CN114318243B

CN114318243B - Patterned film without mask plate and preparation method and application thereof

Info

Publication number: CN114318243B
Application number: CN202210146592.2A
Authority: CN
Inventors: 刘晓燕; 张婷; 周伟家; 刘震; 刘宏
Original assignee: University of Jinan
Current assignee: University of Jinan
Priority date: 2021-05-07
Filing date: 2022-02-17
Publication date: 2023-10-20
Anticipated expiration: 2042-02-17
Also published as: CN114318243A; CN113755798A

Abstract

The application discloses a patterned film without a mask plate, and a preparation method and application thereof. The application adopts laser direct writing, the substrate to be plated is positioned above the coating material or the substrate to be plated is positioned below the coating material, and the laser is focused on the coating material to prepare the patterned film without mask. When the substrate to be plated is glass and the coating material is a metal material with antibacterial capability, the patterned coating can be used as transparent conductive sterilization glass and applied to the sterilization field. When the substrate to be plated is glass and the coating material is a metal material, the prepared patterned coating can form a constant-temperature amplification microfluidic chip with a PDMS (polydimethylsiloxane) substrate with a micro-channel, and is applied to microfluidic detection in various fields such as analytical chemistry, life health, medical research, environmental detection and the like. The method of the application does not use a mask, is simple and practical, has low cost, can simply realize the patterning coating of substrates with various sizes and materials, and has wide application range.

Description

Patterned film without mask plate and preparation method and application thereof

Technical Field

The application relates to the technical field of patterning preparation of film materials, in particular to a patterned film without a mask plate, and a preparation method and application thereof.

Background

The application of the patterning film is very wide, and the patterning film preparation process can be used in the traditional semiconductor photoelectric device/electronic device process, the film battery preparation process, the sensing device preparation process, the emerging biomedical material preparation process such as constant-temperature amplification microfluidic chip and the like, and even in the artwork pattern preparation process in life.

In the prior art, there are two general methods for preparing patterned films on substrates: firstly, preparing a film on a substrate, then preparing a mask, and manufacturing a film pattern by methods of corrosion, etching and the like; alternatively, a pattern is first prepared on a substrate, then a thin film is deposited, and the pattern is transferred to the substrate by a lift-off method or the like. Basically, 2-3 process steps are used in both methods, and the process is complicated. In the two preparation methods, two processes of film plating and photoetching are used. The coating method includes electron beam evaporation, magnetron sputtering, thermal evaporation, electroplating, etc. The coating equipment is expensive, the distance between the coating source and the substrate to be coated is large, and the utilization rate of the evaporation source is low; the electroplating method can generate a large amount of waste liquid polluting the environment and needs to be subjected to further environmental protection treatment. Therefore, the cost of the traditional film coating method is relatively high. In addition, conventional plating and photolithography processes are limited in size, particularly in photolithography equipment, which generally can accommodate substrates having a maximum substrate size of 6-8 inches, and substrates smaller than 1cm are difficult to handle, and thus substrates fabricated using conventional schemes have limited dimensions. In addition, the flatness requirement of the patterned film prepared by the traditional method on the substrate is high. Therefore, a patterning film plating method which is simple and convenient in preparation method, low in cost and capable of preparing substrates with various sizes is needed; in addition, if the multifunctional special glass with transparency, conductivity and sterilization can be prepared on the glass by adopting a patterning coating method, or the prepared patterning film is used for preparing a microfluidic platform, the application field of the patterning film can be further expanded.

Disclosure of Invention

Aiming at the prior art, the application aims to provide a maskless patterned film, and a preparation method and application thereof. The method is simple and practical, has low cost, and can simply realize the patterning coating of the substrate with any size and material. When the substrate to be plated is glass and the coating material is a metal material with antibacterial capability, the patterned coating can be used as transparent conductive sterilization glass and applied to the sterilization field. When the substrate to be plated is glass and the coating material is a metal material, the prepared patterned coating can form a constant-temperature amplification microfluidic chip with a PDMS (polydimethylsiloxane) substrate with a micro-channel, and is applied to microfluidic detection in various fields such as analytical chemistry, life health, medical research, environmental detection and the like.

In order to achieve the above purpose, the application adopts the following technical scheme:

in a first aspect of the present application, there is provided a maskless patterned film prepared by:

plating a coating material on the pretreated substrate to be plated by adopting laser direct writing, and preparing a patterned film on the substrate to be plated without using a mask.

Preferably, the pretreatment method comprises the following steps: the substrate is ultrasonically cleaned with a cleaning agent and then dried.

Preferably, the cleaning agent is acetone, ethanol or deionized water; and the drying is blow-drying or drying.

The cleaning method and the cleaning agent for pretreatment can also be designed according to the size of the substrate to be plated and the requirement of the substrate to be plated.

Preferably, when the laser is used for direct writing, the substrate to be plated is positioned above the coating material, and the laser is focused on the coating material.

Preferably, the substrate to be plated is a material which can transmit laser;

more preferably, the substrate to be plated is quartz, glass, PDMS, polyimide or sapphire.

The substrate to be plated is placed on the coating material, laser irradiates according to a set pattern, the laser penetrates through the substrate to be plated, the sheet-shaped/block-shaped coating material is sprayed on the coating material, clusters of the material are formed by the sprayed coating material (coating source), and the clusters are sputtered on the substrate to be plated.

Preferably, when the laser is used for direct writing, the substrate to be plated is positioned below the coating material, and the laser is focused on the coating material.

