JP6608753B2 - PdRu alloy electrode material and manufacturing method thereof - Google Patents
PdRu alloy electrode material and manufacturing method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims description 77
- 239000007772 electrode material Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 81
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000010419 fine particle Substances 0.000 claims description 27
- 230000005611 electricity Effects 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims description 18
- 230000007423 decrease Effects 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 14
- 239000005518 polymer electrolyte Substances 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002941 palladium compounds Chemical class 0.000 claims description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 3
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
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- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
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- 238000006722 reduction reaction Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- -1 ruthenium ions Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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- 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
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、パラジウムＰｄおよびルテニウムＲｕが固溶したＰｄＲｕ合金の微粒子を導電性担体に固定したＰｄＲｕ合金電極材料の耐久性を高める技術に関する。 The present invention relates to a technique for enhancing the durability of a PdRu alloy electrode material in which fine particles of a PdRu alloy in which palladium Pd and ruthenium Ru are dissolved are fixed to a conductive carrier.
一般に、電気化学反応用の触媒には、たとえば固体高分子形燃料電池ＰＥＦＣの電極触媒としての用途が期待されており、そのような用途に好適な電気化学的反応活性の他に、高い耐久性が望まれる。 In general, a catalyst for an electrochemical reaction is expected to be used, for example, as an electrode catalyst for a polymer electrolyte fuel cell PEFC. In addition to an electrochemical reaction activity suitable for such a use, it has high durability. Is desired.
たとえば、従来の固体高分子形燃料電池ＰＥＦＣの電極触媒において、表面積を拡大するためにナノ粒子化された白金族粒子を導電性担体としてのカーボンに固定して用いることが提案されている。この場合は、ナノ粒子化された電極触媒によって電気化学的反応活性が大幅に高められるが、一般的に徐々に溶出する、粗大化する、酸化するなどして、固体高分子形燃料電池の性能が低下するという問題があった。 For example, in an electrode catalyst of a conventional polymer electrolyte fuel cell PEFC, it has been proposed to use platinum group particles, which are made into nanoparticles, to fix carbon on a conductive carrier in order to increase the surface area. In this case, the electrochemical reaction activity is greatly enhanced by the nanoparticulate electrocatalyst, but generally the performance of the polymer electrolyte fuel cell is gradually eluted, coarsened, oxidized, etc. There was a problem that decreased.
例えば特許文献１に示されるように、ＰｄとＲｕとが固溶したＰｄＲｕ合金が、比較的最近知られるようになった。この材料は、触媒として高い活性を示すものであるが、電気化学反応に対する活性の維持特性など電極材料としての耐久特性については未知であった。 For example, as shown in Patent Document 1, a PdRu alloy in which Pd and Ru are dissolved has come to be known relatively recently. Although this material exhibits high activity as a catalyst, durability characteristics as an electrode material such as an activity maintaining characteristic against an electrochemical reaction have not been known.
本発明は、以上の事情を背景として為されたものであり、その目的とするところは、高い耐久性を有するＰｄＲｕ合金電極材料およびその製造方法を提供することにある。 The present invention has been made against the background described above, and an object of the present invention is to provide a PdRu alloy electrode material having high durability and a method for producing the same.
ところで、たとえば、固体高分子形燃料電池において、カソードでは、（１）式に示される酸素還元反応（ＯＲＲ）が持続され、アノードでは、（２）式に示される水素酸化反応（ＨＯＲ）が持続される。たとえばアノードに対する燃料供給が不足すると（２）式の反応が持続できず、（３）式の酸素発生反応（ＯＥＲ）反応または（４）式の炭素電気化学的酸化反応が生じて電流が流されるが、（４）式に示される反応によるカーボンの腐食を抑制するために、（３）式に示される反応を発生させることが望まれる。 By the way, for example, in a polymer electrolyte fuel cell, an oxygen reduction reaction (ORR) represented by the formula (1) is sustained at the cathode, and a hydrogen oxidation reaction (HOR) represented by the formula (2) is sustained at the anode. Is done. For example, if the fuel supply to the anode is insufficient, the reaction of the formula (2) cannot be sustained, and the oxygen generation reaction (OER) reaction of the formula (3) or the carbon electrochemical oxidation reaction of the formula (4) is caused to flow. However, in order to suppress the corrosion of carbon due to the reaction represented by the formula (4), it is desired to generate the reaction represented by the formula (3).
１／２Ｏ２＋２Ｈ＋＋２ｅ−→Ｈ２Ｏ ・・・（１）
Ｈ２→２Ｈ＋＋２ｅ− ・・・（２）
Ｈ２Ｏ→１／２Ｏ２＋２Ｈ＋＋２ｅ− ・・・（３）
１／２Ｃ＋Ｈ２Ｏ→１／２ＣＯ２＋２Ｈ＋＋２ｅ− ・・・（４）
1 / 2O 2 + 2H + + 2e − → H 2 O (1)
H 2 → 2H + + 2e − (2)
H 2 O → 1 / 2O 2 + 2H + + 2e − (3)
1 / 2C + H 2 O → 1 / 2CO 2 + 2H + + 2e − (4)
本発明者は、以上の事情を背景として種々検討を重ねた結果、上記（１）式の反応、（２）式の反応、および（３）式の反応は、ＰｄＲｕ合金の微粒子から成る電極材料の電気化学的活性表面積（ＥＣＡ）に比例し、その電極材料の電気化学的活性表面積（ＥＣＡ）の維持が耐久性能に関係することに着目し、ＰｄＲｕ合金の微粒子を導電性担体に固定した電極材料において、ＰｄとＲｕとの割合を所定の範囲内とすることにより、ＰｄＲｕ合金の微粒子から成る電極材料の電気化学的活性表面積（ＥＣＡ）を維持して電気化学的な表面活性の低下を抑制でき、少なくともＰｄ単体よりは高い触媒活性を得つつ、耐久性を向上させることができることを見出した。すなわち、本発明者は、ＰｄＲｕ合金の微粒子を導電性担体に固定した電極材料は、ＰｄとＲｕとの割合を所定の範囲内とすることで、少なくともＰｄ単体よりは高い触媒活性を得つつ、高い耐久性を有することを見出した。本発明は、このような知見に基づいて為されたものである。 As a result of various studies conducted by the present inventors against the background described above, the reaction of the above formula (1), the reaction of the formula (2), and the reaction of the formula (3) are electrode materials composed of fine particles of PdRu alloy. Focusing on the fact that the maintenance of the electrochemical active surface area (ECA) of the electrode material is related to the durability performance in proportion to the electrochemically active surface area (ECA) of the electrode, an electrode in which fine particles of PdRu alloy are fixed to a conductive carrier By keeping the ratio of Pd and Ru within the specified range in the material, the electrochemically active surface area (ECA) of the electrode material composed of fine particles of PdRu alloy is maintained, and the decrease in electrochemical surface activity is suppressed. It was found that the durability could be improved while at least obtaining higher catalytic activity than Pd alone. That is, the present inventor has obtained an electrode material in which fine particles of a PdRu alloy are fixed on a conductive carrier, while obtaining a catalytic activity at least higher than that of Pd alone by setting the ratio of Pd and Ru within a predetermined range. It was found to have high durability. The present invention has been made based on such knowledge.
すなわち、第１発明の要旨とするところは、ＰｄとＲｕが固溶しているＰｄＲｕ合金ＰｄｘＲｕ１−ｘの微粒子を導電性担体の表面に固定したＰｄＲｕ合金電極材料であって、ＰｄとＲｕがＰｄのモル比ｘで０．８１以上且つ０．９７以下の範囲内であることにある。すなわち、上記微粒子状のＰｄＲｕ合金ＰｄｘＲｕ１−ｘは、そのモル比ｘが０．８１≦ｘ≦０．９７の範囲である組成を有していることにある。 That is, the gist of the first invention is a PdRu alloy electrode material in which fine particles of a PdRu alloy Pd x Ru 1-x in which Pd and Ru are dissolved are fixed on the surface of the conductive carrier, Ru exists in the range of 0.81 or more and 0.97 or less in the molar ratio x of Pd . That is, the particulate PdRu alloy Pd x Ru 1-x has a composition in which the molar ratio x is in the range of 0.81 ≦ x ≦ 0.97 .
第１発明のＰｄＲｕ合金電極材料は、ＰｄとＲｕがＰｄのモル比ｘで０．８１以上且つ０．９７以下の範囲内である組成を有しているので、少なくともＰｄ単体よりは高い触媒活性を得つつ、ＰｄＲｕ合金の微粒子の電気化学的な活性表面積の低下を抑制して耐久性を向上させることができる。 Since the PdRu alloy electrode material of the first invention has a composition in which Pd and Ru are in the range of 0.81 to 0.97 in terms of the molar ratio x of Pd, at least higher catalytic activity than that of Pd alone In addition, it is possible to improve the durability by suppressing the decrease in the electrochemical active surface area of the fine particles of the PdRu alloy.
ここで、前記ＰｄＲｕ合金電極材料は、電気化学反応用の触媒としての用途に適し、中でも固体高分子形燃料電池ＰＥＦＣの触媒（電極）として好適に用いられるものである。このようにすれば、ＰｄＲｕ合金の微粒子の使用中における電気化学的な活性表面積の低下を抑制して活性を維持することができ、耐久性の高い固体高分子形燃料電池ＰＥＦＣの電極が得られる。たとえば、従来の固体高分子形燃料電池ＰＥＦＣの電極において、表面積を拡大するためにナノ粒子化された白金族粒子が導電性担体としてのカーボンに固定されて用いられる場合は、電圧変動などによって白金族粒子の溶出や、粒子の粗大化および酸化等により、電気化学的に活性を有する表面積が低下し、固体高分子形燃料電池の性能が低下するという問題が一般的にあるが、前記組成のＰｄＲｕ合金の微粒子を導電性担体の表面に固定した電極材料が固体高分子形燃料電池ＰＥＦＣの電極（触媒）として用いられることにより、ＰｄＲｕ合金の微粒子の電気化学的な活性表面積の低下を抑制して活性を維持することができ、固体高分子形燃料電池ＰＥＦＣの耐久性が向上する。 Here, the PdRu alloy electrode material is suitable for use as a catalyst for electrochemical reaction, and is particularly suitable for use as a catalyst (electrode) of a polymer electrolyte fuel cell PEFC. In this way, it is possible to maintain the activity by suppressing the decrease of the electrochemical active surface area during the use of the fine particles of the PdRu alloy, and to obtain a highly durable polymer electrolyte fuel cell PEFC electrode. . For example, in the electrode of a conventional polymer electrolyte fuel cell PEFC, when platinum group particles that have been nanoparticulated to expand the surface area are fixed to carbon as a conductive support, In general, there is a problem that the surface area of electrochemical activity decreases due to elution of group particles, coarsening and oxidation of particles, and the performance of the polymer electrolyte fuel cell decreases. The electrode material in which the fine particles of PdRu alloy are fixed on the surface of the conductive carrier is used as the electrode (catalyst) of the polymer electrolyte fuel cell PEFC, thereby suppressing the decrease in the electrochemically active surface area of the fine particles of the PdRu alloy. Thus, the activity can be maintained, and the durability of the polymer electrolyte fuel cell PEFC is improved.
