CN114188446B - Conductive glass and preparation method and application thereof - Google Patents
Conductive glass and preparation method and application thereof Download PDFInfo
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- CN114188446B CN114188446B CN202111355292.7A CN202111355292A CN114188446B CN 114188446 B CN114188446 B CN 114188446B CN 202111355292 A CN202111355292 A CN 202111355292A CN 114188446 B CN114188446 B CN 114188446B
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- 239000011521 glass Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 38
- 238000005229 chemical vapour deposition Methods 0.000 claims description 15
- 238000005240 physical vapour deposition Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000013077 target material Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 235000014528 Pholiota nameko Nutrition 0.000 description 1
- 244000168667 Pholiota nameko Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0066—Processes relating to semiconductor body packages relating to arrangements for conducting electric current to or from the semiconductor body
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The invention discloses conductive glass and a preparation method and application thereof. A preparation method of conductive glass comprises the following steps: s1, depositing a first conductive layer on the surface of a glass substrate; the preparation raw materials of the first conductive layer comprise silicon dioxide and ITO precursors; s2, arranging a second conductive layer on the first conductive layer; the second conductive layer is made of carbon. According to the invention, the adhesive force between the conductive layer and the glass substrate can be obviously improved by matching the conductive layer materials, and the conductivity of the obtained conductive glass can be improved; and the preparation flow is saved by the mutual coordination of the steps.
Description
Technical Field
The invention belongs to the technical field of LED intelligent glass, and particularly relates to conductive glass and a preparation method and application thereof.
Background
ITO (indium tin oxide) is an N-type oxide semiconductor, which is commonly sprayed on glass, plastic, and electronic display screens as a transparent conductive film due to its excellent conductive and light-transmitting properties, and at the same time, the ITO coating can reduce electron radiation and ultraviolet radiation, infrared radiation harmful to the human body. In general, when an ITO film is used to fabricate a transparent conductive layer of an LED, the ITO film functions to make an electrode of the LED in good ohmic contact with an epitaxial layer.
Although the ITO film has excellent performance and wide application range in various fields, when the ITO is used as an LED light-emitting electrode, an OLED front electrode, a front electrode of a solar cell, a heat mirror, and the like, there are many problems to be solved, such as poor bonding performance between the TIO film and a substrate such as glass, that is, low adhesion, and thus, there is a possibility that accuracy is reduced in the subsequent etching process, or the service life of the finished LED transparent display screen is short.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method of the conductive glass, by matching the materials of the conductive layer, the adhesive force between the conductive layer and the glass substrate can be obviously improved, and meanwhile, the conductivity of the obtained conductive glass can be improved; and the preparation flow is saved by the mutual coordination of the steps.
The invention also provides the conductive glass prepared by the preparation method of the conductive glass.
The invention also provides the LED transparent display glass with the conductive glass.
The invention also provides application of the conductive glass in preparing LED transparent display glass.
In a first aspect of the present invention, a method for preparing conductive glass is provided, comprising the steps of:
s1, depositing a first conductive layer on the surface of a glass substrate; the preparation raw materials of the first conductive layer comprise silicon dioxide and ITO precursors;
s2, arranging a second conductive layer on the first conductive layer; the second conductive layer is made of carbon.
According to the first aspect of the invention, the preparation method of the conductive glass has at least the following beneficial effects:
(1) In the related art, the lattice matching between the glass substrate and the ITO conductive layer is poor, so that the ITO conductive layer may be dropped off during the preparation, transportation and subsequent use.
According to the invention, the silicon dioxide doped in the first conductive layer can improve the adhesive force between the first conductive layer and the glass substrate due to the similarity between the silicon dioxide and the glass substrate; effectively solves the problem that the ITO layer is easy to peel off and then causes failure in the existing ITO glass.
(2) The invention forms the second conductive layer made of carbon on the surface of the first conductive layer by an in-situ synthesis method, and because silicon and tin in the first conductive layer are easy to chemically react with carbon, the invention is equivalent to providing an attached anchor point for the second conductive layer, so that the adhesive force between the first conductive layer and the second conductive layer is higher.
(3) Because the silicon dioxide is doped in the first conductive layer, the purity of the ITO is reduced, and the sheet resistance of the first conductive layer is improved (the resistivity of the pure ITO is 1-3 multiplied by 10) -4 Omega cm); the invention arranges carbon on the surface of the first conductive layerSince conductivity of carbon is good, wherein resistivity of graphene is as low as 10 -6 Omega cm, so that the sheet resistance of the conductive glass can be effectively reduced after the second conductive layer and the first conductive layer are combined.
