JP2006001820A - Carbon-containing titanium oxynitride selective absorption membrane - Google Patents
Carbon-containing titanium oxynitride selective absorption membrane Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 103
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 103
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 102
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 54
- 239000012528 membrane Substances 0.000 title claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 21
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 20
- 239000003273 ketjen black Substances 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 47
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000031700 light absorption Effects 0.000 description 12
- 239000010409 thin film Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000002048 multi walled nanotube Substances 0.000 description 9
- 230000005855 radiation Effects 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- -1 titanium alkoxide Chemical class 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- HWCXFDGMZPRMRX-UHFFFAOYSA-N butan-2-olate;titanium(4+) Chemical compound CCC(C)O[Ti](OC(C)CC)(OC(C)CC)OC(C)CC HWCXFDGMZPRMRX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、カーボン含有チタンオキシナイトライド選択吸収膜に関する。 The present invention relates to a carbon-containing titanium oxynitride selective absorption membrane.
チタンオキシナイトライドは、酸化チタン及び窒化チタン間の中間化学生成物であり、その薄膜は、太陽光の波長の光はよく吸収するが、赤外光の波長の光は外に放射しない性質を持つ。この性質を利用して、チタンオキシナイトライドは太陽光集熱器の選択吸収膜等に広く用いられている。 Titanium oxynitride is an intermediate chemical product between titanium oxide and titanium nitride, and its thin film absorbs light of sunlight wavelength well, but does not radiate infrared light of wavelength. Have. Utilizing this property, titanium oxynitride is widely used for selective absorption films of solar collectors.
一般的に、チタンオキシナイトライド薄膜は、系中の窒素原子含量に依存して可視光吸収率が変化する。窒素原子含量が多すぎると金色光沢が見られ可視光吸収率が低下する。一方、窒素原子含量が少なすぎると、チタンオキシナイトライドの特性である高い可視光吸収率、低い赤外光輻射率が失われる。 In general, the titanium oxynitride thin film changes in the visible light absorption rate depending on the nitrogen atom content in the system. If the nitrogen atom content is too high, a golden luster is observed and the visible light absorptance decreases. On the other hand, if the nitrogen atom content is too small, the high visible light absorption rate and low infrared light radiation rate, which are the characteristics of titanium oxynitride, are lost.
上の結果は、窒素と酸素の比がチタンオキシナイトライドの電子構造を決める重要な要因であることを示している。
さらに窒素原子量と酸素原子量が同程度のチタンオキシナイトライドにおいては、薄膜内部に数１０％の空間構造を持たせることで、可視光吸収率を向上させる検討がなされている（特許文献１参照）。
このことから、チタンオキシナイトライドが可視光領域の光を吸収する原因は、その結晶構造のみならず、結晶中に含まれる空隙も関係していると考えられる。
The above results indicate that the ratio of nitrogen to oxygen is an important factor determining the electronic structure of titanium oxynitride.
Further, in titanium oxynitride having the same amount of nitrogen atoms and oxygen atoms, studies have been made to improve the visible light absorptivity by giving a space structure of several tens of percent inside the thin film (see Patent Document 1). .
From this, it is considered that the reason why titanium oxynitride absorbs light in the visible light region is related not only to its crystal structure but also to voids contained in the crystal.
湿式法で製造されたチタンオキシナイトライド選択吸収膜は、窒素と酸素の比が１：２程度と比較的酸素リッチの膜であり、十分な可視光吸収率と低い熱輻射率が得られないという問題がある。酸化チタン等の選択吸収膜においては、カーボン等の黒体を薄膜中に導入して可視光吸収率を向上させる検討もなされているが、これらのカーボンは不定形のアモルファスカーボンであり、前述したような薄膜中の空間構造を制御することはできない。
また、チタンオキシナイトライドにカーボンのような黒体を導入した場合、可視光吸収率が向上すると同時に、赤外光輻射率も上がるという問題がある。
The titanium oxynitride selective absorption film manufactured by the wet method is a relatively oxygen-rich film with a ratio of nitrogen to oxygen of about 1: 2, and a sufficient visible light absorption rate and low heat radiation rate cannot be obtained. There is a problem. In selective absorption films such as titanium oxide, studies have been made to improve the visible light absorption rate by introducing a black body such as carbon into the thin film. However, these carbons are amorphous amorphous carbon, and are described above. The spatial structure in such a thin film cannot be controlled.
In addition, when a black body such as carbon is introduced into titanium oxynitride, there is a problem that the visible light absorption rate is improved and the infrared light radiation rate is also increased.