また、好適には、前記導電性担体は、カーボン粒子である。このカーボン粒子は、たとえば、グラッシーカーボン、グラファイト、カーボンオニオン、コークス、カーボンシャフト、カーボンナノウオール、カーボンナノコイル、カーボンナノチューブ、カーボンナノツイスト、カーボンナノファイバー、カーボンナノホーン、カーボンナノローブ、カーボンブラックなどのいずれかから成る。 Also preferably, the conductive carrier is carbon particles. The carbon particles may be, for example, glassy carbon, graphite, carbon onion, coke, carbon shaft, carbon nanowall, carbon nanocoil, carbon nanotube, carbon nanotwist, carbon nanofiber, carbon nanohorn, carbon nanolobe, carbon black, etc. Consists of
また、前記ＰｄＲｕ合金の微粒子を導電性担体の表面に固定したＰｄＲｕ合金電極材料は、好適には、還元剤と導電性粒子とを含む加熱された懸濁液に、パラジウム化合物またはパラジウムイオンとルテニウム化合物またはルテニウムイオンと含む溶液を噴霧することで、ＰｄとＲｕとを合金化したＰｄＲｕ合金微粒子を前記導電性微粒子の表面或いは内部に析出させた混合液を得る工程と、前記混合液を所定の温度以上の温度に保持する工程を含む製造工程により製造される。このようにすれば、パラジウムとルテニウムとの合金化と、導電性粒子の表面にその合金の微粒子を導電性担体粒子に析出させる触媒の固定化とが同じ工程内で行なわれるので、工程が簡単となり、製造が容易となる。また、保護剤が無くとも粒子成長を抑えた微粒子を合成でき、さらに、粒子の凝集を少ないままに高濃度で担持可能である。 Further, PdRu alloy electrode material fixed to the surface of the particles a conductive support of said PdRu alloy is preferably a heated suspension containing the reducing agent and conductive particles, and a palladium compound or a palladium ion by spraying a solution containing the Le ruthenium compound or ruthenium ions, obtaining a surface or mixed solution is deposited on the inside of the Pd and PdRu alloy fine particles the conductive fine particles and a Ru alloyed, the mixture Manufactured by a manufacturing process including a process of maintaining the temperature at a predetermined temperature or higher. In this way, the alloying of palladium and ruthenium and the immobilization of the catalyst for depositing the alloy fine particles on the conductive carrier particles on the surface of the conductive particles are performed in the same process, so the process is simple. Thus, the manufacture becomes easy. In addition, fine particles with suppressed particle growth can be synthesized without a protective agent, and furthermore, the particles can be supported at a high concentration with little aggregation of particles.
また、好適には、前記ＰｄＲｕ合金電極材料は、ＰＥＦＣ触媒として用いられるものである。このようにすれば、ＰｄＲｕ合金の微粒子の使用中における電気化学的な活性表面積の低下を抑制して活性を維持することができ、耐久性の高いＰＥＦＣ触媒が得られる。
また、好適には、前記ＰｄとＲｕが、Ｐｄのモル比ｘで０．８８から０．９５の範囲内である。
また、好適には、前記ＰｄＲｕ合金電極材料は、金属比表面積が１０ｍ ２ ／ｇ以上であり、３電極式セルを用い、参照極に対する電位差を０Ｖが３秒、１．０Ｖが３秒を１電位サイクルとしたときに、１電位サイクル当たりの水素吸着電気量Ｑ ｄｅｓ の減少率が２．０×１０ −４ 以下である領域が、電位サイクル幅で１０００サイクル以上存在する。
また、好適には、前記ＰｄＲｕ合金電極材料は、金属比表面積が１０ｍ ２ ／ｇ以上であり、３電極式セルを用い、参照極に対する電位差を０Ｖが３秒、１．０Ｖが３秒を１電位サイクルとしたときに、１電位サイクル当たりの水素吸着電気量Ｑ ｄｅｓ の減少率が５．１×１０ −６ 以下である領域が、電位サイクル幅で１０００サイクル以上存在する。
Preferably, the PdRu alloy electrode material is used as a PEFC catalyst. In this way, the activity can be maintained by suppressing the decrease in the electrochemical active surface area during use of the fine particles of the PdRu alloy, and a highly durable PEFC catalyst can be obtained.
Preferably, the Pd and Ru are within a range of 0.88 to 0.95 in terms of a molar ratio x of Pd.
Preferably, the PdRu alloy electrode material has a metal specific surface area of 10 m 2 / g or more, uses a three-electrode cell, and the potential difference with respect to the reference electrode is 0 V for 3 seconds and 1.0 V for 3 seconds. When a potential cycle is used , a region where the rate of decrease in the amount of hydrogen adsorption electricity Q des per potential cycle is 2.0 × 10 −4 or less is 1000 cycles or more in potential cycle width.
Preferably, the PdRu alloy electrode material has a metal specific surface area of 10 m 2 / g or more, uses a three-electrode cell, and the potential difference with respect to the reference electrode is 0 V for 3 seconds and 1.0 V for 3 seconds. When a potential cycle is used , a region where the reduction rate of the hydrogen adsorption electricity quantity Q des per potential cycle is 5.1 × 10 −6 or less exists in the potential cycle width of 1000 cycles or more.
以下、本発明の一実施例を図面を参照して詳細に説明する。 Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings.
図１は、ＰｄｘＲｕ１−ｘ合金微粒子が導電性担体であるカーボン粒子に担持されたＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の製造工程例を示している。図１において、溶液Ａ調整工程Ｐ１では、導電性担体たとえばキャボット社のＶｕｌｃａｎ ＸＣ−７２という品名のカーボンブラック２３０ｍｇを、還元剤として機能するトリエチレングリコール２００ｍｌに混合して懸濁液である溶液Ａを調整した。また、溶液Ｂ工程Ｐ２では、Ｋ２［ＰｄＣｌ４］とＲｕＣｌ３・ｎＨ２Ｏとを水５０ｍｌに溶解して溶液Ｂを調整した。このとき、Ｋ２［ＰｄＣｌ４］とＲｕＣｌ３・ｎＨ２Ｏとの組成比すなわちＰｄのモル比ｘを、ＰｄとＲｕの合計を１ｍｍｏｌとすることを維持しつつ、変化させて溶液Ｂを調整することができる。後述の組成分析、金属比表面積測定、耐久性評価に用いる試料を作成する場合には、Ｋ２［ＰｄＣｌ４］とＲｕＣｌ３・ｎＨ２Ｏとの組成比すなわちＰｄのモル比ｘを、０．０、０．１０、０．３０、０．５０、０．７０、０．８０、０．８５、０．８８、０．９０、０．９２、０．９５、０．９７、１．０とに変化させることにより、１３種類のＰｄＲｕの組成比の溶液Ｂを調整した。 FIG. 1 shows an example of a manufacturing process of a PdRu alloy electrode material (Pd x Ru 1-x / C) in which Pd x Ru 1-x alloy fine particles are supported on carbon particles as a conductive carrier. In FIG. 1, in the solution A adjustment step P1, a conductive carrier, for example, 230 mg of carbon black having a product name of Vulcan XC-72 manufactured by Cabot Corporation is mixed with 200 ml of triethylene glycol functioning as a reducing agent, and the solution A is a suspension. Adjusted. In the solution B step P2, K 2 [PdCl 4 ] and RuCl 3 · nH 2 O were dissolved in 50 ml of water to prepare a solution B. At this time, the composition B of K 2 [PdCl 4 ] and RuCl 3 · nH 2 O, that is, the molar ratio x of Pd was changed while maintaining the total of Pd and Ru at 1 mmol, thereby adjusting the solution B. can do. In the case of preparing a sample used for composition analysis, metal specific surface area measurement, and durability evaluation described later, the composition ratio of K 2 [PdCl 4 ] and RuCl 3 · nH 2 O, that is, the molar ratio x of Pd 0, 0.10, 0.30, 0.50, 0.70, 0.80, 0.85, 0.88, 0.90, 0.92, 0.95, 0.97, 1.0 Thus, the solution B having a composition ratio of 13 types of PdRu was prepared.
次いで、加熱工程Ｐ３において溶液Ａが２００℃に加熱された後、噴霧工程Ｐ４において、所定の噴霧装置を用いて、加熱された溶液Ａに溶液Ｂを噴霧することでＰｄとＲｕとを合金化するとともにＰｄｘＲｕ１−ｘ合金微粒子をカーボン粒子の表面或いは内部に析出させた混合液Ｃを得た。噴霧終了後、混合液Ｃを保温工程Ｐ５において２００℃に１５分間保持し、冷却工程Ｐ６において室温まで放置冷却した。次いで、分離工程Ｐ７において、遠心分離機を用いて、固型分であるＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）を混合液から分離し、得られた固型分を乾燥工程Ｐ８において６０℃の温度で１８時間乾燥後、さらに１００℃の温度で２時間真空乾燥することにより粉末化し、ＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）を得た。加熱工程Ｐ３、噴霧工程Ｐ４、保温工程Ｐ５、冷却工程Ｐ６、分離工程Ｐ７は、いずれも大気中で行なった。 Next, after the solution A is heated to 200 ° C. in the heating step P3, in the spraying step P4, the solution B is sprayed on the heated solution A by using a predetermined spraying device to alloy Pd and Ru. At the same time, a mixed liquid C was obtained in which Pd x Ru 1-x alloy fine particles were precipitated on the surface or inside of the carbon particles. After spraying, the mixed solution C was kept at 200 ° C. for 15 minutes in the heat retaining step P5, and allowed to cool to room temperature in the cooling step P6. Next, in the separation step P7, the solid component PdRu alloy electrode material (Pd x Ru 1-x / C) is separated from the mixed solution using a centrifuge, and the obtained solid portion is dried in the drying step P8. And dried at 60 ° C. for 18 hours, and further vacuum dried at 100 ° C. for 2 hours to obtain a PdRu alloy electrode material (Pd x Ru 1-x / C). The heating process P3, the spraying process P4, the heat retaining process P5, the cooling process P6, and the separation process P7 were all performed in the atmosphere.
図２は、図１の工程により得られた、ＰｄｘＲｕ１−ｘの組成比（モル比）ｘが相違する１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料についての、粉末Ｘ線回折結果（ＸＲＤパターン）を示している。図２におけるピークから、ＰｄおよびＲｕを含む場合はＰｄとＲｕが合金化（固溶）していること、および、パラジウムＰｄのモル比ｘが大きくなるにつれて、六方細密充填（ｈｃｐ）から面心立方充填（ｆｃｃ）へ変化することが、示されている。 Figure 2 was obtained by the process of FIG. 1, Samples of the composition ratio of Pd x Ru 1-x (molar ratio) x are different 13 types of PdRu alloy electrode material (Pd x Ru 1-x / C) The powder X-ray-diffraction result (XRD pattern) of is shown. From the peak in FIG. 2, when Pd and Ru are included, Pd and Ru are alloyed (solid solution), and from the hexagonal close packing (hcp) to the face center as the molar ratio x of palladium Pd increases. It has been shown to change to cubic filling (fcc).
図３は、図１の工程により得られた１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料のうち、モル比ｘが０．１、０．５０、０．９０である３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料についての、高角散乱環状暗視野走査透過顕微鏡法による像（ＨＡＡＤＦ−ＳＴＥＭ像）を上段に、エネルギ分散型Ｘ線分析装置ＥＤＸによる元素マッピング像を中段および下段に示している。図３の上段に示される像は、ＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）は、ＰｄＲｕの組成比に拘わらず粒子形状であることを示し、図３の中段および下段に示される像は、Ｐｄ元素およびＲｕ元素は、ＰｄＲｕの組成比に拘わらずＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の粒子内に均一に存在していることを示している。 FIG. 3 shows a sample of 13 kinds of PdRu alloy electrode materials (Pd x Ru 1-x / C) obtained by the process of FIG. 1 with a molar ratio x of 0.1, 0.50, and 0.90. Energy dispersive X-ray analysis of a sample of three types of PdRu alloy electrode material (Pd x Ru 1-x / C) by high-angle scattering annular dark-field scanning transmission microscopy (HAADF-STEM image) Element mapping images by the apparatus EDX are shown in the middle and lower stages. The image shown in the upper part of FIG. 3 shows that the PdRu alloy electrode material (Pd x Ru 1-x / C) has a particle shape regardless of the composition ratio of PdRu, and is shown in the middle and lower parts of FIG. The image shows that the Pd element and the Ru element are present uniformly in the particles of the PdRu alloy electrode material (Pd x Ru 1-x / C) regardless of the composition ratio of PdRu.