(4) The structure of the ITO layer formed by direct deposition is not compact enough, the crystallization degree is to be improved, meanwhile, the lattice defects in the ITO film can cause serious internal stress, and in order to avoid cracking and falling of the ITO film caused by the reasons, an annealing step is usually needed to improve the problems;
the invention is equivalent to annealing the ITO layer (the first conductive layer) while arranging the second conductive layer, thereby improving the overall conductivity of the obtained conductive glass.
In some embodiments of the invention, the method of making a conductive glass further comprises cleaning the glass substrate prior to step S1.
In some embodiments of the invention, the cleaning is performed by sequentially washing the glass substrate with acetone, 0.1M lye, and water, followed by drying the glass substrate and heat treating at 300 ℃ for 30 min-2 h.
The cleaning function is to remove impurities attached to the surface of the glass substrate so as to improve the adhesive force between the glass substrate and the first conductive layer.
The alkali liquor is washed for 1-30 min; the action of the step can also form certain roughness on the surface of the glass substrate; improving the adhesive force between the glass substrate and the first conductive layer; within this time frame, the roughness formed does not affect the transparency of the glass substrate.
In some embodiments of the present invention, in step S1, the deposition method is a physical vapor deposition method.
In some embodiments of the invention, the physical vapor deposition method comprises an electron beam evaporation method.
In some embodiments of the present invention, the first conductive layer is prepared from a target material of the physical vapor deposition method.
In some embodiments of the invention, in step S1, the silica comprises 0.5 to 1.5% of the mass of the preparation raw material.
In some embodiments of the invention, in step S1, the silica accounts for 0.6 to 0.8% of the mass of the preparation raw material.
When the addition amount of the silicon dioxide is in the range of 0.5-1.5 wt%, the adhesive force between the first conductive layer and the glass substrate can be improved through the silicon dioxide; the reduction of the conductivity of the first conductive layer caused by the silicon dioxide can be avoided as much as possible.
In some embodiments of the invention, the ITO precursor material is ITO.
In some embodiments of the present invention, in step S1, the ITO precursor is In 2 O 3 And SnO 2 Is a mixture of (a) and (b).
In some embodiments of the invention, the In 2 O 3 And SnO 2 The mass ratio of (2) is 88-92:10.
In some preferred embodiments of the invention, the In 2 O 3 And SnO 2 Is about 90:10 by mass.
In some preferred embodiments of the invention, the ITO precursor is in powder form.
In some embodiments of the invention, the physical vapor deposition method employs a target that is a powdered target.
In some embodiments of the invention, the target has a particle size of 5 to 20 μm.
In some preferred embodiments of the invention, the target has a particle size of 10 to 15 μm.
The adoption of the small-particle-size and powdery target material can reduce the temperature required by the physical vapor deposition method on one hand and is beneficial to uniformly mixing the silicon dioxide and the ITO precursor on the other hand so as to form the first conductive layer with uniform texture.
In some embodiments of the invention, the purity of each component in the target is greater than or equal to 99.9wt%.
In some embodiments of the invention, in step S1, the physical vapor deposition temperature is 160 ℃ to 280 ℃.
In some preferred embodiments of the present invention, in step S1, the physical vapor deposition temperature is 200 ℃ to 250 ℃.
In some embodiments of the invention, the physical vapor deposition has an ambient pressure of 10 -5 Torr～10 - 8 Torr。
In some embodiments of the present invention, between step S1 and step S2, the transfer of the component obtained in step S1 is performed in a protective gas, so as to avoid that components such as water and oxygen in the air affect the performance of the first conductive layer; and also avoid re-contamination with impurities.
In some embodiments of the present invention, in step S2, the method for disposing the second conductive layer is a chemical vapor deposition method.
In some embodiments of the invention, the chemical vapor deposition process is at a temperature of 300 to 600 ℃.
In some embodiments of the invention, the chemical vapor deposition process is at a temperature of 300 to 500 ℃.
Typically, the softening temperature of the glass substrate is greater than or equal to 600 ℃; the annealing temperature for increasing the conductivity of the first conductive layer is also required to be 400-600 ℃; therefore, the invention adopts a chemical vapor deposition method at 300-600 ℃, which not only can ensure that the glass substrate is not deformed, but also can promote the conductivity of the first conductive layer, and can form a carbon layer with uniform thickness.
