CN113265624A - Hollow cathode ion plating method suitable for tin dioxide thin film with complex and vulnerable structure - Google Patents
Hollow cathode ion plating method suitable for tin dioxide thin film with complex and vulnerable structure Download PDFInfo
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- CN113265624A CN113265624A CN202110524231.2A CN202110524231A CN113265624A CN 113265624 A CN113265624 A CN 113265624A CN 202110524231 A CN202110524231 A CN 202110524231A CN 113265624 A CN113265624 A CN 113265624A
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- tin dioxide
- hollow cathode
- cathode ion
- dioxide particles
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000007733 ion plating Methods 0.000 title claims abstract description 10
- 239000010409 thin film Substances 0.000 title description 8
- 239000000758 substrate Substances 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000005361 soda-lime glass Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 15
- 238000002834 transmittance Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 18
- 235000012431 wafers Nutrition 0.000 description 10
- 239000007888 film coating Substances 0.000 description 4
- 238000009501 film coating Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a hollow cathode ion plating method suitable for a tin dioxide film with a complex and easily damaged structure. According to the scheme of the invention, a flat, compact and excellent-light-transmission tin dioxide film can be deposited on a silicon wafer or a glass substrate without any solvent or doping material, and the average transmittance in a visible light region is close to 90%. The method has simple preparation process and short time, can realize large-area large-scale preparation, and has good application prospect in the fields of photoelectric detectors, solar cells and the like.
Description
Technical Field
The invention relates to the technical field of photoelectron materials, in particular to a hollow cathode ion plating method suitable for a tin dioxide film with a complex and easily damaged structure.
Background
In recent years, the semiconductor industry has been rapidly developed, and various semiconductor materials and devices have been widely used in various fields of daily life, especially thin film semiconductor materials. Transparent tin dioxide (tin dioxide) thin films have been the most widely studied and widely used wide bandgap semiconductor materials with important applications in the fields of liquid crystal displays, photodetectors, solar cells, and the like.
At present, the preparation process of the tin dioxide film mainly comprises spray pyrolysis, magnetron sputtering, sol-gel, chemical vapor deposition and the like, and the preparation schemes have respective advantages, such as low cost of spray pyrolysis; the magnetron sputtering process is controllable and has good repeatability; the sol-gel method is easy to operate at low temperature; chemical vapor deposition can produce thin films of uniform thickness on complex substrates. However, these techniques have problems such as poor uniformity of the prepared film, or long process time, and difficulty in continuous industrial production of large area.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a hollow cathode ion plating method suitable for a tin dioxide film with a complex and vulnerable structure.
In order to solve the above problems, the present invention adopts the following technical solutions.
A hollow cathode ion plating method suitable for tin dioxide thin films with complex and vulnerable structures comprises the following steps: the solid tin dioxide particles are put into a metal tantalum boat, then the metal tantalum boat is put into a focusing water-cooled crucible, then a metal tantalum tube is used as a cathode, the focusing water-cooled crucible is used as an anode, argon is introduced into the tantalum tube in the hollow cathode ion gun, the argon is ignited by current to be ionized, a large amount of high-density plasma beams are deflected directionally under the action of an external magnetic field and bombard the tin dioxide particles in the crucible, so that the tin dioxide particles are heated and sublimated, and finally the tin dioxide particles are deposited on a substrate.
As a further improvement of the invention, the purity of the tin dioxide particles is 99%, and the substrate is a silicon wafer or soda-lime glass.
As a further improvement of the invention, the current is 40A, the bombardment time of the hollow cathode ion gun is 20-60 s, and the flow of argon is 100 standard milliliters per minute during film coating.
The invention has the advantages of
Compared with the prior art, the invention has the advantages that:
(1) the scheme has the advantages of good plating winding performance, safe operation, short preparation time, large-area continuous preparation and good application prospect in the preparation of various photoelectric thin film materials.
(2) The prepared tin dioxide film is extremely flat and has excellent optical performance, and the root mean square roughness of the tin dioxide film deposited on the silicon wafer is only about 1 nm; the average visible light transmittance of the tin dioxide film deposited on the glass in a visible light range (380 nm-800 nm) can reach 88.7 percent.
