KR20230079928A - Manufacturing method of tantalum nitride based photoelctrode and tantalum nitride menufactured thereby - Google Patents
Manufacturing method of tantalum nitride based photoelctrode and tantalum nitride menufactured thereby Download PDFInfo
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 239000010409 thin film Substances 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000005121 nitriding Methods 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 14
- 239000010980 sapphire Substances 0.000 claims abstract description 14
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 10
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- 239000002073 nanorod Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ULUYRVWYCIOFRV-UHFFFAOYSA-K 2-ethylhexanoate;iron(3+) Chemical compound [Fe+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O ULUYRVWYCIOFRV-UHFFFAOYSA-K 0.000 description 1
- RURZQVYCZPJWMN-UHFFFAOYSA-N 2-ethylhexanoic acid;nickel Chemical compound [Ni].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O RURZQVYCZPJWMN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
질화탄탈륨 기반 광전극 제조방법으로, 사파이어 기판 상에 티타늄 박막을 증착하는 단계; 상기 티타늄 박막상에 산화탄탈륨 전극물질층을 형성하는 단계; 및 상기 티타늄 박막상에 산화탄탈륨 전극물질층을 질화하여, 질화티타늄/질화탄탈륨층의 광전극을 형성하는 단계;를 포함하는 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법이 제공된다. A method for manufacturing a tantalum nitride-based photoelectrode, comprising: depositing a titanium thin film on a sapphire substrate; forming a tantalum oxide electrode material layer on the titanium thin film; and forming a photoelectrode of a titanium nitride/tantalum nitride layer by nitriding a tantalum oxide electrode material layer on the titanium thin film.
Description
본 발명은 질화탄탈륨 기반 광전극 제조방법, 이에 의하여 제조된 광전극에 관한 것으로, 보다 상세하게는 TiN/Al2O3 기판을 도입함으로써 기존의 탄탈륨 금속 기판을 사용하지 않고도 질화탄탈륨 기반의 광전극 구현이 가능한, 질화탄탈륨 기반 광전극 제조방법, 이에 의하여 제조된 광전극에 관한 것이다. The present invention relates to a method for manufacturing a tantalum nitride-based photoelectrode and a photoelectrode manufactured thereby, and more particularly, to a tantalum nitride-based photoelectrode without using a conventional tantalum metal substrate by introducing a TiN/Al 2 O 3 substrate. It relates to a tantalum nitride-based photoelectrode manufacturing method that can be implemented, and a photoelectrode manufactured thereby.
태양광을 광전극에 입사시켜 생성된 전자와 정공을 이용해 광전극과 전해질 사이의 계면에서 물을 분해하여 수소를 생산하는 태양광 물분해 수소생산 기술의 핵심은 효율적인 광전극의 개발이다. The key to solar water splitting hydrogen production technology is the development of an efficient photoelectrode.
광전기화학적 물분해의 세 가지 단계 (빛 흡수를 통한 전하 생성, 전하 분리, 전하 주입을 통한 계면 반응)에서 빛 흡수를 통한 전하 생성을 증대시키기 위해서는 빛의 세기가 큰 파장대인 가시광선 및 근적외선 영역의 빛을 흡수할 수 있어야 하며, 이는 광전극의 밴드갭이 작을수록 유리하다. In order to increase charge generation through light absorption in the three stages of photoelectrochemical water splitting (charge generation through light absorption, charge separation, and interfacial reaction through charge injection), the visible light and near-infrared region, which are wavelengths with high light intensity, It must be capable of absorbing light, which is advantageous as the band gap of the photoelectrode is small.
또한 물분해 반응을 일으키기에 충분한 광전압을 제공시키기 위해서는 광전극의 밴드갭이 너무 작아서도 안되기 때문에 통상 1.8 ~ 2.1 eV 정도의 밴드갭이 이상적이다. In addition, since the band gap of the photoelectrode should not be too small in order to provide a photovoltage sufficient to cause the water decomposition reaction, a band gap of about 1.8 to 2.1 eV is ideal.
