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WO2021219606A1 - Procédé de production de microstructures et nanostructures - Google Patents

Procédé de production de microstructures et nanostructures Download PDF

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Publication number
WO2021219606A1
WO2021219606A1 PCT/EP2021/060934 EP2021060934W WO2021219606A1 WO 2021219606 A1 WO2021219606 A1 WO 2021219606A1 EP 2021060934 W EP2021060934 W EP 2021060934W WO 2021219606 A1 WO2021219606 A1 WO 2021219606A1
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WO
WIPO (PCT)
Prior art keywords
steps
aluminum substrate
nanostructures
aluminum oxide
nanowires
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2021/060934
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German (de)
English (en)
Inventor
Selma Hansal
Wolfgang Hansal
Gabriela Sirbu
Susanna Anna Weiß
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RENA Technologies Austria GmbH
Original Assignee
RENA Technologies Austria GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RENA Technologies Austria GmbH filed Critical RENA Technologies Austria GmbH
Publication of WO2021219606A1 publication Critical patent/WO2021219606A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/006—Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Definitions

  • the present invention relates to a method for producing metallic micro or nanostructures, preferably nanowires, comprising the steps of providing an aluminum substrate; Oxidation of the aluminum substrate by applying an electrical voltage in an electrolyte; Breaking through the barrier layer by gradually reducing the voltage on the aluminum substrate; electrochemical deposition of micro or nanostructures in the pores of the aluminum oxide layer; Dissolving the aluminum oxide layer surrounding the micro- or nanostructures by adding a solvent for aluminum oxide and releasing the micro- or nanostructures.
  • nanowires are of particular industrial importance.
  • a template i.e. a template
  • a suitable template is e.g. anodic, porous aluminum oxide, in which the corresponding material (e.g. galvanically) is built up and deposited.
  • an aluminum substrate can be anodized in a solution containing oxalic acid.
  • the self-organizing layer forms orderly, parallel pores.
  • a two-step procedure can improve the regular structure of the pores.
  • the pores in the substrate are insulating, chemically stable and they form an ideal template for the deposition of nanowires.
  • the pore diameter can be adjusted using a suitable electrolyte (usually based on organic or inorganic acids) and the corresponding current parameters. It has been observed that, under certain conditions, current oscillations occur during the anodizing process, which manifest themselves in a corrugated shape of the nanotubes.
  • the pore diameter in the template can, however, also be adjusted by chemical etching.
  • the material is removed with diluted acids and the pore diameter is expanded.
  • the distance between the pores can be adjusted by the electrolyte used.
  • the nucleation for pores usually takes place on surface defects.
  • a high-purity aluminum substrate with 99.99 to 99.999% by weight of aluminum is required for a template made of aluminum oxide in order to produce regular pores.
  • Such substrates are extremely expensive and therefore not very suitable for the commercial production of nanowires.
  • the use of less pure aluminum leads to irregular pores.
  • the metallic structure and the surface structures are reflected in the pore growth (e.g. in the case of rolled foils).
  • the anodically produced porous aluminum oxide layers (PAA, porous anodic alumina) have a barrier layer made of aluminum oxide on the side oriented towards the substrate, which barrier layer insulates the substrate material.
  • the barrier layer prevents the electrodeposition of metals in the pores, as it insulates the substrate material as a non-conductive insulator.
  • this barrier layer can be removed by increasing the pH locally. However, this can also damage the PAA layer or the pores. Similar results could be achieved on ITO / Al substrates or on aluminum substrates by chemical etching with phosphoric acid. This allows the conductive substrate to serve as a cathode for the deposition. Alternatively, the entire PAA layer can be coated with gold, whereby the substrate is dissolved and the nanowires are built up using the upside-down method.
  • EP 3 431 637 A1 describes a method for producing metallic microstructures or nanostructures which are formed on a substrate and finally released.
  • the substrate is oxidized by applying an electrical voltage.
  • CH 709 962 describes a method for depositing metals on an aluminum oxide layer, the oxide layer having nanopores.
  • US 2014/342236 A1 describes a method for producing a battery electrode with a nanoporous structure.
  • EP 2 980 014 A1 describes nanowire clusters with different structures in different areas, the nanowires being connected to one another in areas.
  • the known processes for the production of metallic micro- or nanostructures are extremely complex, require very pure substrates and the production rate is low.
  • the object of the present invention is to provide a method for producing nanowires which is tolerant of impurities in the metal substrate material, which does not require expensive, high-purity aluminum or Si wafers, which would make the process uneconomical and nevertheless have high production rates.
  • step (e) optionally subsequent dissolving of the barrier layer formed again in step (d);
  • step (j) If necessary, repeating steps (a) to (h), with rinsing steps being provided between individual or several steps (a) to (i), the method according to the invention being a continuous belt process in which the aluminum substrate forms the belt and each of steps (b), (d), (e), (f), (g), (i) taking place in an active basin and any rinsing steps taking place in a sink.
  • Cleaning steps preferably rinsing with a cleaning agent, can be provided between steps (a) to (i).
  • the technical implementation takes place in the form of a conveyor system.
  • an aluminum substrate is provided in step (a).
  • the aluminum substrate is a metal belt, for example an endless belt.
  • step (b) the aluminum substrate is oxidized by applying an electrical voltage in an electrolyte.
  • an aluminum oxide layer is formed which has a barrier layer which is adjacent to the aluminum substrate and is largely free of pores.
  • the aluminum oxide layer has an aluminum oxide layer with pores, which is adjacent to the barrier layer.
  • Step (b) is preferably carried out by anodic polarization.
  • step (c) the barrier layer is broken by gradually reducing the voltage on the aluminum substrate. This is preferably done in such a way that the voltage is reduced in a step (cl) and the voltage is kept constant for a period of time in a step (c2), steps (cl) and (c2) preferably being repeated at least once. As a result, the pores of the aluminum oxide layer extend through the barrier layer to the aluminum substrate.