Drawings
FIG. 1 is a schematic view of a hollow cathode ion plating apparatus of the present invention:
FIG. 2 is an enlarged view of the vacuum chamber:
FIG. 3 is an atomic force microscope image of tin dioxide films prepared in examples 1, 2 and 3;
FIG. 4 is a graph of the visible light transmission spectra of tin dioxide films prepared in examples 1, 2 and 3;
FIG. 5 shows the fit of FIG. 4 to obtain the forbidden bandwidth of the tin dioxide film;
figure 6 is an X-ray diffraction pattern of the tin dioxide film prepared in example 3.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Referring to FIG. 1, the ion plating apparatus of the present invention mainly comprises a chamber 1 of a vacuum chamber having an ultimate pressure of less than 8X 10-5Pa, working pressure of 1Pa to 5 multiplied by 10-2Pa; the maximum working current of the hollow cathode ion gun 2 is 60A, and the hollow cathode ion gun is connected with a flow monitoring system; and the vacuum system 3 consists of a mechanical pump and a molecular pump.
Example 1
(1) The invention uses two substrates of soda-lime glass and single-side polished silicon wafer. When glass is taken as a substrate, cleaning the surface of the glass by using a detergent, immersing the glass in alcohol for ultrasonic treatment for 20min, and blowing the glass for later use; the silicon wafer is used directly without cleaning.
(2) And starting the equipment, wherein the equipment is started, and an air source and a condensed water switch are opened. Then, a certain amount of solid tin dioxide particles are taken into a tantalum boat and put into a focusing water-cooled crucible, and meanwhile, the cleaned glass and silicon wafers are fixed on a turntable in the cavity. Then closing the hatch door, opening the hatch door, automatically vacuumizing until the pressure of the chamber is lower than 5 multiplied by 10-3And starting coating after Pa. And opening a workpiece to rotate, sequentially opening a focusing coil power supply, a deflection coil power supply and a crucible focusing power supply, starting a main power supply after determining that all the three power supplies are opened, setting the current of the main power supply to be 40A, observing the ignition condition of the tantalum tube when the power supply is opened, and opening a workpiece baffle to start film coating after determining that the power supply is normal, wherein the time is 20 s.
(3) After the film coating is finished, the main power supply, the focusing coil power supply, the deflection coil power supply and the crucible focusing power supply are sequentially turned off, the workpiece baffle is turned off and rotated, then the temperature of the chamber is cooled for 10min, and then the gas is filled for sampling.
(4) Performing atomic force microscope characterization on a sample film prepared based on a silicon wafer, as shown in fig. 3 (a); the sample prepared based on the glass substrate was characterized by uv-vis spectrophotometer as shown in fig. 4 and 5.
Example 2
The procedures (1) and (3) are the same as those in example 1.
(2) And starting the equipment, wherein the equipment is started, and an air source and a condensed water switch are opened. Then, a certain amount of solid tin dioxide particles are taken into a tantalum boat and put into a focusing water-cooled crucible, and meanwhile, the cleaned glass and silicon wafers are fixed on a turntable in the cavity. Then closing the hatch door, opening the hatch door, automatically vacuumizing until the pressure of the chamber is lower than 5 multiplied by 10-3And starting coating after Pa. Turning on the workpiece to rotate, sequentially turning on the focusing coil power supply, the deflection coil power supply and the crucible focusing power supply, and turning on the main power supply after determining that the three power supplies are all turned onThe power supply and the main power supply current are set to be 40A, the ignition condition of the tantalum tube is observed when the power supply is turned on, the workpiece baffle is opened to start coating after the normal operation is determined, and the time is 40 s.
(4) Performing atomic force microscopy characterization on a sample film prepared based on a silicon wafer substrate, as shown in fig. 3 (b); the sample prepared on the basis of the glass substrate was characterized by an ultraviolet-visible spectrophotometer, as shown in fig. 4.
Example 3
The procedures (1) and (3) are the same as those in example 1.
