kg/cm 2 . The spray nozzle is single-opening, and sprays single-beam water under the pressure control of the pump.
Further preferably, the height of the etching solution which is covered by the protective film and passes through the graphene/substrate is 10-50mm, preferably 30mm.
Spraying the etching liquid not only supplements the liquid medicine, but also makes the liquid medicine flow. During etching, the metal substrate is immersed in the middle of the depth of the etching liquid medicine, the height of the liquid medicine which is over the metal substrate is about 10-50mm generally, the liquid medicine sprayed out of the nozzle is buffered in the liquid of 10-50mm, and the formed water jet cutter is not directly contacted with the metal substrate. Combining the height of the metal substrate and the spraying pressure, the water jet formed by the supplemented liquid medicine can not cause damage to the metal substrate, and can fully update the liquid medicine on the metal surface, wherein the liquid medicine generally is selected to be 20-30 mm, particularly 30mm, above the metal substrate, and the spraying pressure of the etching liquid medicine is 1-1.5kg/cm 2 And is most preferred.
According to one aspect of the invention, the spraying of the etching solution is to simultaneously spray the etching solution to both sides of the graphene/substrate covered with the protective film.
When both sides are required to be etched, the two sides are sprayed simultaneously, and the metal substrates on the two sides can be ensured to be contacted with flowing liquid medicine. The method can also be applied to etching in the field of PCB.
Preferably, the pressure of spraying the etching liquid medicine to the upper surface of the graphene/substrate covered with the protective film is 1-1.5kg/cm 2 The pressure of spraying the etching liquid medicine to the lower surface of the graphene/substrate covered with the protective film is 0.3-0.5kg/cm higher than the pressure of spraying the etching liquid medicine to the upper surface 2 。
According to one aspect of the invention, the method for calculating the thickness of the etched metal substrate on the film comprises the following steps:
H＝V1*T；
wherein H is the thickness of the etched metal substrate and the unit is mm;
v1 is the etching rate of the liquid medicine, and the unit is mm/min;
t is the etching time in min.
According to one aspect of the invention, the immersion spray etching method further comprises the step of supplementing the sprayed etching liquid medicine.
In the prior art, a soaking mode is adopted to etch a metal substrate, liquid medicine is in a relatively static state, no fresh liquid medicine flows to the surface of a product quickly, the reaction rate of soaking and etching is slow, and bubbles such as oxygen and the like are easily generated on the surface of the product; the generated bubbles are easy to attach to the surface of the product because of no impact of flowing liquid medicine, and the attachment of the bubbles also prevents the contact of fresh liquid medicine and the metal substrate, so that the liquid medicine can not quickly reach the surface of the metal substrate, the reaction rate is further slowed down, and the etching of the metal substrate is not uniform; and because the specific gravity of the etching liquid is high, the condition that the etching groove is uneven up and down is easily formed by using a soaking etching mode. The flowing of the liquid medicine is an important factor for keeping the etching normally carried out, but if a direct spraying mode is adopted, the sprayed liquid medicine directly impacts the surface of the metal substrate, the impact force is strong, and the microscopic substance of graphene is easily damaged.
In order to achieve uniform etching, it is a condition that the flow rate of the chemical liquid reaching the metal surface is substantially uniform and the chemical liquid composition is uniform. The mode that adopts to soak and spray combines together, make the metal base soak in liquid medicine, spray two surfaces to the metal base simultaneously, liquid has blockked the impact force that sprays liquid medicine, makes graphite alkene not fragile, the liquid medicine that sprays makes the liquid medicine that soaks flow and has still constantly carried out the liquid medicine to the liquid medicine that soaks and supply, make the liquid medicine after supplying can reach the surface of metal base fast, promote the speed of sculpture, reduce the product surface and produce the bubble, make the sculpture of metal base even.
The hydrochloric acid and the hydrogen peroxide are continuously consumed in the etching process of the liquid medicine in the etching groove, and the concentration is reduced. The concentrations of the hydrochloric acid and the hydrogen peroxide of the chemical liquid for supplementing are slightly higher than those of the hydrochloric acid and the hydrogen peroxide in the chemical liquid in the etching tank, so that the chemical liquid in the supplemented etching tank conforms to the concentration index.
According to one aspect of the invention, the immersion spray etching method further comprises air-drying the protective film/graphene after the etching is completed.
The invention also provides a transfer method of the graphene film, which comprises the following steps:
using the immersion spray etching method; and
and attaching the graphene surface of the protective film/graphene to a target substrate, and removing the protective film to finish the transfer of the graphene film.
The invention also provides a soaking spraying etching device, which comprises: the liquid distribution device comprises an etching device, a liquid distribution device, a liquid outlet pipe and a liquid supplementing pipe, wherein the etching device comprises an etching groove, the liquid distribution device comprises a liquid distribution groove, the liquid outlet pipe is communicated with the bottom of the etching groove and the bottom of the liquid distribution groove and used for enabling liquid medicine to flow from the bottom of the etching groove to the bottom of the liquid distribution groove, and the liquid supplementing pipe is communicated with the etching device and the liquid distribution device and used for enabling the liquid medicine to flow from the liquid distribution device to the etching device.
The etching device further comprises an upper sprayer and a supporting plate, wherein the upper sprayer is positioned on the upper side of the supporting plate, and the upper sprayer is communicated with the liquid supplementing pipe.
When the soaking and spraying equipment is used, the metal substrate is placed on the supporting plate and soaked in the etching liquid medicine, and the upper sprayer sprays the metal substrate to etch the metal substrate in the flowing liquid medicine.
According to one aspect of the invention, the support plate is a frame structure.
In order to make the lower surface of the film contact with the liquid medicine, the supporting plate is designed into a frame structure, so that both the upper surface and the lower surface of the film can contact with the liquid medicine.
According to one aspect of the invention, the support plate comprises fixing means.
Preferably, the fixing means employs a pin.
The fixing device is used for fixing the metal substrate placed on the supporting plate and preventing the metal substrate from being influenced by water flow.