기존에 연구가 진행된 TiO2 (3.2 eV), WO3 (2.7 eV), BiVO4 (2.4 eV) 등의 광전극 물질은 밴드갭이 다소 커 빛 흡수를 충분히 하지 못해 낮은 광전류밀도를 생성하기 때문에 새로운 광전극 물질의 개발이 필요하다. Photoelectrode materials such as TiO 2 (3.2 eV), WO 3 (2.7 eV), and BiVO 4 (2.4 eV), which have been studied in the past, have a rather large band gap and do not sufficiently absorb light, resulting in low photocurrent density. It is necessary to develop photoelectrode materials.
2.1 eV의 밴드갭을 갖는 질화탄탈륨 (Ta3N5) 은 물분해 반응에 적합한 물질로 12.9 mA cm-2의 높은 이론 광전류밀도를 생성하는 차세대 광전극 물질이다. 하지만, 전구체로 사용되는 탄탈륨 (Ta)이나 산화탄탈륨 (Ta2O5) 이 질화탄탈륨이 되기 위해 질화되는데 800 ~ 1000 ℃ 이상의 높은 온도가 필요하다. Tantalum nitride (Ta 3 N 5 ), which has a band gap of 2.1 eV, is a material suitable for water splitting and is a next-generation photoelectrode material that generates a high theoretical photocurrent density of 12.9 mA cm −2 . However, tantalum (Ta) or tantalum oxide (Ta 2 O 5 ) used as a precursor is nitrided to become tantalum nitride, but a high temperature of 800 to 1000 °C or more is required.
이와 같이 높은 질화 온도로 인해 기존 광전극의 기판으로 사용되던 산화물 기반 투명전극 물질 (불소도핑산화주석 (FTO), 산화인듐주석 (ITO))은 질화 시에 용해 및 박리되어 부적합하기 때문에, 질화탄탈륨을 형성하기 위해서는 탄탈륨 금속 기판이 유일하게 사용되어왔다. Oxide-based transparent electrode materials (fluorine-doped tin oxide (FTO) and indium tin oxide (ITO)) used as substrates for conventional photoelectrodes are unsuitable because they are dissolved and exfoliated during nitriding due to such a high nitriding temperature. In order to form a tantalum metal substrate has been used exclusively.
금속 기판의 특성상 불투명하여 광전극이 빛을 투과시키지 못하기 때문에 광전극 후면에 다른 광전극을 부착해 추가적인 반응을 일으킬 수 있는 탠덤형 소자의 구성에 한계가 있다. 따라서, 탠덤형 소자의 구현을 위해서는 높은 질화 온도에 견디면서 전도성을 잃지 않으며 투과도가 확보된 하부 기판의 개발이 필수적이다. Due to the nature of the metal substrate, it is opaque and the photoelectrode cannot transmit light, so there is a limit to the configuration of a tandem type device that can cause additional reactions by attaching another photoelectrode to the back of the photoelectrode. Therefore, in order to implement a tandem type device, it is essential to develop a lower substrate that can withstand a high nitridation temperature, does not lose conductivity, and has transmittance.
따라서, 본 발명이 해결하고자 하는 과제는 고온의 질화공정을 견디면서도 우수한 광전극 특성을 갖는 새로운 광전극과 그 제조방법을 제공하는 것이다. Accordingly, an object to be solved by the present invention is to provide a new photoelectrode having excellent photoelectrode characteristics while enduring a high-temperature nitridation process and a manufacturing method thereof.
본 발명은 질화탄탈륨 기반 광전극 제조방법으로, 사파이어 기판 상에 티타늄 박막을 증착하는 단계; 상기 티타늄 박막상에 산화탄탈륨 전극물질층을 형성하는 단계; 및 상기 티타늄 박막상에 산화탄탈륨 전극물질층을 질화하여, 질화티타늄/질화탄탈륨층의 광전극을 형성하는 단계;를 포함하는 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법을 제공한다. The present invention is a method for manufacturing a tantalum nitride-based photoelectrode, comprising the steps of depositing a titanium thin film on a sapphire substrate; forming a tantalum oxide electrode material layer on the titanium thin film; and forming a photoelectrode of a titanium nitride/tantalum nitride layer by nitriding a tantalum oxide electrode material layer on the titanium thin film.
본 발명의 일 실시예에서, 상기 질화탄탈륨 기반 광전극 제조방법은, 상기 형성된 광전극 상에 산소발생촉매를 증착하는 단계를 더 포함하며, 상기 산화탄탈륨 전극물질층은 박막 또는 막대 형태이다. In one embodiment of the present invention, the method of manufacturing the tantalum nitride-based photoelectrode further includes depositing an oxygen generating catalyst on the formed photoelectrode, wherein the tantalum oxide electrode material layer has a thin film or rod shape.