Preferably, the substrate to be plated is a material which can transmit laser or a material which cannot transmit laser;

more preferably, the substrate to be plated is quartz, glass, PDMS, polyimide, sapphire, nickel, copper, iron, stainless steel or wood.

And (3) placing a coating material on the substrate to be coated, irradiating the coating material according to a set pattern, and sputtering the coating material on the substrate to be coated by laser according to the set pattern, wherein the coating material is used as a coating source to form clusters of the material and is sputtered on the substrate to be coated.

Preferably, the coating material is a sheet coating material or a block coating material.

Preferably, the coating material is a metal material or a semiconductor material;

more preferably, the coating material is copper, iron, nickel, tin, gold-tin alloy, ITO, znO or Ga ₂ O ₃ 。

The dimensions of the substrate to be coated and the sheet/block coating material may be the same or different. Therefore, the fixing modes of the substrate to be plated and the sheet-shaped/block-shaped coating materials are various, and the substrate to be plated and the sheet-shaped/block-shaped coating materials can be fixed in a clamping mode by adopting a clamp or in an edge bonding mode.

The laser direct writing process can be completed once or multiple times. If the substrate to be plated is bigger and the plating material is smaller, the whole plating of the substrate to be plated can be finished by a method of moving the plating material and writing the plating material through laser for many times.

Preferably, in the laser direct writing process, hydrogen, oxygen, argon, nitrogen or a mixed gas of the above gases may be introduced.

The laser direct writing coating film with different effects can be realized by adjusting the wavelength of the laser, the power of the laser and the pulse width of the laser.

In a second aspect of the application there is provided the use of a patterned film in at least one of the following 1) to 4):

1) Sterilizing;

2) Conducting electricity;

3) Heating;

4) And preparing the constant-temperature amplification micro-fluidic chip.

In a third aspect of the present application, there is provided a transparent conductive sterilization glass prepared by the following method:

placing a metal film with bacteriostasis capability above a pretreated glass substrate, wherein the thickness of the metal film is 0.01-1 mm, applying laser on a conductive bacteriostasis material and perforating the conductive bacteriostasis material, the laser power is 2-10W, the laser scanning speed is 30-500 mm/s, and depositing the conductive bacteriostasis material on the glass substrate to prepare the transparent conductive bacteriostasis glass.

Preferably, the metal film is silver, copper, gold or tin.

Preferably, the laser may use an ultraviolet laser, a fiber laser or a carbon dioxide laser.

The conductive antibacterial material is deposited on the glass substrate in the shape of stripes, triangles and pentagons.

In a fourth aspect of the application, there is provided the use of transparent electrically conductive sterilising glass for sterilisation and/or electrical conduction.

In a fifth aspect of the application, a microfluidic chip for isothermal amplification is provided, which comprises a glass substrate with a metal heating area, wherein a PDMS substrate attached to the glass substrate is arranged above the glass substrate; the metal heating area is positioned on one side surface of the glass sheet base, and the other side surface of the glass sheet is attached to one side of the PDMS sheet base with the micro-channel; the two ends of the metal heating area are connected with a power supply through wires;

the PDMS sheet base with the micro-flow channel belongs to the prior art, is a common material in a micro-fluidic chip, can be prepared by an existing template casting method, such as the preparation of a PDMS film base flexible micro-nano structure and application research thereof in doctor paper (Meng Yancheng, university of Chinese science and technology, 2019), and the PDMS mixed solution is cast on a template with a microstructure by utilizing the castable characteristic of the PDMS prepolymer solution (the PDMS main solution and the cross-linking agent mixed solution), and after solidification, the surface of the PDMS film can replicate the microstructure.

The glass sheet substrate with the metal heating area is prepared by the following method:

laser is applied to and penetrated through the metal material, the metal material is deposited on the glass sheet base, and the metal heating area is prepared on the glass sheet base.

The micro-fluidic chip for isothermal amplification is prepared by the following method:

and bonding one side of the PDMS substrate with the micro-channel with one side of the glass substrate without the metal heating area to form the micro-fluidic chip for isothermal amplification.

Preferably, the laser power is 2-10W, and the laser scanning speed is 30-500 mm/s; the metal material is silver, copper, gold or aluminum.

The temperature of the isothermal amplification is provided by joule heating in a metallic heating window on the glass substrate. By applying voltage to two ends of the deposited metal, heat is generated when current flows through the metal according to the Joule effect, the constant-temperature amplification of the microfluidic chip is carried out by utilizing the heat to provide temperature, the constant-temperature amplification reaction is integrated on the chip, and the amplified marker enters a detection unit for rapid detection. The method can realize the integration of amplification and detection of the microfluidic chip, and has the characteristics of automation and chipalization.

The pattern and size of the metal heating area is designed by controlling the area where the laser acts. The pattern of metal may be square, rectangular, etc. The optimal scheme can adjust the patterns and the sizes of the metal according to the requirements, so that the heating of different areas is realized, and the amplification of different areas is further realized.

The temperature generated by the deposited metal will vary as different voltages are applied to the metal. The greater the pressurization, the higher the temperature generated by the metal electrode. The temperature of the isothermal amplification has adjustability, corresponding voltage is adjusted according to the required temperature, and the controllable adjustment of the temperature is realized.

The metal used for heating can be a plurality of different metal materials which can be deposited on the glass substrate by laser sputtering, thereby obtaining different metal heating windows such as silver, copper, gold, aluminum and the like. The heat-generating metal has selectivity, so that different materials can be selected for heating while the heating temperature is ensured.

In a sixth aspect of the application, there is provided the use of a isothermal amplification microfluidic chip in microfluidic detection.