本発明は、上記の点に鑑み、従来よりも高い可視光吸収率と低い熱輻射率を具えたチタンオキシナイトライド選択吸収膜及びその製造方法を提供することを目的とする。 An object of this invention is to provide the titanium oxynitride selective absorption film | membrane provided with the visible light absorptivity higher than before, and the heat radiation rate lower than before, and its manufacturing method in view of said point.
本発明は、チタンテトラアルコキシドと含窒素配位子を結合させて得られたチタンオキシナイトライド前駆体にカーボンが添加された溶液を基材に塗布して加熱処理することにより得られるカーボン含有チタンオキシナイトライド選択吸収膜によって、前記の課題を解決した。
前記カーボンは、フラーレン、カーボンナノチューブ、ケッチェンブラックのうち１種類以上を用いるのが好ましい。
また、前記カーボンの添加量は、チタンオキシナイトライド（ＴｉＯxＮ2-x）に対する重量比で３０％以上５００％以下であるのが好ましい。
The present invention relates to a carbon-containing titanium obtained by applying a heat treatment to a base material by applying a solution in which carbon is added to a titanium oxynitride precursor obtained by bonding a titanium tetraalkoxide and a nitrogen-containing ligand. The oxynitride selective absorption film solved the above-mentioned problems.
The carbon is preferably one or more of fullerene, carbon nanotube, and ketjen black.
The amount of carbon added is preferably 30% or more and 500% or less by weight ratio to titanium oxynitride (TiO x N 2-x ).
本発明によれば、チタンオキシナイトライドに添加するカーボンの種類と添加量を最適化することにより、チタンオキシナイトライド選択吸収膜が本来有する低い赤外光輻射率を保持しながら、可視光吸収率を飛躍的に向上させることができる。また、本発明では、湿式法により成膜を行うので、従来よりも製造コストを低減させることができる。
本発明のカーボン含有チタンオキシナイトライド選択吸収膜を太陽光集熱器に用いることにより、従来よりも高温の集熱が可能となる。
According to the present invention, by optimizing the type and amount of carbon added to titanium oxynitride, visible light absorption is maintained while maintaining the low infrared light emissivity inherent in titanium oxynitride selective absorption films. The rate can be improved dramatically. In the present invention, since the film formation is performed by a wet method, the manufacturing cost can be reduced as compared with the conventional method.
By using the carbon-containing titanium oxynitride selective absorption film of the present invention in a solar heat collector, it is possible to collect heat at a higher temperature than before.
本発明について詳しく説明する。本発明者らは、特願２００４−２０７号において、チタンオキシナイトライド前駆体を提案した。本発明では、この前駆体溶液にカーボンを添加してコーティング溶液を調製し、これを基材に塗布して、カーボンを含むチタンオキシナイトライド選択吸収膜を製造する。コーティング溶液にカーボンを添加すると、この後得られるチタンオキシナイトライド選択吸収膜中にカーボンが固定化され、可視光吸収率が向上する。 The present invention will be described in detail. The present inventors have proposed a titanium oxynitride precursor in Japanese Patent Application No. 2004-207. In the present invention, carbon is added to this precursor solution to prepare a coating solution, which is applied to a substrate to produce a titanium oxynitride selective absorption film containing carbon. When carbon is added to the coating solution, the carbon is fixed in the titanium oxynitride selective absorption film obtained thereafter, and the visible light absorption rate is improved.
一般的に、カーボンのような黒体は、可視光吸収率の向上と同時に輻射率を引き上げるという特性を有する。従って、チタンオキシナイトライドが本来有する低い輻射率を保持しながら可視光吸収率の向上を図るためには、カーボン種の選定と添加量の適正化を行う必要がある。 In general, a black body such as carbon has a characteristic of increasing the radiation rate while improving the visible light absorption rate. Therefore, in order to improve the visible light absorption rate while maintaining the low emissivity inherent to titanium oxynitride, it is necessary to select the carbon species and optimize the addition amount.
本発明者らは、フラーレン、カーボンナノチューブ及びケッチェンブラックが、チタンオキシナイトライド薄膜の空間構造を制御するのに最も有効であり、これらがチタンオキシナイトライド薄膜に優れた光学特性を与えることを見出した。
フラーレン、カーボンナノチューブ及びケッチェンブラックは、いずれも、メソスコピックレベルでの空間構造を有しており、チタンオキシナイトライド前駆体に添加された状態でもこの空間構造が維持される。そして、チタンオキシナイトライド前駆体の溶媒及び熱分解性成分が熱処理により除去された後には、これらのカーボンがナノ鋳型として働き、チタンオキシナイトライド薄膜中に特定の空間構造が形成されるものと考えられる。
The inventors have found that fullerenes, carbon nanotubes, and ketjen black are most effective in controlling the spatial structure of titanium oxynitride thin films, and that these provide excellent optical properties for titanium oxynitride thin films. I found it.