図４は、図１の工程により得られたＰｄＲｕの組成比が相違する１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料についての、誘導結合プラズマ発光分光分析装置ＩＣＰ−ＡＥＳ（エスアイアイ・ナノテクノロジー社製 ＳＰＳ５１００）による組成分析結果を示す図表である。なお、ＩＣＰ−ＡＥＳに当たっては、試料をアルカリで溶融分解後、溶融物を塩酸、硝酸で溶解し、超純水で定容して検液とした。この結果から得られたＰｄとＲｕとのモル比は、ＰｄｙＲｕ１−ｙで示されている。図４によれば、ＩＣＰ−ＡＥＳによる組成分析結果で示されたＰｄの組成比（モル比）ｙは、製造時に調合したＰｄの組成比（モル比）ｘと略一致していて、仕込み通りの生成物が得られたことが確認された。 FIG. 4 shows an inductively coupled plasma emission spectrometer ICP- for 13 types of PdRu alloy electrode materials (Pd x Ru 1-x / C) having different PdRu composition ratios obtained by the process of FIG. It is a graph which shows the composition analysis result by AES (SII nanotechnology company make SPS5100). For ICP-AES, the sample was melted and decomposed with alkali, the melt was dissolved with hydrochloric acid and nitric acid, and the volume was adjusted with ultrapure water to prepare a test solution. The molar ratio of Pd and Ru obtained from this result is indicated by Pd y Ru 1-y . According to FIG. 4, the composition ratio (molar ratio) y of Pd indicated by the composition analysis result by ICP-AES is substantially the same as the composition ratio (molar ratio) x of Pd prepared at the time of manufacture, and as prepared. It was confirmed that the product was obtained.
図５は、図１の工程により得られたＰｄＲｕの組成比が相違する１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料についての、ＣＯパルス法による金属表面積測定装置（日本ベル社製 ＢＥＬ−ＭＥＴＡＬ）を用いて測定した結果を示す図表である。この測定結果の計算に必要な触媒組成や担持量として、図４に記載のＩＣＰ−ＡＥＳによる組成分析結果の値を用いている。このＣＯパルス法では、試料を１００℃で加熱後、吸着ガスとして１０％ＣＯガスをパルスで送り熱伝導度検出器ＴＣＤの時間積分強度から吸着ガス量Ｇ（単位：ｍ３／ｇ）が求められ、１個の金属原子に１つのＣＯ分子が吸着すると仮定し、次式（５）により金属表面積Ｓ（単位：ｍ２／ｇ）が求められた。図５によれば、ＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）中の金属比表面積（単位：ｍ２／ｇ−ｍｅｔａｌ）および、これらの計算に用いた金属断面積Ａが示されている。 FIG. 5 shows a metal surface area measuring apparatus by a CO pulse method for 13 types of PdRu alloy electrode materials (Pd x Ru 1-x / C) obtained by the process of FIG. It is a chart which shows the result measured using Nippon Bell Co., Ltd. BEL-METAL). The value of the composition analysis result by ICP-AES shown in FIG. 4 is used as the catalyst composition and the loading amount necessary for calculation of this measurement result. In this CO pulse method, after heating a sample at 100 ° C., 10% CO gas is pulsed as an adsorbed gas, and the adsorbed gas amount G (unit: m 3 / g) is obtained from the time integrated intensity of the thermal conductivity detector TCD. Assuming that one CO molecule is adsorbed on one metal atom, the metal surface area S (unit: m 2 / g) was obtained by the following equation (5). FIG. 5 shows the specific metal surface area (unit: m 2 / g-metal) in the PdRu alloy electrode material (Pd x Ru 1-x / C) and the metal cross-sectional area A used for these calculations. ing.
Ｓ＝（Ｇ／２２．４×１０３）×Ｎ×Ａ×１０−１８・・・（５）
但し、Ｎはアボガドロ数、Ａは金属断面積である。
S = (G / 22.4 × 10 3 ) × N × A × 10 −18 (5)
However, N is Avogadro's number and A is a metal cross-sectional area.
（耐久性評価）
次に、図１の工程により得られたＰｄＲｕの組成比が相違する１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）についての耐久性評価を、電気化学的活性表面積ＥＣＡの低下特性を用いて評価するために、水素吸着電気量Ｑｄｅｓの測定を、以下の測定条件で行なった。
［試料作製条件］
１８．５ｍｇのＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）に、１９．００ｍｌの２−プロパノールと６．００ｍｌの蒸留水と１００μｌの５％Ｎａｆｉｏｎ（登録商標）溶液（５％ナフィオン分散溶液ＤＥ２１ ＣＳタイプ、和光純薬工業株式会社）とを加え、３０分間超音波分散してインクとした。このインク１０μｌを直径５ｍｍのグラッシーカーボン電極に塗布し、乾燥させて１３種類の試料（電極材料ＰｄｘＲｕ１−ｘ／Ｃ）を得た。
［水素吸着電気量変化特性の測定条件］
・３電極式セル：対極：白金、参照極：可逆水素電極ＲＨＥ、電解液：０．１Ｍ過塩素酸、２５℃、Ｎ ２ 飽和
・電流測定装置：ポテンシオスタット（北斗電工社製 ＨＺ５０００）
・測定方法：上記の試料（電極）に、上記３電極式セルを用いて、図６に示すように０Ｖを３秒、１．０Ｖ（ｖｓ．ＲＨＥ）を３秒を１サイクルとするパルス状の電位変動を最大１８０００サイクルまで印加し、その間の０、１００、５００、１０００、２０００、３０００、４０００、１３０００、１８０００サイクル毎にサイクリックボルタンメトリーＣＶを行なった。なお、アノード電極およびカソード電極の両方における使用を想定して、上記のパルス状の電位変動の幅は、０Ｖ〜１．０Ｖと広範囲に設定されている。また、この電位変動サイクルの印加は、水素吸着電気量Ｑｄｅｓが最大値の５０％以下に到達するまで、継続する。上記サイクリックボルタンメトリーＣＶでは、上記３電極式セルを用い、０Ｖ〜１．２の範囲で掃引速度が５０ｍＶ／ｓにて電位Ｅを掃引したとき、得られたサイクリックボルタグラムの０．０４Ｖ〜０．４Ｖ辺りに現れた水素吸着ピークの面積から、水素吸着電気量Ｑｄｅｓを算出した。（６）式から明らかなように、電気化学的活性表面積（ＥＣＡ）と水素吸着電気量Ｑｄｅｓとは、比例する関係にあるので、正規化することにより同じ値となる。
ＥＣＡ＝Ｑｄｅｓ／金属粒子単位表面積当たりの水素吸着電気量 ・・・（６）
(Durability evaluation)
Next, durability evaluation of 13 types of PdRu alloy electrode materials (Pd x Ru 1-x / C) having different PdRu composition ratios obtained by the process of FIG. In order to evaluate using the characteristics, the hydrogen adsorption electricity quantity Q des was measured under the following measurement conditions.
[Sample preparation conditions]
18.5 mg of PdRu alloy electrode material (Pd x Ru 1-x / C), 19.00 ml of 2-propanol, 6.00 ml of distilled water and 100 μl of 5% Nafion® solution (5% Nafion dispersion) Solution DE21 CS type, Wako Pure Chemical Industries, Ltd.) and ultrasonically dispersed for 30 minutes to obtain an ink. 10 μl of this ink was applied to a glassy carbon electrode having a diameter of 5 mm and dried to obtain 13 types of samples (electrode material Pd x Ru 1-x / C).
[Measurement conditions of hydrogen adsorption electricity quantity change characteristics]
3 electrode type cell: counter electrode: platinum, reference electrode: reversible hydrogen electrode RHE, electrolyte: 0.1 M perchloric acid, 25 ° C., N 2 saturation / current measuring device: potentiostat (HZ5000 manufactured by Hokuto Denko)
Measurement method: Using the above-mentioned three-electrode cell for the above-mentioned sample (electrode), as shown in FIG. 6, 0V for 3 seconds and 1.0V (vs. RHE) for 3 seconds for 1 cycle A potential voltammetric CV was applied every 0, 100, 500, 1000, 2000, 3000, 4000, 13000, 18000 cycles. In addition, assuming the use in both the anode electrode and the cathode electrode, the width of the pulse-like potential fluctuation is set in a wide range of 0V to 1.0V. The application of this potential fluctuation cycle is continued until the hydrogen adsorption electricity quantity Q des reaches 50% or less of the maximum value. In the cyclic voltammetry CV, when the potential E is swept at a sweep speed of 50 mV / s in the range of 0 V to 1.2 using the above-mentioned three-electrode cell, 0.04 V of the obtained cyclic voltagram The hydrogen adsorption electricity quantity Q des was calculated from the area of the hydrogen adsorption peak that appeared around 0.4 V. As is clear from the equation (6), the electrochemically active surface area (ECA) and the hydrogen adsorption electricity quantity Q des are in a proportional relationship, and thus are equalized by normalization.
ECA = Q des / hydrogen adsorption electric energy per unit surface area of metal particles (6)
（電気化学的活性表面積の減少特性）
次に、上記のようにして１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料のそれぞれについて、所定サイクル毎にそれぞれ得られた水素吸着電気量Ｑｄｅｓの最大値を１００としたときの相対値すなわち正規化された水素吸着電気量normalizedＱｄｅｓ（無次元）は、図７に示す如くとなる。図８は、サイクル数を示す横軸と正規化した水素吸着電気量normalizedＱｄｅｓを示す縦軸とから成る二次元座標に、正規化された水素吸着電気量normalizedＱｄｅｓをプロットしてグラフ化した図である。図８から明らかなように、正規化した水素吸着電気量normalizedＱｄｅｓは、サイクル数の増加にともなって５０付近まで低下した後、その低下速度が著しく低下した。そこで、触媒性能の低下速度を表す指標として、５０％ｒａｔｅを次のように定義した。すなわち、図８において、正規化した水素吸着電気量normalizedＱｄｅｓが５０となる直前のデータポイントと直後のデータポイントとを結ぶ直線の傾きの絶対値を、５０％ｒａｔｅ（単位：サイクル−１）と定義した。この指標５０％ｒａｔｅは、正規化した水素吸着電気量normalizedＱｄｅｓが５０付近における低下速度に対応しており、その値が小さいほど、ＰｄＲｕ合金の微粒子の電気化学的な表面活性の低下が小さくて活性が維持され、耐久性が高いことを意味している。
(Reduction characteristics of electrochemically active surface area)
Next, for each of the 13 types of PdRu alloy electrode material (Pd x Ru 1-x / C) samples as described above, the maximum value of the hydrogen adsorption electricity quantity Q des obtained for each predetermined cycle is set to 100. The relative value when normalized, that is, the normalized hydrogen adsorption electricity quantity normalizedQ des (dimensionless) is as shown in FIG. Figure 8 is a two-dimensional coordinate composed of the vertical axis indicating the horizontal axis and the normalized hydrogen adsorbed amount of electricity NormalizedQ des indicating the number of cycles, and graphed by plotting the normalized hydrogen adsorbed amount of electricity NormalizedQ des Figure It is. As apparent from FIG. 8, normalized hydrogen adsorbed amount of electricity NormalizedQ des, after dropped to around 50 with increasing number of cycles, the decrease rate was significantly decreased. Therefore, 50% rate was defined as follows as an index representing the rate of decrease in catalyst performance. That is, in FIG. 8, the absolute value of the slope of the straight line connecting the data point immediately before the normalized hydrogen adsorption electricity quantity normalizedQ des becomes 50 and the data point immediately after is 50% rate (unit: cycle −1 ). Defined. This index 50% rate corresponds to the rate of decrease in the normalized hydrogen adsorption electricity quantity normalized Q des near 50, and the smaller the value, the smaller the decrease in the electrochemical surface activity of the fine particles of the PdRu alloy. It means that the activity is maintained and the durability is high.