The application has the beneficial effects that:

(1) Compared with the traditional method for preparing the patterned film, the method for preparing the laser direct writing film coating is provided, a mask is not used, the preparation of the patterned film can be realized in one step, the step of preparing the patterned film is simplified, the method is simple, and the method can be used for preparing the patterned film in a large scale. Compared with the traditional method for preparing the patterned film, the high-cost equipment of the application only needs a laser, and the price of the laser is far lower than that of the traditional film plating equipment such as electron beam evaporation and the like and a photoetching machine, and the cost of the equipment is greatly reduced. In addition, the substrate to be plated and the flaky/blocky coating material are in a bonding state during coating, the distance is small, the utilization rate of the material is high, and the cost of raw materials is greatly reduced. In conclusion, the method greatly reduces the cost for preparing the patterned film. In the traditional coating process, because the coating process is carried out in the coating cavity, the metal film, the nonmetal film and the like with large differences in melting points need to be coated by adopting different equipment, so that cross contamination is avoided. The method for patterning coating by laser direct writing provided by the application has the advantages that the coating process is carried out between the substrate to be coated and the sheet/block coating material, and the coating distance is short. The preparation of different films only needs to change the flaky/blocky coating materials. One laser can realize the coating requirements of various materials, so that the flexibility of coating is increased and the cost of coating is reduced. Compared with the traditional method for preparing the patterned film, the method for preparing the patterned film by adopting the laser direct writing method does not need to use chemical substances such as electroplating liquid, photoresist and the like which pollute the environment in the preparation process and does not need secondary treatment, so the method is environment-friendly. Compared with the traditional film plating and photoetching, in the method for preparing the patterned film by laser direct writing, the laser, the substrate to be plated and the sheet/block film plating material are separate systems, and the substrate to be plated and the sheet/block film plating material do not need to be loaded in a fixed cavity or a container, so that the method can be suitable for patterning film plating of the substrate to be plated in different sizes and different states. Meanwhile, the sizes of the substrate to be coated and the flaky/blocky coating materials can be different, and the whole coating is finished by a mobile flaky/blocky coating method. Therefore, the method provided by the application solves the limitation of the size of the substrate to be plated in the traditional patterning film preparation. The method for preparing the patterned film by adopting laser sputtering has low requirement on the flatness of the substrate, can be even used for preparing the patterned film on a three-dimensional graph, and widens the application range of the patterned film. The application adopts the flaky coating material to coat the substrate to be coated, and the laser penetrates the coating material to sputter the substrate to be coated to finish the coating process, so the application can coat the film on any substrate without light transmission requirement on the substrate. The application successfully solves the problems of complex process, high cost, limited size of the substrate to be plated, environmental pollution and the like of the traditional patterned film preparation; the method for patterning the coating film is simple, low in cost, flexible and changeable in coating film type, environment-friendly, large-size in manufacturing and capable of being prepared on any substrate, and greatly expands the application space of the patterning coating film.

(2) The application adopts the laser sputtering technology to deposit the antibacterial material on the glass substrate, thereby realizing the glass with the characteristics of transparency, conductivity and sterilization; the construction of the special glass can be realized in one step, the preparation process of the special glass is simplified, the operation is simple, and the cost is low; the pattern, the size and the duty ratio of the metal electrode on the substrate can be adjusted to meet the adjustment of the transmittance, the conductive area and the sterilization area to meet the actual requirements; the duty ratio of the antibacterial material on the glass substrate is controlled by adjusting the pattern and the size of the pattern, so that the adjustment of the light transmittance can be realized without changing the light transmittance of the glass; suitable metal materials can be selected according to actual needs. The antibacterial material patterns deposited on the glass substrate are diversified, and antibacterial areas with different patterns and different sizes can be constructed according to actual requirements; the processing of the three-dimensional structure can be realized, the processing of different plane and non-plane structures can be satisfied, and the transparent conductive sterilizing glass with plane and non-plane is constructed. Compared with the transparent conductive sterilization glass prepared by the prior art, the transparent conductive sterilization glass prepared by the application has obvious sterilization effect. The application can also adjust the laser parameters to prepare products with the same appearance but different resistances. Products with different resistances can be applied to different fields, the heating value is adjusted according to the different resistances, the heating value is extremely low (the temperature is low) and can be used for preparing electronic components, and the heating value is high (the temperature is high) and can be used for sterilization. The application adopts free diffusion of metal ions for sterilization, simplifies the preparation process of the sterilization material, has obvious sterilization effect, low consumption and energy conservation, and is environment-friendly.

(3) The application adopts the Joule heat of the metal heating window to provide the temperature of constant-temperature amplification, and can realize the integration of amplification, detection and the like of the microfluidic chip. The microfluidic isothermal amplification chip can realize the chipization of isothermal amplification and has the characteristics of miniaturization, integration, automation and the like; and (3) the isothermal amplification is chipized, and the amplified marker sample is directly loaded to a sensing detection unit to obtain an integrated chip for isothermal amplification and rapid detection. The integrated chip has the characteristics of simplicity and portability, and can be monitored in real time; the metal is deposited on the glass substrate by adopting a laser sputtering technology, so that the construction of a metal heating window can be realized in one step, and different patterns and different sizes can be selectively designed according to requirements to meet the amplification of different areas, so that the amplification has area selectivity; the metal deposited on the glass substrate using laser sputtering techniques can be adjusted in temperature by applying different voltages across the metal. Therefore, the corresponding voltage can be selectively applied according to the required temperature, the electric energy consumption is avoided, and the electric energy is reasonably utilized. Based on the Joule heat principle, after voltage is applied, current flows through metal to generate heat so as to realize isothermal amplification. Thus, the flexibility of metal patterning enables control of the temperature zone distribution. After the voltage is applied, the area with metal deposition can generate heat, and the area without metal electrode deposition can only have the phenomenon of temperature diffusion due to the heat conduction of the glass sheet base, and can not generate heat by itself.