During etching, the support plate is located at the middle position of the liquid medicine depth, the distance between the sprayer and the support plate is 10-50mm, and the pressure of the sprayer is setPlacing at 1-1.5kg/cm 2 . The liquid medicine in the sprayer is buffered by the etching liquid medicine with the depth of 10-50mm in the process of flowing to the support plate, so that the metal substrate on the support plate is not directly washed away.
According to one aspect of the invention, the etching device further comprises a roller, and the support plate is arranged on the roller.
The rotation of gyro wheel drives the backup pad and moves forward, makes the sculpture operation of film go on in succession, accords with industrial production's demand to the time of backup pad motion is the sculpture time of film, and the thickness that makes each film sculpture is even unanimous through the sculpture time of control film. The method for calculating the thickness of the etched metal substrate on the film comprises the following steps:
H＝V1*S/V2；
wherein H is the thickness of the etched metal substrate and the unit is mm;
v1 is the etching rate of the liquid medicine, and the unit is mm/min;
s is the moving distance of the support plate, and the unit is mm;
v2 is the linear speed of the roller wheel rotation, and the unit is mm/min.
According to one aspect of the invention, the upper sprayer comprises a medicine feeding water pipe and a plurality of upper nozzles arranged on the medicine feeding water pipe, and the medicine feeding water pipe is communicated with the liquid supplementing pipe.
Preferably, the distance between the upper nozzle and the support plate is 10-50mm, preferably 30mm.
When the graphene/substrate covered with the protective film is etched, liquid medicine needs to flow on the etched surface, the upper sprayer is communicated with the liquid supplementing pipe, the metal substrate faces upwards, and new liquid medicine is sprayed from top to bottom through the liquid supplementing pipe, so that the flowing liquid medicine reaches the surface of the metal substrate.
Preferably, the medicine feeding water pipes are multiple, and the upper nozzles on every two adjacent medicine feeding water pipes are staggered. The nozzles are staggered with each other, so that the nozzles on the adjacent medicine feeding water pipes can make up gaps with each other, and the uneven flow of the medicine water in partial areas caused by conventional array arrangement is avoided.
According to one aspect of the invention, the etching device further comprises a lower sprayer, the lower sprayer is positioned on the lower side of the supporting plate, and the lower sprayer is communicated with the liquid supplementing pipe.
Preferably, the distance between the lower nozzle and the support plate is 10-50mm, preferably 30mm.
Besides the etching in the graphene field, the etching method can also be used for etching in the PCB substrate field. When the PCB substrate is subjected to double-sided etching, liquid medicine flows on the two sides of the film, and the sprayer is arranged on the lower surface of the film, so that the flowing liquid medicine can reach the lower surface of the film.
According to one aspect of the invention, the lower sprayer comprises a medicine discharging pipe and a plurality of lower nozzles arranged on the medicine discharging pipe, and the medicine feeding pipe and the medicine discharging pipe are both communicated with the liquid supplementing pipe.
Preferably, the dosing water pipe is provided with a plurality of dosing water pipes, and the lower nozzles on every two adjacent dosing water pipes are staggered. The nozzles are staggered with each other, so that the gaps of the lower nozzles on the adjacent medicine water feeding pipes can be mutually compensated, and uneven medicine water flow in partial areas caused by conventional array arrangement is avoided.
Further preferably, the lower sprayer further comprises a valve.
When single-side etching is carried out, only one metal substrate needs to be etched, the metal substrate is placed upwards, and only the upper sprayer needs to be opened to close the valve of the lower sprayer; when double-sided etching is carried out, the metal substrates on two sides need to be etched, and at the moment, the lower sprayer and the lower sprayer are opened simultaneously, so that flowing liquid medicine is arranged on the upper surface and the lower surface of the metal substrate. The device can also be applied to the etching of the PCB substrate in the PCB field.
According to one aspect of the invention, the nozzle is a single-port nozzle.
The nozzle sprays the single beam of water under the pressure control of the pump of the liquid supplementing pipe. The water jet cutter for the liquid medicine sprayed from the nozzle is a complete and uniform water jet cutter, the water jet cutter is positioned on a line, and the nozzle can be perpendicular to the supporting plate or inclined at a certain angle according to production requirements so as to control water flow.
According to one aspect of the invention, the liquid preparation device is provided with a liquid medicine adding port.
Preferably, the number of the liquid medicine adding ports is 2, and the liquid medicine adding ports are respectively used for adding hydrochloric acid and hydrogen peroxide.
Because the hydrochloric acid and the hydrogen peroxide are directly mixed to cause the consumption of the liquid medicine and generate chlorine, the hydrochloric acid and the hydrogen peroxide are not directly mixed together when the liquid medicine is added, and the position of a liquid medicine adding port is determined by the scene of adding the liquid medicine. For the condition of simultaneously adding hydrochloric acid and hydrogen peroxide, the positions of the hydrochloric acid adding port and the hydrogen peroxide adding port are far away; if the liquid medicines are not added simultaneously but are staggered in time, one liquid medicine is uniformly mixed in the liquid preparation device, and then the other liquid medicine is added, the distance between the positions of the hydrochloric acid adding port and the hydrogen peroxide adding port can be set to be relatively short.
Further preferably, the liquid preparation device is provided with a conductivity meter, a hydrometer and a hydrogen peroxide detection device for detecting the content of the components of the liquid medicine. The invention adopts the on-line automatic detection of conductivity and hydrometer and hydrogen peroxide, and combines the addition of hydrochloric acid and hydrogen peroxide to control the hydrochloric acid concentration, copper ion concentration and hydrogen peroxide concentration of the liquid medicine in the liquid preparation tank. The electric conductivity meter, the hydrometer and the sensor of the hydrogen peroxide detection device are arranged near the liquid supplementing pipe and used for detecting the concentration of the liquid medicine entering the etching device.