図９は、正規化したnormalized水素吸着電気量Ｑｄｅｓ＝５０付近の水素吸着電気量normalizedＱｄｅｓの低下率を示す指標である５０％ｒａｔｅを、１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料について示す図表である。図１０は、図９に示される５０％ｒａｔｅを、前記１３種類のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の試料についての組成比（モル比ｘ）を示す横軸と５０％ｒａｔｅを示す縦軸とから成る二次元座標にプロットしてグラフ化した図である。 9, the 50% rate is an index showing the decrease rate of the hydrogen adsorption electric quantity NormalizedQ des nearby normalized hydrogen adsorption quantity of electricity Q des = 50 normalized, 13 kinds of PdRu alloy electrode material (Pd x Ru 1- It is a graph shown about the sample of x / C). FIG. 10 shows the 50% rate shown in FIG. 9 with the horizontal axis showing the composition ratio (molar ratio x) of the 13 types of PdRu alloy electrode materials (Pd x Ru 1-x / C) and 50%. It is the figure plotted and plotted on the two-dimensional coordinate which consists of the vertical axis | shaft which shows rate.
上記図９および図１０に示されるように、モル比ｘが０．８５≦ｘ≦０．９５の範囲内である場合には、水素吸着電気量normalizedＱｄｅｓの低下率を示す指標値である５０％ｒａｔｅの値が著しく低く、ＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の耐久性が高い。また、その事実は、さらに続けて電位サイクルを印加したとしても、高い電気化学的活性表面積ＥＣＡを保つことを示唆している。 As shown in FIG. 9 and FIG. 10, when the molar ratio x is in the range of 0.85 ≦ x ≦ 0.95, it is an index value indicating the rate of decrease in the hydrogen adsorbed electricity amount normalized Q des 50 The value of% rate is remarkably low, and the durability of the PdRu alloy electrode material (Pd x Ru 1-x / C) is high. The fact also suggests that a high electrochemically active surface area ECA is maintained even when a potential cycle is subsequently applied.
（金属比表面積を考慮した耐久性評価）
以上の事実は、モル比ｘが０．８５≦ｘ≦０．９５の範囲内である場合には、正規化された水素吸着電気量normalizedＱｄｅｓの耐久性が著しく高いことを示唆しているが、これらのデータには、モル比（組成比）ｘ以外の耐久性に影響する因子である金属比表面積が考慮されねばならない。金属比表面積が小さい試料ほど耐久性が高くなる傾向を示すことは当然であるから、金属比表面積が小さい組成との比較において、上記モル比ｘの範囲０．８５≦ｘ≦０．９５の優位性が示される必要がある。
(Durability evaluation considering specific metal surface area)
The above facts suggest that when the molar ratio x is in the range of 0.85 ≦ x ≦ 0.95, the durability of the normalized hydrogen adsorption electricity quantity normalizedQ des is remarkably high. In these data, the specific metal surface area, which is a factor affecting the durability other than the molar ratio (composition ratio) x, must be considered. Since it is natural that a sample having a smaller metal specific surface area tends to have higher durability, in comparison with a composition having a smaller metal specific surface area, the above range of molar ratio x is in the range of 0.85 ≦ x ≦ 0.95. Gender needs to be shown.
そこで、モル比ｘ＝０の試料に窒素雰囲気中、２５０℃、２時間という熱処理を施すことで金属比表面積を低下させた試料を作成して比較例１とした。また、元々金属比表面積が小さい、モル比ｘが０．３０、０．５０、０．７０、０．８０、１．０の試料を比較例２、３、４、５、６とし、また、モル比ｘが０．８５、０．８８、０．９０、０．９２、０．９５の試料を実施例１、２、３、４、５とした。これにより、実施例１〜５の金属比表面積の値は、比較例１〜６の金属比表面積以上の値とされた。そして、それら実施例１〜５および比較例１〜６の試料について、前述と同様の条件で、ＣＯパルス法を用いた金属比表面積（ｍ２／ｇ−ｍｅｔａｌ）、各サイクル数における正規化した水素吸着電気量normalizedＱｄｅｓ、５０％ｒａｔｅをそれぞれ求めた。 Therefore, a sample with a reduced metal specific surface area was prepared by subjecting a sample with a molar ratio x = 0 to a heat treatment at 250 ° C. for 2 hours in a nitrogen atmosphere to obtain Comparative Example 1. Samples having a originally low metal specific surface area and a molar ratio x of 0.30, 0.50, 0.70, 0.80, 1.0 are referred to as Comparative Examples 2, 3, 4, 5, 6, Samples having a molar ratio x of 0.85, 0.88, 0.90, 0.92, and 0.95 were designated as Examples 1, 2, 3, 4, and 5, respectively. Thereby, the value of the metal specific surface area of Examples 1-5 was made into the value more than the metal specific surface area of Comparative Examples 1-6. And about the sample of those Examples 1-5 and Comparative Examples 1-6, it normalized in the metal specific surface area (m < 2 > / g-metal) and each cycle number using the CO pulse method on the same conditions as the above-mentioned. The hydrogen adsorption electricity quantity normalized Q des and 50% rate were determined, respectively.
図１１は、上記実施例１〜５および比較例１〜６の試料についてそれぞれ求められた、ＣＯパルス法を用いた金属比表面積（ｍ２／ｇ−ｍｅｔａｌ）と、図６の印加電位変動サイクル数の各値における正規化した水素吸着電気量normalizedＱｄｅｓと、５０％ｒａｔｅを示す図表である。図１２は、図１１に示されたデータのうち、図６の印加電位変動サイクルの増加に伴う、正規化した水素吸着電気量normalizedＱｄｅｓの変化を、実施例１〜５および比較例１〜６の試料のそれぞれについてグラフ化した図である。図１３は、図１１に示されたデータのうち、実施例１〜５および比較例１〜６の試料のモル比ｘと５０％ｒａｔｅとの関係をグラフ化した図である。 FIG. 11 shows the specific metal surface area (m 2 / g-metal) obtained using the CO pulse method and the applied potential fluctuation cycle shown in FIG. 6 obtained for the samples of Examples 1 to 5 and Comparative Examples 1 to 6, respectively. It is a chart which shows normalized hydrogen adsorption electric energy normalizedQ des in each value of number, and 50% rate. FIG. 12 shows changes in normalized hydrogen adsorption electricity quantity normalizedQ des accompanying the increase in the applied potential fluctuation cycle of FIG. 6 among the data shown in FIG. 11, in Examples 1-5 and Comparative Examples 1-6. It is the figure graphed about each of these samples. FIG. 13 is a graph of the relationship between the molar ratio x of samples of Examples 1 to 5 and Comparative Examples 1 to 6 and 50% rate in the data shown in FIG.
図１１、図１２、図１３に示すように、Ｐｄのモル比ｘが０．８５≦ｘ≦０．９５の範囲内である実施例１〜５は、比較例１〜６よりも、金属比表面積が大きいすなわち小径粒にも拘わらず、耐久性が著しく高い。すなわち、モル比ｘが０．８５≦ｘ≦０．９５の範囲内である実施例１〜５の耐久性の高さは、その組成すなわちＰｄのモル比ｘによることが明確に示されている。 As shown in FIGS. 11, 12, and 13, Examples 1 to 5 in which the molar ratio x of Pd is in the range of 0.85 ≦ x ≦ 0.95 are higher than the comparative examples 1 to 6 Despite its large surface area, that is, small-diameter grains, the durability is remarkably high. That is, it is clearly shown that the high durability of Examples 1 to 5 in which the molar ratio x is in the range of 0.85 ≦ x ≦ 0.95 depends on the composition, that is, the molar ratio x of Pd. .
なお、図１１に示されていないが図４、図５、図７、図９のｘ＝０．９７（実施例６）は、５０％ｒａｔｅにおいて比較例６と同様であったが、比表面積が比較例６よりもかなり大きいため（図５）、組成の影響による実質的な耐久性は高いと言える。 Although not shown in FIG. 11, x = 0.97 (Example 6) in FIGS. 4, 5, 7, and 9 was the same as that in Comparative Example 6 at 50% rate. Is considerably larger than Comparative Example 6 (FIG. 5), it can be said that the substantial durability due to the influence of the composition is high.
ここで、ｘ＝０．８〜１の５０％ｒａｔｅを通る曲線補間式の上で５０％ｒａｔｅがＰｄよりも小さくなる領域を示すために、５０％ｒａｔｅの組成比ｘに対する変化、すなわち５０％ｒａｔｅの組成比ｘに対する関係を最小自乗法を用いて二次関数としてフィッティングした。図１４はその結果を示し、その二次関数（回帰式）は次式（７）にて表される。図１４において、回帰式の決定係数Ｒ２は、０．９５２２である。決定係数の値が１に近いことから，良好なフィッティングが得られたことがわかる。また、図１４の曲線で示される回帰式から、０．８１≦ｘ＜１の範囲において、５０％ｒａｔｅがｘ＝１の場合（比較例６）よりも小さくなることが推定される。つまり、０．８１≦ｘ＜１の範囲において耐久性が高いと推定される。 Here, in order to show a region where 50% rate is smaller than Pd on the curve interpolation formula passing through 50% rate of x = 0.8 to 1, a change with respect to the composition ratio x of 50% rate, that is, 50% The relation of the rate to the composition ratio x was fitted as a quadratic function using the method of least squares. FIG. 14 shows the result, and its quadratic function (regression equation) is expressed by the following equation (7). In FIG. 14, the regression coefficient determination coefficient R 2 is 0.9522. Since the coefficient of determination is close to 1, it can be seen that a good fitting was obtained. Further, from the regression equation shown by the curve of FIG. 14, it is estimated that 50% rate is smaller than that in the case of x = 1 (Comparative Example 6) in the range of 0.81 ≦ x <1. That is, it is estimated that durability is high in the range of 0.81 ≦ x <1.
５０％ｒａｔｅ＝１．８５４３ｘ２−３．３５２６ｘ＋１．５１５５ ・・・（７） 50% rate = 1.8543x 2 −3.3526x + 1.5155 (7)
上述のように、本実施例のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）によれば、Ｐｄのモル比ｘが０．８１≦ｘ＜１の範囲内であるので、ＰｄＲｕ合金の微粒子の電気化学的な表面活性の低下を抑制して活性を維持することができ、高い耐久性が得られる。 As described above, according to the PdRu alloy electrode material (Pd x Ru 1-x / C) of this example, the Pd molar ratio x is in the range of 0.81 ≦ x <1, The activity can be maintained by suppressing the decrease in electrochemical surface activity of the fine particles, and high durability can be obtained.
また、本実施例のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）は、固体高分子形燃料電池ＰＥＦＣの電極（触媒）として用いられる場合には、耐久性の高い固体高分子形燃料電池ＰＥＦＣの電極が得られる。 In addition, when the PdRu alloy electrode material (Pd x Ru 1-x / C) of this example is used as an electrode (catalyst) of a polymer electrolyte fuel cell PEFC, it is a highly durable polymer electrolyte fuel. An electrode of the battery PEFC is obtained.
また、本実施例のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の導電性担体は、還元剤と、導電性担体粒子と、パラジウム化合物またはパラジウムイオンと、ルテニウム化合物またはルテニウムイオンと含む溶液を、所定の温度以上の温度に保持する保温工程Ｐ５を含む製造工程により製造される。このようにすれば、パラジウムとルテニウムとの合金化と、導電性粒子の表面にその合金の微粒子を導電性担体粒子に析出させる触媒の固定化とが同じ噴霧工程Ｐ４内で行なわれるので、工程が簡単となり、製造が容易となる。また、保護剤が無くとも粒子成長を抑えた微粒子を合成でき、さらに、粒子の凝集を少ないままに高濃度に坦持可能である。 Further, the conductive carrier of the PdRu alloy electrode material (Pd x Ru 1-x / C) of this example includes a reducing agent, conductive carrier particles, a palladium compound or palladium ion, and a ruthenium compound or ruthenium ion. The solution is manufactured by a manufacturing process including a heat retaining process P5 for holding the solution at a temperature equal to or higher than a predetermined temperature. In this way, the alloying of palladium and ruthenium and the immobilization of the catalyst for depositing fine particles of the alloy on the conductive carrier particles on the surface of the conductive particles are performed in the same spraying step P4. Becomes simple and easy to manufacture. In addition, fine particles with suppressed particle growth can be synthesized without a protective agent, and further, the particles can be supported at a high concentration with little aggregation.