Drawings

FIG. 1 is a schematic diagram of a patterned copper film prepared by laser direct writing in example 1 of the present application;

FIG. 2 is a photograph of a patterned copper film prepared in example 1 of the present application;

FIG. 3 is a photograph (a), a detail scanning electron microscope (b) and a photograph (c) of copper element distribution of the patterned copper film prepared in example 2 of the present application;

FIG. 4 copper films of various patterns prepared on quartz substrates in example 3: a is a triangular pattern, b is a five-pointed star pattern, c is a UJN letter pattern;

fig. 5 copper films of various patterns prepared on polyimide substrates in example 4: a is a triangular pattern, b is a five-pointed star pattern, c is a UJN letter pattern;

FIG. 6 is a schematic diagram of a patterned nickel oxide film prepared by laser direct writing in example 5 of the present application;

FIG. 7 is a schematic diagram of a patterned gold-tin film prepared by direct laser writing in example 6 of the present application;

FIG. 8 is a schematic diagram of a patterned nickel film prepared by laser direct writing in example 7 of the present application;

in fig. 1, 6-8, 1 a substrate to be plated, 2 a coating material, 3 a clamp and 4 a laser light source.

FIG. 9 is a photograph (a) and a detailed scanning electron microscope (b) of the patterned nickel thin film prepared in example 7 of the present application.

FIG. 10 is a schematic view of the transparent conductive glass prepared in example 8;

FIG. 11 is a striped physical pattern of the transparent conductive sterilizing glass prepared in example 8;

FIG. 12 is a schematic diagram showing the structure of the stripes of the transparent conductive clear glass prepared in example 8;

FIG. 13 is a graph showing the transmittance properties of the transparent conductive sterilization glass prepared in example 8;

FIG. 14 is a schematic view of the transparent conductive sterilizing glass prepared in example 8 when energized; copper stripes and glass substrates;

FIG. 15 is a graph showing the temperature distribution of the copper stripe array of the transparent conductive and bactericidal glass prepared in example 8;

FIG. 16 is a graph showing the comparative effect of the copper stripe array on E.coli cells on the transparent conductive glass prepared in example 9;

FIG. 17 is a comparative graph of the presence or absence of copper streaks on the transparent conductive and bactericidal glass prepared in example 9 for the formation of E.coli colonies, a is a graph of E.coli colonies formed by culturing at the site without copper streaks, and b is a graph of E.coli colonies formed by culturing at the site with copper streaks;

FIG. 18 is a diagram showing the appearance of bacteria after the copper bar array of the transparent conductive and bactericidal glass prepared in example 9 acts on E.coli, a is a diagram showing the appearance of E.coli under low magnification, and b is a diagram showing the appearance of E.coli under high magnification;

FIG. 19 is a graph showing the comparative effect of the presence or absence of the copper stripe array on the transparent conductive bactericidal glass prepared in example 9 on the bactericidal effect against Staphylococcus aureus;

FIG. 20 is a graph showing the comparison of the presence or absence of copper stripes on the transparent conductive and bactericidal glass prepared in example 9 to the formation of staphylococcus aureus colonies, wherein a is a picture of staphylococcus aureus colonies cultured at a position without copper stripes, and b is a picture of staphylococcus aureus colonies cultured at a position with copper stripes;

FIG. 21 is a diagram showing the appearance of bacteria after the copper bar array of the transparent conductive and bactericidal glass prepared in example 10 acts on staphylococcus aureus, a is a diagram showing the appearance of staphylococcus aureus at low magnification, and b is a diagram showing the appearance of staphylococcus aureus at high magnification;

FIG. 22 is a diagram showing the lattice structure of the transparent conductive and bactericidal glass prepared in example 11;

fig. 23 is a graph showing the transmittance properties of the copper stripe array of the transparent conductive and bactericidal glass prepared in example 11.

FIG. 24 is a graph showing the temperature distribution of the copper stripe array of the transparent conductive and bactericidal glass prepared in example 13;

FIG. 25 is a graph showing the temperature distribution of the copper stripe array of the transparent conductive and bactericidal glass prepared in example 14.

FIG. 26 is a schematic structural diagram of a thermostatically amplified microfluidic chip according to example 16; 6, a glass substrate, 7, a PDMS sheet substrate, 8, a metal heating area, 9 and a micro-channel;

FIG. 27 is a schematic view of the heating region of a thermostatically amplified microfluidic chip of example 16;

FIG. 28 is a temperature distribution of a thermostatically amplified microfluidic chip of example 16 when heated;

FIG. 29 is a plot of temperature versus applied voltage time for a copper bar of 100 μm width of example 16;

FIG. 30 is a graph of temperature versus applied voltage time for a 500 μm wide copper bar of example 17 in operation;

FIG. 31 is a graph of the heating cycle performance of the copper stripe of example 17;

FIG. 32 is a graph of long term heat durability of the copper stripe of example 17;

FIG. 33 is a plot of temperature versus applied voltage time for a 1000 μm wide copper bar of example 18;

FIG. 34 is a square copper metal deposited on the glass substrate in example 19;

FIG. 35 is a block diagram showing an integrated system of isothermal amplification and detection processes in example 20.

