CN102534531A - Preparation method of titanium dioxide/titanium nitride composite film with adjustable band gaps - Google Patents
Preparation method of titanium dioxide/titanium nitride composite film with adjustable band gaps Download PDFInfo
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- CN102534531A CN102534531A CN201210006431XA CN201210006431A CN102534531A CN 102534531 A CN102534531 A CN 102534531A CN 201210006431X A CN201210006431X A CN 201210006431XA CN 201210006431 A CN201210006431 A CN 201210006431A CN 102534531 A CN102534531 A CN 102534531A
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Abstract
The invention discloses a preparation method of a titanium dioxide/titanium nitride composite film with adjustable band gaps, belonging to the field of semiconductor energy-band engineering. According to the preparation method, a titanium nitride film is deposited on a substrate by adopting a radio-frequency magnetron sputtering method, and composite films with different optical band gaps can be obtained by carrying out annealing treatment on the film at different temperatures and time in air. The composite film shows excellent band-gap-controlled adjustment characteristics in a treatment process at specific temperature and time for annealing; and the preparation method has the advantages of simplicity, fastness, low cost, stronger controllability and excellent application prospect in surface self-cleaning materials and the energy source and environment field of the preparation of hydrogen by catalytically decomposing water and the degradation of harmful organic substances under the conditions of visible light.
Description
Technical field
The invention belongs to the semiconductor energy gap field of engineering technology, particularly the method for titanium dioxide optical catalyst band gap adjusting.
Background technology
The energy and environmental problem are two significant problems that the puzzlement human development needs to be resolved hurrily.Titanium oxide as a kind of semiconductor light-catalyst have nontoxic, inexpensive, efficient, selectivity is low, the advantage of non-secondary pollution, it is degraded at environmental pollutant, fields such as photolysis water hydrogen manufacturing have wide practical use.
Titanium oxide has big energy gap: anatase octahedrite is 3.2eV mutually; Rutile is 3.0eV mutually, be equivalent to utilize only account in the sunshine 10% less than 388nm and the UV-light below the 414nm wavelength, serious limit to the utilization ratio of sunshine; How to regulate and control the titanium oxide energy gap; Improving spectral response, is the central issue of titanium dioxide semiconductor photocatalysis technology research, also is the key issue that must solve in the titanium oxide practicability process.
Utilize metallic cation, metalloid anion to mix, cation-anion co-doping is assorted can to carry out the band gap regulation and control to titanium deoxid film with the compound of multilayer film, but exists setting range narrower, the problem that controllability is not high.The preparation of titanium nitride, titania coextruded film can be carried out controlled adjustment to the titanium oxide band gap in a big way.
Summary of the invention
The preparation method who the purpose of this invention is to provide the adjustable titanium oxide/titanium nitride compound film of a kind of band gap.
In order to achieve the above object; The technical scheme that the present invention adopts is: use magnetron sputtering coater; Adopt titanium nitride as target, on substrate, deposit, make uniform film titanium nitride membrane with radio-frequency magnetron sputter method; The prepared titanium nitride film is chosen differing temps and different time carries out anneal under air conditions, can obtain the adjustable titanium nitride of band gap, titania coextruded film.The band gap width of made laminated film is adjustable from 1.5～3.3eV band gap.
For technical scheme of the present invention is described, the enforcement of the inventive method may further comprise the steps:
A. use radio-frequency magnetron sputter method depositing titanium nitride film on substrate;
B. with the prepared titanium nitride film under air conditions, at 473K～973K 10min～180min that anneals, obtain titanium oxide/titanium nitride compound film.
The concrete steps of step a are following:
(1) silicon base or quartz substrate are carried out pre-treatment;
(2) pretreated substrate is fixed on the sample table of magnetron sputtering coater;
(3) adopting titanium nitride is target, and it is 6 * 10 that the magnetron sputtering coater chamber is evacuated to pressure
-4Below the Pa;
(4) feed argon gas and nitrogen, keep operating air pressure 0.8～4Pa, preferred 1.0Pa;
(5) the thick titanium nitride membrane of 200～1000nm of in the substrate of sample table, growing, preferred thickness 800nm;
The said pretreated method of step (1) is: with acetone, alcohol and deionized water ultrasonic cleaning successively, and dry.
Pressure is generally (2～6) * 10 in the step (3)
-4Pa.
The volume(tric)fraction of nitrogen is 3～20% in the step (4).
Sample table is static or with the speed rotation of 0.1～0.6rpm in the step (5).
To adjust the angle of target and sample table before the sputter, make the two over against, target and sample table are apart from keeping 6～15cm.
In the step (5) during sputter the temperature of sample table be 273～373K.
The preferred 623K of annealing temperature among the step b.
Under the certain temperature, band gap shortens along with annealing time and reduces; Under the certain hour, band gap reduces along with annealing temperature and reduces.