Fullerene, carbon nanotube, and ketjen black all have a spatial structure at a mesoscopic level, and this spatial structure is maintained even when added to the titanium oxynitride precursor. Then, after the solvent and thermally decomposable components of the titanium oxynitride precursor are removed by heat treatment, these carbons function as nanotemplates, and a specific spatial structure is formed in the titanium oxynitride thin film. Conceivable.
前記チタンオキシナイトライド前駆体の製造工程については、特願２００４−２０７号中に詳述されているので、以下、簡単に説明する。 The production process of the titanium oxynitride precursor is described in detail in Japanese Patent Application No. 2004-207, and will be briefly described below.
まず、溶媒に、チタンテトラアルコキシドを攪拌しながら入れ、チタンアルコキシド溶液を調整する。前記チタンテトラアルコキシドとしては、チタンイソプロポキシド、チタンエトキシド、チタンプロポキシド、チタン-ｎ-ブトキシド、チタン-iso-ブトキシド、チタン-sec-ブトキシド、チタン-ter-ブトキシド等が使用できる。溶媒としては、アルコール類が好ましく、例えばエタノール、メタノール、ブタノール、プロパノール、エトキシエタノール等が用いられる。 First, a titanium tetraalkoxide is put into a solvent while stirring to prepare a titanium alkoxide solution. Examples of the titanium tetraalkoxide include titanium isopropoxide, titanium ethoxide, titanium propoxide, titanium-n-butoxide, titanium-iso-butoxide, titanium-sec-butoxide, titanium-ter-butoxide, and the like. As the solvent, alcohols are preferable. For example, ethanol, methanol, butanol, propanol, ethoxyethanol and the like are used.
次に、含窒素配位子を含む組成物の溶液を調製し、そこに前記チタンテトラアルコキシド溶液を攪拌しながら添加する。含窒素配位子を含む組成物とは、酸素原子に対する窒素原子のモル比が１以上の窒素化合物であり、好適には尿素、アミノアルコール、ピペリジン、1,2,4,トリアゾール等が用いられる。アミノアルコールの種類は、前記モル比が１以上であれば特に限定されない。 Next, a solution of a composition containing a nitrogen-containing ligand is prepared, and the titanium tetraalkoxide solution is added thereto while stirring. The composition containing a nitrogen-containing ligand is a nitrogen compound having a molar ratio of nitrogen atom to oxygen atom of 1 or more, and preferably urea, amino alcohol, piperidine, 1,2,4, triazole, etc. are used. . The type of amino alcohol is not particularly limited as long as the molar ratio is 1 or more.
前記含窒素配位子の組成物とチタンテトラアルコキシド溶液を混合した後、この溶液を８０℃で２時間、攪拌、加熱、還流する。例として含窒素配位子にプロパノールアミンを用いた場合、この工程において次のような反応が生じる。 After the composition of the nitrogen-containing ligand and the titanium tetraalkoxide solution are mixed, the solution is stirred, heated and refluxed at 80 ° C. for 2 hours. For example, when propanolamine is used as the nitrogen-containing ligand, the following reaction occurs in this step.
(RO)3TiOR + HO-(CH2)3-NH2 → (RO)3TiO-(CH2)3-NH2 + ROH (RO) 3 TiOR + HO- (CH 2 ) 3 -NH 2 → (RO) 3 TiO- (CH 2 ) 3 -NH 2 + ROH
前記反応式において、Rはアルキル基である。含窒素配位子（プロパノールアミン）中の窒素はチタンに対して配位結合し、チタンオキシナイトライド前駆体である(RO)3TiO-(CH2)3-NH2 が合成される。この工程によりチタンテトラアルコキシド溶液に窒素の導入が行われ、酸窒化物であるチタンオキシナイトライド前駆体が合成される。このあと、この溶液を室温まで冷却し、減圧濃縮を行うことにより、反応生成物の２プロパノール（イソプロパノール）を留去し、さらに溶液中のＴｉＯxＮ2-x濃度が約８．５重量％程度になるように調整し、チタンオキシナイトライド前駆体溶液を得る。 In the reaction formula, R is an alkyl group. Nitrogen in the nitrogen-containing ligand (propanolamine) is coordinated to titanium to synthesize (RO) 3 TiO— (CH 2 ) 3 —NH 2 which is a titanium oxynitride precursor. Through this step, nitrogen is introduced into the titanium tetraalkoxide solution, and a titanium oxynitride precursor that is an oxynitride is synthesized. Thereafter, the solution was cooled to room temperature and concentrated under reduced pressure to distill off the reaction product 2-propanol (isopropanol), and the TiO x N 2-x concentration in the solution was about 8.5% by weight. It adjusts so that it may become a grade, and obtains a titanium oxynitride precursor solution.