Detailed Description

It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. 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 application belongs.

As described in the background section, prior art coatings have been applied by electron beam evaporation, magnetron sputtering, thermal evaporation, electroplating, and the like. The coating equipment used by the coating methods is expensive, the distance between a coating source and a substrate to be coated is large, and the utilization rate of an evaporation source is low; the electroplating method can generate a large amount of waste liquid polluting the environment and needs to be subjected to further environmental protection treatment. In addition, conventional plating and photolithography processes are limited in size. And transparent, conductive and bactericidal multifunctional glasses are not common. In addition, the prior art can not prepare transparent conductive sterilizing glass with complex patterns, and can not prepare three-dimensional transparent conductive sterilizing glass. And the temperature of the micro-fluidic chip for isothermal amplification is provided by an amplification instrument or an incubator. Although the methods can provide the temperature required by isothermal amplification, specific instruments and equipment are required for providing the temperature, the dependence on the equipment is high, the operation process is complex, the isothermal amplification at the chip level cannot be realized, and the integration, the chip formation and the automation of the amplification and the detection process are not facilitated.

Based on this, the present application aims to provide a method for preparing a patterned film. The application adopts laser direct writing to carry out film coating. When the substrate to be plated is positioned above the coating material, the coating material is placed on the substrate to be plated, laser irradiates according to a set pattern, the laser penetrates through the substrate to be plated, the laser is focused on the sheet-shaped/block-shaped coating material, and the coating material focused by the laser (coating source) forms clusters of the material and is sputtered on the substrate to be plated. When the substrate to be plated is positioned below the coating material, the coating material is placed on the substrate to be plated, laser irradiates according to a set pattern, the laser is focused on the coating material and penetrates through the coating material, and the coating material is used as a coating source to form clusters of the material and is sputtered on the substrate to be plated. According to the effect and the requirement of the coating, the substrate to be coated and the coating material can be attached together or have a certain distance; the dimensions of the substrate to be coated and the sheet/block coating material may be the same or different. Therefore, the fixing modes of the substrate to be plated and the sheet-shaped/block-shaped coating materials are various, and the substrate to be plated and the sheet-shaped/block-shaped coating materials can be fixed in a clamping mode by adopting a clamp or in an edge bonding mode. The laser direct writing process can be completed once or multiple times. If the substrate to be plated is bigger and the plating material is smaller, the whole plating of the substrate to be plated can be finished by a method of moving the plating material and writing the plating material through laser for many times. The laser direct writing coating film with different effects can be realized by adjusting the wavelength of the laser, the power of the laser and the pulse width of the laser.

The application also provides transparent conductive bactericidal glass, patterning preparation can be realized on a substrate in one step by a laser sputtering method, and the light transmittance can be regulated by regulating the pattern and the size thereof and controlling the duty ratio of the antibacterial material on the glass substrate. Applying a voltage to the deposited metal, a current is generated; the metal ions deposited on the glass substrate can achieve the effects of bacteriostasis, antibiosis and sterilization through free diffusion. The application simplifies the preparation process of the bactericidal glass and greatly reduces the cost. Meanwhile, the metal electrode prepared by the application is obtained by laser sputtering, is not a completely compact metal film, comprises metal particles, metal oxide particles and the like, and has resistance between the metal particles, resistance between the metal oxide particles and the metal oxide particles or resistance between the metal particles and the metal oxide particles, and resistance between the particles and a gas medium. The temperature is different and the resistance will vary. When the applied voltage is high, the generated temperature is high, and the high temperature can sinter the particles of the metal electrode together, so that the resistance is smaller than that at low voltage. The size of the resistor can be adjusted according to the change of the voltage, so that the resistor can be applied to different fields.

The application also prepares the isothermal amplification microfluidic chip by using the patterned film, and the isothermal amplification microfluidic chip is formed by bonding a glass sheet base with a metal heating area and a PDMS sheet base with a micro-channel, wherein the metal heating area is arranged below the glass sheet base, and the micro-channel is arranged above the glass sheet base. The amplified marker sample can be directly loaded to the detection unit on the microfluidic chip, the isothermal amplification and the rapid detection chip integration are realized, and the method can be used for sample real-time monitoring. The metal heating region is a region for depositing metal on the glass substrate by laser sputtering. The laser acts on the metal material, the laser penetrates the metal foil material, and the metal particles move downwards at a certain speed and are deposited on the glass sheet substrate right below. A voltage is applied across the electrodes, and when a current flows through the metal, heat is generated inside the metal, thereby achieving the temperature required for isothermal amplification. According to the Joule principle, voltage is applied to two ends of the metal heating area to realize heating and further realize isothermal amplification, so that the chip-level isothermal amplification microfluidic chip is obtained. Meanwhile, the metal electrode prepared by the application is obtained by laser sputtering, is not a completely compact metal film, comprises metal particles, metal oxide particles and the like, and has resistance between the metal particles, resistance between the metal oxide particles and the metal oxide particles or resistance between the metal particles and the metal oxide particles, and resistance between the particles and a gas medium. The temperature is different and the resistance will vary. When the applied voltage is high, the generated temperature is high, and the high temperature can sinter the particles of the metal electrode together, so that the resistance is smaller than that at low voltage. The resistance can be regulated according to the voltage change to obtain different heating temperatures.

In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail with reference to specific embodiments.

The test materials used in the examples of the present application are all conventional in the art and are commercially available.

