CN106637117A - High-efficiency preparation method for nitrogen-doped titanium dioxide film - Google Patents

High-efficiency preparation method for nitrogen-doped titanium dioxide film Download PDF

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Publication number
CN106637117A
CN106637117A CN201611188589.8A CN201611188589A CN106637117A CN 106637117 A CN106637117 A CN 106637117A CN 201611188589 A CN201611188589 A CN 201611188589A CN 106637117 A CN106637117 A CN 106637117A
Authority
CN
China
Prior art keywords
nitrogen
titanium dioxide
radio
doped titanium
sputtering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611188589.8A
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Chinese (zh)
Inventor
彭寿
马立云
杨勇
姚婷婷
李刚
金克武
沈洪雪
王天齐
甘治平
徐根保
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Triumph International Engineering Co Ltd
CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
Bengbu Glass Industry Design and Research Institute
Original Assignee
China Triumph International Engineering Co Ltd
Bengbu Glass Industry Design and Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Triumph International Engineering Co Ltd, Bengbu Glass Industry Design and Research Institute filed Critical China Triumph International Engineering Co Ltd
Priority to CN201611188589.8A priority Critical patent/CN106637117A/en
Publication of CN106637117A publication Critical patent/CN106637117A/en
Pending legal-status Critical Current

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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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • 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
    • C23C14/083—Oxides of refractory metals or yttrium

Abstract

The invention discloses a high-efficiency preparation method for a nitrogen-doped titanium dioxide film. The method comprises the steps that (1) a glass substrate is cleaned and then blow-dried by using high-pressure N2; and (2) the nitrogen-doped titanium dioxide film is deposited by adopting a direct-current coupling radio-frequency magnetron sputtering method, namely, a radio-frequency power supply is connected to a matcher and then together with a direct-current power supply is connected to a wave filter, wherein the wave filter is directly connected to a cathode, and the radio-frequency power supply and the direct-current power supply are used for supplying power to the cathode. According to the high-efficiency preparation method of the nitrogen doped titanium dioxide film, the nitrogen-doped titanium dioxide film is deposited by adopting the direct-current coupling radio-frequency magnetron sputtering method so that the film with a high deposition rate and high film quality can be obtained, the technology is simple, the conditions are easy to control, the preparation period is short, scale preparation is easy, and the prepared nitrogen doped titanium dioxide film is high in crystallinity, firm in combination with a substrate, good in stability and reusable.