In summary, by adjusting the parameters of step S2 in the present invention, the annealing step of the conventional ITO layer (the first conductive layer) is omitted, thereby saving energy and manufacturing process.
In some embodiments of the invention, the pressure of the chemical vapor deposition process is 1to 8Torr.
In some embodiments of the invention, the carbon source of the chemical vapor deposition process is a hydrocarbon.
In some embodiments of the invention, the hydrocarbon is selected from at least one of an alkane, an alkene, and an aromatic hydrocarbon.
In some preferred embodiments of the invention, the alkane is selected from at least one of methane and ethane.
In some preferred embodiments of the present invention, the aromatic hydrocarbon includes at least one of benzene and toluene.
Since the main material of the first conductive layer is ITO, the material is sensitive to water and oxygen, and although carbon sources such as alcohols and ethers can also be formed into a carbon layer by chemical vapor deposition, a certain amount of water vapor is generated at the same time, which may affect the performance of the first conductive layer, so the carbon source of the present invention is preferably hydrocarbon.
In some preferred embodiments of the invention, the product of chemical vapor deposition of the hydrocarbon comprises graphene.
In some embodiments of the invention, the carbon source has a flow rate of 0.8 to 2. Mu. Mol/min.
In some embodiments of the invention, the carrier gas of the chemical vapor deposition process is mixed with a reducing gas and a shielding gas.
In some embodiments of the invention, the reducing gas comprises hydrogen.
In some embodiments of the invention, the volume ratio of the reducing gas to the shielding gas is 10:1-90.
In some embodiments of the invention, the shielding gas comprises at least one of nitrogen and an inert gas.
In some embodiments of the invention, the carrier gas has a flow rate of 200 to 300sccm.
In a second aspect of the present invention, there is provided a conductive glass produced by the method for producing a conductive glass.
According to the second aspect of the invention, the conductive glass has at least the following beneficial effects:
the adhesive force between the conductive layers (including the first conductive layer and the second conductive layer) and between the conductive layers and the glass substrate is excellent, so that the service life of the conductive glass can be prolonged, and the application range of the conductive glass can be widened.
The conductive layer of the conductive glass has excellent conductivity, so that the conductivity of the conductive glass is improved, and the application effect of the conductive glass in the field of LED display is improved.
In some embodiments of the invention, the conductive glass comprises the glass substrate, the first conductive layer, and the second conductive layer, stacked in that order.
In some embodiments of the invention, the first conductive layer has a thickness of 60 to 1000nm.
In some embodiments of the invention, the first conductive layer is a silicon dioxide doped ITO layer.
In some embodiments of the invention, the second conductive layer has a thickness of 100 to 300nm.
In some embodiments of the invention, the second conductive layer is a carbon layer.
In some preferred embodiments of the present invention, the material of the second conductive layer is graphene.
In a third aspect of the present invention, an LED transparent display glass is provided, including the conductive glass.
In some embodiments of the invention, the LED transparent display glass may be used to make at least one of building partitions, glass curtain walls, and vehicle windows.
According to the third aspect of the invention, the LED transparent display glass has at least the following beneficial effects:
the LED transparent display glass has transparency and display property; after the conductive glass provided by the invention is adopted, the display property and the service life of the conductive glass can be further improved.
In a third aspect of the invention, an application of the conductive glass in preparing LED transparent display glass is provided.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Unless otherwise specified, the glass substrates used in the embodiments were all purchased from Shenzhen glass float glass Co., ltd, and had a thickness of 6mm.
Example 1
The embodiment prepares the conductive glass, which comprises the following specific processes:
A1. pretreatment of a glass substrate:
sequentially soaking a glass substrate in acetone for 10min, soaking in 0.1M sodium hydroxide aqueous solution for 5min, washing with water until the wastewater is nearly neutral, drying the obtained glass substrate, placing in a PVD (physical vapor deposition) cavity filled with nitrogen, and performing heat treatment at 300 ℃ for 30min;
A2. preparing a first conductive layer:
the mass percentage of the silicon dioxide (purchased from Jiangsu province crystal Rui quartz industry development institute, inc., D50 is 8 μm, the content is more than or equal to 99.995%) in the target material is 0.6wt%; the mass percentage of the ITO precursor is 99.4wt%;
the ITO precursor is ITO powder, and the D50 particle size is 6 mu m; purchased from guangdong, nalo chemical technologies limited;
mixing silicon dioxide and ITO powder to obtain a target material;
adopting an electron beam evaporation method, taking the target as a raw material, and arranging a first conductive layer with the thickness of about 800nm on the glass substrate obtained in the step A1;
wherein the temperature of the electron beam evaporation method is 220 ℃ and the environmental pressure is 10 -6 Torr；
A3. Providing a second conductive layer:
transferring the component obtained in the step A2 into a cavity of a chemical vapor deposition method under the protection of nitrogen;
benzene is used as a carbon source, mixed gas of hydrogen and nitrogen is used as carrier gas (volume ratio is 1:9), and a second conductive layer with the thickness of about 150nm is arranged on the surface of the first conductive layer, and the specific conditions are as follows:
under the protection of carrier gas (the flow rate is 260 sccm), firstly heating to 450 ℃, keeping the temperature for 10min, and then introducing a carbon source (the carrier gas is not stopped) at the flow rate of 1 mu mol/mm; the chamber pressure in the process is 1Torr; and after the carbon source is introduced (the total consumption is calculated by the thickness of the glass substrate), cooling under the protection of nitrogen, and thus obtaining the conductive glass.