Example 1

As shown in fig. 1 and 2, a method for preparing a patterned thin film on a small-sized substrate by using a laser direct writing method includes the steps of:

1) And cleaning the substrate to be plated, namely, quartz plates, sequentially immersing the substrate to be plated in acetone, ethanol and DI water, ultrasonically cleaning for 5 minutes, and flushing with the DI water. And drying the substrate after cleaning.

2) And fixing the substrate to be plated and the coating material. The coating material is copper sheet; the substrate to be plated is placed under, and the coating material is placed on the substrate to be plated and fixed by a clamp.

3) Pattern design and parameter setting. The copper sheet is processed by laser scanning set by software installed on a computer. A square pattern of 2X 2cm was set on the software and treated with a laser having a scanning speed of 10mm/s and a power of 1.8W.

4) And (5) laser direct writing. And (3) introducing nitrogen into the clamp for protection, and scanning and irradiating the fixed coating material by adopting a laser light source. The laser penetrates the coating material, and the bombarded copper clusters are sputtered onto the substrate 1 to be coated to form a patterned copper film, as shown in fig. 2.

Example 2

As shown in fig. 3, a method for preparing a patterned thin film using a laser direct writing method suitable for a large-sized substrate is different from example 1 in that:

step 1) cleaning a substrate to be plated, namely, glass, directly flushing the substrate to be plated by a DI water gun, and blow-drying the substrate to be plated by a nitrogen gun after cleaning.

And 2) fixing the substrate to be plated and the coating material. The coating material is copper foil; and placing the substrate to be plated under, and adhering the periphery of the coating material to the substrate to be plated.

And 4) scanning and irradiating the fixed substrate to be plated and the coating material by adopting a laser light source. Setting the diameter of a laser spot to be 10 micrometers, enabling the laser scanning interval to be 1 millimeter, bombarding the coating material by laser, and sputtering the bombarded copper clusters on a substrate to be coated until an equidistant copper line pattern is formed. Fig. 3 shows a photograph of a copper wire, a scanning electron microscope and a copper element distribution diagram.

Example 3

As shown in fig. 4, this embodiment is different from embodiment 1 in that:

step 4) laser direct writing. The laser procedure was set to triangle, pentagon and english letter "UJN", and the coated material copper foil was written directly onto the quartz of the substrate to be coated, as in the different pattern scanning electron microscope patterns of fig. 4.

Example 4

This embodiment differs from embodiment 1 in that:

and 2) fixing the substrate to be plated and the coating material. The substrate to be plated is polyimide, and the coating material is copper foil; the substrate to be plated is placed under and the coating material is placed on top. Laser writing copper foil onto polyimide film, triangular, pentagonal and english letter "UJN" patterns are shown in fig. 5.

Example 5

As shown in fig. 6, this embodiment is different from embodiment 1 in that:

and 2) fixing the substrate to be plated and the coating material. The coating material is nickel sheet; the size of the substrate to be plated is very small and is far smaller than that of a coating material, and the substrate to be plated is fixed by a clamp or a bonding mode.

Step 4) laser direct writing. Introducing oxygen into the clamp, and scanning and irradiating the fixed substrate to be plated and the coating material by adopting a laser light source. The laser bombards the coating material through the substrate to be coated, the bombarded nickel clusters react with oxygen to form nickel oxide, and a patterned nickel oxide film is formed on the substrate to be coated by sputtering.

Example 6

As shown in fig. 7, a method for preparing a patterned thin film using a laser direct writing method suitable for a large-sized substrate is different from example 1 in that:

step 1) cleaning a substrate to be plated, namely, stainless steel sheets, directly flushing the substrate to be plated by a DI water gun, and blow-drying the substrate by a nitrogen gun after cleaning.

And 2) fixing the substrate to be plated and the coating material. The coating material is a gold-tin flake; and placing the substrate to be plated under, and adhering the periphery of the coating material to the substrate to be plated.

And 4) scanning and irradiating the fixed coating material by adopting a laser source. The laser bombards through the coating material, and the bombarded gold-tin clusters are sputtered on the substrate to be coated to form partial patterns.

Step 5) the coating material is moved to the next area needing to prepare the pattern, and the operation of step 4) is repeated, so that the final needed complete patterned gold-tin film is formed.

The method for preparing the patterned gold-tin film is completed by adopting the same piece of gold-tin coating material through a moving method, the distance between the coating material and the substrate is small, the consumed gold-tin coating material is less, meanwhile, the gold-tin coating material can be repeatedly used for multiple times, and compared with the traditional method, the consumption of the gold-tin coating material can be greatly saved. Because the gold tin plating material is expensive, the patterned Jin Xibao film prepared by the method can save cost very effectively.

Example 7

As shown in fig. 8 and 9, a method for preparing a patterned thin film on a small-sized substrate by using a laser direct writing method includes the steps of:

1) And cleaning the substrate to be plated, namely, quartz plates, sequentially immersing the substrate to be plated in acetone, ethanol and DI water, ultrasonically cleaning for 5 minutes, and flushing with the DI water. And drying the substrate to be plated after cleaning.

2) The substrate to be plated and the plating film material are fixed. The coating material is nickel sheet, the substrate to be coated is placed on the upper surface, and the coating material is placed under the lower surface and fixed by a clamp.

3) Pattern design and parameter setting. The nickel flakes are processed by laser scanning at a power set by software installed on a computer. A rectangular pattern of 1X 2cm was set on the software, and the treatment was performed with a laser beam of 1.6W at a scanning speed of 10 mm/s.