Description

A kind of preparation method of efficient nitrogen-doped titanium dioxide thin film
Technical field
The invention belongs to catalysis material technical field, more particularly to a kind of preparation of efficient nitrogen-doped titanium dioxide thin film Method.
Technical background
Conductor photocatalysis material can be degraded various hazardous contaminants due to its powerful oxidability, meanwhile, Its is environmentally friendly, and using solar energy, reaction condition is gentle, and it is front to make it have extremely wide application the features such as low cost Scape, is increasingly subject to the extensive concern of Chinese scholars.Wherein, TiO2It is the semiconductor material with wide forbidden band of current most application potential One of, especially light excites the ability for producing electron-hole pair to be widely used in photocatalysis field.
But due to TiO2Energy gap is larger, and its photocatalysis just can only can be excited under ultraviolet light so as to using receiving Restriction is arrived, in order to improve the effectively utilizes to sunlight, to TiO2It is doped to extend its photoresponse scope so as to improve Its photocatalytic activity has become current TiO2One of research topic of photocatalysis field.In recent years, to TiO2Doping research it is main It is divided into metal-doped and nonmetal doping.Calendar year 2001 R.Asahi etc. reports the TiO of N doping2With visible light-responded, concurrently Existing nitrogen substitutes a small amount of Lattice Oxygen can make the band gap of titanium dioxide narrow, and while activity under not reducing ultraviolet light dioxy is made Change titanium and there is visible light activity.N adulterates due to its excellent performance, increasingly obtains the attention of people.
The TiO of N doping at present2The preparation method of thin film mainly has sputtering method, pulsed laser deposition, sol-gel process etc.. Sputtering method becomes current research meanses due to its plurality of advantages.Using single magnetically controlled DC sputtering or list more than research worker One rf magnetron sputtering, but both approaches have the shortcomings that its own.Direct current magnetron sputtering process sedimentation rate is fast, but due to Its ion energy is relatively low, causes its film quality not good.Radio-frequency magnetron sputter method ion energy is high, and the film quality of deposition is good, But its sedimentation rate is low.
The content of the invention
Present invention aims to the defect existing for the single sputtering method of prior art, there is provided a kind of efficient nitrogen is mixed The preparation method of miscellaneous titanium deoxid film.
In order to achieve the above object, present invention employs following technical scheme：
A kind of preparation method of efficient nitrogen-doped titanium dioxide thin film, comprises the steps：
（1）Cleaning glass substrate, uses afterwards high pressure N2Dry up；
（2）Glass substrate is put in magnetron sputtering apparatus and is connected with anode, TiO2Ceramic target is arranged on negative electrode, radio-frequency power supply with Adapter is connected to wave filter together with DC source after being connected, wave filter is directly connected to negative electrode, radio-frequency power supply and unidirectional current Source supplies electricity to together negative electrode, i.e., using the method for magnetically controlled DC sputtering coupled RF magnetron sputtering, nitrogen is sputtered on a glass substrate Titania-doped thin film；
（3）Preparation technology parameter is as follows：
Base vacuum≤8 × 10-4Pa；
Operating pressure：4～8 × 10-1Pa；
Sputtering power：50～100W；
Radio-frequency sputtering power：100～250W；
Sputtering technology gas Ar flows：20～30sccm；
Reacting gas N2Flow：4～8sccm；
Deposition plating thickness：400-600nm.
The present invention prepares N doping TiO using direct-current coupling radio-frequency magnetron sputter method2Thin film, this method is conducive to overcoming The shortcoming of two methods of magnetically controlled DC sputtering and rf magnetron sputtering, the N doping TiO for obtaining2Crystalline property is good, connects with substrate Connect performance good, photocatalysis effect is good, available wave-length coverage is wide.
The present invention has compared with prior art following advantage,
（1）The sedimentation rate of film layer can be controlled by the regulation of Dc source power；
（2）Film quality can be controlled by the regulation of radio-frequency power supply power；
（3）As a result of direct-current coupling radiofrequency magnetron sputtering technology, can obtain that sedimentation rate is fast, high thin of film quality Film, by the regulation of direct current and radio-frequency power, can simultaneously realize the control to sedimentation rate and film quality.
Description of the drawings
Fig. 1 is the schematic diagram of invention.
Specific embodiment
Embodiment one
As shown in figure 1, in magnetron sputtering chamber, glass substrate is arranged on anode, TiO2Ceramic target is arranged on negative electrode, radio frequency electrical Source is connected to wave filter after being connected with adapter together with DC source, and wave filter is directly connected to negative electrode.Radio-frequency power supply and straight Stream power supply supplies electricity to together negative electrode.
A kind of efficient nitrogen-doped titanium dioxide thin film of the present invention, is obtained through following steps：
（1）The cleaning of glass substrate surface：It is put in ultrasonic washing unit from glass substrate of the thickness for 1.1mm, first with third Ketone ultrasound 20min, then with ethanol ultrasound 20min, last deionized water ultrasound 20min, use high pressure N2Dry up.
（2）Glass substrate is taken out, in being put into magnetron sputtering apparatus（Anode）, target（Negative electrode）：TiO2Ceramic target（Purity is 99.99%）；
Preparation technology parameter is as follows：
Base vacuum≤8 × 10-4Pa；
Operating pressure：5×10-1Pa；
Sputtering power：50W；
Radio-frequency sputtering power：150W；
Sputtering technology gas Ar flows：30sccm；
Reacting gas N2Flow：5sccm；
Deposition plating thickness：400nm.
Embodiment two
（1）The cleaning of glass substrate surface：It is put in ultrasonic washing unit from glass substrate of the thickness for 0.7mm, first with third Ketone ultrasound 20min, then with ethanol ultrasound 20min, last deionized water ultrasound 20min, use high pressure N2Dry up.
（2）Glass substrate is taken out, deposition nitrogen-doped titanium dioxide thin film, preparation technology parameter in magnetron sputtering apparatus is put into It is as follows：
Target：TiO2Ceramic target（Purity：99.99%）
Base vacuum≤8 × 10-4Pa；
Operating pressure：6×10-1Pa；
Sputtering power：75W；
Radio-frequency sputtering power：175W；
Sputtering technology gas Ar flows： 25sccm；
Reacting gas N2Flow：6sccm；
Deposition plating thickness：500nm.