また、本実施例のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）は、高い耐久性を示す。 Further, the PdRu alloy electrode material (Pd x Ru 1-x / C) of this example shows high durability.
また、本実施例のＰｄＲｕ合金電極材料（ＰｄｘＲｕ１−ｘ／Ｃ）の導電性担体は、ＰｄＲｕ合金の微粒子が導電性担体であるカーボン粒子に直接析出させられることにより固定されているので、ＰｄＲｕ合金の微粒子がカーボン粒子に高濃度で担持され、同量であれば電極触媒性能が高められ、同じ性能であれば粉体を少なくできて、電極の電気抵抗を低くできる利点がある。 In addition, since the conductive support of the PdRu alloy electrode material (Pd x Ru 1-x / C) of this example is fixed by directly depositing the fine particles of the PdRu alloy on the carbon particles as the conductive support, The fine particles of the PdRu alloy are supported on the carbon particles at a high concentration, and if the amount is the same, the electrode catalyst performance is enhanced, and if the performance is the same, the powder can be reduced and the electrical resistance of the electrode can be lowered.
なお、上述したのはあくまでも一実施形態であり、本発明は当業者の知識に基づいて種々の変更、改良を加えた態様で実施することができる。 The above description is only an embodiment, and the present invention can be implemented in variously modified and improved forms based on the knowledge of those skilled in the art.
Ｐ４：噴霧工程
Ｐ５：保温工程（工程）
P4: Spraying process P5: Thermal insulation process (process)
Claims (7)
前記ＰｄとＲｕが、Ｐｄのモル比ｘで０．８１≦ｘ≦０．９７の範囲内である
ことを特徴とするＰｄＲｕ合金電極材料。 A PdRu alloy electrode material in which fine particles of a PdRu alloy Pd x Ru 1-x in which Pd and Ru are dissolved are fixed to the surface of a conductive carrier,
The PdRu alloy electrode material , wherein the Pd and Ru are in a range of 0.81 ≦ x ≦ 0.97 in terms of a molar ratio x of Pd .
ことを特徴とする請求項１のＰｄＲｕ合金電極材料。 The PdRu alloy electrode material according to claim 1, wherein the Pd and Ru are in a range of 0.88 to 0.95 in terms of a molar ratio x of Pd .
３電極式セルを用い、参照極に対する電位差を０Ｖが３秒、１．０Ｖが３秒を１電位サイクルとしたときに、１電位サイクル当たりの水素吸着電気量Ｑ Using a three-electrode type cell, when the potential difference with respect to the reference electrode is 0 V for 3 seconds and 1.0 V for 3 seconds for one potential cycle, the amount of hydrogen adsorption electricity per Q cycle Q ｄｅｓdes の減少率が２．０×１０Decrease rate of 2.0 × 10 −４-4 以下である領域が、電位サイクル幅で１０００サイクル以上存在するThe following areas exist at 1000 cycles or more in potential cycle width
ことを特徴とする請求項１のＰｄＲｕ合金電極材料。 The PdRu alloy electrode material according to claim 1.
３電極式セルを用い、参照極に対する電位差を０Ｖが３秒、１．０Ｖが３秒を１電位サイクルとしたときに、１電位サイクル当たりの水素吸着電気量Ｑ Using a three-electrode type cell, when the potential difference with respect to the reference electrode is 0 V for 3 seconds and 1.0 V for 3 seconds for one potential cycle, the amount of hydrogen adsorption electricity per Q cycle Q ｄｅｓdes の減少率が５．１×１０Reduction rate of 5.1 × 10 −６-6 以下である領域が、電位サイクル幅で１０００サイクル以上存在するThe following areas exist at 1000 cycles or more in potential cycle width
ことを特徴とする請求項２のＰｄＲｕ合金電極材料。 The PdRu alloy electrode material according to claim 2.
ことを特徴とする請求項１から４のいずれか１のＰｄＲｕ合金電極材料。 The PdRu alloy electrode material according to any one of claims 1 to 4, wherein the PdRu alloy electrode material is used as a catalyst electrode of a polymer electrolyte fuel cell PEFC.
ことを特徴とする請求項１から５のいずれか１のＰｄＲｕ合金電極材料。 The conductive support, any one of PdRu alloy electrode material of claims 1 to 5, characterized in that the carbon particles.
還元剤と導電性粒子とを含む加熱された懸濁液に、パラジウム化合物またはパラジウムイオンとルテニウム化合物またはルテニウムイオンと含む溶液を噴霧することで、ＰｄとＲｕとを合金化したＰｄＲｕ合金微粒子を前記導電性微粒子の表面或いは内部に析出させた混合液を得る工程と、
前記混合液を所定の温度以上の温度に保持する工程とを、含む
ことを特徴とするＰｄＲｕ合金電極材料の製造方法。 A method for producing a PdRu alloy electrode material in which the fine particles of the PdRu alloy according to any one of claims 1 to 6 are fixed to a conductive carrier,
The heated suspension containing the reducing agent and conductive particles, by spraying a solution containing a palladium compound or a palladium ion and Le ruthenium compound or ruthenium ion, PdRu alloy microparticles alloying Pd and Ru A step of obtaining a mixed liquid in which the conductive fine particles are deposited on the surface or inside of the conductive fine particles;
Holding the mixed liquid at a temperature equal to or higher than a predetermined temperature. A method for producing a PdRu alloy electrode material , comprising:
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9394608B2 (en) | 2009-04-06 | 2016-07-19 | Asm America, Inc. | Semiconductor processing reactor and components thereof |
| US8802201B2 (en) | 2009-08-14 | 2014-08-12 | Asm America, Inc. | Systems and methods for thin-film deposition of metal oxides using excited nitrogen-oxygen species |
| US9312155B2 (en) | 2011-06-06 | 2016-04-12 | Asm Japan K.K. | High-throughput semiconductor-processing apparatus equipped with multiple dual-chamber modules |
| US10854498B2 (en) | 2011-07-15 | 2020-12-01 | Asm Ip Holding B.V. | Wafer-supporting device and method for producing same |
| US20130023129A1 (en) | 2011-07-20 | 2013-01-24 | Asm America, Inc. | Pressure transmitter for a semiconductor processing environment |
| US9017481B1 (en) | 2011-10-28 | 2015-04-28 | Asm America, Inc. | Process feed management for semiconductor substrate processing |
| US10714315B2 (en) | 2012-10-12 | 2020-07-14 | Asm Ip Holdings B.V. | Semiconductor reaction chamber showerhead |
| US10683571B2 (en) | 2014-02-25 | 2020-06-16 | Asm Ip Holding B.V. | Gas supply manifold and method of supplying gases to chamber using same |
| US10167557B2 (en) | 2014-03-18 | 2019-01-01 | Asm Ip Holding B.V. | Gas distribution system, reactor including the system, and methods of using the same |
| US11015245B2 (en) | 2014-03-19 | 2021-05-25 | Asm Ip Holding B.V. | Gas-phase reactor and system having exhaust plenum and components thereof |
| US10858737B2 (en) | 2014-07-28 | 2020-12-08 | Asm Ip Holding B.V. | Showerhead assembly and components thereof |
| US9890456B2 (en) | 2014-08-21 | 2018-02-13 | Asm Ip Holding B.V. | Method and system for in situ formation of gas-phase compounds |
| US9657845B2 (en) | 2014-10-07 | 2017-05-23 | Asm Ip Holding B.V. | Variable conductance gas distribution apparatus and method |
| US10941490B2 (en) | 2014-10-07 | 2021-03-09 | Asm Ip Holding B.V. | Multiple temperature range susceptor, assembly, reactor and system including the susceptor, and methods of using the same |
| US10276355B2 (en) | 2015-03-12 | 2019-04-30 | Asm Ip Holding B.V. | Multi-zone reactor, system including the reactor, and method of using the same |
| US10458018B2 (en) | 2015-06-26 | 2019-10-29 | Asm Ip Holding B.V. | Structures including metal carbide material, devices including the structures, and methods of forming same |
| US10600673B2 (en) | 2015-07-07 | 2020-03-24 | Asm Ip Holding B.V. | Magnetic susceptor to baseplate seal |
| US10211308B2 (en) | 2015-10-21 | 2019-02-19 | Asm Ip Holding B.V. | NbMC layers |
| US11139308B2 (en) | 2015-12-29 | 2021-10-05 | Asm Ip Holding B.V. | Atomic layer deposition of III-V compounds to form V-NAND devices |
| US10529554B2 (en) | 2016-02-19 | 2020-01-07 | Asm Ip Holding B.V. | Method for forming silicon nitride film selectively on sidewalls or flat surfaces of trenches |
| US10190213B2 (en) | 2016-04-21 | 2019-01-29 | Asm Ip Holding B.V. | Deposition of metal borides |
| US10865475B2 (en) | 2016-04-21 | 2020-12-15 | Asm Ip Holding B.V. | Deposition of metal borides and silicides |
| US10032628B2 (en) | 2016-05-02 | 2018-07-24 | Asm Ip Holding B.V. | Source/drain performance through conformal solid state doping |
| US10367080B2 (en) | 2016-05-02 | 2019-07-30 | Asm Ip Holding B.V. | Method of forming a germanium oxynitride film |
| US11453943B2 (en) | 2016-05-25 | 2022-09-27 | Asm Ip Holding B.V. | Method for forming carbon-containing silicon/metal oxide or nitride film by ALD using silicon precursor and hydrocarbon precursor |
| US9859151B1 (en) | 2016-07-08 | 2018-01-02 | Asm Ip Holding B.V. | Selective film deposition method to form air gaps |
| US10612137B2 (en) | 2016-07-08 | 2020-04-07 | Asm Ip Holdings B.V. | Organic reactants for atomic layer deposition |
| US10714385B2 (en) | 2016-07-19 | 2020-07-14 | Asm Ip Holding B.V. | Selective deposition of tungsten |
| KR102532607B1 (en) | 2016-07-28 | 2023-05-15 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus and method of operating the same |
| US9812320B1 (en) | 2016-07-28 | 2017-11-07 | Asm Ip Holding B.V. | Method and apparatus for filling a gap |
| US9887082B1 (en) | 2016-07-28 | 2018-02-06 | Asm Ip Holding B.V. | Method and apparatus for filling a gap |
| US10643826B2 (en) | 2016-10-26 | 2020-05-05 | Asm Ip Holdings B.V. | Methods for thermally calibrating reaction chambers |
| US11532757B2 (en) | 2016-10-27 | 2022-12-20 | Asm Ip Holding B.V. | Deposition of charge trapping layers |
| US10714350B2 (en) | 2016-11-01 | 2020-07-14 | ASM IP Holdings, B.V. | Methods for forming a transition metal niobium nitride film on a substrate by atomic layer deposition and related semiconductor device structures |
| US10229833B2 (en) | 2016-11-01 | 2019-03-12 | Asm Ip Holding B.V. | Methods for forming a transition metal nitride film on a substrate by atomic layer deposition and related semiconductor device structures |
| US10643904B2 (en) | 2016-11-01 | 2020-05-05 | Asm Ip Holdings B.V. | Methods for forming a semiconductor device and related semiconductor device structures |
| US10134757B2 (en) | 2016-11-07 | 2018-11-20 | Asm Ip Holding B.V. | Method of processing a substrate and a device manufactured by using the method |
| KR102546317B1 (en) | 2016-11-15 | 2023-06-21 | 에이에스엠 아이피 홀딩 비.브이. | Gas supply unit and substrate processing apparatus including the same |
| KR20180068582A (en) | 2016-12-14 | 2018-06-22 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus |
| US11581186B2 (en) | 2016-12-15 | 2023-02-14 | Asm Ip Holding B.V. | Sequential infiltration synthesis apparatus |
| US11447861B2 (en) | 2016-12-15 | 2022-09-20 | Asm Ip Holding B.V. | Sequential infiltration synthesis apparatus and a method of forming a patterned structure |
| KR20180070971A (en) | 2016-12-19 | 2018-06-27 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus |
| US10269558B2 (en) | 2016-12-22 | 2019-04-23 | Asm Ip Holding B.V. | Method of forming a structure on a substrate |
| US10867788B2 (en) | 2016-12-28 | 2020-12-15 | Asm Ip Holding B.V. | Method of forming a structure on a substrate |