  • step (d) the pores can be enlarged by adding a solvent.
  • the solvent is preferably a dilute mineral acid, for example dilute phosphoric acid.
  • a barrier layer can again form. This can optionally be dissolved, for example with zincate (step e).
  • metallic microstructures or nanostructures are deposited by applying a voltage to the substrate and suitable electrolyte solutions.
  • the electrochemically deposited nanowires are preferably an alloy containing at least one of the metals Ni, Co or Fe.
  • the metals to be deposited or their alloys (in this case Ni, Co or Fe), as well as inert materials such as noble metals or carbon, are suitable as counter electrodes in this step.
  • Electrolytes can be used as electrolytes, including metal ions that correspond to the reduced metal in the metallic micro- or nanostructure. The corresponding metal ions in the electrolyte are required for the deposition of nanowires made of Ni, Co, Fe and their alloys.
  • Electrolytes with Ni 2+ ions can be used for the deposition of Ni nanowires, electrolytes with Ni 2+ and Co 2+ ions for NiCo nanowires and an electrolyte comprising Ni 2+ , Co 2+ and Fe 2+ for CoNiFe nanowires Ions.
  • the following table 1 shows concentrations of electrolytes for the corresponding alloys.
  • Concentration Metallic micro- or nanostructures preferably
  • the metallic micro- or nanostructures, preferably nanowires, now deposited in the pores of the aluminum oxide layer are surrounded by the aluminum oxide layer of the pores.
  • the aluminum oxide layer is dissolved by adding a solvent in step (g).
  • a solvent for example, chromic acid or an alkaline solution, in particular NaOH, can be added as a solvent.
  • the aluminum substrate can be regenerated in step (i) (e.g. by electropolishing or mechanical processes such as grinding or polishing).
  • All process steps take place on a tape that is formed from the original aluminum substrate.
  • the aluminum substrate is a metal strip, the individual steps (b), (c), (d), (e), (f), (g), (i), and any rinsing steps being carried out continuously on the aluminum substrate.
  • Step (h) takes place separately from the aluminum strip and can also be carried out in a continuous operation.
  • Al aluminum substrate
  • BL barrier layer
  • PAA porous aluminum oxide layer
  • FIG. 2a shows a top view of a porous aluminum oxide layer, so that the pores can be seen.
  • top a barrier layer (middle) and a porous aluminum oxide layer (top).
  • NiCo nanowires which, according to the invention, have been deposited and released in an aluminum oxide layer.
  • FIG. 4 shows the cleaned NiCo nanowires from FIG. 3 after cleaning.
  • Fig. 6 shows schematically a belt system for carrying out the invention
  • step (b) the aluminum substrate is oxidized by applying an electrical voltage in an electrolyte, so that the surface of the aluminum substrate is oxidized.
  • a barrier layer is formed which is adjacent to the aluminum substrate and an aluminum oxide layer with pores.
  • This step (b) can be carried out by cathodic polarization.
  • an electrolyte with 3 mol / l oxalic acid in which the aluminum substrate is anodically polarized 60 V at 5-10 ° C.
  • FIG. 1 shows a schematic cross-section through the structure of a template with the aluminum substrate A1 and an aluminum oxide layer arranged thereon, which has a barrier layer BL and a subsequent porous aluminum oxide layer PAA.
  • FIGS. 2a and 2b scanning electron microscope images of the porous aluminum oxide layer and a section through a template with an aluminum substrate layer, a barrier layer and a porous aluminum oxide layer are shown.
  • step (c) The interfering barrier layer is then removed in step (c). A potential reduction of 2 V every 30 s has proven suitable. The barrier layer breaks through. This is mandatory for the later assembly of the nanowires.
  • the pores are widened by adding a solvent, a solution of 5% by weight phosphoric acid being found to be suitable and the pores being widened to the final diameter.
  • the treatment time is e.g. 45 minutes and determines the final diameter (e.g. 80-120 nm).
  • step (d) Since, after step (d), a thin oxide layer is formed again at the pore attachments (new barrier layer), this must be removed before the nanowires are built up. This can be dissolved with zincate according to the following conditions: Ultrasound-assisted treatment at 30 ° C for 40 s in the following solution:
  • step (e) nanowires are deposited by applying a voltage to the substrate and suitable electrolyte solutions.
  • the aluminum oxide layer surrounding the nanowires is dissolved, for example, by chromic acid or NaOH: a) Chromic acid: 0.5 M phosphoric acid and 0.2 M chromium (VI) oxide at 60 ° C for 30 min, then supported by ultrasound for 10 min. In this case, the aluminum substrate is not attacked and can be used for further syntheses. b) NaOH: the PAA layer is removed in a NaOH solution. In this case, the aluminum substrate is also attacked and must be pretreated for further use.
  • the nanowires can now be released. This can be supported by ultrasound cleaning for e.g. 10 minutes in 2.5 M NaOH, 0.5 g / L SDS. The solution stays there overnight. The sample is further purified with water using decanting / centrifuging / dialysis or similar methods. Optionally, the nanowires can be dried in a drying cabinet or by means of lyophilization.
  • the aluminum substrate can be electropolished in step (i), for example in 40.8% by volume H3PO4, 38.8% by volume of ethanol and 20.4% by volume of water at 30 V and 42-45 ° C. for 5 minutes polished or treated using a mechanical process.
  • the process according to the invention is a continuous process, each of steps (b) to (i) taking place in an active basin, it being possible for rinsing to take place in rinsing basins between the steps.
  • the individual steps are shown schematically in FIG. 6.
  • the nanowires are isolated from basin 5 and released and cleaned according to step (i).
  • the nanowires can be transferred from basin 5 to cleaning by means of settling / suctioning, centrifuging or by means of an electromagnet (in the case of magnetic nanowires).
  • the nanowires can be separated or concentrated from the process medium by means of an electromagnet or a continuous centrifuge.
  • step f current parameters from the literature (Tang, "Pulse reversal plating of nickel alloys," Transactions of the Institute of Metal Finishing 85, 2007) were used in step f (FIG. 4). Due to the pulse parameters, which have been optimized for deposition on planar substrates, the nanowires grow together and form an agglomerate that can no longer be separated from one another.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

