JP2002030417A - Method for manufacturing titanium oxide single crystal thin film of anatase-type crystal structure - Google Patents
Method for manufacturing titanium oxide single crystal thin film of anatase-type crystal structureInfo
- Publication number
- JP2002030417A JP2002030417A JP2000213765A JP2000213765A JP2002030417A JP 2002030417 A JP2002030417 A JP 2002030417A JP 2000213765 A JP2000213765 A JP 2000213765A JP 2000213765 A JP2000213765 A JP 2000213765A JP 2002030417 A JP2002030417 A JP 2002030417A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- thin film
- titanium dioxide
- anatase
- plane
- 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.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000013078 crystal Substances 0.000 title claims abstract description 56
- 239000010409 thin film Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 31
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- -1 lanthanum aluminate Chemical class 0.000 claims abstract description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002294 SrAl0.5Ta0.5O3 Inorganic materials 0.000 claims abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 abstract description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 238000000608 laser ablation Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 229910002244 LaAlO3 Inorganic materials 0.000 abstract 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000010586 diagram Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、アナターゼ型結晶
構造の二酸化チタン単結晶膜を作製する方法に関するも
のであり、二酸化チタンの薄膜を単結晶化することによ
り膜内の結晶欠陥などを軽減させ、光触媒反応効率なと
の特性を向上させようとするものである。即ちその単結
晶薄膜を光触媒として用いることにより窒素酸化物等の
有害ガスの分解、除去を行う反応効率の向上を目的とし
ている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a titanium dioxide single crystal film having an anatase type crystal structure, and reduces a crystal defect and the like in the film by monocrystallizing a titanium dioxide thin film. It is intended to improve the characteristics of high photocatalytic reaction efficiency. That is, the purpose is to improve the reaction efficiency of decomposing and removing harmful gases such as nitrogen oxides by using the single crystal thin film as a photocatalyst.
【0002】[0002]
【従来の技術】真空蒸着法やゾル・ゲル法によりアナタ
ーゼ型の二酸化チタン膜の作製が行われているが、これ
までの薄膜は多結晶構造のものしか作製できなかった。
また、これまでの二酸化チタン薄膜にはルチル型および
アナターゼ型の二酸化チタンが混在しており光触媒反応
効率の高いアナターゼ型のみの単結晶薄膜を作製するこ
とは困難であった。2. Description of the Related Art Anatase-type titanium dioxide films have been produced by a vacuum evaporation method or a sol-gel method, but only thin films having a polycrystalline structure can be produced so far.
Further, rutile-type and anatase-type titanium dioxide are mixed in the conventional titanium dioxide thin film, and it has been difficult to produce a single crystal thin film of only anatase type having high photocatalytic efficiency.
【0003】[0003]
【発明が解決しようとする課題】二酸化チタンは高温側
(800℃以上)ではルチル型が安定なため、融体から
の結晶成長法によるアナターゼ型の単結晶の製造は困難
である。本発明の課題は高品質なアナターゼ型結晶構造
の二酸化チタン単結晶薄膜を作製することにある。Since titanium dioxide is stable in rutile on the high temperature side (800 ° C. or higher), it is difficult to produce anatase-type single crystals by crystal growth from a melt. An object of the present invention is to produce a high-quality titanium dioxide single crystal thin film having an anatase crystal structure.
【0004】[0004]
【課題を解決するための手段】本発明は、アナターゼ型
の二酸化チタン単結晶薄膜を作製する手段として、レー
ザアブレーション成膜法によりランタンアルミネート
(LaAlO3)、酸化マグネシウム(MgO)、安定
化ジルコニア(YSZ)、又はLSAT([LaAlO
3])0.3−[SrAl0.5Ta0.5O3]0.7)単結晶基板上
にアナターゼ型の二酸化チタンを基板温度、酸素分圧、
蒸着速度を制御して単結晶薄膜を作製するものである。According to the present invention, as a means for producing an anatase type titanium dioxide single crystal thin film, lanthanum aluminate (LaAlO 3 ), magnesium oxide (MgO), stabilized zirconia by a laser ablation method. (YSZ) or LSAT ([LaAlO
3]) 0.3 - [SrAl 0.5 Ta 0.5 O 3] 0.7) titanium dioxide substrate temperature of anatase type on a single crystal substrate, the oxygen partial pressure,
A single crystal thin film is produced by controlling the deposition rate.