The invention has the beneficial effects as follows through to titanium nitride membrane differing temps and carry out anneal under the time in air; Can obtain titanium nitride, the titania coextruded film of different optical band gap; Laminated film has shown the controlled adjustment characteristic of good band gap in specific annealing temperature and time treating processes; Thereby help strengthening the response of laminated film, improve the utilization ratio of visible light visible light.This method is simple, quick, cost is low, Modulatory character good.Under surperficial automatically cleaning material, visible light condition catalytically decomposed water prepare hydrogen and the degraded harmful organic substance the energy and environmental area good prospects for application is arranged.
Embodiment
The present invention is a method of utilizing the rf magnetron sputtering plated film, depositing titanium nitride on silicon base or quartz substrate, and film differing temps and time in air of preparation carried out anneal, just can obtain the adjustable titanium nitride of band gap, titanium oxide composite film.
To specify the present invention with embodiment below.Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
(1) with silicon base with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) pretreated substrate is fixed on the sample table of magnetron sputtering;
(3) adopting titanium nitride is target, and the magnetron sputtering coater chamber is evacuated to 2 * 10
-4The high vacuum of Pa;
(4) feed argon gas and nitrogen, keep operating air pressure 1.0Pa, wherein the volume(tric)fraction of nitrogen is 10%;
(5) angle of adjustment target and sample table, make the two over against, target and sample table be apart from keeping 10cm, and sample table is rotated with the speed of 0.2rpm, the temperature of sample table remains on 333K, the thick titanium nitride membrane of 800nm of in the substrate of sample table, growing;
(6) with the prepared titanium nitride film 60min that under the 623K temperature, in air atmosphere, anneals, from lehre, shift out and reduce to room temperature then, obtain titanium oxide/titanium nitride compound film, band gap width Eg=2.7eV.
Embodiment 2
(1) with silicon base with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) pretreated substrate is fixed on the sample table of magnetron sputtering;
(3) adopting titanium nitride is target, and the magnetron sputtering coater chamber is evacuated to 2 * 10
-4The high vacuum of Pa;
(4) feed argon gas and nitrogen, keep operating air pressure 1.0Pa, wherein the volume(tric)fraction of nitrogen is 10%;
(5) angle of adjustment target and sample table, make the two over against, target and sample table be apart from keeping 10cm, and sample table is rotated with the speed of 0.2rpm, the temperature of sample table remains on 333K, the thick titanium nitride membrane of 800nm of in the substrate of sample table, growing;
(6) with the prepared titanium nitride film under air atmosphere, the 45min that anneals under the 623K temperature obtains the laminated film of titanium nitride and titanium oxide, band gap width Eg=2.4eV.
Embodiment 3
(1) with silicon base with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) pretreated substrate is fixed on the sample table of magnetron sputtering;
(3) adopting titanium nitride is target, and the magnetron sputtering coater chamber is evacuated to 2 * 10
-4The high vacuum of Pa;
(4) feed argon gas and nitrogen, keep operating air pressure 1.0Pa, wherein the volume(tric)fraction of nitrogen is 10%;
(5) angle of adjustment target and sample table, make the two over against, target and sample table be apart from keeping 10cm, and sample table is rotated with the speed of 0.2rpm, the temperature of sample table remains on 333K, the thick titanium nitride membrane of 800nm of in the substrate of sample table, growing;
(6) with the prepared titanium nitride film under air conditions, at temperature 623K annealing 15min, obtain the laminated film of titanium nitride and titanium oxide, band gap width Eg=2.0eV.
Embodiment 4
(1) with quartz substrate with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) pretreated substrate is fixed on the sample table of magnetron sputtering;
(3) adopting titanium nitride is target, and the magnetron sputtering coater chamber is evacuated to 5 * 10
-4The high vacuum of Pa;
(4) feed argon gas and nitrogen, keep operating air pressure 2Pa, wherein the dividing potential drop of nitrogen is 0.06Pa;
(5) angle of adjustment target and sample table, make the two over against, target and sample table are apart from maintenance 7cm, sample table is static, the temperature of sample table remains between 273K and the 373K, the thick titanium nitride membrane of 300nm of in the substrate of sample table, growing;
(6) with the prepared titanium nitride film under the temperature of 500K, the 150min that in air atmosphere, anneals obtains the laminated film of titanium nitride and titanium oxide, band gap width Eg=3.0eV.
Embodiment 5
(1) with silicon base with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) pretreated substrate is fixed on the sample table of magnetron sputtering;
(3) adopting titanium nitride is target, and the magnetron sputtering coater chamber is evacuated to 3 * 10
-4The high vacuum of Pa;
(4) feed argon gas and nitrogen, keep operating air pressure 3.0Pa, the dividing potential drop of nitrogen is 0.6Pa;
(5) angle of adjustment target and sample table; Make the two over against, target and sample table be apart from keeping 13cm, and make the speed rotation of sample table with 0.5rpm; The temperature of sample table remains between 273K and the 373K, the thick titanium nitride membrane of growth 600nm in the substrate of sample table;
(6) with the prepared titanium nitride film under air conditions, the 30min that anneals under the 900K temperature obtains the laminated film of titanium nitride and titanium oxide, band gap width Eg=2.8eV.