L'invention concerne un procédé de production de microstructures et nanostructures, de préférence des nanofils, comportant les étapes consistant : (a) à fournir un substrat en aluminium ; (b) à oxyder le substrat en aluminium par application d'une tension électrique dans un électrolyte, une partie du substrat en aluminium étant oxydée afin de former une couche d'oxyde d'aluminium, une couche barrière étant adjacente au substrat en aluminium et comportant une couche d'oxyde d'aluminium qui comporte des pores et est adjacente à la couche barrière ; (c) à traverser la couche barrière par réduction discontinue de la tension sur le substrat en aluminium ; (d) à élargir facultativement les pores par ajout d'un solvant ; (e) à dissoudre facultativement la couche barrière reformée à l'étape (d) ; (f) à déposer électrochimiquement des microstructures ou des nanostructures métalliques, de préférence des nanofils, dans les pores de la couche d'oxyde d'aluminium ; (g) à dissoudre la couche d'oxyde d'aluminium entourant les microstructures ou les nanostructures métalliques, de préférence des nanofils, par ajout d'un solvant de l'oxyde d'aluminium et à libérer les microstructures ou nanostructures métalliques, de préférence des nanofils ; (h) à nettoyer facultativement la suspension de nanofils et, le cas échéant, à la sécher ; (i) à régénérer facultativement le substrat d'aluminium ; et (j) à répéter facultativement les étapes (a) à (h), des étapes de rinçage étant éventuellement effectuées entre des étapes (a) à (i) individuelles ou multiples, le procédé étant un procédé à bande continue dans lequel le substrat d'aluminium forme la bande, chacune des étapes (b), (d), (e), (f), (g), (i), et (j) étant effectuées dans un bassin actif, et toutes les étapes de rinçage possibles étant effectuées dans un bassin de rinçage.
PCT/EP2021/060934 2020-04-27 2021-04-27 Procédé de production de microstructures et nanostructures Ceased WO2021219606A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20171561.2 2020-04-27
EP20171561.2A EP3904561A1 (fr) 2020-04-27 2020-04-27 Procédé de fabrication de micro- et nanostructures