【0005】本発明においては、金属チタンを低圧酸素
ガス雰囲気で、レーザ照射によって蒸発させ、無機ある
いは金属の平滑表面あるいは単結晶表面の基板にアナタ
ーゼ型の二酸化チタンの形態で蒸着させて、薄膜状の結
晶を成長させるものである。In the present invention, metallic titanium is evaporated by laser irradiation in a low-pressure oxygen gas atmosphere, and is vapor-deposited in the form of anatase-type titanium dioxide on a substrate having a smooth inorganic or metal surface or a single crystal surface. Is grown.
【0006】この作製条件としては、レーザの出力と照
射方法、酸素雰囲気の圧力、基板の種類と温度が重要な
項目である。As the manufacturing conditions, the laser output and irradiation method, the pressure of the oxygen atmosphere, the type and temperature of the substrate are important items.
【0007】[0007]
【発明の実施の形態】即ち、本発明は、低圧酸素雰囲気
10mTorr〜100mTorr(好ましくは20m
Torr〜70mTorr、最も好ましくは30mTo
rr〜40mTorr)でレーザアブレーション成膜法
により、ランタンアルミネート(LaAlO3)、酸化
マグネシウム(MgO)、安定化ジルコニア(YS
Z)、又はLSAT([LaAlO3])0.3−[SrA
l0.5Ta0.5O3]0.7)の平滑な単結晶基板上に厚さが
10nm(ナノメータ)から2μmの範囲に制御された
アナターゼ型の二酸化チタンの単結晶薄膜を作製するも
のである。DESCRIPTION OF THE PREFERRED EMBODIMENTS That is, the present invention relates to a low-pressure oxygen atmosphere of 10 mTorr to 100 mTorr (preferably 20 mTorr).
Torr to 70 mTorr, most preferably 30 mTo
rr to 40 mTorr) by lanthanum aluminate (LaAlO 3 ), magnesium oxide (MgO), stabilized zirconia (YS)
Z), or LSAT ([LaAlO 3]) 0.3 - [SrA
l 0.5 Ta 0.5 O 3] 0.7 smooth single crystal thickness on the substrate of) are those to produce the single-crystal thin film of 10 nm (nanometers) from the controlled anatase in the range of 2μm titanium dioxide.
【0008】アナターゼ型の単結晶を形成させる基板温
度は、360℃〜520℃(好ましくは400℃〜50
0℃、最も好ましくは450℃〜490℃)に制御され
る条件、酸素ガス圧は10mTorr〜100mTor
r(好ましくは20mTorr〜80mTorr、最も
好ましくは30mTorr〜40mTorr)に制御さ
れる条件とする。以下、本発明を実施例に基づいて説明
する。[0008] The substrate temperature for forming an anatase type single crystal is 360 ° C to 520 ° C (preferably 400 ° C to 50 ° C).
0 ° C., most preferably 450 ° C. to 490 ° C.), and the oxygen gas pressure is 10 mTorr to 100 mTorr.
r (preferably 20 mTorr to 80 mTorr, most preferably 30 mTorr to 40 mTorr). Hereinafter, the present invention will be described based on examples.
【0009】[0009]
【実施例1】1パルス当たり40mJ、繰り返し周波数
10HzのYAG(イットリウムアルミニウムガーネッ
ト)レーザ(波長532nm)を低圧酸素雰囲気中(3
5mTorr)に置いた金属チタンターゲットに直径1
mmに集光させて入射した。金属チタンターゲットより
5cmの距離に基板温度480℃に保持した各種の単結
晶基板を設置し、2時間のレーザー照射で二酸化チタン
膜を作製した。得られた二酸化チタン薄膜は厚さ0.2
μmであった。Example 1 A YAG (yttrium aluminum garnet) laser (wavelength: 532 nm) having a pulse frequency of 40 mJ and a repetition frequency of 10 Hz was placed in a low-pressure oxygen atmosphere (3
5 mTorr) on a titanium metal target placed at 1 mTorr
mm. Various single crystal substrates kept at a substrate temperature of 480 ° C. were placed at a distance of 5 cm from the metal titanium target, and a titanium dioxide film was formed by laser irradiation for 2 hours. The obtained titanium dioxide thin film has a thickness of 0.2
μm.