(2) And starting the equipment, wherein the equipment is started, and an air source and a condensed water switch are opened. Then, a certain amount of solid tin dioxide particles are taken into a tantalum boat and put into a focusing water-cooled crucible, and meanwhile, the cleaned glass and silicon wafers are fixed on a turntable in the cavity. Then closing the hatch door, opening the hatch door, automatically vacuumizing until the pressure of the chamber is lower than 5 multiplied by 10-3And starting coating after Pa. And opening a workpiece to rotate, sequentially opening a focusing coil power supply, a deflection coil power supply and a crucible focusing power supply, starting a main power supply after determining that all the three power supplies are opened, setting the current of the main power supply to be 40A, observing the ignition condition of the tantalum tube when the power supply is opened, and opening a workpiece baffle to start film coating after determining that the power supply is normal, wherein the time is 60 s.
(4) Performing atomic force microscopy characterization on a sample film prepared based on a silicon wafer substrate, as shown in fig. 3 (c); samples prepared based on the glass substrate were subjected to uv-vis spectrophotometer and X-ray diffraction analysis, respectively, as shown in fig. 4 and 6.
The samples prepared in each example were characterized by atomic force microscopy and the results are shown in fig. 3. As the deposition time is prolonged, the root mean square roughness of the tin dioxide film surface is slightly increased, and is respectively 0.726nm, 0.781nm and 1.386nm, and the surface fluctuation of only about 1nm shows that the tin dioxide film deposited by the hollow cathode ion plating is extremely flat. In addition, the tin dioxide thin film becomes thicker as the deposition time becomes longer, and the transmittance in the visible light wavelength range becomes lower, as shown in fig. 4. The transmittance of the glass substrate is about 90%, the transmittance is slightly reduced in the wavelength range of 380 nm-600 nm after 20s or 40s of tin dioxide film deposition, but the average transmittance of the whole glass substrate still reaches 88.7% and 84.2%, and compared with the glass substrate, the transmittance is basically not reduced, and the light transmittance is very excellent; after the tin dioxide film is deposited for 60s, the light transmittance is obviously reduced, and the average transmittance is 66.06%. The linear fitting of the transmission curve of example 1 resulted in a tin dioxide sample prepared in this way having an energy gap (Eg) of about 4.2eV, except that, since the tin dioxide sample prepared in example 3 was thickest and subjected to X-ray diffraction testing, the crystallinity was not very good since the sample was not sintered at high temperature, and a peak corresponding to the (100) crystal plane appeared only at about 26.5 °.
The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (3)
1. The hollow cathode ion plating method of the tin dioxide film suitable for the complex and vulnerable structure is characterized by comprising the following steps: the solid tin dioxide particles are put into a metal tantalum boat, then the metal tantalum boat is put into a focusing water-cooled crucible, then a metal tantalum tube is used as a cathode, the focusing water-cooled crucible is used as an anode, argon is introduced into the tantalum tube in the hollow cathode ion gun, the argon is ignited by current to be ionized, a large amount of high-density plasma beams are deflected directionally under the action of an external magnetic field and bombard the tin dioxide particles in the crucible, so that the tin dioxide particles are heated and sublimated, and finally the tin dioxide particles are deposited on a substrate.
2. The method of claim 1, wherein the tin dioxide particles are 99% pure and the substrate is a silicon wafer or soda-lime glass.
3. The method of claim 1, wherein the current is 40A, the bombardment time with the hollow cathode ion gun is 20 s-60 s, and the flow rate of argon gas during coating is 100 standard milliliters per minute.
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CN202110524231.2A CN113265624A (en) | 2021-05-13 | 2021-05-13 | Hollow cathode ion plating method suitable for tin dioxide thin film with complex and vulnerable structure |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010095764A (en) * | 2008-10-16 | 2010-04-30 | Japan Carlit Co Ltd:The | Electrode for electrolysis and method for producing the same |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2010095764A (en) * | 2008-10-16 | 2010-04-30 | Japan Carlit Co Ltd:The | Electrode for electrolysis and method for producing the same |
Non-Patent Citations (1)
Title |
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胡传炘: "《表面处理技术手册(修订版)》", 31 July 2009, 北京工业大学出版社 * |
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Application publication date: 20210817 |