4) And (5) laser direct writing. And introducing nitrogen into the clamp for protection, and scanning and irradiating the fixed substrate to be plated and the coating material by adopting a laser light source. The laser bombards the coating material through the substrate to be coated, and the bombarded nickel clusters sputter the substrate to be coated to form a patterned film as shown in fig. 9.

Example 8

FIG. 10 is a schematic diagram showing the construction of linear copper stripes on a glass substrate. Placing the copper foil above the quartz plate to enable the copper foil and the quartz plate to be tightly attached; laser acts on the copper foil to punch through the copper foil; copper atoms collided by laser photons at high speed are deposited on the quartz plate, and a preset array can be formed. The laser power was 6W, the scanning speed was 100mm/s, the deposition pitch was 0.3cm and the line length was 0.5cm on the glass surface, and an array with a total area of 1 cm. Times.1.3 cm was formed, and the physical diagram was shown in FIG. 11. Fig. 12 is a schematic diagram of the embodiment, wherein the thickness of the copper stripe deposited on the glass substrate is about ten micrometers. The transmittance of linear copper stripes built on a glass substrate is shown in fig. 13. By comparison, the transmittance of such glass sheets carrying an array of copper stripes was found to be inferior to bare glass sheets.

The copper stripe can be operated by connecting the power supply and the wires in the manner of fig. 14. The glass comprises copper strips deposited on a glass substrate, the glass substrate, an external power supply and wires, wherein the copper strips are directly connected with the external power supply through the wires. The resistance of the copper stripe when a 2V dc voltage is applied is about 5 Ω. When an electric current flows through the conductor, the conductor can generate heat due to the joule effect. The conductor properties of the copper stripes in the present application were verified with a thermal imager in this example. Fig. 15 is a graph showing the temperature profile of copper stripes under an applied voltage of 2V.

Example 9

This example differs from example 8 in that the striped array is deposited with metallic copper on the glass substrate. The laser power was 6W, the scanning speed was 10mm/s, the deposition pitch was 0.03cm and the line length was 0.5cm on the glass surface, and an array with a total area of 0.37 cm. Times.0.05 cm was formed. The copper streak-carrying side was covered with a medium, on which a strain of Escherichia coli was applied, and after culturing at 37℃for 24 hours, the bacteria adhered to the glass surface by ultrasonic extraction were applied to an agar plate and again cultured at 37℃for 16 hours, and the antibacterial rate was measured. The antibacterial rate of the copper streak-loaded glass was found to be as high as 95% and much higher than that of bare glass pieces, as shown in fig. 16 and 17. And most cell membranes of the escherichia coli on the glass surface carrying the copper stripes shrink, deform and even break, as shown in fig. 18, which shows that the copper stripe array prepared by laser has good diffusion effect and shows good antibacterial effect.

Example 10

This example differs from example 9 in that the copper streak-carrying side was covered with a culture medium, on which was applied a species of staphylococcus aureus, the antimicrobial rate of the copper streak-carrying glass was up to 95%, much higher than that of the bare glass sheet, as shown in fig. 19 and 20. And most of the cell membranes of staphylococcus aureus on the surface of the glass carrying the copper stripes shrink, deform and even break, as shown in fig. 21, which shows that the copper stripe array prepared by laser has good diffusion effect and shows good antibacterial effect.

Example 11

This example differs from example 8 in that a bacteriostatic region of copper lattice structure was deposited on the glass sheet. The laser power was 8W, the scanning speed was 300mm/s, and the deposition pitch was 0.03cm and the spot diameter was 20. Mu.m, on the glass surface, to form an array having a total area of 0.05 cm. Times.0.05 cm, as shown in FIG. 22. The adjustment of metal light transmittance, conductivity and sterilization effect is realized through the adjustment of the lattice size and the distance. Fig. 23 is a performance display of the light transmittance of the above-described lattice.

Example 12

A single copper stripe with the line length of 0.5cm and the line width of 0.05cm is prepared on the glass sheet by adopting laser parameters with the power of 6W and the scanning speed of 100 mm/s. The circuit was connected in the manner of fig. 14, and a dc voltage of 0.2V was applied across the copper bar, at which point the resistance was 7.5 Ω. The temperature generated after pressurization for 1min is about 28 DEG C

Example 13

A single copper stripe with the line length of 0.5cm and the line width of 0.05cm is prepared on the glass sheet by adopting laser parameters with the power of 6W and the scanning speed of 100 mm/s. The circuit was connected in the manner of fig. 14, and a dc voltage of 0.5V was applied across the copper bar, at which point the resistance was 7Ω. The temperature generated after 1min of pressurization was about 62℃as shown in FIG. 24.

Example 14

The difference from example 4 is that a DC voltage of 2V was applied across the copper bar, at which point the resistance was 4Ω. The temperature generated after 1min of pressurization was about 155 ℃ as shown in FIG. 25.

Example 15

The difference from example 11 is that a DC voltage of 2.5V was applied across the copper bar, at which point the resistance was 3.8Ω and the temperature developed after 1min of pressurization was about 275 ℃.

Example 16

FIG. 26 is a schematic diagram showing the structure of a micro-fluidic chip for isothermal amplification. Rectangular copper stripes (0.1 cm. Times.4 cm) were built on glass substrates. Placing the copper foil above the glass substrate to enable the copper foil and the glass substrate to be closely attached; the laser acts on the copper foil to just punch through the copper foil; copper atoms collided by laser photons at high speed are deposited on the glass substrate, and a preset pattern can be formed.