| US11390950B2 (en) | 2017-01-10 | 2022-07-19 | Asm Ip Holding B.V. | Reactor system and method to reduce residue buildup during a film deposition process |
| US10655221B2 (en) | 2017-02-09 | 2020-05-19 | Asm Ip Holding B.V. | Method for depositing oxide film by thermal ALD and PEALD |
| US10468261B2 (en) | 2017-02-15 | 2019-11-05 | Asm Ip Holding B.V. | Methods for forming a metallic film on a substrate by cyclical deposition and related semiconductor device structures |
| US10529563B2 (en) | 2017-03-29 | 2020-01-07 | Asm Ip Holdings B.V. | Method for forming doped metal oxide films on a substrate by cyclical deposition and related semiconductor device structures |
| USD876504S1 (en) | 2017-04-03 | 2020-02-25 | Asm Ip Holding B.V. | Exhaust flow control ring for semiconductor deposition apparatus |
| KR102457289B1 (en) | 2017-04-25 | 2022-10-21 | 에이에스엠 아이피 홀딩 비.브이. | Method for depositing a thin film and manufacturing a semiconductor device |
| US10770286B2 (en) | 2017-05-08 | 2020-09-08 | Asm Ip Holdings B.V. | Methods for selectively forming a silicon nitride film on a substrate and related semiconductor device structures |
| US10892156B2 (en) | 2017-05-08 | 2021-01-12 | Asm Ip Holding B.V. | Methods for forming a silicon nitride film on a substrate and related semiconductor device structures |
| US11306395B2 (en) | 2017-06-28 | 2022-04-19 | Asm Ip Holding B.V. | Methods for depositing a transition metal nitride film on a substrate by atomic layer deposition and related deposition apparatus |
| US10685834B2 (en) | 2017-07-05 | 2020-06-16 | Asm Ip Holdings B.V. | Methods for forming a silicon germanium tin layer and related semiconductor device structures |
| KR20190009245A (en) | 2017-07-18 | 2019-01-28 | 에이에스엠 아이피 홀딩 비.브이. | Methods for forming a semiconductor device structure and related semiconductor device structures |
| US11374112B2 (en) | 2017-07-19 | 2022-06-28 | Asm Ip Holding B.V. | Method for depositing a group IV semiconductor and related semiconductor device structures |
| US10541333B2 (en) | 2017-07-19 | 2020-01-21 | Asm Ip Holding B.V. | Method for depositing a group IV semiconductor and related semiconductor device structures |
| US11018002B2 (en) | 2017-07-19 | 2021-05-25 | Asm Ip Holding B.V. | Method for selectively depositing a Group IV semiconductor and related semiconductor device structures |
| US10590535B2 (en) | 2017-07-26 | 2020-03-17 | Asm Ip Holdings B.V. | Chemical treatment, deposition and/or infiltration apparatus and method for using the same |
| US10770336B2 (en) | 2017-08-08 | 2020-09-08 | Asm Ip Holding B.V. | Substrate lift mechanism and reactor including same |
| US10692741B2 (en) | 2017-08-08 | 2020-06-23 | Asm Ip Holdings B.V. | Radiation shield |
| US11769682B2 (en) | 2017-08-09 | 2023-09-26 | Asm Ip Holding B.V. | Storage apparatus for storing cassettes for substrates and processing apparatus equipped therewith |
| US10249524B2 (en) | 2017-08-09 | 2019-04-02 | Asm Ip Holding B.V. | Cassette holder assembly for a substrate cassette and holding member for use in such assembly |
| US11139191B2 (en) | 2017-08-09 | 2021-10-05 | Asm Ip Holding B.V. | Storage apparatus for storing cassettes for substrates and processing apparatus equipped therewith |
| USD900036S1 (en) | 2017-08-24 | 2020-10-27 | Asm Ip Holding B.V. | Heater electrical connector and adapter |
| US11830730B2 (en) | 2017-08-29 | 2023-11-28 | Asm Ip Holding B.V. | Layer forming method and apparatus |
| KR102491945B1 (en) | 2017-08-30 | 2023-01-26 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus |
| US11295980B2 (en) | 2017-08-30 | 2022-04-05 | Asm Ip Holding B.V. | Methods for depositing a molybdenum metal film over a dielectric surface of a substrate by a cyclical deposition process and related semiconductor device structures |
| US11056344B2 (en) | 2017-08-30 | 2021-07-06 | Asm Ip Holding B.V. | Layer forming method |
| KR102630301B1 (en) | 2017-09-21 | 2024-01-29 | 에이에스엠 아이피 홀딩 비.브이. | Method of sequential infiltration synthesis treatment of infiltrateable material and structures and devices formed using same |
| US10844484B2 (en) | 2017-09-22 | 2020-11-24 | Asm Ip Holding B.V. | Apparatus for dispensing a vapor phase reactant to a reaction chamber and related methods |
| US10658205B2 (en) | 2017-09-28 | 2020-05-19 | Asm Ip Holdings B.V. | Chemical dispensing apparatus and methods for dispensing a chemical to a reaction chamber |
| US10403504B2 (en) | 2017-10-05 | 2019-09-03 | Asm Ip Holding B.V. | Method for selectively depositing a metallic film on a substrate |
| US10319588B2 (en) | 2017-10-10 | 2019-06-11 | Asm Ip Holding B.V. | Method for depositing a metal chalcogenide on a substrate by cyclical deposition |
| US10923344B2 (en) | 2017-10-30 | 2021-02-16 | Asm Ip Holding B.V. | Methods for forming a semiconductor structure and related semiconductor structures |
| US10910262B2 (en) | 2017-11-16 | 2021-02-02 | Asm Ip Holding B.V. | Method of selectively depositing a capping layer structure on a semiconductor device structure |
| KR102443047B1 (en) | 2017-11-16 | 2022-09-14 | 에이에스엠 아이피 홀딩 비.브이. | Method of processing a substrate and a device manufactured by the same |
| US11022879B2 (en) | 2017-11-24 | 2021-06-01 | Asm Ip Holding B.V. | Method of forming an enhanced unexposed photoresist layer |
| WO2019103613A1 (en) | 2017-11-27 | 2019-05-31 | Asm Ip Holding B.V. | A storage device for storing wafer cassettes for use with a batch furnace |
| KR102633318B1 (en) | 2017-11-27 | 2024-02-05 | 에이에스엠 아이피 홀딩 비.브이. | Devices with clean compact zones |
| US10872771B2 (en) | 2018-01-16 | 2020-12-22 | Asm Ip Holding B. V. | Method for depositing a material film on a substrate within a reaction chamber by a cyclical deposition process and related device structures |
| TWI799494B (en) | 2018-01-19 | 2023-04-21 | 荷蘭商Ａｓｍ 智慧財產控股公司 | Deposition method |
| CN111630203A (en) | 2018-01-19 | 2020-09-04 | Asm Ip私人控股有限公司 | Method for depositing gap filling layer by plasma auxiliary deposition |
| USD903477S1 (en) | 2018-01-24 | 2020-12-01 | Asm Ip Holdings B.V. | Metal clamp |
| US11018047B2 (en) | 2018-01-25 | 2021-05-25 | Asm Ip Holding B.V. | Hybrid lift pin |
| USD880437S1 (en) | 2018-02-01 | 2020-04-07 | Asm Ip Holding B.V. | Gas supply plate for semiconductor manufacturing apparatus |
| US11081345B2 (en) | 2018-02-06 | 2021-08-03 | Asm Ip Holding B.V. | Method of post-deposition treatment for silicon oxide film |
| US10896820B2 (en) | 2018-02-14 | 2021-01-19 | Asm Ip Holding B.V. | Method for depositing a ruthenium-containing film on a substrate by a cyclical deposition process |
| CN116732497A (en) | 2018-02-14 | 2023-09-12 | Asm Ip私人控股有限公司 | Method for depositing ruthenium-containing films on substrates by cyclical deposition processes |
| US10731249B2 (en) | 2018-02-15 | 2020-08-04 | Asm Ip Holding B.V. | Method of forming a transition metal containing film on a substrate by a cyclical deposition process, a method for supplying a transition metal halide compound to a reaction chamber, and related vapor deposition apparatus |
| KR102636427B1 (en) | 2018-02-20 | 2024-02-13 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing method and apparatus |
| US10658181B2 (en) | 2018-02-20 | 2020-05-19 | Asm Ip Holding B.V. | Method of spacer-defined direct patterning in semiconductor fabrication |
| US10975470B2 (en) | 2018-02-23 | 2021-04-13 | Asm Ip Holding B.V. | Apparatus for detecting or monitoring for a chemical precursor in a high temperature environment |
| US11473195B2 (en) | 2018-03-01 | 2022-10-18 | Asm Ip Holding B.V. | Semiconductor processing apparatus and a method for processing a substrate |
| US11629406B2 (en) | 2018-03-09 | 2023-04-18 | Asm Ip Holding B.V. | Semiconductor processing apparatus comprising one or more pyrometers for measuring a temperature of a substrate during transfer of the substrate |
| US11114283B2 (en) | 2018-03-16 | 2021-09-07 | Asm Ip Holding B.V. | Reactor, system including the reactor, and methods of manufacturing and using same |
| KR102646467B1 (en) | 2018-03-27 | 2024-03-11 | 에이에스엠 아이피 홀딩 비.브이. | Method of forming an electrode on a substrate and a semiconductor device structure including an electrode |
| US11088002B2 (en) | 2018-03-29 | 2021-08-10 | Asm Ip Holding B.V. | Substrate rack and a substrate processing system and method |
| US11230766B2 (en) | 2018-03-29 | 2022-01-25 | Asm Ip Holding B.V. | Substrate processing apparatus and method |
| KR102501472B1 (en) | 2018-03-30 | 2023-02-20 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing method |
| KR20190128558A (en) | 2018-05-08 | 2019-11-18 | 에이에스엠 아이피 홀딩 비.브이. | Methods for depositing an oxide film on a substrate by a cyclical deposition process and related device structures |
| TWI816783B (en) | 2018-05-11 | 2023-10-01 | 荷蘭商Ａｓｍ 智慧財產控股公司 | Methods for forming a doped metal carbide film on a substrate and related semiconductor device structures |
| KR102596988B1 (en) | 2018-05-28 | 2023-10-31 | 에이에스엠 아이피 홀딩 비.브이. | Method of processing a substrate and a device manufactured by the same |
| US11718913B2 (en) | 2018-06-04 | 2023-08-08 | Asm Ip Holding B.V. | Gas distribution system and reactor system including same |
| TW202013553A (en) | 2018-06-04 | 2020-04-01 | 荷蘭商Ａｓｍ 智慧財產控股公司 | Wafer handling chamber with moisture reduction |
| US11286562B2 (en) | 2018-06-08 | 2022-03-29 | Asm Ip Holding B.V. | Gas-phase chemical reactor and method of using same |
| US10797133B2 (en) | 2018-06-21 | 2020-10-06 | Asm Ip Holding B.V. | Method for depositing a phosphorus doped silicon arsenide film and related semiconductor device structures |
| KR102568797B1 (en) | 2018-06-21 | 2023-08-21 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing system |
| CN112292478A (en) | 2018-06-27 | 2021-01-29 | Asm Ip私人控股有限公司 | Cyclic deposition methods for forming metal-containing materials and films and structures containing metal-containing materials |
| CN112292477A (en) | 2018-06-27 | 2021-01-29 | Asm Ip私人控股有限公司 | Cyclic deposition methods for forming metal-containing materials and films and structures containing metal-containing materials |
| KR20200002519A (en) | 2018-06-29 | 2020-01-08 | 에이에스엠 아이피 홀딩 비.브이. | Method for depositing a thin film and manufacturing a semiconductor device |