본 발명의 일 실시예에서, 상기 산소발생촉매는 NiFeOx 촉매를 포함한다. In one embodiment of the present invention, the oxygen generating catalyst includes a NiFeO x catalyst.
본 발명의 일 실시예에서, 상기 광전극의 최대 광전류밀도를 갖는 상기 티타늄 박막의 두께는, 상기 질화공정에 온도에 따라 달라지며, 상기 질화온도가 낮아질수록 상기 티타늄 박막은 더 두꺼워진다. In one embodiment of the present invention, the thickness of the titanium thin film having the maximum photocurrent density of the photoelectrode varies depending on the temperature in the nitriding process, and the lower the nitriding temperature, the thicker the titanium thin film.
본 발명은 또한 사파이어 기판; 상기 사파이어 기판 상에 형성된 질화티타늄; 상기 질화티타늄층 상에 적층된 질화탄탈륨층을 포함하는 광전극을 제공한다. The present invention also relates to a sapphire substrate; titanium nitride formed on the sapphire substrate; A photoelectrode including a tantalum nitride layer stacked on the titanium nitride layer is provided.
본 발명의 일 실시예에서, 상기 광전극은, 상기 질화탄탈륨층 상에 적층된 산소발생촉매층을 더 포함한다. In one embodiment of the present invention, the photoelectrode further includes an oxygen generating catalyst layer stacked on the tantalum nitride layer.
본 발명의 일 실시예에서, 상기 광전극은 상술한 방법에 의하여 제조되며, 상기 질화티타늄과 상기 질화탄탈륨층간에는 옴 접합이 형성된다. In one embodiment of the present invention, the photoelectrode is manufactured by the above-described method, and an ohmic junction is formed between the titanium nitride and the tantalum nitride layer.
본 발명은 상술한 광전극을 포함하는 태양광 물분해 장치를 제공한다. The present invention provides a solar water splitting device including the photoelectrode described above.
본 발명에 따르면, TiN/Al2O3 기판을 도입함으로써 기존의 탄탈륨 금속 기판을 사용하지 않고도 Ta3N5 기반의 광전극 구현이 가능해진다. 또한 TiN 위에 Ta3N5 형성 시 그 계면에서 옴 접촉 (ohmic contact)이 일어나기 때문에 빛 흡수로 Ta3N5 내부에서 발생한 전자가 TiN 전극으로 효율적으로 이동 가능하다. 또한 투명한 Al2O3 기판에 형성되는 TiN의 두께를 조절하면 Ta3N5에서 흡수하지 못한 일부의 빛이 반사되거나 산란되지 않고, 투과가 가능해지기 때문에, 광전극 후면에 태양전지나 광전극 등의 다른 광전자 소자를 부착하는 탠덤형 소자 구현이 가능하다. 탠덤형 소자는 광전극이 흡수하지 못하는 나머지 빛을 이용해 부가적인 광전압을 제공하기 때문에 전체 물분해 수소생산 효율을 높일 수 있다.According to the present invention, by introducing a TiN/Al 2 O 3 substrate, it is possible to implement a Ta 3 N 5 based photoelectrode without using a conventional tantalum metal substrate. In addition, since ohmic contact occurs at the interface when Ta 3 N 5 is formed on TiN, electrons generated inside Ta 3 N 5 due to light absorption can efficiently move to the TiN electrode. In addition, if the thickness of TiN formed on the transparent Al 2 O 3 substrate is adjusted, some of the light not absorbed by Ta 3 N 5 is not reflected or scattered and can be transmitted. It is possible to implement a tandem type device in which other optoelectronic devices are attached. Since the tandem type device uses the remaining light that the photoelectrode cannot absorb to provide additional photovoltage, it can increase the overall water splitting hydrogen production efficiency.
도 1은 본 발명의 일 실시예에 따른 박막 구조 또는 나노 막대 구조를 갖는 NiFeOx/Ta3N5/TiN/Al2O3 광전극의 단면을 나타낸다.
도 2는 본 발명의 일 실시예에 따른 광전극의 제작 공정의 단계도이다.