According to one aspect of the invention, the liquid dispensing device further comprises a stirrer. The liquid medicine in the liquid preparation device comprises liquid medicine flowing from the liquid outlet pipe, new liquid medicine added from the adding port and the liquid medicine in the liquid preparation device, the component contents of the three liquid medicines are different, and a long time is needed for mixing the three liquid medicines together. The stirrer is arranged in the liquid preparation device, so that the three types of liquid medicines can be quickly mixed and dispersed. When the stirrer in the liquid preparation device stirs, the liquid in the liquid preparation device flows relatively, but the liquid preparation device and the etching device are separated from each other, so that the fluidity of the etching metal substrate liquid medicine in the etching device is not influenced.
According to one aspect of the invention, the liquid supplementing pipe is provided with a filtering device and a pump, and the liquid medicine prepared by the liquid preparing device is firstly filtered by the filtering device and then pumped into the etching device by the pump. The pump adopts a chemical corrosion resistant pump and is used for operating the liquid medicine and conveying the prepared liquid medicine into the etching device. The filtering device filters impurities such as purchased chemical raw materials in the liquid medicine, welding materials in the liquid preparation device and the etching device, and prevents the impurities from blocking the nozzle to cause uneven flow of the nozzle.
The invention has the beneficial effects that:
according to the method, the flow of the liquid medicine on the surface of the metal substrate is controlled, the added and mixed liquid medicine synchronously flows to the surface of the metal substrate at a constant speed, the metal substrate is stably and uniformly etched, and the resistance value of graphene is kept uniform and stable. The advantages of the invention are illustrated by the following points:
(1) The invention combines two modes of soaking and spraying, the metal substrate is soaked in the liquid medicine, enough liquid medicine etches the metal substrate, the liquid medicine is supplemented in a spraying mode, the soaked liquid medicine can flow, the content difference of each component in the liquid medicine is reduced, and meanwhile, the soaked liquid medicine enables the sprayed liquid medicine to be buffered, and the impact force of directly spraying the metal substrate is reduced. The two modes are combined to make up for the deficiency, so that the etching rate of the metal substrate is improved, and the graphene with uniform resistance is etched.
If the metal substrate is etched in a soaking mode, the etching uniformity can only reach about 75%, but the etching uniformity can reach over 90% and even 95% when the metal substrate is etched in a soaking and spraying combined mode, and the uniformity of the sheet resistance value of the same graphene product is improved.
The etching uniformity (c.o.v) is calculated as:
C.O.V＝1-S/th*100％；
wherein S is a standard deviation of a thickness of a metal substrate,
th is the average thickness of the metal substrate etched away, th = (th 1+ th2+. + thn)/N;
n is the number of the sampling points, and the number is calculated according to the condition that N is 121 in the test;
th1, th2, … thn represent the thickness of the metal substrate at each sampling point, respectively.
(2) The etching device and the liquid preparation device are separated, the liquid mobility of the etching liquid in the etching device is not influenced by the flow of the liquid generated in the process of preparing the liquid medicine, the liquid medicine is recycled by communicating the etching device and the liquid preparation device, and unnecessary waste is reduced.
(3) The automatic detection device for the conductivity meter, the hydrometer and the hydrogen peroxide is arranged in the liquid preparation device, and the concentration of hydrochloric acid, copper ions and the hydrogen peroxide in the liquid preparation device is stable through the accurate calculation of a computer, so that the uniformity of the concentration of supplemented liquid medicine is ensured, and the etching rate of the copper foil is kept in a stable range.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural diagram of a soaking and spraying etching apparatus;
FIG. 2 is a schematic structural diagram of an etching apparatus;
FIG. 3 is a schematic view of the liquid dispensing apparatus;
FIG. 4 is a schematic structural view of an upper sprayer;
FIG. 5 is a schematic structural view of the support plate;
wherein, 1 is etching device, 11 is the etching groove, 12 is the top shower, 121 is the liquid medicine water pipe, 122 is the upper nozzle, 13 is the backup pad, 131 is fixing device, 14 is the bottom shower, 141 is the liquid medicine water pipe down, 142 is the lower nozzle, 143 is the valve, 15 is the gyro wheel, 2 is joining the liquid device, 21 is joining the liquid groove, 22 is the interpolation mouth, 23 is the conductivity table, 24 is the hydrometer, 25 is hydrogen peroxide solution detection device, 26 is the agitator, 3 is the drain pipe, 4 is the fluid infusion pipe, 5 is filter equipment, 6 is the pump.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
According to a first embodiment of the present invention, there is provided a dip shower etching method including: covering a protective film on one surface of a substrate on which graphene grows, wherein the surface of the substrate is provided with a graphene film which needs to be retained; and then placing the graphene/substrate covered with the protective film in etching liquid medicine for soaking, spraying the etching liquid medicine on the surface of the substrate on which the graphene grows, continuously supplementing the sprayed etching liquid medicine to form the protective film/graphene, and air-drying.
The substrate is a metal substrate, including a copper substrate, a nickel substrate or a copper-nickel alloy substrate. The etching liquid medicine is hydrochloric acid/hydrogen peroxide solution, wherein the content of HCL is 35-50g/L, for example: 35g/L, 36g/L, 37g/L, 38g/L, 39g/L, 40g/L, 42g/L, 44g/L, 45g/L, 46g/L, 48g/L, 49g/L, 50g/L, etc. H 2 O 2 In an amount of 0.7-0.95M, for example: 0.7M, 0.71M, 0.72M, 0.73M, 0.74M, 0.75M, 0.78M, 0.8M, 0.82M, 0.83M, 0.85M, 0.86M, 0.88M, 0.89M, 0.9M, 0.91M, 0.92M, 0.93M, 0.94M, 0.95M, etc. The temperature of the hydrochloric acid/hydrogen peroxide solution is controlled between 20 and 25 ℃, for example: 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, etc.