上記の工程を経て得られたチタンオキシナイトライド前駆体溶液と、前記カーボン及びコーティング溶媒を混合し、チタンオキシナイトライド前駆体コーティング溶液を調製する。 The titanium oxynitride precursor solution obtained through the above steps is mixed with the carbon and the coating solvent to prepare a titanium oxynitride precursor coating solution.
前記３種類のカーボン、すなわち、フラーレン、カーボンナノチューブ及びケッチェンブラックは、１種類のみを単独で用いてもよいが、２種類以上を混合して用いても同様の効果を得ることができる。
また、前記カーボンの添加量は、チタンオキシナイトライド（ＴｉＯxＮ2-x）に対する重量比で３０％以上５００％以下である。カーボンの添加量が５００％を超えた場合、赤外光輻射率が抑制されず、添加量が３０％未満の場合には可視光吸収率の向上が認められない。
Of the three types of carbon, that is, fullerene, carbon nanotube, and ketjen black, only one type may be used alone, but the same effect can be obtained by mixing two or more types.
The amount of carbon added is 30% or more and 500% or less by weight ratio to titanium oxynitride (TiO x N 2-x ). When the added amount of carbon exceeds 500%, the infrared light emissivity is not suppressed, and when the added amount is less than 30%, the improvement of the visible light absorption rate is not recognized.
前記チタンオキシナイトライド前駆体コーティング溶液を基材にディップコーティングし、電気炉を用いて不活性雰囲気、５００℃で加熱し、カーボン含有チタンオキシナイトライド薄膜を得る。 The titanium oxynitride precursor coating solution is dip coated on a substrate and heated at 500 ° C. in an inert atmosphere using an electric furnace to obtain a carbon-containing titanium oxynitride thin film.
なお、本発明で用いるチタンオキシナイトライド前駆体は既に酸窒化物であり、前駆体の段階で十分に窒素が導入されているので、焼結の際に窒化を行わない。従って、高活性なアンモニアガスを使用する必要はなく、不活性雰囲気且つ低温で加熱処理することができる。不活性ガスは、窒素ガス、アルゴンガス、ヘリウムガスのうちいずれかを用いることができる。又は、これらの混合ガスを用いてもよい。 The titanium oxynitride precursor used in the present invention is already an oxynitride, and nitrogen is sufficiently introduced at the precursor stage, so that nitriding is not performed during sintering. Therefore, it is not necessary to use highly active ammonia gas, and heat treatment can be performed in an inert atmosphere and at a low temperature. As the inert gas, any of nitrogen gas, argon gas, and helium gas can be used. Alternatively, a mixed gas of these may be used.
以下、実施例によって本発明を具体的に説明する。但し、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to these examples.
（実施例１〜実施例７、比較例１）カーボンの種類：水酸化フラーレン
（実施例１）
まず、チタンオキシナイトライド前駆体を以下の方法により製造した。
エトキシエタノール１６．９５ｇとエタノール１５０ｇが入っている三角フラスコ内にチタンイソプロポキシド９９．１５ｇを攪拌しながらゆっくり入れ、チタンイソプロポキシド溶液を調製した。
含窒素配位子の尿素１６．９５ｇと１−アミノ−２−プロパノール１６．９５ｇ及びメタノール４５０．００ｇを丸底フラスコに入れて尿素を溶解させた後、この丸底フラスコ内に、三角フラスコ内のチタンイソプロポキシド溶液を攪拌しながらゆっくり入れた。
この丸底フラスコをオイルバス中にセットし、オイルバスの温度を室温から８０℃に上げた後、２時間８０℃で加熱、還流、攪拌した。その後、丸底フラスコをオイルバスから取り出し、室温まで冷却した。
丸底フラスコ内の溶液をナス型フラスコに移し替えた後、これをロータリーエバポレーターにセットし、溶液を濃縮した。ロータリーエバポレータは回転数６０ｒｐｍに設定し、最初に１００ｔｏｒｒで減圧し、徐々に圧力を下げ、最終的に５０ｔｏｒｒまで減圧しながら、ＴｉＯxＮ2-x濃度８．５％になるまで溶液を濃縮して、チタンオキシナイトライド前駆体溶液を得た。
(Examples 1 to 7, Comparative Example 1) Type of carbon: fullerene hydroxide (Example 1)
First, a titanium oxynitride precursor was produced by the following method.