도 3은 본 발명의 일 실시예에 따른 Ta3N5/TiN/Al2O3 광전극의 상 분석을 위한 엑스선 회절 분석 결과이다.
도 4는 본 발명의 일 실시예에 따른 Ta3N5/TiN/Al2O3 광전극의 밴드 구조를 나타낸다.
도 5는 본 발명의 일 실시예에 따른 Ta3N5/TiN/Al2O3 광전극의 주사전자현미경 분석 결과이다.
도 6은 질화 온도 및 TiN 박막 두께에 따른 NiFeOx/Ta3N5/TiN/Al2O3 광전극의 선형주사전위법 (LSV) 측정 결과이다. 1 shows a cross-section of a NiFeO x /Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode having a thin film structure or a nanorod structure according to an embodiment of the present invention.
2 is a step diagram of a manufacturing process of a photoelectrode according to an embodiment of the present invention.
3 is an X-ray diffraction analysis result for phase analysis of a Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to an embodiment of the present invention.
4 shows a band structure of a Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to an embodiment of the present invention.
5 is a scanning electron microscope analysis result of a Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to an embodiment of the present invention.
6 is a linear scanning potential (LSV) measurement result of the NiFeO x /Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to the nitridation temperature and the thickness of the TiN thin film.
이하, 도면을 참조하여 본 발명의 구체적인 실시형태를 설명하기로 한다. 그러나 이는 예시에 불과하며 본 발명은 이에 제한되지 않는다.Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, this is only an example and the present invention is not limited thereto.
본 발명을 설명함에 있어서, 본 발명과 관련된 공지기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략하기로 한다. 그리고, 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로서 이는 사용자, 운용자의 의도 또는 관례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다. In describing the present invention, if it is determined that a detailed description of the known technology related to the present invention may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, terms to be described later are terms defined in consideration of functions in the present invention, which may vary according to the intention or custom of a user or operator. Therefore, the definition should be made based on the contents throughout this specification.
본 발명의 기술적 사상은 청구범위에 의해 결정되며, 이하의 실시예는 본 발명의 기술적 사상을 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 효율적으로 설명하기 위한 일 수단일 뿐이다. The technical spirit of the present invention is determined by the claims, and the following examples are only one means for efficiently explaining the technical spirit of the present invention to those skilled in the art to which the present invention belongs.
상술한 문제를 해결하기 위하여, 본 발명은 기존의 탄탈륨 금속 기판을 사용하지 않고도 Ta3N5 기반의 광전극 구현하기 위하여, TiN/Al2O3 기판을 도입한다.In order to solve the above problems, the present invention introduces a TiN/Al 2 O 3 substrate to implement a Ta 3 N 5 based photoelectrode without using a conventional tantalum metal substrate.
도 1은 본 발명의 일 실시예에 따른 박막 구조 또는 나노 막대 구조를 갖는 NiFeOx/Ta3N5/TiN/Al2O3 광전극의 단면을 나타낸다.1 shows a cross-section of a NiFeO x /Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode having a thin film structure or a nanorod structure according to an embodiment of the present invention.
도 1을 참조하면, 기판(100), 상기 기판(100) 상에 증착된 TiN 박막 하부전극(200), 상기 하부전극(200)상에 증착된 Ta3N5 광전극(300), 그리고 상기 광전극(300) 상에 증착된 산소발생촉매층(400)이 구비된다. Referring to FIG. 1 , a
본 발명의 일 실시예에서 상기 기판(100)은 사파이어 기판이며, 상기 하부전극은 기판(100) 상에 증착된 티타늄(Ti)층을 고온으로 질화시켜 형성된다. 특히 본 발명은 이러한 고온의 질화공정을 견디는 하부 기판의 도입과, 연속된 동시 질화공정을 통하여 기존의 탄탈륨 금속 기판을 사용하지 않고도 질화탄탈륨(Ta3N5) 기반의 광전극 구현이 가능해진다. In one embodiment of the present invention, the
도 2는 본 발명의 일 실시예에 따른 광전극의 제작 공정의 단계도이다. 2 is a step diagram of a manufacturing process of a photoelectrode according to an embodiment of the present invention.
도 2를 참조하면, 고온의 질화공정을 견디는 사파이어 기판 상에 티타늄(Ti) 박막을 증착하고(S100), 이후 산화탄탈륨 박막 또는 나노막대 전극을 형성한다(S200). Referring to FIG. 2 , a titanium (Ti) thin film is deposited on a sapphire substrate that endures a high-temperature nitriding process (S100), and then a tantalum oxide thin film or nanorod electrode is formed (S200).