| US10612136B2 (en) | 2018-06-29 | 2020-04-07 | ASM IP Holding, B.V. | Temperature-controlled flange and reactor system including same |
| US10755922B2 (en) | 2018-07-03 | 2020-08-25 | Asm Ip Holding B.V. | Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition |
| US10388513B1 (en) | 2018-07-03 | 2019-08-20 | Asm Ip Holding B.V. | Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition |
| US10767789B2 (en) | 2018-07-16 | 2020-09-08 | Asm Ip Holding B.V. | Diaphragm valves, valve components, and methods for forming valve components |
| US11053591B2 (en) | 2018-08-06 | 2021-07-06 | Asm Ip Holding B.V. | Multi-port gas injection system and reactor system including same |
| US10883175B2 (en) | 2018-08-09 | 2021-01-05 | Asm Ip Holding B.V. | Vertical furnace for processing substrates and a liner for use therein |
| US10829852B2 (en) | 2018-08-16 | 2020-11-10 | Asm Ip Holding B.V. | Gas distribution device for a wafer processing apparatus |
| US11430674B2 (en) | 2018-08-22 | 2022-08-30 | Asm Ip Holding B.V. | Sensor array, apparatus for dispensing a vapor phase reactant to a reaction chamber and related methods |
| KR20200030162A (en) | 2018-09-11 | 2020-03-20 | 에이에스엠 아이피 홀딩 비.브이. | Method for deposition of a thin film |
| US11024523B2 (en) | 2018-09-11 | 2021-06-01 | Asm Ip Holding B.V. | Substrate processing apparatus and method |
| US11049751B2 (en) | 2018-09-14 | 2021-06-29 | Asm Ip Holding B.V. | Cassette supply system to store and handle cassettes and processing apparatus equipped therewith |
| CN110970344A (en) | 2018-10-01 | 2020-04-07 | Asm Ip控股有限公司 | Substrate holding apparatus, system including the same, and method of using the same |
| US11232963B2 (en) | 2018-10-03 | 2022-01-25 | Asm Ip Holding B.V. | Substrate processing apparatus and method |
| KR102592699B1 (en) | 2018-10-08 | 2023-10-23 | 에이에스엠 아이피 홀딩 비.브이. | Substrate support unit and apparatuses for depositing thin film and processing the substrate including the same |
| US10847365B2 (en) | 2018-10-11 | 2020-11-24 | Asm Ip Holding B.V. | Method of forming conformal silicon carbide film by cyclic CVD |
| US10811256B2 (en) | 2018-10-16 | 2020-10-20 | Asm Ip Holding B.V. | Method for etching a carbon-containing feature |
| KR102605121B1 (en) | 2018-10-19 | 2023-11-23 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus and substrate processing method |
| KR102546322B1 (en) | 2018-10-19 | 2023-06-21 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus and substrate processing method |
| USD948463S1 (en) | 2018-10-24 | 2022-04-12 | Asm Ip Holding B.V. | Susceptor for semiconductor substrate supporting apparatus |
| US11087997B2 (en) | 2018-10-31 | 2021-08-10 | Asm Ip Holding B.V. | Substrate processing apparatus for processing substrates |
| KR20200051105A (en) | 2018-11-02 | 2020-05-13 | 에이에스엠 아이피 홀딩 비.브이. | Substrate support unit and substrate processing apparatus including the same |
| US11572620B2 (en) | 2018-11-06 | 2023-02-07 | Asm Ip Holding B.V. | Methods for selectively depositing an amorphous silicon film on a substrate |
| US11031242B2 (en) | 2018-11-07 | 2021-06-08 | Asm Ip Holding B.V. | Methods for depositing a boron doped silicon germanium film |
| US10847366B2 (en) | 2018-11-16 | 2020-11-24 | Asm Ip Holding B.V. | Methods for depositing a transition metal chalcogenide film on a substrate by a cyclical deposition process |
| US10818758B2 (en) | 2018-11-16 | 2020-10-27 | Asm Ip Holding B.V. | Methods for forming a metal silicate film on a substrate in a reaction chamber and related semiconductor device structures |
| US10559458B1 (en) | 2018-11-26 | 2020-02-11 | Asm Ip Holding B.V. | Method of forming oxynitride film |
| US11217444B2 (en) | 2018-11-30 | 2022-01-04 | Asm Ip Holding B.V. | Method for forming an ultraviolet radiation responsive metal oxide-containing film |
| KR102636428B1 (en) | 2018-12-04 | 2024-02-13 | 에이에스엠 아이피 홀딩 비.브이. | A method for cleaning a substrate processing apparatus |
| US11158513B2 (en) | 2018-12-13 | 2021-10-26 | Asm Ip Holding B.V. | Methods for forming a rhenium-containing film on a substrate by a cyclical deposition process and related semiconductor device structures |
| JP2020096183A (en) | 2018-12-14 | 2020-06-18 | エーエスエム・アイピー・ホールディング・ベー・フェー | Method of forming device structure using selective deposition of gallium nitride, and system for the same |
| TWI819180B (en) | 2019-01-17 | 2023-10-21 | 荷蘭商Ａｓｍ 智慧財產控股公司 | Methods of forming a transition metal containing film on a substrate by a cyclical deposition process |
| KR20200091543A (en) | 2019-01-22 | 2020-07-31 | 에이에스엠 아이피 홀딩 비.브이. | Semiconductor processing device |
| CN111524788B (en) | 2019-02-01 | 2023-11-24 | Asm Ip私人控股有限公司 | Method for topologically selective film formation of silicon oxide |
| TW202044325A (en) | 2019-02-20 | 2020-12-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method of filling a recess formed within a surface of a substrate, semiconductor structure formed according to the method, and semiconductor processing apparatus |
| KR102626263B1 (en) | 2019-02-20 | 2024-01-16 | 에이에스엠 아이피 홀딩 비.브이. | Cyclical deposition method including treatment step and apparatus for same |
| KR20200102357A (en) | 2019-02-20 | 2020-08-31 | 에이에스엠 아이피 홀딩 비.브이. | Apparatus and methods for plug fill deposition in 3-d nand applications |
| TW202104632A (en) | 2019-02-20 | 2021-02-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Cyclical deposition method and apparatus for filling a recess formed within a substrate surface |
| TW202100794A (en) | 2019-02-22 | 2021-01-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Substrate processing apparatus and method for processing substrate |
| KR20200108243A (en) | 2019-03-08 | 2020-09-17 | 에이에스엠 아이피 홀딩 비.브이. | Structure Including SiOC Layer and Method of Forming Same |
| KR20200108242A (en) | 2019-03-08 | 2020-09-17 | 에이에스엠 아이피 홀딩 비.브이. | Method for Selective Deposition of Silicon Nitride Layer and Structure Including Selectively-Deposited Silicon Nitride Layer |
| KR20200108248A (en) | 2019-03-08 | 2020-09-17 | 에이에스엠 아이피 홀딩 비.브이. | STRUCTURE INCLUDING SiOCN LAYER AND METHOD OF FORMING SAME |
| US11192091B2 (en) * | 2019-03-22 | 2021-12-07 | The Hong Kong University Of Science And Technology | Palladium-ruthenium alloys for electrolyzers |
| JP2020167398A (en) | 2019-03-28 | 2020-10-08 | エーエスエム・アイピー・ホールディング・ベー・フェー | Door opener and substrate processing apparatus provided therewith |
| KR20200116855A (en) | 2019-04-01 | 2020-10-13 | 에이에스엠 아이피 홀딩 비.브이. | Method of manufacturing semiconductor device |
| KR20200123380A (en) | 2019-04-19 | 2020-10-29 | 에이에스엠 아이피 홀딩 비.브이. | Layer forming method and apparatus |
| KR20200125453A (en) | 2019-04-24 | 2020-11-04 | 에이에스엠 아이피 홀딩 비.브이. | Gas-phase reactor system and method of using same |
| KR20200130118A (en) | 2019-05-07 | 2020-11-18 | 에이에스엠 아이피 홀딩 비.브이. | Method for Reforming Amorphous Carbon Polymer Film |
| KR20200130121A (en) | 2019-05-07 | 2020-11-18 | 에이에스엠 아이피 홀딩 비.브이. | Chemical source vessel with dip tube |
| KR20200130652A (en) | 2019-05-10 | 2020-11-19 | 에이에스엠 아이피 홀딩 비.브이. | Method of depositing material onto a surface and structure formed according to the method |
| JP2020188255A (en) | 2019-05-16 | 2020-11-19 | エーエスエム アイピー ホールディング ビー．ブイ． | Wafer boat handling device, vertical batch furnace, and method |
| USD975665S1 (en) | 2019-05-17 | 2023-01-17 | Asm Ip Holding B.V. | Susceptor shaft |
| USD947913S1 (en) | 2019-05-17 | 2022-04-05 | Asm Ip Holding B.V. | Susceptor shaft |
| USD935572S1 (en) | 2019-05-24 | 2021-11-09 | Asm Ip Holding B.V. | Gas channel plate |
| USD922229S1 (en) | 2019-06-05 | 2021-06-15 | Asm Ip Holding B.V. | Device for controlling a temperature of a gas supply unit |
| KR20200141002A (en) | 2019-06-06 | 2020-12-17 | 에이에스엠 아이피 홀딩 비.브이. | Method of using a gas-phase reactor system including analyzing exhausted gas |
| KR20200143254A (en) | 2019-06-11 | 2020-12-23 | 에이에스엠 아이피 홀딩 비.브이. | Method of forming an electronic structure using an reforming gas, system for performing the method, and structure formed using the method |
| USD944946S1 (en) | 2019-06-14 | 2022-03-01 | Asm Ip Holding B.V. | Shower plate |
| USD931978S1 (en) | 2019-06-27 | 2021-09-28 | Asm Ip Holding B.V. | Showerhead vacuum transport |
| KR20210005515A (en) | 2019-07-03 | 2021-01-14 | 에이에스엠 아이피 홀딩 비.브이. | Temperature control assembly for substrate processing apparatus and method of using same |
| JP2021015791A (en) | 2019-07-09 | 2021-02-12 | エーエスエム アイピー ホールディング ビー．ブイ． | Plasma device and substrate processing method using coaxial waveguide |
| CN112216646A (en) | 2019-07-10 | 2021-01-12 | Asm Ip私人控股有限公司 | Substrate supporting assembly and substrate processing device comprising same |
| KR20210010307A (en) | 2019-07-16 | 2021-01-27 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus |
| KR20210010820A (en) | 2019-07-17 | 2021-01-28 | 에이에스엠 아이피 홀딩 비.브이. | Methods of forming silicon germanium structures |
| KR20210010816A (en) | 2019-07-17 | 2021-01-28 | 에이에스엠 아이피 홀딩 비.브이. | Radical assist ignition plasma system and method |
| US11643724B2 (en) | 2019-07-18 | 2023-05-09 | Asm Ip Holding B.V. | Method of forming structures using a neutral beam |
| CN112242296A (en) | 2019-07-19 | 2021-01-19 | Asm Ip私人控股有限公司 | Method of forming topologically controlled amorphous carbon polymer films |
| CN112309843A (en) | 2019-07-29 | 2021-02-02 | Asm Ip私人控股有限公司 | Selective deposition method for achieving high dopant doping |
| CN112309900A (en) | 2019-07-30 | 2021-02-02 | Asm Ip私人控股有限公司 | Substrate processing apparatus |
| CN112309899A (en) | 2019-07-30 | 2021-02-02 | Asm Ip私人控股有限公司 | Substrate processing apparatus |
| US11227782B2 (en) | 2019-07-31 | 2022-01-18 | Asm Ip Holding B.V. | Vertical batch furnace assembly |
| US11587815B2 (en) | 2019-07-31 | 2023-02-21 | Asm Ip Holding B.V. | Vertical batch furnace assembly |
| US11587814B2 (en) | 2019-07-31 | 2023-02-21 | Asm Ip Holding B.V. | Vertical batch furnace assembly |
| KR20210018759A (en) | 2019-08-05 | 2021-02-18 | 에이에스엠 아이피 홀딩 비.브이. | Liquid level sensor for a chemical source vessel |
| USD965044S1 (en) | 2019-08-19 | 2022-09-27 | Asm Ip Holding B.V. | Susceptor shaft |