【0010】ここで用いた単結晶基板は、(100)面
のランタンアルミネート(LaAlO3)、(100)
面の酸化マグネシウム(MgO)、(100)面の安定
化ジルコニア(YSZ)、(100)面のLSAT
([LaAlO3])0.3−[SrAl0.5Ta
0.5O3]0.7)であり、各基板は鏡面研磨処理をしている
ものを使用した。これらの基板上の成膜した二酸化チタ
ン薄膜をX線回折法により結晶構造の評価したところ、
各基板と成膜した二酸化チタン薄膜の結晶方位関係は、 (100)面のLaAlO3基板上に(001)面のT
iO2 (100)面のMgO基板上に(100)面のTiO2 (100)面のYSZ基板上に(001)面のTiO2 (100)面のLSAT基板上に(001)面のTiO
2 であった。The single crystal substrate used here is a (100) plane of lanthanum aluminate (LaAlO 3 ), (100)
Magnesium oxide (MgO) on the plane, stabilized zirconia (YSZ) on the (100) plane, LSAT on the (100) plane
([LaAlO 3]) 0.3 - [SrAl 0.5 Ta
0.5 O 3 ] 0.7 ), and each substrate used had been subjected to mirror polishing. When the crystal structure of the titanium dioxide thin film formed on these substrates was evaluated by X-ray diffraction,
The crystal orientation relationship between each substrate and the deposited titanium dioxide thin film is as follows: the (001) plane TAl on the (100) plane LaAlO 3 substrate.
iO 2 (100) plane of the MgO substrate (100) plane of TiO 2 (100) plane YSZ on a substrate (001) plane TiO 2 (100) plane LSAT on the substrate of the (001) plane of TiO
Was 2 .
【0011】即ち、図1は、(100)面のLaAlO
3単結晶基板上に成膜したTiO2膜のX線回折(θ−2
θ)図である。2θ:37.8°にあるピークはTiO
2(004)からのピークであり、LaAlO3(10
0)面上にアナターゼ型のTiO2(001)面が単結
晶成長していることが確認できる。That is, FIG. 1 shows a (100) plane of LaAlO.
3 X-ray diffraction (θ-2) of TiO 2 film formed on single crystal substrate
FIG. The peak at 2θ: 37.8 ° is TiO
2 is a peak from (004) and LaAlO 3 (10
It can be confirmed that the anatase-type TiO 2 (001) plane grows on the (0) plane as a single crystal.
【0012】図2は、(100)面のMgO単結晶基板
上に成膜したTiO2膜のX線回折(θ−2θ)図であ
る。2θ:48.07°にあるピークはTiO2(20
0)からのピークであり、MgO(100)面上にアナ
ターゼ型のTiO2(001)面が単結晶成長している
ことが確認できる。FIG. 2 is an X-ray diffraction (θ-2θ) diagram of a TiO 2 film formed on a (100) plane MgO single crystal substrate. 2θ: The peak at 48.07 ° is TiO 2 (20
0), from which it can be confirmed that the anatase-type TiO 2 (001) plane is growing as a single crystal on the MgO (100) plane.
【0013】図3は(100)面のYSZ単結晶基板上
に成膜したTiO2膜のX線回折(θ−2θ)図であ
る。2θ:37.8°にあるピークはTiO2(00
4)からのピークであり、YSZ(100)面上にアナ
ターゼ型のTiO2(001)面が単結晶成長している
ことが確認できる。FIG. 3 is an X-ray diffraction (θ-2θ) diagram of a TiO 2 film formed on a (100) plane YSZ single crystal substrate. 2θ: The peak at 37.8 ° is TiO 2 (00
This is a peak from 4), and it can be confirmed that the anatase-type TiO 2 (001) plane is growing as a single crystal on the YSZ (100) plane.
【0014】図4は(100)面のLSAT単結晶基板
上に成膜したTiO2膜のX線回折(θ−2θ)図であ
る。2θ:37.8°にあるピークはTiO2(00
4)からのピークであり、LSAT(100)面上にア
ナターゼ型のTiO2(001)面が単結晶成長してい
ることが確認できる。FIG. 4 is an X-ray diffraction (θ-2θ) diagram of a TiO 2 film formed on a (100) plane LSAT single crystal substrate. 2θ: The peak at 37.8 ° is TiO 2 (00
This is a peak from 4), and it can be confirmed that the anatase-type TiO 2 (001) plane is growing as a single crystal on the LSAT (100) plane.