이후 암모니아 등을 사용한 질화공정을 통하여 전극을 질화하여, 질화탄탈륨층/질화티타늄/사파이어 기판(Ta3N5/TiN/Al2O3) 구조의 광전극을 형성하고(S200-1), 이후 산소발생촉매(예를들어 NiFeOx 촉매)를 형성한다(S300). Thereafter, the electrode is nitrided through a nitriding process using ammonia, etc. to form a photoelectrode having a tantalum nitride layer/titanium nitride/sapphire substrate (Ta 3 N 5 /TiN/Al 2 O 3 ) structure (S200-1). An oxygen generating catalyst (eg NiFeO x catalyst) is formed (S300).
본 발명에 따른 방법은 불투명한 탄탈륨 금속 기판을 사용하지 않고 사파이어 기판 상에 전극 증착 및 질화공정을 연속적으로 수행하여 효과적인 광전극 제조가 가능하다. According to the method according to the present invention, it is possible to manufacture an effective photoelectrode by continuously performing electrode deposition and nitriding processes on a sapphire substrate without using an opaque tantalum metal substrate.
이하 본 발명의 일 실시예를 통하여 본 발명을 보다 상세히 설명한다. 하지만 본 발명의 범위는 하기 실시예에 의하여 제한되지 않는다. Hereinafter, the present invention will be described in more detail through an embodiment of the present invention. However, the scope of the present invention is not limited by the following examples.
실시예 1Example 1
전자빔 증착을 통한 사파이어 (AlSapphire (Al) via electron beam deposition 22 OO 33 ) 기판 상부에 Ti 박막 형성) Formation of Ti thin film on the substrate
본 발명의 일 실시예에서, 먼저 전자빔 증착기를 통해 사파이어 (Al2O3) 기판 상부에 Ti 박막을 형성한다. 전자빔 증착기에 Ti 소스와 세척 완료된 Al2O3 기판을 넣고 Ti 박막을 70 ~ 600 nm 두께로 증착한다. 증착 속도는 0.5 ~ 1 Ås-1 로 하며, 챔버 진공은 1 e-7 ~ 1e-6 으로 한다.In one embodiment of the present invention, first, a Ti thin film is formed on a sapphire (Al 2 O 3 ) substrate through an electron beam evaporator. A Ti source and a cleaned Al 2 O 3 substrate are placed in an electron beam evaporator and a Ti thin film is deposited to a thickness of 70 to 600 nm. The deposition rate is 0.5 to 1 Ås -1 , and the chamber vacuum is 1 e-7 to 1e-6 .
실시예 2Example 2
전자빔 증착을 통한 Ti/AlTi/Al via e-beam deposition 22 OO 33 기판 상부에 Ta Ta on the top of the substrate 22 OO 55 박막 또는 나노 막대 형성 Formation of thin films or nanorods
실시예 1에서 형성된 Ti/Al2O3 기판 상부에 전자빔 증착기를 통해 Ta2O5 박막 또는 나노 막대를 형성한다. A Ta 2 O 5 thin film or nanorod is formed on the Ti/Al 2 O 3 substrate formed in Example 1 through an electron beam evaporator.
Ta2O5 박막의 경우는 다음과 같다. 전자빔 증착기에 Ta2O5 소스와 Ti/Al2O3 기판을 넣고 Ta2O5 박막을 200 ~ 1000 nm 두께로 증착한다. 증착 속도는 1 ~ 2 Å s-1 로 하며, 챔버 진공은 1e-6 ~ 1e-5 으로 한다. The case of the Ta 2 O 5 thin film is as follows. A Ta 2 O 5 source and a Ti/Al 2 O 3 substrate are placed in an electron beam evaporator and a Ta 2 O 5 thin film is deposited to a thickness of 200 to 1000 nm. The deposition rate is 1 to 2 Å s -1 , and the chamber vacuum is 1e-6 to 1e-5 .
