CN109192655B - C (C) 3 N 4 Modified TCO glass and preparation method thereof - Google Patents
C (C) 3 N 4 Modified TCO glass and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 25
- 239000010439 graphite Substances 0.000 claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011787 zinc oxide Substances 0.000 abstract description 8
- 238000002834 transmittance Methods 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen modified zinc oxide Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02697—Forming conducting materials on a substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
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- Glass Compositions (AREA)
Abstract
The invention discloses a C 3 N 4 Modified TCO glass and preparation method thereof, wherein the TCO glass is made of silicon plateAZO glass as substrate by graphite phase C 3 N 4 Doped zinc oxide to obtain zinc oxide-C 3 N 4 TCO glass of the film. The invention overcomes the problem of high resistivity of the TCO film in the prior art, and adopts the technical proposal to improve the carrier mobility of the TCO film, so that the TCO film has low resistivity and high light transmittance; the manufacturing cost of TCO glass is effectively reduced; the preparation method is simple, the experimental conditions are mild, no toxic or side crop is produced, and the cost is low.
Description
Technical Field
The invention relates to the field of conductive glass, in particular to a conductive glassC (C) 3 N 4 Modified TCO glass and a method for preparing the same.
Background
In recent years, with the rising of the solar cell industry, especially the forensic projection of the film battery, the requirement of the invention TCO glass as a transparent electrode of the film battery is increasing, and the method for preparing the TCO glass is also being studied intensively. With the development and application of TCOs, the research on the conduction mechanism and optical performance of TCOs is also becoming deeper; however, due to its complex structure and doping mechanism, the basic properties of the material are still largely unknown, which results in insufficient process realization. The process parameters such as the doping proportion of the raw materials and the plating thickness have obvious influence on the process parameters, and more technological parameters are determined by further experimental data obtained through a large number of repeated experiments. By improving the carrier mobility of the TCO film, the low resistivity and the high transmittance of the TCO film, namely 1, the contradictory and mutually restricted parameters are combined most reasonably, and the TCO film is a main research direction for expanding the application range and improving the use performance of the TCO film.
g-C 3 N 4 I.e. graphite phase C 3 N 4 Is a nonmetallic semiconductor, which is composed of C, N elements with high content on earth, the semiconductor has a lamellar structure similar to graphite, the lamellar layers are stacked along the direction of the C-axis, and C is formed by C, N elements through sp hybridization 3 N 3 Ring or C 6 N 7 The ring is formed, the ring and the ring are connected through N atoms to form an infinitely extended plane, the band gap is about 2.7eV, the electron transfer performance is realized, the corrosion resistance to acid, alkali and light is realized, the stability is good, and the structure and the performance are easy to regulate and control.
For example, a transparent silicon-based thin film solar cell structure with a novel structure disclosed in Chinese patent literature and a preparation method thereof have the technical proposal that: (1) depositing an intrinsic silicon thin film layer on the TCO glass; (2) depositing a p-type silicon thin film doping layer on the intrinsic silicon thin film layer; (3) and depositing a TCO film conductive layer on the p-type silicon film doped layer, and forming a built-in electric field through the p-type silicon film doped layer and TCO glass, thereby forming the transparent film solar cell with a novel structure. Although the transmittance of the TCO glass structure is high, the process is complex, and the film resistivity is high, so that the TCO glass cannot be effectively applied.
Disclosure of Invention
The invention aims to solve the problem of high resistivity of TCO film in the prior art and provides a C 3 N 4 Modified TCO glass and method for producing same, by C 3 N 4 The doping modification is used for improving the carrier mobility of the TCO film, so that the aim of low resistivity is fulfilled.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a C3N4 modified TCO glass is AZO glass with a silicon plate as a substrate and passes through a graphite phase C 3 N 4 Doped zinc oxide to obtain zinc oxide-C 3 N 4 TCO glass of the film. g-C 3 N 4 Has a graphene-like structure, and has excellent electron transport performance due to rich N content, and g-C is utilized 3 N 4 The doped zinc oxide can effectively compensate the problem of low conductivity of the zinc oxide, thereby improving the conductivity of TCO glass and further realizing single-layer g-C 3 N 4 Almost transparent, and the compound TCO glass has the characteristics of low resistivity and high light transmittance due to the requirements of conductivity and light transmittance, so that the performance of the TCO glass is improved. g-C 3 N 4 The preparation method is simple and various, the sources of raw materials are wide and low, and g-C is adopted 3 N 4 The oxygen modified zinc oxide saves the manufacturing cost of TCO glass.