The height of the etching liquid medicine which does not cover the graphene/substrate covered with the protective film is 10-50mm, for example: 10mm, 12mm, 14mm, 16mm, 18mm, 20mm, 22mm, 24mm, 26mm, 28mm, 30mm, 32mm, 34mm, 36mm, 38mm, 40mm, 42mm, 45mm, 46mm, 47mm, 48mm, 49mm, 50mm, and the like. As a preferred embodiment, the height of the etching solution passing through the graphene/substrate covered with the protective film is 30mm. When single-side etching is carried out, the metal substrate is placed upwards, etching liquid medicine is sprayed on the upper surface of the graphene/substrate covered with the protective film, and the pressure of the sprayed etching liquid medicine is 1-1.5kg/cm 2 For example: 1kg/cm 2 、1.02kg/cm 2 、1.06kg/cm 2 、1.08kg/cm 2 、1.1kg/cm 2 、1.2kg/cm 2 、1.3kg/cm 2 、1.4kg/cm 2 、1.42kg/cm 2 、1.44kg/cm 2 、1.46kg/cm 2 、1.48kg/cm 2 、1.5kg/cm 2 And so on. When double-sided etching is carried out, etching liquid medicine is sprayed on the upper surface and the lower surface, and the pressure of the etching liquid medicine sprayed on the upper surface is 1-1.5kg/cm 2 For example: 1kg/cm 2 、1.02kg/cm 2 、1.06kg/cm 2 、1.08kg/cm 2 、1.1kg/cm 2 、1.2kg/cm 2 、1.3kg/cm 2 、1.4kg/cm 2 、1.42kg/cm 2 、1.44kg/cm 2 、1.46kg/cm 2 、1.48kg/cm 2 、1.5kg/cm 2 And so on. The pressure of the lower surface is 0.3-0.5kg/cm greater than that of the upper surface 2 For example: 0.3kg/cm 2 、0.32kg/cm 2 、0.34kg/cm 2 、0.35kg/cm 2 、0.37kg/cm 2 、0.4kg/cm 2 、0.42kg/cm 2 、0.45kg/cm 2 、0.48kg/cm 2 、0.5kg/cm 2 And so on. The method for calculating the etched thickness of the metal substrate on the film comprises the following steps: h = V1 × T; wherein H is the thickness of the etched metal substrate, and the unit is mm; v1 is the etching rate of the liquid medicine, and the unit is mm/min; t is the etching time in min.
In the prior art, a soaking mode is adopted to etch a metal substrate, liquid medicine is in a relatively static state, no fresh liquid medicine flows to the surface of a product quickly, the reaction rate of soaking and etching is slow, and bubbles such as oxygen and the like are easily generated on the surface of the product; the generated bubbles are easy to attach to the surface of a product because of no impact of flowing liquid medicine, and the attachment of the bubbles also prevents the contact of fresh liquid medicine and the metal substrate, so that the liquid medicine cannot quickly reach the surface of the metal substrate, the reaction rate is further slowed down, and the etching of the metal substrate is uneven; and because the specific gravity of the etching liquid is high, the condition that the etching groove is uneven up and down is easily formed by using a soaking etching mode. The flowing of the liquid medicine is an important factor for keeping the etching normally carried out, but if a direct spraying mode is adopted, the sprayed liquid medicine directly impacts the surface of the metal substrate, the impact force is strong, and the microscopic substance of graphene is easily damaged. In order to achieve uniform etching, it is a condition that the flow rate of the chemical liquid reaching the metal surface is substantially uniform and the chemical liquid composition is uniform. According to the invention, the soaking mode and the spraying mode are combined, so that the metal substrate is soaked in the liquid medicine, the two surfaces of the metal substrate are sprayed simultaneously, the liquid blocks the impact force of the sprayed liquid medicine, the graphene is not easy to damage, the soaked liquid medicine flows by the sprayed liquid medicine, and the liquid medicine is continuously supplemented to the soaked liquid medicine, so that the supplemented liquid medicine can quickly reach the surface of the metal substrate, the etching speed is increased, the generation of bubbles on the surface of a product is reduced, and the metal substrate is uniformly etched. The hydrochloric acid and the hydrogen peroxide are continuously consumed in the etching process of the liquid medicine in the etching groove, and the concentration is reduced. The concentration of the hydrochloric acid and the hydrogen peroxide of the chemical liquid for supplementing is slightly higher than that of the hydrochloric acid and the hydrogen peroxide in the chemical liquid in the etching groove, so that the chemical liquid in the etching groove after supplementing meets the concentration index.
According to a second embodiment of the present invention, there is provided a method for transferring a graphene thin film, including: and (3) using the immersion spray etching method of the first embodiment, attaching the graphene surface of the protective film/graphene to the target substrate, and removing the protective film to complete the transfer of the high-graphene film.
According to a third embodiment of the present invention, there is provided a dip shower etching apparatus, as shown in fig. 1, 2 and 3, including: etching device 1, join in marriage liquid device 2, drain pipe 3 and fluid infusion pipe 4, etching device 1 includes etching tank 11, go up spray thrower 12, backup pad 13, lower spray thrower 14 and gyro wheel 15, join in marriage liquid device 2 and include joining in marriage cistern 21, add mouth 22, electric conductivity table 23, hydrometer 24, hydrogen peroxide solution detection device 25 and agitator 26, drain pipe 3 intercommunication etching tank 11's bottom and the bottom of joining in marriage cistern 21 for the liquid medicine flows to joining in marriage the cistern 21 bottom from etching tank 11 bottom, fluid infusion pipe 4 intercommunication etching device 1 and join in marriage liquid device 2, be used for the liquid medicine to flow to etching device 1 from joining in marriage liquid device 2.