【0015】[0015]
【比較例1】実施例1と同様の条件で(110)面のL
aAlO3、(110)面及び(111)面のMgO、
単結晶基板に厚さ0.2μmの二酸化チタン膜を作製し
た。X線回折法によりこれらの二酸化チタン膜の結晶構
造を評価したところ、多結晶のルチル型二酸化チタンで
あった。COMPARATIVE EXAMPLE 1 Under the same conditions as in Example 1, the L of the (110) plane
aAlO 3 , (110) plane and (111) plane MgO,
A titanium dioxide film having a thickness of 0.2 μm was formed on a single crystal substrate. When the crystal structures of these titanium dioxide films were evaluated by X-ray diffraction, they were polycrystalline rutile-type titanium dioxide.
【0016】[0016]
【比較例2】実施例1と同様の条件で(100)面のL
aAlO3単結晶基板の基板温度を350℃とし、厚さ
0.2μmの二酸化チタン膜を作製した。X線回折法に
よりTiO2(004)からの回折ピークの半値幅を評
価したところ、基板温度480℃で作製した二酸化チタ
ン膜に比べて、半値幅が10%広くなった。即ち、基板
温度を480℃から350℃に下げると二酸化チタン膜
の結晶性が低下した。COMPARATIVE EXAMPLE 2 Under the same conditions as in Example 1, the L of the (100) plane
The substrate temperature of the aAlO 3 single crystal substrate was set to 350 ° C., and a titanium dioxide film having a thickness of 0.2 μm was formed. When the half-width of the diffraction peak from TiO 2 (004) was evaluated by the X-ray diffraction method, the half-width was 10% wider than that of a titanium dioxide film formed at a substrate temperature of 480 ° C. That is, when the substrate temperature was lowered from 480 ° C. to 350 ° C., the crystallinity of the titanium dioxide film was lowered.
【0017】[0017]
【比較例3】実施例1と同様の条件で蒸着基板(000
1)面のサファイア(α−Al2O3)とし、厚さ0.2
μmの二酸化チタン膜を作製した。この二酸化チタン膜
をX線回折法により結晶構造を評価したところ、アナタ
ーゼ型のTiO2(001)とルチル型のTiO2(10
0)が混合した二酸化チタン膜であった。Comparative Example 3 A deposition substrate (000) was prepared under the same conditions as in Example 1.
1) Surface sapphire (α-Al 2 O 3 ) with a thickness of 0.2
A μm titanium dioxide film was produced. When the crystal structure of this titanium dioxide film was evaluated by an X-ray diffraction method, anatase TiO 2 (001) and rutile TiO 2 (10
0) was a mixed titanium dioxide film.
【0018】さらに実施例1と同様な条件で基板温度を
350℃、530℃とし、(0001)面のサファイア
(α−Al2O3)基板上に二酸化チタン膜(厚さ0.2
μm)を作製した。いずれのもアナターゼ型のTiO2
(001)とルチル型のTiO2(001)が混合した
二酸化チタン膜であった。Further, under the same conditions as in Example 1, the substrate temperature was set to 350 ° C. and 530 ° C., and a titanium dioxide film (thickness: 0.2) was formed on a (0001) plane sapphire (α-Al 2 O 3 ) substrate.
μm). Both are anatase TiO 2
This was a titanium dioxide film in which (001) and rutile-type TiO 2 (001) were mixed.
【0019】[0019]
【発明の効果】単結晶で作製したアナターゼ型結晶構造
の二酸化チタン膜は、結晶の欠陥が格段に軽減するため
光触媒反応効率を向上させることができる。According to the titanium dioxide film of anatase type crystal structure made of a single crystal, the crystal defects are remarkably reduced, so that the photocatalytic reaction efficiency can be improved.
【図1】図1は、(100)面のLaAlO3単結晶基
板上に成膜したTiO2膜のX線回折(θ−2θ)図で
ある。FIG. 1 is an X-ray diffraction (θ-2θ) diagram of a TiO 2 film formed on a (100) plane LaAlO 3 single crystal substrate.