Ta2O5 나노 막대의 경우는 다음과 같다. 전자빔 증착기에 Ta2O5 소스와 Ti/Al2O3 기판을 넣고 나노 막대의 부착력을 높이기 위해 Ta2O5 박막을 50 ~ 100 nm 두께로 증착한다. 그 후 기판 전체를 70 ~ 85°의 glancing angle로 기울이고 70 ~ 90 rpm으로 회전시키면서 나노 막대를 증착한다. 나노 막대의 길이는 500 ~ 3000 nm 두께로 하고, 증착 속도는 1 ~ 2 Å s-1 로 하며, 챔버 진공은 1e-6 ~ 1e-5 으로 한다.The case of Ta 2 O 5 nanorods is as follows. A Ta 2 O 5 source and a Ti/Al 2 O 3 substrate are placed in an electron beam evaporator, and a Ta 2 O 5 thin film is deposited to a thickness of 50 to 100 nm to increase the adhesion of the nanorods. Then, nanorods are deposited while tilting the entire substrate at a glancing angle of 70 to 85° and rotating at 70 to 90 rpm. The length of the nanorods is 500 to 3000 nm thick, the deposition rate is 1 to 2 Å s -1 , and the chamber vacuum is 1e-6 to 1e-5.
실시예 3Example 3
암모니아 분위기 열처리를 통한 TaTa through ammonia atmosphere heat treatment 22 OO 55 /Ti/Al/Ti/Al 22 OO 33 전극에서 Ta Ta at the electrode 33 NN 55 /TiN/Al/TiN/Al 22 OO 33 광전극으로의 질화 Nitriding to photoelectrode
실시예 2에서 형성된 Ta2O5/Ti/Al2O3 전극을 암모니아 분위기에서 열처리하여 Ta3N5/TiN/Al2O3 광전극으로 질화한다. 이를 위하여 알루미나 보트에 Ta2O5/Ti/Al2O3 전극을 담아 튜브 전기로에 넣고, 질소로 퍼징한다. 이때의 유량은 50 ~ 100 sccm, 시간은 30분 ~ 1시간으로 한다. 그 후 150 ~ 250 sccm의 유량의 암모니아로 20 ~ 40분 퍼징한다. 퍼징 후에 분당 2 ~ 10 ℃의 승온 속도, 800 ~ 1000 ℃ 의 온도, 1 ~ 3 시간 동안 열처리한다. 열처리 종료 후 50 ~ 100 sccm의 유량의 질소로 30분 ~ 1시간 퍼징한다. 이러한 동시 열처리 질화 공정을 통하여 Ta3N5/TiN 사이에는 옴 접합이 형성되는데,이것은 Ta3N5의 전자 이동에 유리한 특성이 된다. The Ta 2 O 5 /Ti/Al 2 O 3 electrode formed in Example 2 is heat-treated in an ammonia atmosphere to nitride the Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode. To this end, a Ta 2 O 5 /Ti/Al 2 O 3 electrode is put in an alumina boat, put into a tube electric furnace, and purged with nitrogen. At this time, the flow rate is 50 to 100 sccm, and the time is 30 minutes to 1 hour. Thereafter, purging is performed for 20 to 40 minutes with ammonia at a flow rate of 150 to 250 sccm. After purging, heat treatment is performed at a heating rate of 2 to 10 ° C per minute at a temperature of 800 to 1000 ° C for 1 to 3 hours. After the heat treatment is finished, purging is performed with nitrogen at a flow rate of 50 to 100 sccm for 30 minutes to 1 hour. An ohmic junction is formed between Ta 3 N 5 /TiN through this simultaneous heat treatment nitriding process, which is advantageous for electron movement of Ta 3 N 5 .
실시예 4Example 4
Ta Ta 33 NN 55 /TiN/Al/TiN/Al 22 OO 33 광전극 상부에 NiFeO NiFeO on top of the photoelectrode xx 촉매 코팅 catalyst coating
실시예 3형성된 Ta3N5/TiN/Al2O3 광전극 상부에 drop casting을 통해 NiFeOx 산소발생촉매를 코팅한다. 이를 위하여 Iron(III) 2-ethylhexanoate 와 nickel(II) 2-ethylhexanoate을 농도 10 ~ 20% w/w이 되도록 hexane에 용해시킨다. 광전극 표면에 용액을 drop casting하고 100 ~ 200 ℃ 의 온도에서 30분 ~ 1시간 동안 건조시킨다. 이후 hexane으로 세척 후 상온에서 건조시킨다.Example 3 An NiFeO x oxygen generating catalyst was coated on top of the formed Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode through drop casting. For this purpose, iron(III) 2-ethylhexanoate and nickel(II) 2-ethylhexanoate are dissolved in hexane to a concentration of 10 to 20% w/w. The solution is drop-casted on the surface of the photoelectrode and dried for 30 minutes to 1 hour at a temperature of 100 ~ 200 ℃. Then, wash with hexane and dry at room temperature.