As shown in fig. 2, the upper sprayer 12, the support plate 13 and the lower sprayer 14 are all disposed in the etching groove 11, the upper sprayer 12 is disposed on the upper side of the support plate 13, the lower sprayer 14 is disposed on the lower side of the support plate 13, and the upper sprayer 12 and the lower sprayer 14 are communicated with the fluid infusion pipe 4. The upper sprayer 12 comprises an upper liquid medicine pipe 121 and a plurality of upper nozzles 122 arranged on the upper liquid medicine pipe 121, the lower sprayer 14 comprises a lower liquid medicine pipe 141 and a plurality of lower nozzles 142 arranged on the lower liquid medicine pipe 141, and the upper liquid medicine pipe 121 and the lower liquid medicine pipe 141 are communicated with the liquid supplementing pipe 4. The upper nozzle 122 and the lower nozzle 142 are each spaced from the support plate 13 by a distance of 10-50mm, for example: 10mm, 12mm, 14mm, 16mm, 18mm, 20mm, 22mm, 24mm, 26mm, 28mm, 30mm, 32mm, 34mm, 36mm, 38mm, 39mm, 40mm, 41mm, 42mm, 43mm, 45mm, 46mm, 47mm, 48mm, 49mm, 50mm, and the like. In a preferred embodiment, the upper nozzle 122 and the lower nozzle 142 are both spaced 30mm from the support plate. As shown in fig. 4, the plurality of the upper chemical supply pipes 121 are provided, the upper nozzles 122 of every two adjacent upper chemical supply pipes 121 are staggered from each other, the plurality of the lower chemical supply pipes 141 are provided, and the lower nozzles 142 of every two adjacent lower chemical supply pipes 141 are staggered from each other. The upper nozzles 122 are staggered with each other, and the lower nozzles 142 are staggered with each other, so that the upper nozzles 122 of the adjacent upper liquid medicine water pipes 121 can make up gaps with each other, and the lower nozzles 142 of the adjacent lower liquid medicine water pipes 141 can make up gaps with each other, thereby avoiding uneven liquid medicine flow in partial areas caused by conventional array arrangement. The upper nozzle 122 and the lower nozzle 142 are each a single-port nozzle. The lower sprayer 14 also comprises a valve 143, and when single-side etching is carried out, the valve 143 is closed to carry out single-side etching on the product; when double-sided etching is carried out, the valve 143 is opened, and double-sided etching is carried out on the product. As shown in fig. 5, the supporting plate 13 is a frame structure, a fixing device 131 is disposed on the frame and used for fixing the graphene film on the supporting plate 131 to prevent the graphene film from being affected by water flow, and the fixing device 131 is a titanium pin.
When the soaking and spraying equipment is used, the film is fixed on the supporting plate 13 through the fixing device 131, the supporting plate 13 is placed on the roller 15, the film is soaked in the etching liquid medicine, and the upper sprayer 12 and the lower sprayer 14 simultaneously spray the metal substrate, so that the metal substrate is etched in the flowing liquid medicine. The rotation of the roller 15 drives the supporting plate to move forwards, so that the etching operation of the thin film can be continuously carried out, the requirement of industrial production is met, the moving time of the supporting plate 13 is the etching time of the thin film, and the etching thickness of each thin film is uniform and consistent by controlling the etching time of the thin film. The method for calculating the thickness of the etched metal substrate on the film comprises the following steps:
H＝V1*S/V2；
wherein H is the thickness of the etched metal substrate, and the unit is mm;
v1 is the etching rate of the liquid medicine, and the unit is mm/min;
s is the moving distance of the support plate, and the unit is mm;
v2 is the linear speed of the roller wheel rotation, and the unit is mm/min.
As shown in fig. 3, two chemical solution adding ports 22 are provided for adding hydrochloric acid and hydrogen peroxide, respectively, and the electric conductivity meter 23, the specific gravity meter 24, and the hydrogen peroxide detection device 25 are provided for detecting the content of the chemical solution components. The conductivity meter 23, the specific gravity meter 24, and the hydrogen peroxide solution detection device 25 are preferably provided near the fluid infusion tube 4, and the components of the liquid medicine to be infused into the fluid infusion tube 4 can be measured more accurately. The invention adopts the on-line automatic detection of conductivity and specific gravity meters and hydrogen peroxide, and combines the addition of hydrochloric acid and hydrogen peroxide to control the hydrochloric acid concentration, the copper ion concentration and the hydrogen peroxide concentration of the liquid medicine in the liquid preparation tank. The stirrer 26 is used for uniformly stirring the liquid medicine in the liquid preparation tank 21, the liquid medicine in the liquid preparation tank 21 comprises the liquid medicine flowing from the liquid outlet pipe 3, new liquid medicine added from the adding port 22 and the liquid medicine in the liquid preparation tank 21, the component contents of the three liquid medicines are different, and a long time is required for mixing the three liquid medicines together. The stirrer 26 is arranged in the liquid preparation tank 21, so that the three liquid medicines can be quickly mixed and dispersed. When the stirrer 26 stirs, the liquid in the liquid preparation tank 21 flows relatively largely, but the liquid preparation device 2 is separated from the etching device 1, so that the fluidity of the chemical liquid for etching the metal substrate in the etching device 1 is not affected.
The liquid supplementing pipe 4 is provided with a filtering device 5 and a pump 6, and liquid medicine prepared by the liquid preparing device 2 passes through the filtering device 5 and then is pumped into the etching device 1 by the pump 6. The pump 6 is a chemical corrosion resistant pump for operating the chemical liquid and delivering the prepared chemical liquid into the etching device 1. The filtering device 5 filters impurities such as chemical materials purchased in the chemical solution and welding materials in the liquid distribution device 2 and the etching device 1, and prevents the impurities from blocking the nozzle 122 or the nozzle 142 and causing non-uniform flow of the nozzle 122 or the nozzle 142.