Claims (1)

1. a kind of preparation method of efficient nitrogen-doped titanium dioxide thin film, it is characterised in that comprise the following steps：
（1）Cleaning glass substrate, uses afterwards high pressure N2Dry up；
（2）Glass substrate is put in magnetron sputtering apparatus and is connected with anode, TiO2Ceramic target is arranged on negative electrode, radio-frequency power supply with Orchestration is connected to wave filter together with DC source after being connected, wave filter is directly connected to negative electrode, radio-frequency power supply and DC source Negative electrode is supplied electricity to together, i.e., using the method for magnetically controlled DC sputtering coupled RF magnetron sputtering, nitrogen is sputtered on a glass substrate and is mixed Miscellaneous titanium deoxid film；
（3）Preparation technology parameter is as follows：
Base vacuum≤8 × 10-4Pa；
Operating pressure：4～8 × 10-1Pa；
Sputtering power：50～100W；
Radio-frequency sputtering power：100～250W；
Sputtering technology gas Ar flows：20～30sccm；
Reacting gas N2Flow：4～8sccm；
Deposition plating thickness：400-600nm.
CN201611188589.8A 2016-12-21 2016-12-21 High-efficiency preparation method for nitrogen-doped titanium dioxide film Pending CN106637117A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611188589.8A CN106637117A (en) 2016-12-21 2016-12-21 High-efficiency preparation method for nitrogen-doped titanium dioxide film

Publications (1)

Publication Number Publication Date
CN106637117A true CN106637117A (en) 2017-05-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112626474A (en) * 2020-12-14 2021-04-09 中建材蚌埠玻璃工业设计研究院有限公司 Preparation method of lithium tantalate thin film in electrochromic film system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1594646A (en) * 2004-06-30 2005-03-16 武汉理工大学 Hydrophobic and ultraviolet radiation proof transparent film and preparation thereof
CN1653206A (en) * 2002-05-17 2005-08-10 应用菲林公司 System and apparatus for control of sputter deposition process
CN102300383A (en) * 2010-06-23 2011-12-28 北京北方微电子基地设备工艺研究中心有限责任公司 Inductance coupling apparatus and plasma processing equipment applying same
CN102864425A (en) * 2011-07-08 2013-01-09 曹宝成 Method for attaching nitrogen doped TiO<2-x>Nx films on metal bracket surface by radio frequency magnetron sputtering method
CN202717840U (en) * 2012-06-28 2013-02-06 北儒精密股份有限公司 Continuous sputtering coating equipment
CN105951053A (en) * 2016-05-20 2016-09-21 郑州大学 Production method for titanium dioxide transparent conductive oxide mixed with niobium and titanium dioxide transparent conductive oxide mixed with niobium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1653206A (en) * 2002-05-17 2005-08-10 应用菲林公司 System and apparatus for control of sputter deposition process
CN1594646A (en) * 2004-06-30 2005-03-16 武汉理工大学 Hydrophobic and ultraviolet radiation proof transparent film and preparation thereof
CN102300383A (en) * 2010-06-23 2011-12-28 北京北方微电子基地设备工艺研究中心有限责任公司 Inductance coupling apparatus and plasma processing equipment applying same
CN102864425A (en) * 2011-07-08 2013-01-09 曹宝成 Method for attaching nitrogen doped TiO<2-x>Nx films on metal bracket surface by radio frequency magnetron sputtering method
CN202717840U (en) * 2012-06-28 2013-02-06 北儒精密股份有限公司 Continuous sputtering coating equipment
CN105951053A (en) * 2016-05-20 2016-09-21 郑州大学 Production method for titanium dioxide transparent conductive oxide mixed with niobium and titanium dioxide transparent conductive oxide mixed with niobium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112626474A (en) * 2020-12-14 2021-04-09 中建材蚌埠玻璃工业设计研究院有限公司 Preparation method of lithium tantalate thin film in electrochromic film system
CN112626474B (en) * 2020-12-14 2023-02-17 中建材玻璃新材料研究院集团有限公司 Preparation method of lithium tantalate thin film in electrochromic film system

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Application publication date: 20170510