실험예 1Experimental Example 1
엑스선 회절 분석X-ray diffraction analysis
도 3은 본 발명의 일 실시예에 따른 Ta3N5/TiN/Al2O3 광전극의 상 분석을 위한 엑스선 회절 분석 결과이다. 3 is an X-ray diffraction analysis result for phase analysis of a Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to an embodiment of the present invention.
도 3을 참조하면, sapphire 기판에 큐빅 구조의 TiN이 (111), (200) 방향으로 잘 형성됨을 확인했고, 모노클리닉(monoclinic) 구조의 Ta3N5이 잘 형성됨을 확인할 수 있다. 따라서, 본 발명에 따른 공정에 의하여 Ta3N5/TiN이 사파이어 기판상에 잘 형성되었음을 알 수 있다. Referring to FIG. 3 , it was confirmed that TiN having a cubic structure was well formed in the (111) and (200) directions on the sapphire substrate, and Ta 3 N 5 having a monoclinic structure was well formed. Therefore, it can be seen that Ta 3 N 5 /TiN was well formed on the sapphire substrate by the process according to the present invention.
실험예 2Experimental Example 2
밴드구조 분석Band structure analysis
도 4는 본 발명의 일 실시예에 따른 Ta3N5/TiN/Al2O3 광전극의 밴드 구조를 나타낸다. 4 shows a band structure of a Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to an embodiment of the present invention.
도 4를 참조하면, 동시 질화에 따라 형성된 TiN와 Ta3N5의 일함수 (work function)에 의해 두 물질이 접합 시 옴 접합 (ohmic junction)이 일어남을 확인하였고, 이는 Ta3N5의 전자 이동에 유리한 구조임을 알 수 있다. (혹시 질화공정을 동시에 함으로써 얻는 효과라고 할 수 없을까요?) Referring to FIG. 4, it was confirmed that an ohmic junction occurs when the two materials are joined by the work function of TiN and Ta 3 N 5 formed by simultaneous nitridation, which indicates that the electrons of Ta 3 N 5 It can be seen that the structure is advantageous for movement. (Can't it be said that this is the effect obtained by simultaneously performing the nitriding process?)
실험예 3Experimental Example 3
주사전자현미경 분석Scanning electron microscopy analysis
도 5는 본 발명의 일 실시예에 따른 Ta3N5/TiN/Al2O3 광전극의 주사전자현미경 분석 결과이다. 5 is a scanning electron microscope analysis result of a Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to an embodiment of the present invention.
도 5를 참조하면, 사전자현미경을 통한 광전극 표면 구조 분석 결과 Ta3N5 나노 막대 구조가 잘 형성됨을 확인할 수 있다. Referring to FIG. 5 , as a result of analyzing the surface structure of the photoelectrode through a scanning electron microscope, it can be confirmed that the Ta 3 N 5 nanorod structure is well formed.
실험예 4Experimental Example 4
선형주사전위법 (LSV) 분석Linear Scanning Potential (LSV) Analysis
도 6은 질화 온도 및 TiN 박막 두께에 따른 NiFeOx/Ta3N5/TiN/Al2O3 광전극의 선형주사전위법 (LSV) 측정 결과이다. 6 is a linear scanning potential (LSV) measurement result of the NiFeO x /Ta 3 N 5 /TiN/Al 2 O 3 photoelectrode according to the nitridation temperature and the thickness of the TiN thin film.