The metal heating window can be operated by connecting the power supply and the wire in the manner of fig. 27. FIG. 27 is a schematic diagram of the operation of the micro-fluidic chip of the present embodiment when heated, comprising a glass substrate and a metal deposited on the glass substrate, and an external power source and wires, wherein the metal is directly connected to the external power source via the wires.

When in use, a certain voltage is applied to the two ends of the deposited metal copper, and the current flows through the copper to generate heat, so that the heating effect can be achieved. FIG. 28 is a graph showing the temperature distribution of copper stripes at 2V, where the heating window constructed of metallic copper has a pronounced temperature zoned distribution where there is metal deposition, where the temperature is significantly higher than where there is no metal deposition, which allows for zoned control of the temperature.

FIG. 29 is a graph showing the temperature change of copper bars having a length of 5mm and a width of 100 μm at various voltages. The copper stripes will raise the temperature correspondingly by applying different voltages. After about one minute at a voltage of 0.5V, the metallic copper electrode is raised from the original temperature of 25 ℃ to 28.7 ℃; whereas at a voltage of 2V, the metallic copper electrode can be raised from the original temperature of 25 ℃ to 78.9 ℃. After the voltage is cut off, the metal electrode can be restored to the original temperature within ten seconds, so that the temperature can be controlled, the required temperature can be reached under the condition of small voltage, and the metal electrode belongs to a low-consumption energy-saving environment-friendly heating device.

Example 17

The difference between this example and example 16 is that the metallic copper stripe is a copper stripe having a length of 5mm and a width of 500 μm, and the temperature change is shown in FIG. 30. At 2.5V, the maximum saturation temperature of the copper stripe can reach 274 ℃.

Fig. 31 is a graph of thermal cycling stability at 2V voltage for copper bars of this size, each thermal cycle consistent with the temperature profile of fig. 28, without significant reduction in heating performance, demonstrating good thermal stability and switching performance of the copper bars.

Fig. 32 is a thermal cycling stability long term heating durability display of copper bars at 1V voltage at this size. After 12 hours of continuous heating, the temperature remains substantially unchanged, demonstrating good long-term heating durability of the copper bars.

Example 18

The difference between this example and example 16 is that the metallic copper stripe is a copper stripe having a length of 5mm and a width of 1000 μm, and the temperature change is shown in FIG. 33. At 2V, the maximum saturation temperature of the copper stripe can reach 266 ℃.

Example 19

This example differs from example 16 in that square copper metal (1 cm. Times.1 cm) was deposited on the glass substrate 1, as shown in FIG. 34.

Example 20

A schematic of a microfluidic chip integrated with isothermal amplification and detection (each line representing a flow channel) is shown in fig. 35. On one side of the glass substrate in the amplification zone, the deposited metal, i.e., the metal heating zone, is attached to the PDMS substrate with the fluidic channels on the other side to provide temperature. The sample to be detected enters from the sample inlet, constant-temperature amplification is realized in the amplification area, and then the sample enters into the detection area for detection.

The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. The maskless patterned film is characterized by being prepared by the following steps:

plating a coating material on the pretreated substrate to be plated by adopting laser direct writing, and preparing a patterned film on the substrate to be plated without using a mask;

when the laser is used for direct writing, a substrate to be plated is placed on the coating material, laser irradiates according to a set pattern, the laser penetrates through the substrate to be plated, the laser is focused on the sheet-shaped/block-shaped coating material, the coating material focused by the laser forms clusters of the material, and the clusters are sputtered on the substrate to be plated; the substrate to be plated is quartz, glass, PDMS, polyimide or sapphire;

or when the laser is used for direct writing, a coating material is placed on the substrate to be coated, laser is irradiated according to a set pattern, the laser is focused on the coating material and penetrates through the coating material, and the coating material is used as a coating source to form clusters of the material and is sputtered on the substrate to be coated; the substrate to be plated is quartz, glass, PDMS, polyimide, sapphire, nickel, copper, iron, stainless steel or wood;

the coating material is gold, silver, copper, iron, nickel, tin, gold-tin alloy, ITO, znO or Ga ₂ O ₃ 。

2. Use of the patterned film of claim 1 in at least one of the following 1) to 4):

1) Sterilizing;

2) Conducting electricity;

3) Heating;

4) And preparing the constant-temperature amplification micro-fluidic chip.

3. The transparent conductive sterilization glass is characterized by being prepared by the following steps:

and placing a metal film with bacteriostasis capability above the pretreated glass substrate, wherein the thickness of the metal film is 0.01-1 mm, applying laser to the conductive bacteriostasis material and perforating the conductive bacteriostasis material, the laser power is 2-10W, the laser scanning speed is 30-500 mm/s, and depositing the conductive bacteriostasis material on the glass substrate to prepare the transparent conductive bacteriostasis glass.

4. Use of the transparent conductive sterilizing glass according to claim 3 for sterilization and/or conduction.

5. The microfluidic chip with the isothermal amplification is characterized by comprising a glass sheet base with a metal heating area, wherein a PDMS sheet base attached to the glass sheet base is arranged above the glass sheet base; the metal heating area is positioned on one side surface of the glass sheet base, and the other side surface of the glass sheet is bonded with one side of the PDMS sheet base with the micro-channel; the two ends of the metal heating area are connected with a power supply through wires;

laser is acted on and penetrated through a metal material, the metal material is deposited on a glass sheet substrate, and a metal heating area is prepared on the glass sheet substrate;

the laser power is 2-10W, and the laser scanning speed is 30-500 mm/s; the metal material is silver, copper, gold or aluminum.

6. The use of the isothermal amplification microfluidic chip according to claim 5 in microfluidic detection.