| USD965524S1 (en) | 2019-08-19 | 2022-10-04 | Asm Ip Holding B.V. | Susceptor support |
| JP2021031769A (en) | 2019-08-21 | 2021-03-01 | エーエスエム アイピー ホールディング ビー．ブイ． | Production apparatus of mixed gas of film deposition raw material and film deposition apparatus |
| KR20210024423A (en) | 2019-08-22 | 2021-03-05 | 에이에스엠 아이피 홀딩 비.브이. | Method for forming a structure with a hole |
| USD979506S1 (en) | 2019-08-22 | 2023-02-28 | Asm Ip Holding B.V. | Insulator |
| USD930782S1 (en) | 2019-08-22 | 2021-09-14 | Asm Ip Holding B.V. | Gas distributor |
| USD940837S1 (en) | 2019-08-22 | 2022-01-11 | Asm Ip Holding B.V. | Electrode |
| USD949319S1 (en) | 2019-08-22 | 2022-04-19 | Asm Ip Holding B.V. | Exhaust duct |
| KR20210024420A (en) | 2019-08-23 | 2021-03-05 | 에이에스엠 아이피 홀딩 비.브이. | Method for depositing silicon oxide film having improved quality by peald using bis(diethylamino)silane |
| US11286558B2 (en) | 2019-08-23 | 2022-03-29 | Asm Ip Holding B.V. | Methods for depositing a molybdenum nitride film on a surface of a substrate by a cyclical deposition process and related semiconductor device structures including a molybdenum nitride film |
| KR20210029090A (en) | 2019-09-04 | 2021-03-15 | 에이에스엠 아이피 홀딩 비.브이. | Methods for selective deposition using a sacrificial capping layer |
| KR20210029663A (en) | 2019-09-05 | 2021-03-16 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus |
| US11562901B2 (en) | 2019-09-25 | 2023-01-24 | Asm Ip Holding B.V. | Substrate processing method |
| CN112593212B (en) | 2019-10-02 | 2023-12-22 | Asm Ip私人控股有限公司 | Method for forming topologically selective silicon oxide film by cyclic plasma enhanced deposition process |
| TW202129060A (en) | 2019-10-08 | 2021-08-01 | 荷蘭商Ａｓｍ Ｉｐ控股公司 | Substrate processing device, and substrate processing method |
| KR20210043460A (en) | 2019-10-10 | 2021-04-21 | 에이에스엠 아이피 홀딩 비.브이. | Method of forming a photoresist underlayer and structure including same |
| KR20210045930A (en) | 2019-10-16 | 2021-04-27 | 에이에스엠 아이피 홀딩 비.브이. | Method of Topology-Selective Film Formation of Silicon Oxide |
| US11637014B2 (en) | 2019-10-17 | 2023-04-25 | Asm Ip Holding B.V. | Methods for selective deposition of doped semiconductor material |
| KR20210047808A (en) | 2019-10-21 | 2021-04-30 | 에이에스엠 아이피 홀딩 비.브이. | Apparatus and methods for selectively etching films |
| US11646205B2 (en) | 2019-10-29 | 2023-05-09 | Asm Ip Holding B.V. | Methods of selectively forming n-type doped material on a surface, systems for selectively forming n-type doped material, and structures formed using same |
| KR20210054983A (en) | 2019-11-05 | 2021-05-14 | 에이에스엠 아이피 홀딩 비.브이. | Structures with doped semiconductor layers and methods and systems for forming same |
| US11501968B2 (en) | 2019-11-15 | 2022-11-15 | Asm Ip Holding B.V. | Method for providing a semiconductor device with silicon filled gaps |
| KR20210062561A (en) | 2019-11-20 | 2021-05-31 | 에이에스엠 아이피 홀딩 비.브이. | Method of depositing carbon-containing material on a surface of a substrate, structure formed using the method, and system for forming the structure |
| CN112951697A (en) | 2019-11-26 | 2021-06-11 | Asm Ip私人控股有限公司 | Substrate processing apparatus |
| KR20210065848A (en) | 2019-11-26 | 2021-06-04 | 에이에스엠 아이피 홀딩 비.브이. | Methods for selectivley forming a target film on a substrate comprising a first dielectric surface and a second metallic surface |
| CN112885693A (en) | 2019-11-29 | 2021-06-01 | Asm Ip私人控股有限公司 | Substrate processing apparatus |
| CN112885692A (en) | 2019-11-29 | 2021-06-01 | Asm Ip私人控股有限公司 | Substrate processing apparatus |
| JP2021090042A (en) | 2019-12-02 | 2021-06-10 | エーエスエム アイピー ホールディング ビー．ブイ． | Substrate processing apparatus and substrate processing method |
| KR20210070898A (en) | 2019-12-04 | 2021-06-15 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus |
| US11885013B2 (en) | 2019-12-17 | 2024-01-30 | Asm Ip Holding B.V. | Method of forming vanadium nitride layer and structure including the vanadium nitride layer |
| KR20210080214A (en) | 2019-12-19 | 2021-06-30 | 에이에스엠 아이피 홀딩 비.브이. | Methods for filling a gap feature on a substrate and related semiconductor structures |
| KR20210095050A (en) | 2020-01-20 | 2021-07-30 | 에이에스엠 아이피 홀딩 비.브이. | Method of forming thin film and method of modifying surface of thin film |
| TW202130846A (en) | 2020-02-03 | 2021-08-16 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method of forming structures including a vanadium or indium layer |
| TW202146882A (en) | 2020-02-04 | 2021-12-16 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method of verifying an article, apparatus for verifying an article, and system for verifying a reaction chamber |
| US11776846B2 (en) | 2020-02-07 | 2023-10-03 | Asm Ip Holding B.V. | Methods for depositing gap filling fluids and related systems and devices |
| US11781243B2 (en) | 2020-02-17 | 2023-10-10 | Asm Ip Holding B.V. | Method for depositing low temperature phosphorous-doped silicon |
| KR20210116249A (en) | 2020-03-11 | 2021-09-27 | 에이에스엠 아이피 홀딩 비.브이. | lockout tagout assembly and system and method of using same |
| KR20210116240A (en) | 2020-03-11 | 2021-09-27 | 에이에스엠 아이피 홀딩 비.브이. | Substrate handling device with adjustable joints |
| KR20210124042A (en) | 2020-04-02 | 2021-10-14 | 에이에스엠 아이피 홀딩 비.브이. | Thin film forming method |
| TW202146689A (en) | 2020-04-03 | 2021-12-16 | 荷蘭商Ａｓｍ Ｉｐ控股公司 | Method for forming barrier layer and method for manufacturing semiconductor device |
| TW202145344A (en) | 2020-04-08 | 2021-12-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Apparatus and methods for selectively etching silcon oxide films |
| US11821078B2 (en) | 2020-04-15 | 2023-11-21 | Asm Ip Holding B.V. | Method for forming precoat film and method for forming silicon-containing film |
| US11898243B2 (en) | 2020-04-24 | 2024-02-13 | Asm Ip Holding B.V. | Method of forming vanadium nitride-containing layer |
| KR20210132605A (en) | 2020-04-24 | 2021-11-04 | 에이에스엠 아이피 홀딩 비.브이. | Vertical batch furnace assembly comprising a cooling gas supply |
| KR20210132600A (en) | 2020-04-24 | 2021-11-04 | 에이에스엠 아이피 홀딩 비.브이. | Methods and systems for depositing a layer comprising vanadium, nitrogen, and a further element |
| KR20210134869A (en) | 2020-05-01 | 2021-11-11 | 에이에스엠 아이피 홀딩 비.브이. | Fast FOUP swapping with a FOUP handler |
| KR20210141379A (en) | 2020-05-13 | 2021-11-23 | 에이에스엠 아이피 홀딩 비.브이. | Laser alignment fixture for a reactor system |
| KR20210143653A (en) | 2020-05-19 | 2021-11-29 | 에이에스엠 아이피 홀딩 비.브이. | Substrate processing apparatus |
| KR20210145078A (en) | 2020-05-21 | 2021-12-01 | 에이에스엠 아이피 홀딩 비.브이. | Structures including multiple carbon layers and methods of forming and using same |
| TW202201602A (en) | 2020-05-29 | 2022-01-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Substrate processing device |
| TW202218133A (en) | 2020-06-24 | 2022-05-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method for forming a layer provided with silicon |
| TW202217953A (en) | 2020-06-30 | 2022-05-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Substrate processing method |
| TW202219628A (en) | 2020-07-17 | 2022-05-16 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Structures and methods for use in photolithography |
| TW202204662A (en) | 2020-07-20 | 2022-02-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method and system for depositing molybdenum layers |
| TW202212623A (en) | 2020-08-26 | 2022-04-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method of forming metal silicon oxide layer and metal silicon oxynitride layer, semiconductor structure, and system |
| USD990534S1 (en) | 2020-09-11 | 2023-06-27 | Asm Ip Holding B.V. | Weighted lift pin |
| USD1012873S1 (en) | 2020-09-24 | 2024-01-30 | Asm Ip Holding B.V. | Electrode for semiconductor processing apparatus |
| TW202229613A (en) | 2020-10-14 | 2022-08-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method of depositing material on stepped structure |
| TW202217037A (en) | 2020-10-22 | 2022-05-01 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method of depositing vanadium metal, structure, device and a deposition assembly |
| TW202223136A (en) | 2020-10-28 | 2022-06-16 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Method for forming layer on substrate, and semiconductor processing system |
| TW202235675A (en) | 2020-11-30 | 2022-09-16 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Injector, and substrate processing apparatus |
| US11946137B2 (en) | 2020-12-16 | 2024-04-02 | Asm Ip Holding B.V. | Runout and wobble measurement fixtures |
| TW202231903A (en) | 2020-12-22 | 2022-08-16 | 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 | Transition metal deposition method, transition metal layer, and deposition assembly for depositing transition metal on substrate |
| USD980813S1 (en) | 2021-05-11 | 2023-03-14 | Asm Ip Holding B.V. | Gas flow control plate for substrate processing apparatus |
| USD980814S1 (en) | 2021-05-11 | 2023-03-14 | Asm Ip Holding B.V. | Gas distributor for substrate processing apparatus |
| USD981973S1 (en) | 2021-05-11 | 2023-03-28 | Asm Ip Holding B.V. | Reactor wall for substrate processing apparatus |
| USD990441S1 (en) | 2021-09-07 | 2023-06-27 | Asm Ip Holding B.V. | Gas flow control plate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1409260A (en) * | 1971-12-29 | 1975-10-08 | Exxon Research Engineering Co | Fuel cell having non-alloyed palladium-ruthenium anode catalyst |
| US4460660A (en) * | 1982-12-22 | 1984-07-17 | Rca Corporation | Negative hydrogen electrode comprising an alloy palladium and rutherium |
| GB0614909D0 (en) * | 2006-07-27 | 2006-09-06 | Johnson Matthey Plc | Catalyst |
| US9452417B2 (en) * | 2012-09-18 | 2016-09-27 | Japan Science And Technology Agency | Catalyst using Pd-Ru solid solution alloy fine particles |
| EP3192596A4 (en) * | 2014-09-09 | 2018-04-11 | Kyoto University | Alloy microparticles and method for producing same, alloy microparticle cluster, catalyst, and method for producing same |
| JP6541373B2 (en) * | 2015-02-28 | 2019-07-10 | 株式会社ノリタケカンパニーリミテド | PdRu alloy electrode material and method of manufacturing the same |
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