【図2】図2は(100)面のMgO単結晶基板上に成
膜したTiO2膜のX線回折(θ−2θ)図である。FIG. 2 is an X-ray diffraction (θ-2θ) diagram of a TiO 2 film formed on a (100) plane MgO single crystal substrate.
【図3】図3は(100)面のYSZ単結晶基板上に成
膜したTiO2膜のX線回折(θ−2θ)図である。FIG. 3 is an X-ray diffraction (θ-2θ) diagram of a TiO 2 film formed on a (100) plane YSZ single crystal substrate.
【図4】図4は(100)面のLSAT単結晶基板上に
成膜したTiO2膜のX線回折(θ−2θ)図である。FIG. 4 is an X-ray diffraction (θ-2θ) diagram of a TiO 2 film formed on a (100) plane LSAT single crystal substrate.
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Claims (2)
ンタンアルミネート(LaAlO3)、酸化マグネシウ
ム(MgO)、安定化ジルコニア(YSZ)、LSAT
([LaAlO3])0.3− [SrAl0.5Ta0.5O3]
0.7)単結晶基板上にアナターゼ型結晶構造の二酸化チ
タン(TiO2)単結晶薄膜を作製する方法。1. A lanthanum aluminate (LaAlO 3 ), magnesium oxide (MgO), stabilized zirconia (YSZ), LSAT
([LaAlO 3 ]) 0.3 − [SrAl 0.5 Ta 0.5 O 3 ]
0.7 ) A method of forming a titanium dioxide (TiO 2 ) single crystal thin film having an anatase crystal structure on a single crystal substrate.
結晶薄膜を形成させる基板温度は、360℃〜520℃
に制御され、酸素ガス圧は10mTorr〜100mT
orrに制御する請求項1に記載の方法。2. A substrate temperature for forming a titanium dioxide single crystal thin film having an anatase type crystal structure is 360 ° C. to 520 ° C.
And the oxygen gas pressure is from 10 mTorr to 100 mT
The method according to claim 1, wherein the control is performed at orr.
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WO2004108283A1 (en) * | 2003-06-09 | 2004-12-16 | Nippon Sheet Glass Co., Ltd. | Photocatalyst member |
JP2009208985A (en) * | 2008-03-03 | 2009-09-17 | Fujifilm Corp | Functional oxide structure and method for manufacturing functional oxide structure |
US7612015B2 (en) | 2001-12-21 | 2009-11-03 | Nippon Sheet Glass Company, Limited | Member having photocatalytic function and method for manufacture thereof |
CN109402583A (en) * | 2018-11-22 | 2019-03-01 | 湖北大学 | A kind of titania-doped Anatase of niobium and Rutile Type double-layer compound film gas sensor and preparation method thereof |
WO2020155212A1 (en) * | 2019-02-01 | 2020-08-06 | 中国科学院福建物质结构研究所 | Titanium dioxide single-crystal material and growing method therefor |
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2000
- 2000-07-14 JP JP2000213765A patent/JP4701447B2/en not_active Expired - Fee Related
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JPN6010016351, H.Yoon et al., "Structural Properties of TiO2 Films Grown by Pulsed Laser Deposition", Bulletin of the Korean Chemical Society, 19970620, Vol.18, No.6, pp.640−643 * |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7612015B2 (en) | 2001-12-21 | 2009-11-03 | Nippon Sheet Glass Company, Limited | Member having photocatalytic function and method for manufacture thereof |
WO2004108283A1 (en) * | 2003-06-09 | 2004-12-16 | Nippon Sheet Glass Co., Ltd. | Photocatalyst member |
JP2009208985A (en) * | 2008-03-03 | 2009-09-17 | Fujifilm Corp | Functional oxide structure and method for manufacturing functional oxide structure |
CN109402583A (en) * | 2018-11-22 | 2019-03-01 | 湖北大学 | A kind of titania-doped Anatase of niobium and Rutile Type double-layer compound film gas sensor and preparation method thereof |
WO2020155212A1 (en) * | 2019-02-01 | 2020-08-06 | 中国科学院福建物质结构研究所 | Titanium dioxide single-crystal material and growing method therefor |
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