Preferably, a C 3 N 4 A method of preparing a modified TCO glass, the method comprising the steps of:
(1)C 3 N 4 is prepared from the following steps: placing melamine in a muffle furnace, programming to 500-600deg.C, and calcining for 1-3 hr to obtain graphite phase C 3 N 4 Then graphite phase C 3 N 4 Manually grinding for 30-60min;
(2) Zinc oxide-C 3 N 4 Is prepared from the following steps: weighing the ground graphite phase C in the step (1) 3 N 4 Adding into BUltrasonic oscillating in glycol for 30-60min to obtain C 3 N 4 Dispersing liquid, dissolving zinc salt in glycol to obtain zinc-containing solution, adding the solution into the C 3 N 4 In the dispersion liquid, uniformly mixing, performing reaction by adopting a microwave hydrothermal method, centrifugally separating the obtained mixed solution after the reaction is finished to obtain a solid, and drying the solid for 15-30h under a vacuum condition to obtain the zinc oxide-C 3 N 4 I.e. CZO powder;
(3) Preparation of TCO glass: and (3) weighing the CZO powder in the step (2), adding the CZO powder into ethylene glycol, performing ultrasonic dispersion for 2-5h to obtain a CZO dispersion liquid with the concentration of 0.8-1.5mg/ml, taking a silicon wafer as a substrate, and performing spin coating on the CZO dispersion liquid on a spin coater to obtain the TCO glass. The preparation method of the technical scheme of the invention is simple, the experimental conditions are mild, no toxic or side crop is produced, and the cost is low.
Preferably, in the step (1), the specific temperature programming process is as follows: heating to 350-400deg.C at a rate of 10-12deg.C/min, maintaining for 1-2 hr, and heating to 500-600deg.C at a rate of 10-12deg.C/min. g-C prepared by adopting temperature programming 3 N 4 The nano-size can be achieved, the specific surface area is larger, the electron transmission performance is higher, the conductivity of the TCO glass is further improved, and the resistivity is reduced.
Preferably, in the step (1), melamine is placed in a crucible, the volume of the melamine is 1/2-2/3 of the volume of the crucible, and the crucible opening is closed and then placed in a muffle furnace for calcination. In the preparation process, the crucible opening is firstly sealed by tin foil paper, and then the crucible cover is covered to isolate the air contact between the inside of the crucible and the outside, so that the melamine has proper carbonization degree in the heating process, the electron transmission performance is maximized, the excessive oxidative degradation caused by the contact with the air is prevented, the product is not only lost, but also the g-C meeting the requirements is not easily obtained 3 N 4 。
Preferably, in the step (2), the zinc salt is selected from any one of zinc nitrate, zinc chloride, zinc sulfate and zinc acetate.
Preferably, in step (2), the graphite phase C 3 N 4 And zinc saltsThe addition mass ratio of the C is 1:15-25 3 N 4 The concentration of the dispersion liquid is 0.5-2mg/ml, and the concentration of the zinc-containing solution is 30-35mg/ml.
Preferably, in the step (2), the microwave hydrothermal reaction is carried out for 30-60min under the pressure of 180-200Mpa and the temperature of 180-230 ℃.
Therefore, the invention has the following beneficial effects: (1) The carrier mobility of the TCO film is improved, so that the TCO film has low resistivity and high light transmittance; (2) the manufacturing cost of TCO glass is effectively reduced; (3) The preparation method is simple, the experimental conditions are mild, no toxic or side crop is produced, and the cost is low.
Detailed Description
The invention is further described below in connection with the following detailed description. The reagents used in the invention are all obtained by routine experiments or commercially available.
Example 1:
c (C) 3 N 4 A method of preparing a modified TCO glass, the method comprising the steps of:
(1)C 3 N 4 is prepared from the following steps: placing melamine into a crucible, wherein the volume of the melamine is 1/2 of the volume of the crucible, sealing a crucible opening, placing the crucible opening into a muffle furnace for calcination, heating to 350 ℃ at the speed of 10 ℃/min for 1h, heating to 500 ℃ at the speed of 10 ℃/min, and calcining for 1h to obtain graphite phase C 3 N 4 Manually grinding graphite phase C3N4 for 30min;
(2) Zinc oxide-C 3 N 4 Is prepared from the following steps: weighing the ground graphite phase C in the step (1) 3 N 4 Adding into ethylene glycol, and performing ultrasonic vibration for 30min to obtain C with concentration of 0.5mg/ml 3 N 4 Dispersing liquid, dissolving zinc nitrate in glycol to obtain zinc-containing solution with concentration of 30mg/ml, adding the solution into the C 3 N 4 Uniformly mixing the dispersion liquid, then adopting a microwave hydrothermal method, reacting for 30min at 180Mpa and 180 ℃, centrifugally separating the obtained mixed solution after the reaction is finished to obtain solid, and drying the solid for 15h under vacuum condition to obtain the zinc oxide-C 3 N 4 I.e. CZO powder; graphite phase C 3 N 4 And zinc salt in the mass ratio of 1:15;
(3) Preparation of TCO glass: and (3) weighing the CZO powder in the step (2), adding the CZO powder into ethylene glycol, performing ultrasonic dispersion for 2 hours to obtain CZO dispersion liquid with the concentration of 0.8mg/ml, taking a silicon wafer as a substrate, and performing spin coating on the CZO dispersion liquid on a spin coater to obtain the TCO glass.