Into an Erlenmeyer flask containing 16.95 g of ethoxyethanol and 150 g of ethanol, 99.15 g of titanium isopropoxide was slowly put with stirring to prepare a titanium isopropoxide solution.
16.95 g of nitrogen-containing ligand urea, 16.95 g of 1-amino-2-propanol and 450.00 g of methanol were placed in a round bottom flask to dissolve the urea, and then this round bottom flask was placed in an Erlenmeyer flask. Of titanium isopropoxide was slowly added with stirring.
This round bottom flask was set in an oil bath, the temperature of the oil bath was raised from room temperature to 80 ° C., and then heated, refluxed and stirred at 80 ° C. for 2 hours. Then, the round bottom flask was taken out from the oil bath and cooled to room temperature.
After the solution in the round bottom flask was transferred to the eggplant type flask, it was set on a rotary evaporator and the solution was concentrated. The rotary evaporator is set at a rotational speed of 60 rpm, and the pressure is first reduced at 100 torr, gradually decreasing the pressure, and finally reducing the pressure to 50 torr while concentrating the solution to a TiO x N 2-x concentration of 8.5%. Thus, a titanium oxynitride precursor solution was obtained.
次に、水酸化フラーレン０．５ｇ、コーティング溶媒のジメチルフォルムアミド３２．３９ｇ、前記チタンオキシナイトライド前駆体溶液１７．６１ｇを混合し、これらを超音波洗浄機を利用して溶解させて、チタンオキシナイトライドコーティング溶液を得た。この場合、チタンオキシナイトライド前駆体溶液中のＴｉＯxＮ2-xの質量は１．５ｇになるから、ＴｉＯxＮ2-xに対する水酸化フラーレンの重量比は３３．３％である。 Next, 0.5 g of fullerene hydroxide, 32.39 g of dimethylformamide as a coating solvent, and 17.61 g of the titanium oxynitride precursor solution are mixed and dissolved using an ultrasonic cleaner to obtain titanium. An oxynitride coating solution was obtained. In this case, since the mass of TiO x N 2-x in the titanium oxynitride precursor solution is 1.5 g, the weight ratio of fullerene hydroxide to TiO x N 2-x is 33.3%.
５ｃｍ四方の銅板を、予め蒸留水と洗剤を入れて超音波で洗浄した後、流水で洗剤を流し、メタノール１００ｍｌを銅板表面に流して水滴がない状態にし、４０℃で乾燥させた。前記チタンオキシナイトライドコーティング溶液中に、この銅板を入れてディップコーティングした後、引き上げ速度２０ｃｍ/ｍｉｎで銅 板を引き上げ、１０分間室温にて乾燥させた。
銅板を電気炉に入れ、電気炉内の真空引きを３．８ｔｏｒｒまで行った後、窒素５Ｌ/ｍｉｎを流し１気圧で熱処理を行った。昇温速度は５００℃/ｍｉｎで５００℃まで加熱し、１５分保持した。その後、室温まで冷却して、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
A 5 cm square copper plate was preliminarily washed with distilled water and detergent, and then washed with running water, and 100 ml of methanol was poured onto the surface of the copper plate to make it free from water droplets, and dried at 40 ° C. The copper plate was placed in the titanium oxynitride coating solution and dip coated, and then the copper plate was pulled up at a pulling rate of 20 cm / min and dried at room temperature for 10 minutes.
The copper plate was put into an electric furnace, and the inside of the electric furnace was evacuated to 3.8 torr. Then, 5 L / min of nitrogen was passed and heat treatment was performed at 1 atm. The heating rate was 500 ° C / min up to 500 ° C and held for 15 minutes. Then, it cooled to room temperature and obtained the carbon containing titanium oxynitride selective absorption film.
（実施例２）
実施例１において、水酸化フラーレンの添加量を１．０ｇ（ＴｉＯxＮ2-xに対する重量比で６６．７％）に変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 2)
In Example 1, the addition amount of the fullerene hydroxide was changed to 1.0 g (66.7% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynite was otherwise obtained in the same manner as in Example 1. A ride selective absorption membrane was obtained.
（実施例３）
実施例１において、水酸化フラーレンの添加量を１．５ｇ（ＴｉＯxＮ2-xに対する重量比で１００％）に変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
Example 3
In Example 1, the addition amount of fullerene hydroxide was changed to 1.5 g (100% by weight with respect to TiO x N 2-x ), and other than that, the carbon-containing titanium oxynitride was selected in the same manner as in Example 1. An absorption film was obtained.