도 6은 KOH 전해질에서 빛을 전면입사 시켜 선형주사전위법으로 측정한 결과 950 ℃의 질화 온도에서는 300nm의 TiN이, 850 ℃의 질화 온도에서는 150 nm의 TiN이 RHE 기준 1.23 V에서 가장 높은 광전류밀도를 보이는 것을 알 수 있다. 이것은 질화온도에 따라 적절한 두께의 Ti층 형성, 또는 일정 두께의 Ti층에 대응하는 적절한 질화공정을 통하여 높은 광전류밀도를 제어할 수 있음을 시사한다. 6 is a result of measuring by the linear scanning potential method by front incident light in KOH electrolyte, TiN of 300 nm at a nitridation temperature of 950 ° C and TiN of 150 nm at a nitridation temperature of 850 ° C have the highest photocurrent density at 1.23 V based on RHE It can be seen that the This suggests that a high photocurrent density can be controlled by forming a Ti layer of an appropriate thickness according to the nitriding temperature or by an appropriate nitridation process corresponding to a Ti layer of a certain thickness.
본 발명에 따라 제조된 광전극은 광전기화학 기반 태양광 물분해 수소생산 분야에 이용 가능하며, 나아가 태양연료 생산 분야 전반에 응용할 수 있다. The photoelectrode manufactured according to the present invention can be used in the photoelectrochemical-based solar water splitting hydrogen production field, and can be further applied to the entire solar fuel production field.
Claims (11)
사파이어 기판 상에 티타늄 박막을 증착하는 단계;
상기 티타늄 박막상에 산화탄탈륨 전극물질층을 형성하는 단계; 및
상기 티타늄 박막상에 산화탄탈륨 전극물질층을 질화하여, 질화티타늄/질화탄탈륨층의 광전극을 형성하는 단계;를 포함하는 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법.As a tantalum nitride-based photoelectrode manufacturing method,
depositing a titanium thin film on a sapphire substrate;
forming a tantalum oxide electrode material layer on the titanium thin film; and
and forming a photoelectrode of a titanium nitride/tantalum nitride layer by nitriding a tantalum oxide electrode material layer on the titanium thin film.
상기 형성된 광전극 상에 산소발생촉매를 증착하는 단계를 더 포함하는 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법.The method of claim 1, wherein the tantalum nitride-based photoelectrode manufacturing method,
The tantalum nitride-based photoelectrode manufacturing method further comprising depositing an oxygen generating catalyst on the formed photoelectrode.
상기 산화탄탈륨 전극물질층은 박막 또는 막대 형태인 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법.According to claim 1,
The tantalum oxide electrode material layer is a tantalum nitride-based photoelectrode manufacturing method, characterized in that in the form of a thin film or rod.
상기 산소발생촉매는 NiFeOx 촉매를 포함하는 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법.According to claim 1,
The oxygen generating catalyst is a tantalum nitride-based photoelectrode manufacturing method, characterized in that it comprises a NiFeO x catalyst.
상기 광전극의 최대 광전류밀도를 갖는 상기 티타늄 박막의 두께는, 상기 질화공정에 온도에 따라 달라지는 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법.According to claim 1,
The method of manufacturing a tantalum nitride-based photoelectrode, characterized in that the thickness of the titanium thin film having the maximum photocurrent density of the photoelectrode varies depending on the temperature in the nitriding process.
상기 질화온도가 낮아질수록 상기 티타늄 박막은 더 두꺼워지는 것을 특징으로 하는 질화탄탈륨 기반 광전극 제조방법.According to claim 5,
The tantalum nitride-based photoelectrode manufacturing method, characterized in that the titanium thin film becomes thicker as the nitriding temperature decreases.
상기 사파이어 기판 상에 형성된 질화티타늄;
상기 질화티타늄층 상에 적층된 질화탄탈륨층을 포함하는 광전극.sapphire substrate;
titanium nitride formed on the sapphire substrate;
A photoelectrode comprising a tantalum nitride layer stacked on the titanium nitride layer.
상기 질화탄탈륨층 상에 적층된 산소발생촉매층을 더 포함하는 것을 특징으로 하는 광전극.The method of claim 7, wherein the photoelectrode,
The photoelectrode further comprising an oxygen generating catalyst layer stacked on the tantalum nitride layer.
상기 광전극은 제 1항 내지 제 6항 중 어느 한 항에 따른 방법에 의하여 제조된 것을 특징으로 하는 광전극.According to claim 8,
The photoelectrode is characterized in that it is manufactured by the method according to any one of claims 1 to 6.
상기 질화티타늄과 상기 질화탄탈륨층간에는 옴 접합이 형성된 것을 특징으로 하는 광전극.According to claim 7,
An ohmic junction is formed between the titanium nitride and the tantalum nitride layer.
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