Example 2:
c (C) 3 N 4 A method of preparing a modified TCO glass, the method comprising the steps of:
(1)C 3 N 4 is prepared from the following steps: placing melamine into a crucible, wherein the volume of the melamine is 2/3 of the volume of the crucible, sealing a crucible opening, placing the crucible opening into a muffle furnace for calcination, heating to 400 ℃ at a speed of 12 ℃/min and keeping the temperature for 2 hours, heating to 600 ℃ at a speed of 12 ℃/min, and calcining for 3 hours to obtain a graphite phase C 3 N 4 Manually grinding graphite phase C3N4 for 60min;
(2) Zinc oxide-C 3 N 4 Is prepared from the following steps: weighing the ground graphite phase C in the step (1) 3 N 4 Adding into ethylene glycol, and performing ultrasonic vibration for 60min to obtain C with concentration of 2mg/ml 3 N 4 Dispersing liquid, dissolving zinc chloride in glycol to obtain zinc-containing solution with concentration of 35mg/ml, adding the solution into the C 3 N 4 Uniformly mixing the dispersion liquid, then adopting a microwave hydrothermal method, reacting for 60min at the temperature of 230 ℃ under the pressure of 200Mpa, centrifugally separating the obtained mixed solution after the reaction is finished to obtain solid, and drying the solid for 30h under the vacuum condition to obtain the zinc oxide-C 3 N 4 I.e. CZO powder; graphite phase C 3 N 4 And zinc salt in the mass ratio of 1:25;
(3) Preparation of TCO glass: and (3) weighing the CZO powder in the step (2), adding the CZO powder into ethylene glycol, performing ultrasonic dispersion for 5 hours to obtain CZO dispersion liquid with the concentration of 1.5mg/ml, taking a silicon wafer as a substrate, and performing spin coating on the CZO dispersion liquid on a spin coater to obtain the TCO glass.
Example 3:
c (C) 3 N 4 A method of preparing a modified TCO glass, the method comprising the steps of:
(1)C 3 N 4 is prepared from the following steps: placing melamine into a crucible, wherein the volume of the melamine is between 2/5 of the volume of the crucible, sealing a crucible opening, placing the crucible opening into a muffle furnace for calcination, heating to 365 ℃ at the speed of 11 ℃/min and keeping for 1.4h, heating to 550 ℃ at the speed of 10.8 ℃/min, and calcining for 2h to obtain graphite phase C 3 N 4 Then graphite phase C 3 N 4 Manually grinding for 40min;
(2) Zinc oxide-C 3 N 4 Is prepared from the following steps: weighing the ground graphite phase C3N4 in the step (1), adding into glycol, and performing ultrasonic vibration for 40min to obtain C with a concentration of 1mg/ml 3 N 4 Dissolving zinc acetate in ethylene glycol to obtain a zinc-containing solution with the concentration of 32mg/ml, adding the solution into the C3N4 dispersion, uniformly mixing, then adopting a microwave hydrothermal method, reacting for 50min under the pressure of 190Mpa and the temperature of 200 ℃, centrifuging the obtained mixed solution after the reaction is finished to obtain a solid, and drying the solid for 24h under the vacuum condition to obtain zinc oxide-C3N 4, namely CZO powder; graphite phase C 3 N 4 And zinc salt in the mass ratio of 1:20;
(3) Preparation of TCO glass: and (3) weighing the CZO powder in the step (2), adding the CZO powder into ethylene glycol, performing ultrasonic dispersion for 3 hours to obtain CZO dispersion liquid with the concentration of 1.2mg/ml, taking a silicon wafer as a substrate, and performing spin coating on the CZO dispersion liquid on a spin coater to obtain the TCO glass.