（実施例４）
実施例１において、水酸化フラーレンの添加量を３ｇ（ＴｉＯxＮ2-xに対する重量比で２００％）に変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
Example 4
In Example 1, the addition amount of fullerene hydroxide was changed to 3 g (200% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynitride selective absorption membrane was otherwise obtained in the same manner as in Example 1. Got.
（実施例５）
実施例１において、水酸化フラーレンの添加量を４．５ｇ（ＴｉＯxＮ2-xに対する重量比で３００％）に変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 5)
In Example 1, the addition amount of fullerene hydroxide was changed to 4.5 g (300% by weight with respect to TiO x N 2-x ), and other than that, selection of carbon-containing titanium oxynitride was performed in the same manner as in Example 1. An absorption film was obtained.
（実施例６）
実施例１において、水酸化フラーレンの添加量を６ｇ（ＴｉＯxＮ2-xに対する重量比で４００％）に変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 6)
In Example 1, the addition amount of fullerene hydroxide was changed to 6 g (400% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynitride selective absorption film was otherwise obtained in the same manner as in Example 1. Got.
（実施例７）
実施例１において、水酸化フラーレンの添加量を７．５ｇ（ＴｉＯxＮ2-xに対する重量比で５００％）に変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 7)
In Example 1, the addition amount of the fullerene hydroxide was changed to 7.5 g (500% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynitride was selected in the same manner as in Example 1 except that. An absorption film was obtained.
（比較例１）
実施例１において、水酸化フラーレンの添加量を０．１５ｇ（ＴｉＯxＮ2-xに対する重量比で１０％）に変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Comparative Example 1)
In Example 1, the addition amount of fullerene hydroxide was changed to 0.15 g (10% by weight with respect to TiO x N 2-x ), and other than that, the carbon-containing titanium oxynitride was selected in the same manner as in Example 1. An absorption film was obtained.
（実施例８〜実施例１４、比較例２）カーボンの種類：多層カーボンナノチューブ
（実施例８）
実施例１において、添加するカーボンを水酸化フラーレンから多層カーボンナノチューブに変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Examples 8 to 14, Comparative Example 2) Type of carbon: multi-walled carbon nanotube (Example 8)
In Example 1, carbon to be added was changed from fullerene hydroxide to multi-walled carbon nanotubes, and a carbon-containing titanium oxynitride selective absorption film was obtained in the same manner as in Example 1 except that.
（実施例９）
実施例８において、多層カーボンナノチューブの添加量を１．０ｇ（ＴｉＯx Ｎ2-xに対する重量比で６６．７％）に変え、それ以外は実施例８と同様にして 、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
Example 9
In Example 8, the amount of multi-walled carbon nanotubes added was changed to 1.0 g (66.7% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynite was otherwise obtained in the same manner as in Example 8. A ride selective absorption membrane was obtained.
（実施例１０）
実施例８において、多層カーボンナノチューブの添加量を１．５ｇ（ＴｉＯx Ｎ2-xに対する重量比で１００％）に変え、それ以外は実施例８と同様にして、 カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 10)
In Example 8, the addition amount of multi-walled carbon nanotubes was changed to 1.5 g (100% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynitride was selected in the same manner as in Example 8 except that. An absorption film was obtained.
（実施例１１）
実施例１において、多層カーボンナノチューブの添加量を３ｇ（ＴｉＯxＮ2-xに対する重量比で２００％）に変え、それ以外は実施例８と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 11)
In Example 1, the carbon-containing titanium oxynitride selective absorption film was changed in the same manner as in Example 8 except that the amount of multi-walled carbon nanotubes added was changed to 3 g (200% by weight with respect to TiO x N 2-x ). Got.
（実施例１２）
実施例８において、多層カーボンナノチューブの添加量を４．５ｇ（ＴｉＯx Ｎ2-xに対する重量比で３００％）に変え、それ以外は実施例８と同様にして、 カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 12)
In Example 8, the addition amount of multi-walled carbon nanotubes was changed to 4.5 g (300% by weight with respect to TiO x N 2-x ), and other than that, the carbon-containing titanium oxynitride was selected in the same manner as in Example 8. An absorption film was obtained.
（実施例１３）
実施例８において、多層カーボンナノチューブの添加量を６ｇ（ＴｉＯxＮ2-xに対する重量比で４００％）に変え、それ以外は実施例８と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 13)
In Example 8, the carbon-containing titanium oxynitride selective absorption film was changed in the same manner as in Example 8 except that the amount of multi-walled carbon nanotubes added was changed to 6 g (400% by weight with respect to TiO x N 2-x ). Got.