The third embodiment of the immersion spray etching apparatus and the first embodiment of the immersion spray etching method are used to etch a graphene film, and the following embodiments of the present invention are further illustrated by examples:
first set of examples (half etching of copper foil substrate on graphene film):
example 1:
the preparation of the immersion spray etching apparatus according to this embodiment, as shown in fig. 1, fig. 2 and fig. 3, includes: etching device 1, join in marriage liquid device 2, drain pipe 3 and moisturizing pipe 4, etching device 1 includes etching groove 11, go up spray thrower 12, backup pad 13, lower spray thrower 14 and gyro wheel 15, it includes liquid mixing groove 21 to join in marriage liquid device 2, add a mouthful 22, electric conductivity table 23, hydrometer 24, hydrogen peroxide solution detection device 25 and agitator 26, drain pipe 3 intercommunication etching groove 11's bottom and the bottom of liquid mixing groove 21 for the liquid medicine flows from etching groove 11 bottom to liquid mixing groove 21 bottom, liquid replenishing pipe 4 intercommunication etching device 1 and liquid mixing device 2, be used for the liquid medicine to be provided with filter equipment 5 and pump 6 on the moisturizing pipe 4 of etching device 1 from liquid mixing device 2 flow direction etching device 2. The upper sprayer 12, the supporting plate 13 and the lower sprayer 14 are all arranged in the etching groove 11, the upper sprayer 12 is distributed on the upper side of the supporting plate 13, the lower sprayer 14 is distributed on the lower side of the supporting plate 13, and the upper sprayer 12 and the lower sprayer 14 are communicated with the liquid supplementing pipe 4. The upper sprayer 12 comprises an upper liquid medicine pipe 121 and a plurality of upper nozzles 122 arranged on the upper liquid medicine pipe 121, the lower sprayer 14 comprises a lower liquid medicine pipe 141 and a plurality of lower nozzles 142 arranged on the lower liquid medicine pipe 141, and the upper liquid medicine pipe 121 and the lower liquid medicine pipe 141 are communicated with the liquid supplementing pipe 4. As shown in fig. 4, the plurality of the upper chemical supply pipes 121 are provided, the upper nozzles 122 of every two adjacent upper chemical supply pipes 121 are staggered from each other, the plurality of the lower chemical supply pipes 141 are provided, and the lower nozzles 142 of every two adjacent lower chemical supply pipes 141 are staggered from each other. The support plate 13 further includes titanium pins 131 for fixing the graphene thin film placed on the support plate 13. Two liquid medicine adding ports 22 are respectively used for adding hydrochloric acid and hydrogen peroxide.
In this embodiment, the prepared immersion spray etching apparatus is used to perform half etching on the copper substrate, and the etching uniformity of the copper substrate is calculated. The method comprises the following steps:
preparing a tested copper substrate, measuring the thickness of the copper substrate, and covering a protective film on one side of the graphene film needing to be retained of the copper substrate on which the graphene is grown. Adding etching liquid medicine into the etching groove 11, starting the soaking and spraying etching equipment, opening a sprayer to circulate the liquid medicine for 15 minutes and uniformly mixing due to the fact that the specific gravity of the etching liquid medicine is large and the specific gravity difference exists between the upper part and the lower part during standing. Fixing the graphene/copper substrate covered with the protective film on a support plate 13 in the etching device 1, enabling the copper substrate to face upwards, placing the support plate 13 on a roller 15 to enable etching liquid medicine to be 20cm higher than the graphene/copper substrate placed on the support plate 13, closing a valve 143 of a lower sprayer 14, starting the roller 15, adjusting the speed of the roller 15, spraying the etching liquid medicine to the upper surface of the graphene/copper substrate covered with the protective film, wherein the spraying pressure is 1.0kg/cm 2 . In order to detect the etching uniformity conveniently, the graphene/copper substrate covered with the protective film is subjected to half etching, namely, only part of the copper foil is etched. And taking out the etched graphene/copper substrate covered with the protective film, air-drying, putting the graphene/copper substrate into an oven, and baking at low temperature for 20 minutes to measure the thickness of the copper substrate. The thickness of the copper substrate was measured by measuring the thickness of the copper substrate at a total of 121 points, 11 points being taken in each of the horizontal and vertical directions on the surface of the copper substrate. Calculating the average value and standard deviation to obtain uniform etchingThe degree was 92%.
Comparative example 2:
in the comparative example, the copper substrate is half-etched in a soaking etching mode, and the etching uniformity of the copper substrate is calculated. The method comprises the following steps:
preparing a tested copper substrate, measuring the thickness of the copper substrate, and covering a protective film on one side of the graphene film needing to be retained of the copper substrate on which the graphene is grown. And adding etching liquid medicine into the etching groove, placing the graphene/copper substrate covered with the protective film into the etching groove, so that the etching liquid medicine submerges the graphene/copper substrate, and performing half-etching on the copper substrate. And taking out the etched graphene/copper substrate covered with the protective film, air-drying, putting the graphene/copper substrate into an oven, and baking at low temperature for 20 minutes to measure the thickness of the copper substrate. The thickness of the copper substrate was measured by measuring the thickness of the copper substrate at a total of 121 points, 11 points being taken in each of the horizontal and vertical directions on the surface of the copper substrate. The average and standard deviation were calculated to obtain an etch uniformity of 74.5%.
Comparative example 3:
the comparative example uses a spray etching mode to carry out half etching on the copper substrate, and calculates the etching uniformity of the copper substrate. The method comprises the following steps:
preparing a tested copper substrate, measuring the thickness of the copper substrate, and covering a protective film on one side of the graphene film needing to be retained of the copper substrate on which the graphene is grown. Horizontally placing the graphene/copper substrate covered with the protective film, enabling the copper substrate surface to face upwards, opening a spraying device, spraying two sides of the graphene/copper substrate, and enabling the spraying pressure of the upper surface to be 1.0kg/cm 2 The spraying pressure of the lower surface is 1.3kg/cm 2 And carrying out half etching on the copper substrate. And taking out the etched graphene/copper substrate covered with the protective film, air-drying, putting the graphene/copper substrate into an oven, and baking at low temperature for 20 minutes to measure the thickness of the copper substrate. The thickness of the copper substrate was measured by measuring the thickness of the copper substrate at a total of 121 points, 11 points being taken in each of the horizontal and vertical directions on the surface of the copper substrate. The average and standard deviation were calculated to obtain an etch uniformity of 87%.