Example 2
The difference between the specific process and the specific process of the embodiment 1 is that:
(1) In the step A2, the mass percentage of the silicon dioxide in the target material is 1.3wt%.
Example 3
The difference between the specific process and the specific process of the embodiment 1 is that:
(1) In the step A2, the thickness of the first conductive layer is 300nm;
(2) In step A3, the thickness of the second conductive layer is 250nm.
Example 4
The difference between the specific process and the specific process of the embodiment 1 is that:
(1) In step A2, the ITO precursor was indium oxide powder (commercially available from Kagaku Co., ltd., purity. Gtoreq.99.99%, D50 about 10 μm) and tin oxide powder (commercially available from Shanghai Nameko Nano technology Co., ltd., D50 about 8 μm) mixed in a mass ratio of 9:1.
Comparative example 1
To investigate the effect of silicon dioxide in the first conductive layer, a conductive glass was prepared in this comparative example, which differs from example 1 in that:
(1) The target material adopted in the step A2 does not comprise silicon dioxide.
Comparative example 2
To investigate the effect of the second conductive layer, a conductive glass was prepared in this comparative example, which differs from example 1 in that:
(1) The step A3 does not include a carbon source and is only annealed.
Comparative example 3
In order to compare the properties of the conductive glass prepared in the present invention with those of the conventional ITO conductive glass, a conductive glass was prepared in this comparative example, which is different from example 1 in that:
(1) Step A2 does not include silica;
(2) In the step A3, the carbon source is not introduced, and only annealing treatment is performed.
Test examples
This test example tests the properties of the conductive glasses prepared in examples 1to 4 and comparative examples 1to 3. Wherein:
the visible light transmittance test standard is GB/T2680, and after the first conductive layer and the second conductive layer are arranged, the visible light transmittance change relative to the glass substrate is calculated;
the test standard of the sheet resistance is GB/T1552-1995;
the alkali resistance test method is that the sheet resistance change value is not more than 10% after immersing in sodium hydroxide solution with the concentration of 10% at 60 ℃ for 5min, and is qualified, otherwise, is unqualified;
the adhesion test criteria were: GBT4677.7-1984, specifically, after three continuous tearing tape tests, records the change rate of the rear resistance after the test compared with that before the test.
The apparent properties were observed by visual observation (with the aid of a magnifying glass) for the presence of defects such as cracks.
The specific test results are shown in table 1.
TABLE 1 statistics of the properties of the conductive glasses obtained in examples 1to 3 and comparative examples 1to 3
As can be seen from the results in Table 1, the conductive glass obtained in examples 1to 4 provided by the invention can reduce the sheet resistance by 1to 2 orders of magnitude after being matched with the first conductive layer (the ITO layer doped with silicon dioxide) because the graphene has extremely low resistivity; the silicon dioxide has excellent fixing effect on the glass substrate and the second conductive layer (carbon layer), so that the adhesive force of the silicon dioxide is obviously improved, and particularly, after the silicon dioxide is torn and pulled for a plurality of times by an adhesive tape, the change value of the sheet resistance is within 5 percent; the conductive glasses obtained in examples 1to 4 also have excellent appearance and alkali resistance.
Comparative example 1 was devoid of silica compared to example 1, thus leading to a decrease in adhesion between the first conductive layer and the second conductive layer, and between the first conductive layer and the glass substrate, directly leading to failure of the adhesion and alkali resistance test; meanwhile, due to the reduction of bonding compactness between layers, the sheet resistance of the ITO in the first conductive layer is obviously improved even if the purity of the ITO in the first conductive layer is very high.