（実施例１４）
実施例８において、多層カーボンナノチューブの添加量を７．５ｇ（ＴｉＯx Ｎ2-xに対する重量比で５００％）に変え、それ以外は実施例８と同様にして、 カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 14)
In Example 8, the addition amount of multi-walled carbon nanotubes was changed to 7.5 g (500% by weight with respect to TiO x N 2-x ), and other than that, the carbon-containing titanium oxynitride was selected in the same manner as in Example 8. An absorption film was obtained.
（比較例２）
実施例８において、多層カーボンナノチューブの添加量を０．１５ｇ（ＴｉＯxＮ2-xに対する重量比で１０％）に変え、それ以外は実施例８と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Comparative Example 2)
In Example 8, the amount of multi-walled carbon nanotubes added was changed to 0.15 g (10% by weight with respect to TiO x N 2-x ), and other than that, carbon-containing titanium oxynitride was selected in the same manner as in Example 8. An absorption film was obtained.
（実施例１５〜実施例２１、比較例３）カーボンの種類：ケッチェンブラック
（実施例１５）
実施例１において、添加するカーボンを水酸化フラーレンからケッチェンブラックに変え、それ以外は実施例１と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Examples 15 to 21, Comparative Example 3) Type of carbon: Ketjen black
(Example 15)
In Example 1, the carbon to be added was changed from fullerene hydroxide to ketjen black, and other than that was obtained in the same manner as in Example 1 to obtain a carbon-containing titanium oxynitride selective absorption film.
（実施例１６）
実施例１５において、ケッチェンブラックの添加量を１．０ｇ（ＴｉＯxＮ2-xに対する重量比で６６．７％）に変え、それ以外は実施例１５と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 16)
In Example 15, the addition amount of ketjen black was changed to 1.0 g (66.7% by weight with respect to TiO x N 2-x ), and other than that, in the same manner as in Example 15, the carbon-containing titanium oxynite A ride selective absorption membrane was obtained.
（実施例１７）
実施例１５において、ケッチェンブラックの添加量を１．５ｇ（ＴｉＯxＮ2-xに対する重量比で１００％）に変え、それ以外は実施例１５と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 17)
In Example 15, the amount of ketjen black added was changed to 1.5 g (100% by weight with respect to TiO x N 2-x ), and other than that, carbon-containing titanium oxynitride was selected in the same manner as in Example 15. An absorption film was obtained.
（実施例１８）
実施例１５において、ケッチェンブラックの添加量を３ｇ（ＴｉＯxＮ2-xに対する重量比で２００％）に変え、それ以外は実施例１５と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 18)
In Example 15, the addition amount of ketjen black was changed to 3 g (200% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynitride selective absorption film was otherwise obtained in the same manner as in Example 15. Got.
（実施例１９）
実施例１５において、ケッチェンブラックの添加量を４．５ｇ（ＴｉＯxＮ2-xに対する重量比で３００％）に変え、それ以外は実施例１５と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 19)
In Example 15, the amount of ketjen black added was changed to 4.5 g (300% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynitride was selected in the same manner as in Example 15 except that. An absorption film was obtained.
（実施例２０）
実施例１５において、ケッチェンブラックの添加量を６ｇ（ＴｉＯxＮ2-xに対する重量比で４００％）に変え、それ以外は実施例１５と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 20)
In Example 15, the amount of ketjen black added was changed to 6 g (400% by weight with respect to TiO x N 2 -x ), and the carbon-containing titanium oxynitride selective absorption film was otherwise obtained in the same manner as in Example 15. Got.
（実施例２１）
実施例１５において、ケッチェンブラックの添加量を７．５ｇ（ＴｉＯxＮ2-xに対する重量比で５００％）に変え、それ以外は実施例１５と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Example 21)
In Example 15, the amount of ketjen black added was changed to 7.5 g (500% by weight with respect to TiO x N 2-x ), and the carbon-containing titanium oxynitride was selected in the same manner as in Example 15 except that. An absorption film was obtained.
（比較例３）
実施例１５において、ケッチェンブラックの添加量を０．１５ｇ（ＴｉＯxＮ2-xに対する重量比で１０％）に変え、それ以外は実施例１５と同様にして、カーボン含有チタンオキシナイトライド選択吸収膜を得た。
(Comparative Example 3)
In Example 15, the amount of ketjen black added was changed to 0.15 g (10% by weight with respect to TiO x N 2-x ), and other than that, carbon-containing titanium oxynitride was selected in the same manner as in Example 15. An absorption film was obtained.