Comparative example 1:
a method of preparing TCO glass, the method comprising the steps of:
(1) Preparation of zinc oxide: dissolving zinc acetate in ethylene glycol to obtain a zinc-containing solution with the concentration of 32mg/ml, carrying out a reaction for 50min under the pressure of 190Mpa and the temperature of 200 ℃ by adopting a microwave hydrothermal method, centrifuging the obtained mixed solution after the reaction is finished to obtain a solid, and drying the solid under the vacuum condition for 24h to obtain the zinc oxide;
(2) Preparation of TCO glass: and (3) weighing zinc oxide in the step (1), adding the zinc oxide into ethylene glycol, performing ultrasonic dispersion for 3 hours to obtain zinc oxide dispersion liquid with the concentration of 1.2mg/ml, taking a silicon wafer as a substrate, and performing spin coating on the zinc oxide dispersion liquid on a spin coater to obtain the TCO glass.
The conductivity of the TCO glasses prepared in each example and comparative example was measured by a four-probe method, and the results are shown in table 1:
table 1 resistivity test results for each example and comparative example:
| test case | current/mA | voltage/V | Resistivity/Ω·cm |
| Example 1 | 100 | 1.2*10-2 | 1.05*10-5 |
| Example 2 | 100 | 1.2*10-2 | 1.01*10-5 |
| Example 3 | 100 | 1.2*10-2 | 1.06*10-5 |
| Comparative example 1 | 100 | 1.2*10-2 | 1.25*10-3 |
As can be seen from the data in the tables, the graphite phase C is passed through 3 N 4 The modified zinc oxide is used for preparing the TCO film, so that the resistivity of the TCO glass is obviously reduced.
Claims (6)
1. C (C) 3 N 4 A method for preparing a modified TCO glass, said method comprising the steps of:
C 3 N 4 is prepared from the following steps: placing melamine in a muffle furnace, programming to 500-600deg.C, and calcining for 1-3 hr to obtain graphite phase C 3 N 4 Then graphite phase C 3 N 4 Manually grinding for 30-60min;
zinc oxide-C 3 N 4 Is prepared from the following steps: weighing the ground graphite phase C in the step (1) 3 N 4 Adding into ethylene glycol, and performing ultrasonic vibration for 30-60min to obtain C 3 N 4 Dispersing liquid, dissolving zinc salt in glycol to obtain zinc-containing solution, adding the solution into the C 3 N 4 In the dispersion liquid, uniformly mixing, performing reaction by adopting a microwave hydrothermal method, centrifugally separating the obtained mixed solution after the reaction is finished to obtain a solid, and drying the solid for 15-30h under a vacuum condition to obtain the zinc oxide-C 3 N 4 I.e. CZO powder;
preparation of TCO glass: and (3) weighing the CZO powder in the step (2), adding the CZO powder into ethylene glycol, performing ultrasonic dispersion for 2-5h to obtain a CZO dispersion liquid with the concentration of 0.8-1.5mg/ml, taking a silicon wafer as a substrate, and performing spin coating on the CZO dispersion liquid on a spin coater to obtain the TCO glass.
2. A C according to claim 1 3 N 4 A process for preparing a modified TCO glass, characterized in that in step (1), theThe specific process of programming the temperature is as follows: heating to 350-400deg.C at a rate of 10-12deg.C/min, maintaining for 1-2 hr, and heating to 500-600deg.C at a rate of 10-12deg.C/min.
3. A C according to claim 1 or 2 3 N 4 The preparation method of the modified TCO glass is characterized in that in the step (1), melamine is placed in a crucible, the volume of the melamine is 1/2-2/3 of the volume of the crucible, and then the crucible opening is closed and then placed in a muffle furnace for calcination.
4. A C according to claim 1 3 N 4 The preparation method of the modified TCO glass is characterized in that in the step (2), the zinc salt is selected from any one of zinc nitrate, zinc chloride, zinc sulfate or zinc acetate.
5. A C according to claim 1 or 4 3 N 4 A process for preparing a modified TCO glass, characterized in that in step (2), the graphite phase C 3 N 4 And zinc salt in the mass ratio of 1:15-25, wherein the C is as follows 3 N 4 The concentration of the dispersion liquid is 0.5-2mg/ml, and the concentration of the zinc-containing solution is 30-35mg/ml.
6. A C according to claim 5 3 N 4 The preparation method of the modified TCO glass is characterized in that in the step (2), the microwave hydrothermal reaction is carried out for 30-60min under the pressure of 180-200Mpa and the temperature of 180-230 ℃.
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