Second set of examples (full etch of copper foil substrate on graphene film):
example 4:
the preparation of the immersion spray etching apparatus according to this embodiment, as shown in fig. 1, fig. 2 and fig. 3, includes: etching device 1, join in marriage liquid device 2, drain pipe 3 and moisturizing pipe 4, etching device 1 includes etching tank 11, go up spray thrower 12, backup pad 13, lower spray thrower 14 and gyro wheel 15, it includes liquid mixing tank 21 to join in marriage liquid device 2, add mouthful 22, electric conductivity table 23, hydrometer 24, hydrogen peroxide solution detection device 25 and agitator 26, drain pipe 3 intercommunication etching tank 11's bottom and the bottom of liquid mixing tank 21 are used for the liquid medicine to flow to liquid mixing tank 21 bottom from etching tank 11 bottom, liquid replenishing pipe 4 intercommunication etching device 1 and liquid mixing device 2 are used for the liquid medicine to be provided with filter equipment 41 and pump 42 on the moisturizing pipe 4 of etching device 1 from liquid mixing device 2 flow direction. The upper sprayer 12, the supporting plate 13 and the lower sprayer 14 are all arranged in the etching groove 11, the upper sprayer 12 is distributed on the upper side of the supporting plate 13, the lower sprayer 14 is distributed on the lower side of the supporting plate 13, and the upper sprayer 12 and the lower sprayer 14 are communicated with the liquid supplementing pipe 4. The upper sprayer 12 comprises an upper liquid medicine pipe 121 and a plurality of upper nozzles 122 arranged on the upper liquid medicine pipe 121, the lower sprayer 14 comprises a lower liquid medicine pipe 141 and a plurality of lower nozzles 142 arranged on the lower liquid medicine pipe 141, and the upper liquid medicine pipe 121 and the lower liquid medicine pipe 141 are communicated with the liquid supplementing pipe 4. As shown in fig. 4, the plurality of the upper chemical supply pipes 121 are provided, the upper nozzles 122 of every two adjacent upper chemical supply pipes 121 are staggered from each other, the plurality of the lower chemical supply pipes 141 are provided, and the lower nozzles 142 of every two adjacent lower chemical supply pipes 141 are staggered from each other. The support plate 13 further includes titanium pins 131 for fixing the graphene thin film placed on the support plate 13. Two liquid medicine adding ports 22 are respectively used for adding hydrochloric acid and hydrogen peroxide.
In this embodiment, the prepared immersion spray etching apparatus is used to completely etch a copper substrate, and the performance of the etched graphene is detected. The method comprises the following steps:
covering a protective film on one surface of the copper substrate with the graphene, which is provided with the graphene film needing to be retained. Adding etching liquid medicine into the etching groove 11, starting the soaking and spraying etching equipment, opening a sprayer to circulate the liquid medicine for 15 minutes and uniformly mixing due to the fact that the specific gravity of the etching liquid medicine is large and the specific gravity difference exists between the upper part and the lower part during standing. Will coverFixing the graphene/copper substrate covered with the protective film on a support plate 13 in the etching device 1, enabling the copper substrate to face upwards, placing the support plate 13 on a roller 15 to enable etching liquid medicine to be 30mm higher than the graphene/copper substrate placed on the support plate 13, closing a valve 143 of a lower sprayer 14, starting the roller 15, adjusting the speed of the roller 15, spraying the etching liquid medicine to the upper surface of the graphene/copper substrate covered with the protective film, wherein the spraying pressure is 1.5kg/cm 2 . And after the etching is finished, taking out the etched graphene covered with the protective film and air-drying. The sheet resistance value of graphene on the electrostatic film is measured, the average resistance value is 182 omega/□, the standard deviation of the resistance value is 5.8, the product appearance is normal, and no abnormality exists when the electrostatic film is transferred to a downstream process.
Comparative example 5:
the comparative example uses a soaking etching mode to completely etch the copper substrate, and detects the performance of the etched graphene. The method comprises the following steps:
preparing a tested copper substrate, measuring the thickness of the copper substrate, and covering a protective film on one side of the graphene film needing to be retained of the copper substrate on which the graphene is grown. And adding etching liquid medicine into the etching groove, placing the graphene/copper substrate covered with the protective film into the etching groove, so that the etching liquid medicine submerges the graphene/copper substrate, and etching the copper substrate. And after the etching is finished, taking out the etched graphene covered with the protective film and air-drying. The sheet resistance of graphene on the electrostatic film was measured, and the average resistance was 194 Ω/□, and the standard deviation of the resistance was 10.7.
Comparative example 6:
the comparative example uses a spray etching mode to completely etch the copper substrate, and detects the performance of the etched graphene. The method comprises the following steps:
preparing a tested copper substrate, measuring the thickness of the copper substrate, and covering a protective film on one side of the graphene film needing to be retained of the copper substrate on which the graphene is grown. Horizontally placing the graphene/copper substrate covered with the protective film, enabling the copper substrate surface to face upwards, opening a spraying device, spraying two sides of the graphene/copper substrate, wherein the spraying pressure of the upper surface is 1.5kg/cm 2 The spraying pressure of the lower surface is 1.8kg/cm 2 Etching the copper substrateAnd (5) etching. And after the etching is finished, taking out the etched graphene covered with the protective film and air-drying. The sheet resistance of graphene on the electrostatic film was measured, with an average resistance of 190 Ω/□ and a standard deviation of 9.6.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (35)
1. The utility model provides a soak and spray etching equipment which characterized in that includes: the etching device comprises an etching groove, the liquid distribution device comprises a liquid distribution groove, the liquid outlet pipe is communicated with the bottom of the etching groove and the bottom of the liquid distribution groove and used for enabling liquid medicine to flow from the bottom of the etching groove to the bottom of the liquid distribution groove, and the liquid distribution pipe is communicated with the etching device and the liquid distribution device and used for enabling the liquid medicine to flow from the liquid distribution device to the etching device; the etching device further comprises an upper sprayer and a supporting plate, the upper sprayer is located on the upper side of the supporting plate and communicated with the liquid supplementing pipe, and the height of the liquid medicine which submerges in the substrate is 10-50mm.