（比較例４）カーボンを添加しない場合
チタンオキシナイトライド前駆体溶液にカーボンを添加せず、それ以外は実施例１と同様にして、チタンオキシナイトライド選択吸収膜を得た。
(Comparative Example 4) When no carbon was added A titanium oxynitride selective absorption film was obtained in the same manner as in Example 1 except that no carbon was added to the titanium oxynitride precursor solution.
実施例１〜２１、及び比較例１〜３におけるカーボン含有チタンオキシナイトライド選択吸収膜及び比較例４におけるチタンオキシナイトライド選択吸収膜の反射率と赤外光輻射率を測定した。 The reflectances and infrared light emissivities of the carbon-containing titanium oxynitride selective absorption films in Examples 1 to 21 and Comparative Examples 1 to 3 and the titanium oxynitride selective absorption film in Comparative Example 4 were measured.
反射率は、紫外可視分光光度計を用いて、入射光角度６０°で絶対反射率を測
定した。測定結果を図１、３、５に示す。また、図１、３、５の可視光領域（波長２５０ｎｍ〜１０００ｎｍ）を拡大したグラフを図２、４、６に示す。
The reflectance was measured using an ultraviolet-visible spectrophotometer at an incident light angle of 60 °. The measurement results are shown in FIGS. Moreover, the graph which expanded the visible region (wavelength 250nm-1000nm) of FIG.
赤外光輻射率は、赤外分光光度計を用いて、赤外発光測定法により測定した。輻射率の算出方法は、１００℃におけるカーボン含有チタンオキシナイトライド選択吸収膜の輻射エネルギーと、１００℃におけるハイテンプブラックペイント（標準物質）の輻射エネルギーをそれぞれ測定し、その比により算出した。波数１２８８ｃｍ-1における輻射率を表１に示す。 The infrared light emissivity was measured by an infrared emission measurement method using an infrared spectrophotometer. The calculation method of the emissivity was carried out by measuring the radiation energy of the carbon-containing titanium oxynitride selective absorption film at 100 ° C. and the radiation energy of high-temp black paint (standard substance) at 100 ° C., and calculating the ratio. Table 1 shows the emissivity at a wave number of 1288 cm −1 .
図１、３、５より、チタンオキシナイトライドに対する各カーボンの重量比が３３．４％の場合、可視光吸収率の向上が認められることが分かる。また、図２、４、６より、６６．７０％以上になると、可視光領域（波長範囲２５０〜１０００ｎｍ）において、反射率が１％〜３．５％程度となっていることが分かる。
この結果より、カーボンを添加しない従来のチタンオキシナイトライド選択吸収膜と比較して、本発明のカーボン含有チタンオキシナイトライド選択吸収膜が、可視光吸収率に非常に優れていることが分かる。
また、表１より、実施例における赤外光輻射率は、比較例２における従来のチタンオキシナイトライド選択吸収膜と同程度の低い輻射率を保持していることが分かる。カーボン添加量が５００重量％を超えると、可視光吸収率には優れるが、輻射率が高くなる。
1, 3, and 5, it can be seen that when the weight ratio of each carbon to titanium oxynitride is 33.4%, an improvement in visible light absorption is observed. 2, 4, and 6, it can be seen that when it is 66.70% or more, the reflectance is about 1% to 3.5% in the visible light region (
From this result, it can be seen that the carbon-containing titanium oxynitride selective absorption film of the present invention is very excellent in visible light absorptivity as compared with the conventional titanium oxynitride selective absorption film to which no carbon is added.
Further, from Table 1, it can be seen that the infrared light emissivity in the examples maintains the same low emissivity as that of the conventional titanium oxynitride selective absorption film in Comparative Example 2. When the amount of carbon added exceeds 500% by weight, the visible light absorption rate is excellent, but the radiation rate becomes high.
本発明によれば、チタンオキシナイトライドコーティング溶液にカーボンを添加することにより、チタンオキシナイトライド薄膜にカーボンが導入され、薄膜の光学特性を容易に改善することができる。本発明のカーボン含有チタンオキシナイトライド選択吸収膜を太陽光集熱器に用いることにより、従来にない高温の集熱が可能となる。また、湿式法により成膜を行うため、選択吸収膜の製造コストを低減させることができる。 According to the present invention, by adding carbon to the titanium oxynitride coating solution, carbon is introduced into the titanium oxynitride thin film, and the optical characteristics of the thin film can be easily improved. By using the carbon-containing titanium oxynitride selective absorption film of the present invention for a solar heat collector, unprecedented high temperature heat collection becomes possible. In addition, since the film formation is performed by a wet method, the manufacturing cost of the selective absorption film can be reduced.
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