Comparative example 2 by default of the second conductive layer compared to example 1, although the introduction of silica in ITO improved adhesion, the sheet resistance of the conductive glass was also significantly improved with only the first conductive layer.
Comparative example 3 is an imitation of the industrially usual method for producing ITO glass, and the results show that the sheet resistance, adhesion, and alkali resistance of the conductive glass provided in examples 1to 4 of the present invention are all superior to those of the ITO glass in comparative example 3.
Most importantly, the ITO glass provided by the invention does not obviously cause the reduction of the transparency of the glass, and ensures the application of the ITO glass in the field of LED transparent display glass.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (15)
1. The preparation method of the conductive glass is characterized by comprising the following steps of:
s1, depositing a first conductive layer on the surface of a glass substrate; the preparation raw materials of the first conductive layer comprise twoSilicon oxide and ITO precursor; the ITO precursor is In 2 O 3 And SnO 2 Is a mixture of (a) and (b);
s2, arranging a second conductive layer on the first conductive layer; the second conductive layer is made of carbon; in step S2, the method for disposing the second conductive layer is a chemical vapor deposition method, a carbon source of the chemical vapor deposition method is hydrocarbon, and a product of the chemical vapor deposition includes graphene.
2. The method for producing a conductive glass according to claim 1, wherein the In 2 O 3 And SnO 2 The mass ratio of (2) is 88-92:10.
3. The method according to claim 1, wherein in the step S1, the silica accounts for 0.5 to 1.5% of the mass of the raw material for the production.
4. The method of claim 1, wherein in step S1, the deposition method is a physical vapor deposition method, and the temperature of the physical vapor deposition is 160 ℃ to 280 ℃.
5. The method according to claim 4, wherein the physical vapor deposition ambient pressure is 10 -5 Torr～10 -8 Torr。
6. The method according to claim 1, wherein in the step S2, the chemical vapor deposition method is performed at a temperature of 300 to 600 ℃.
7. The method according to claim 1, wherein in the step S2, the pressure of the chemical vapor deposition method is 1to 8Torr.
8. A conductive glass produced by the method for producing a conductive glass according to any one of claims 1to 7.
9. The conductive glass of claim 8, wherein the conductive glass comprises the glass substrate, the first conductive layer, and the second conductive layer stacked in sequence.
10. The conductive glass according to claim 9, wherein the thickness of the first conductive layer is 60 to 1000nm.
11. The conductive glass according to claim 9, wherein the thickness of the second conductive layer is 100 to 300nm.
12. The conductive glass of claim 9, wherein the first conductive layer is a silicon dioxide doped ITO layer.
13. The conductive glass of claim 8, wherein the second conductive layer is a carbon layer.
14. An LED transparent display glass comprising the conductive glass of any one of claims 8to 13.
15. Use of a conductive glass according to any one of claims 8to 13 for the preparation of LED transparent display glass.
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| CN102950829A (en) * | 2011-08-30 | 2013-03-06 | 中国南玻集团股份有限公司 | Conducting glass and preparation method thereof |
| CN105645778A (en) * | 2014-12-03 | 2016-06-08 | 北京大学 | Super graphene glass, and preparation method and applications thereof |
| CN107188429A (en) * | 2017-05-27 | 2017-09-22 | 苏州东杏表面技术有限公司 | It is a kind of that there is antistatic, the touch panel glass of anti-pollution function and its preparation method |
| CN112908517A (en) * | 2021-01-19 | 2021-06-04 | 大正(江苏)微纳科技有限公司 | Transparent conductive film and preparation method thereof |
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| CN103176650B (en) * | 2013-03-01 | 2016-09-28 | 南昌欧菲光科技有限公司 | Conducting glass substrate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950829A (en) * | 2011-08-30 | 2013-03-06 | 中国南玻集团股份有限公司 | Conducting glass and preparation method thereof |
| CN105645778A (en) * | 2014-12-03 | 2016-06-08 | 北京大学 | Super graphene glass, and preparation method and applications thereof |
| CN107188429A (en) * | 2017-05-27 | 2017-09-22 | 苏州东杏表面技术有限公司 | It is a kind of that there is antistatic, the touch panel glass of anti-pollution function and its preparation method |
| CN112908517A (en) * | 2021-01-19 | 2021-06-04 | 大正(江苏)微纳科技有限公司 | Transparent conductive film and preparation method thereof |
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