2. The immersion spray etching apparatus according to claim 1, wherein the support plate is a frame structure.
3. The immersion spray etching apparatus of claim 1, wherein the support plate comprises a fixture.
4. The immersion spray etching apparatus according to claim 3, wherein the fixing means employs pins.
5. The immersion spray etching apparatus according to claim 1, wherein the etching device further comprises a roller, and the support plate is disposed on the roller.
6. The immersion spray etching apparatus according to claim 1, wherein the upper sprayer comprises a chemical feeding water pipe and a plurality of upper nozzles disposed on the chemical feeding water pipe, and the chemical feeding water pipe is communicated with the liquid replenishing pipe.
7. The immersion spray etching apparatus according to claim 6, wherein the distance between the upper nozzle and the support plate is 10-50mm.
8. The immersion spray etching apparatus according to claim 7, wherein the distance between the upper nozzle and the support plate is 30mm.
9. The immersion spray etching apparatus according to claim 6, wherein the plurality of the chemical feeding pipes are provided, and the upper nozzles of every two adjacent chemical feeding pipes are staggered.
10. The immersion spray etching apparatus according to claim 6, wherein the etching device further comprises a lower sprayer, the lower sprayer is located on the lower side of the support plate, and the lower sprayer is communicated with the liquid replenishing pipe.
11. The immersion spray etching apparatus according to claim 10, wherein the lower sprayer comprises a chemical feed water pipe and a plurality of lower nozzles disposed on the chemical feed water pipe, the chemical feed water pipe being communicated with the liquid replenishment pipe.
12. The immersion spray etching apparatus according to claim 11, wherein the distance between the lower nozzle and the support plate is 10-50mm.
13. The immersion spray etching apparatus according to claim 12, wherein the distance between the lower nozzle and the support plate is 30mm.
14. The immersion spray etching apparatus according to claim 11, wherein the plurality of the lower chemical supply pipes are provided, and the lower nozzles of every two adjacent lower chemical supply pipes are staggered.
15. The immersion spray etching apparatus of claim 11, wherein the lower sprayer further comprises a valve.
16. The immersion spray etching apparatus according to claim 11, wherein the upper nozzle and the lower nozzle are single-port nozzles.
17. The immersion spray etching apparatus according to claim 1, wherein the liquid preparation device is provided with a liquid medicine adding port.
18. The immersion spray etching apparatus according to claim 17, wherein the number of the liquid medicine addition ports is 2, and the liquid medicine addition ports are used for adding hydrochloric acid and hydrogen peroxide, respectively.
19. The soaking and spraying etching equipment as claimed in claim 1, wherein the liquid preparation device is provided with a conductivity meter, a hydrometer and a hydrogen peroxide detection device for detecting the content of the components of the liquid medicine.
20. The immersion spray etching apparatus according to claim 1, wherein the liquid preparation device further comprises a stirrer.
21. The soaking and spraying etching equipment according to claim 1, wherein the liquid supplementing pipe is provided with a filtering device and a pump, and liquid medicine prepared by the liquid preparation device is firstly filtered by the filtering device and then pumped into the etching device by the pump.
22. A soaking spray etching method, characterized in that, the soaking spray etching method is carried out by using the soaking spray etching device of any one of claims 1 to 21, and comprises the following steps:
covering a protective film on one surface of a substrate on which graphene grows, wherein the surface of the substrate is provided with a graphene film which needs to be retained;
then adding the substrate into flowing etching liquid medicine to etch the substrate to form a protective film/graphene;
wherein the height of the etching liquid medicine covering the graphene/substrate covered with the protective film is 10-50mm;
the method for adding the etching solution into the flowing etching solution to etch the substrate comprises the following steps: and soaking the graphene/substrate covered with the protective film in etching liquid medicine, and spraying the etching liquid medicine on the surface of the substrate on which the graphene grows.
23. The immersion spray etching method according to claim 22, wherein the substrate is a metal substrate.
24. The immersion spray etching method according to claim 23, wherein the substrate is a copper substrate, a nickel substrate, or a copper-nickel alloy substrate.
25. The immersion spray etching method according to claim 22, wherein the etching solution is a hydrochloric acid/hydrogen peroxide solution.
26. The immersion spray etching method according to claim 25, wherein the hydrochloric acid/hydrogen peroxide solution has a HCL content of 35-50g/L, H 2 O 2 The content of (A) is 0.7-0.95M.
27. The immersion spray etching method according to claim 22, wherein the temperature of the etching solution is controlled to be 20-25 ℃.
28. The immersion spray of claim 22The spray etching method is characterized in that the pressure of the sprayed etching liquid medicine is 1-1.5kg/cm 2 。
29. The immersion spray etching method according to claim 22, wherein the height of the etching solution over the graphene/substrate covered with the protective film is 30mm.
30. The immersion spray etching method according to claim 22, wherein the spraying of the etching solution is to simultaneously spray the etching solution to both sides of the graphene/substrate covered with the protective film.
31. The immersion spray etching method according to claim 30, wherein the pressure of spraying the etching solution to the upper surface of the graphene/substrate covered with the protective film is 1 to 1.5kg/cm 2 The pressure of spraying the etching liquid medicine to the lower surface of the graphene/substrate covered with the protective film is 0.3-0.5kg/cm higher than the pressure of spraying the etching liquid medicine to the upper surface 2 。
32. The immersion lithography method as claimed in claim 22, wherein the thickness of the metal substrate etched on the thin film is calculated by:
H=V1*T；
wherein H is the thickness of the etched metal substrate, and the unit is mm;
v1 is the etching rate of the liquid medicine, and the unit is mm/min;
t is the etching time in min.
33. The immersion spray etching method according to any one of claims 22 to 32, further comprising replenishing the chemical solution to the sprayed etching chemical solution.
34. The immersion spray etching method according to claim 33, further comprising air-drying the protective film/graphene after the etching is completed.
35. A method for transferring a graphene film is characterized by comprising the following steps:
using the immersion spray etching method of any one of claims 22 to 34; and
and attaching the graphene surface of the protective film/graphene to a target substrate, and removing the protective film to finish the transfer of the graphene film.
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