Claims (10)
1. the preparation method of the adjustable titanium oxide/titanium nitride compound film of a band gap, it is characterized in that: this method comprises the steps:
A. use radio-frequency magnetron sputter method depositing titanium nitride film on substrate;
B. with the prepared titanium nitride film under air conditions, at 473K～973K 10min～180min that anneals, obtain titanium oxide/titanium nitride compound film.
2. method according to claim 1 is characterized in that: the concrete steps of step a are following:
(1) silicon base or quartz substrate are carried out pre-treatment;
(2) pretreated substrate is fixed on the sample table of magnetron sputtering coater;
(3) adopting titanium nitride is target, and it is 6 * 10 that the magnetron sputtering coater chamber is evacuated to pressure
-4Below the Pa;
(4) feed argon gas and nitrogen, keep operating air pressure 0.8～4Pa;
(5) the thick titanium nitride membrane of 200～1000nm of in the substrate of sample table, growing.
3. method according to claim 1 is characterized in that: annealing temperature is 623K.
4. method according to claim 2 is characterized in that: pressure is (2～6) * 10 in the step (3)
-4Pa.
5. method according to claim 2 is characterized in that: sample table is static or with the speed rotation of 0.1～0.6rpm in the step (5).
6. method according to claim 2 is characterized in that: to adjust the angle of target and sample table before the sputter, make the two over against, target and sample table are apart from keeping 6～15cm.
7. method according to claim 2 is characterized in that: in the step (5) during sputter the temperature of sample table be 273～373K.
8. method according to claim 2 is characterized in that: the volume(tric)fraction of nitrogen is 3～20% in the step (4).
9. method according to claim 2 is characterized in that: the said pretreated method of step (1) is: with acetone, alcohol and deionized water ultrasonic cleaning successively and dry.
10. method according to claim 2 is characterized in that: the thickness of titanium nitride membrane is 800nm in the step (5).
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Cited By (8)
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|---|---|---|---|---|
| CN103736500A (en) * | 2013-12-23 | 2014-04-23 | 清华大学 | Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN105026606A (en) * | 2013-05-15 | 2015-11-04 | 株式会社尼康 | Compound film production method |
| CN107974661A (en) * | 2016-10-21 | 2018-05-01 | 江苏今道投资发展有限公司 | A kind of preparation method of the titania-doped film of tantalum |
| CN108675794A (en) * | 2018-06-06 | 2018-10-19 | 上海海事大学 | A kind of ceramic material and preparation method thereof with controllable negative dielectric properties |
| CN109836050A (en) * | 2019-04-08 | 2019-06-04 | 浙江大学 | A kind of tandem type TiN/TiO2Laminated film and its preparation method and application |
| CN112779509A (en) * | 2019-11-07 | 2021-05-11 | 有研工程技术研究院有限公司 | Transition metal nitride core-shell structure film and preparation method thereof |
| CN113943929A (en) * | 2021-10-18 | 2022-01-18 | 河南科技大学 | Preparation method of TiLaN composite film and wear-resistant product |
| TWI818610B (en) * | 2022-06-30 | 2023-10-11 | 國立中興大學 | Photoelectrochemical device |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026606A (en) * | 2013-05-15 | 2015-11-04 | 株式会社尼康 | Compound film production method |
| CN103736500A (en) * | 2013-12-23 | 2014-04-23 | 清华大学 | Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN103736500B (en) * | 2013-12-23 | 2016-06-15 | 清华大学 | A kind of Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN107974661A (en) * | 2016-10-21 | 2018-05-01 | 江苏今道投资发展有限公司 | A kind of preparation method of the titania-doped film of tantalum |
| CN108675794A (en) * | 2018-06-06 | 2018-10-19 | 上海海事大学 | A kind of ceramic material and preparation method thereof with controllable negative dielectric properties |
| CN108675794B (en) * | 2018-06-06 | 2021-04-13 | 上海海事大学 | Ceramic material with adjustable negative dielectric property and preparation method thereof |
| CN109836050A (en) * | 2019-04-08 | 2019-06-04 | 浙江大学 | A kind of tandem type TiN/TiO2Laminated film and its preparation method and application |
| CN112779509A (en) * | 2019-11-07 | 2021-05-11 | 有研工程技术研究院有限公司 | Transition metal nitride core-shell structure film and preparation method thereof |
| CN113943929A (en) * | 2021-10-18 | 2022-01-18 | 河南科技大学 | Preparation method of TiLaN composite film and wear-resistant product |
| TWI818610B (en) * | 2022-06-30 | 2023-10-11 | 國立中興大學 | Photoelectrochemical device |
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Application publication date: 20120704 |