Publications (1)

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WO2021219606A1 true WO2021219606A1 (fr) 2021-11-04

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140342236A1 (en) 2009-08-04 2014-11-20 Ut-Battelle, Llc Scalable fabrication of one-dimensional and three-dimensional, conducting, nanostructured templates for diverse applications such as battery electrodes for next generation batteries
EP2980014A1 (fr) 2014-07-31 2016-02-03 IMEC vzw Procédé de formation d'agrégats de nanofils interconnectés utilisant un gabarit d'oxyde d'alumnium anodique (AAO)
CH709962A2 (de) * 2014-08-05 2016-02-15 Empa Eidgenössische Materialprüfungs Und Forschungsanstalt Elektrochemisches Verfahren zum Herstellen haftender Metallbeschichtungen auf Aluminiumflächen.
EP3431637A1 (fr) 2017-07-18 2019-01-23 IMEC vzw Matériaux solides poreux et leurs procédés de fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140342236A1 (en) 2009-08-04 2014-11-20 Ut-Battelle, Llc Scalable fabrication of one-dimensional and three-dimensional, conducting, nanostructured templates for diverse applications such as battery electrodes for next generation batteries
EP2980014A1 (fr) 2014-07-31 2016-02-03 IMEC vzw Procédé de formation d'agrégats de nanofils interconnectés utilisant un gabarit d'oxyde d'alumnium anodique (AAO)
CH709962A2 (de) * 2014-08-05 2016-02-15 Empa Eidgenössische Materialprüfungs Und Forschungsanstalt Elektrochemisches Verfahren zum Herstellen haftender Metallbeschichtungen auf Aluminiumflächen.
EP3431637A1 (fr) 2017-07-18 2019-01-23 IMEC vzw Matériaux solides poreux et leurs procédés de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TANG: "Pulse reversal plating of nickel alloys", TRANSACTIONS OF THE INSTITUTE OFMETAL FINISHING, 2007, pages 85

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