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WO2010057652A1 - Nanofils à la surface d'un substrat, leur procédé de fabrication et d'utilisation - Google Patents

Nanofils à la surface d'un substrat, leur procédé de fabrication et d'utilisation Download PDF

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Publication number
WO2010057652A1
WO2010057652A1 PCT/EP2009/008277 EP2009008277W WO2010057652A1 WO 2010057652 A1 WO2010057652 A1 WO 2010057652A1 EP 2009008277 W EP2009008277 W EP 2009008277W WO 2010057652 A1 WO2010057652 A1 WO 2010057652A1
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WO
WIPO (PCT)
Prior art keywords
nanowires
nanoparticles
nanoclusters
solution
substrate surface
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/EP2009/008277
Other languages
German (de)
English (en)
Other versions
WO2010057652A8 (fr
Inventor
Stefan Kudera
Eva Bock
Joachim P. Spatz
Liberato Manna
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.)
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Fondazione Istituto Italiano di Tecnologia
Original Assignee
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Fondazione Istituto Italiano di Tecnologia
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 Max Planck Gesellschaft zur Foerderung der Wissenschaften eV, Fondazione Istituto Italiano di Tecnologia filed Critical Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Priority to US13/130,234 priority Critical patent/US20110284820A1/en
Priority to CN200980146632.6A priority patent/CN102301479B/zh
Priority to EP09763848A priority patent/EP2351087A1/fr
Publication of WO2010057652A1 publication Critical patent/WO2010057652A1/fr
Anticipated expiration legal-status Critical
Publication of WO2010057652A8 publication Critical patent/WO2010057652A8/fr
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/10—Shapes, relative sizes or dispositions of the regions of the semiconductor bodies; Shapes of the semiconductor bodies
    • H10D62/117—Shapes of semiconductor bodies
    • H10D62/118—Nanostructure semiconductor bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/10—Shapes, relative sizes or dispositions of the regions of the semiconductor bodies; Shapes of the semiconductor bodies
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/10—Shapes, relative sizes or dispositions of the regions of the semiconductor bodies; Shapes of the semiconductor bodies
    • H10D62/117—Shapes of semiconductor bodies
    • H10D62/118—Nanostructure semiconductor bodies
    • H10D62/119—Nanowire, nanosheet or nanotube semiconductor bodies
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/10—Shapes, relative sizes or dispositions of the regions of the semiconductor bodies; Shapes of the semiconductor bodies
    • H10D62/117—Shapes of semiconductor bodies
    • H10D62/118—Nanostructure semiconductor bodies
    • H10D62/119—Nanowire, nanosheet or nanotube semiconductor bodies
    • H10D62/121—Nanowire, nanosheet or nanotube semiconductor bodies oriented parallel to substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • H10K30/352—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices

Definitions

  • Nanowires and methods for their preparation are used in many technical fields, for example in the Halbleitertechnk, optics and photovoltaic, of great interest and were ei ⁇ ne number of different approaches to sol ⁇ che nanowires, that is fine wire or filament-like structures a typical diameter of 1-100 nm and lengths up to the micrometer range, different from Ma ⁇ terialien, usually made of metals, semi-metals and metal alloys ⁇ , but also from organic compounds to manufacture.
  • the method according to the invention for the production of anchored nanowires on a substrate according to claim 1 does not include any deposition steps from the gas phase and comprises at least the following steps: a) providing a substrate surface with a given two-dimensional geometric arrangement of nanoparticles or nanoclusters; b) contacting the substrate surface with the nanoparticles or nanoclusters with at least one solution of the material forming the nanowires, wherein the material forming the nanowires selectively deposits on the nanoparticles or nanoclusters and continues to grow there.
  • the inventive method further comprises that in step a) the application of a seed material on the nanoparticles or nanoclusters by contacting the substrate surface with a solution of the seed material takes place such that the seed material selectively deposited on the nanoparticles or nanoclusters and that in step b ) selectively deposits the material forming the nanowires on the nanoparticles or nanoclusters provided with seed material and continues to grow there.
  • the substrate surface is basically not particularly limited and may include any material as long as it is stable under the conditions of the process of the present invention and does not interfere with or interfere with the reactions taking place.
  • the substrate can be selected, for example, from glass, silicon, metals, polymers, etc. For certain applications, transparent substrates such as glass or ITO on glass are preferred.
  • the predetermined two-dimensional geometric arrangement of the nanoparticles on the substrate surface has as a characteristic predetermined minimum or average particle spacings, wherein these predetermined particle spacings may be the same in all regions of the substrate surface or different regions may have different predetermined particle spacings.
  • Such a geometric arrangement can in principle be realized with any suitable method of the prior art.
  • the two-dimensional array of nanoparticles or nanoclusters be produced by a micelle-diblock copolymer nanolithography technique as described, for example, in EP 1 027 157 Bl and DE 197 47 815 A1.
  • micellar nanolithography a micellar solution of a block copolymer is deposited onto a substrate, for example by dip coating, and forms an ordered film structure of chemically distinct polymer domains under appropriate conditions on the surface, which depends, inter alia, on the type, molecular weight and concentration of the block copolymer.
  • the micelles in the solution can be loaded with inorganic salts, which can be oxidized or reduced to inorganic nanoparticles after deposition with the polymer film.
  • a substrate surface with a specific geometric arrangement of nanoparticles, including predetermined particle spacings, and a predetermined particle size is an essential framework condition for the method according to the invention.
  • the material of the nanoparticles or nanoclusters is not particularly limited and may include any material known in the art for such nanoparticles.
  • the material is selected from the group consisting of Au, Pt, Pd, Ag, In, Fe, Zr, Al, Co, Ni, Ga, Sn, Zn, Ti, Si, and Ge, and more preferably gold.
  • the nanoparticles are coated in step a) with a seed material, which mediates the adhesion and growth of the actual nanowire material on these nanoparticles.
  • This seed material is preferably selected from the group consisting of Bi, In and alloys of these metals, with Bi being particularly preferred.
  • the seed material may also be dispensable.
  • the coating is typically carried out by immersing the substrate with the nanoparticles, preferably gold nanoparticles, in a hot solution of a salt of the seed material, for example Bi (III) 2-ethylhexanoate for Bi, in a suitable solvent at a temperature in the range of 13O 0 C to 200 0 C, preferably from 160 0 C to 170 0 C.
  • a salt of the seed material for example Bi (III) 2-ethylhexanoate for Bi
  • a suitable solvent at a temperature in the range of 13O 0 C to 200 0 C, preferably from 160 0 C to 170 0 C.
  • the bismuth is selectively deposited on the nanoparticles.
  • the residence time determines the diameter of the bismuth layer on the nanoparticles.
  • the growth process is stopped by withdrawing the substrate from the solution and washing the substrate, for example with isopropanol.
  • the material forming the nanowires is a semiconductor material.
  • the nanowire material is selected from the group consisting of CdSe, CdTe, CdS, PbSe, PbTe, PbS, InP, InAs, GaP, GaAs, ZnO, (ZnMg) O, Si, and doped Si.
  • the substrate with the optionally coated nanoparticles is immersed in at least one solution of the material intended for forming the nanowires.
  • this material is a metal / metalloid or an alloy of metals / semimetals and the solution of this material used in step b) of the invention comprises a solution of one or more salts of this metal / metal or these metals / semimetals.
  • a solution used is, for example, a solution of cadmium stearate in tri-n-octylphosphine oxide (TOPO) or cadmium oxide in TOPO and a phosphorus-containing acid with a longer alkyl chain (eg "octadecylphosphonic acid”) or cadmium oxide in Olive oil (according to Sapra et al., Journal of Materials Chemistry, 2006.
  • the temperature for the growth of the nanowires can be adjusted as needed and depending on the components used.
  • the temperature is typically in a range of 150 ° - 250 0 C.
  • the concentration of the components, such as Cd and Se / Te the temperature and reaction time, the length of the nanowires can be varied.
  • nanowires with a length of about 10 nanometers to several micrometers are produced by the method according to the invention.
  • the production method according to the invention can be carried out in a very material-saving manner by minimizing the amount of solutions used, which flows over the substrates.
  • Another procedural advantage over many known production methods for nanowires is that the inventive method can be performed in parallel with many samples / batches.
  • the inventive method provides substrates with a defined arrangement of anchored nanowires at predetermined intervals, wherein the nanowires have a fixed epitaxial connection with the nanoparticles of the substrate surface. From Fig. Ic and Id it can be seen that a nanoparticle the starting point for more than one nanowire. The production of branched nanowires is also possible in principle.
  • the products of the method according to the invention offer wide application possibilities in the fields of electronics and piezoelectronics, in particular nanopiezoelectronics, semiconductor technology, optics, sensor technology, photovoltaics and generally chemical storage elements.
  • Some non-limiting examples thereof are use in solar cells, transistors, diodes, chemical storage elements or sensors.
  • a particularly preferred application relates to use in solar cells.
  • Semiconductor nanowires and nanocrystals are known to efficiently absorb light in the visible spectrum.
  • a mixture of colloidal nanocrystals with a conductive polymer Kel and Scholes, Microchimica Acta 2008, Vol.
  • the surface is conductive, the charges generated in the absorption process can be stored directly.
  • Such an assembly with ZnO-based anchored nanowires immersed in a liquid electrolyte has been proposed by Law et al., Nature Materials 2005, 4, 455-459.
  • the synthetic method described therein is not transferable to other nanowire materials such as CdSe and CdTe, and no substrate surface having a given two-dimensional geometric arrangement is used for the growth of the nanowires.
  • Fig. 1 shows SEM images of samples at various stages of the manufacturing process of the invention.
  • FIG. 2 schematically shows the structure of an electrode arrangement using the nanowires anchored on a substrate according to the invention as an element of a solar cell.
  • a substrate surface eg glass or ITO on glass
  • micellar nanolithography with gold dots / gold nanoparticles.
  • one of the protocols described in EP 1 027 157 Bl, DE 197 47 815 A1 or DE 10 2007 017 032 A1 can be followed.
  • the method involves depositing a micellar solution of a block copolymer (eg, polystyrene (n) -b-poly (2-vinylpyridine (m)) on the substrate, eg, by dip coating, thereby forming an ordered film structure of polymer domains on the surface becomes.
  • a block copolymer eg, polystyrene (n) -b-poly (2-vinylpyridine (m)
  • the micelles in the solution are loaded with a gold salt, preferably HAuCl 4 , which is reduced to the gold nanoparticles after deposition with the polymer film.
  • the reduction may be chemically effected, for example with hydrazine, or by means of ener ⁇ yaw Eicher radiation such as electron beam radiation or light.
  • the polymer film is removed (eg by plasma etching with Ar, H or O ions).
  • the solution is heated to 100-150 0 C and evacuated several times and then purged with nitrogen.
  • the solution is further heated to 210 ° C under nitrogen and the samples are suspended in the solution.
  • Se-TOP 200mg selenium-powder selenium solution injected: 400mg TOP (tri-n-octylphosphine from Sigma-Aldrich dissolved in 800mg TOP)
  • reaction is allowed to proceed for about 30 minutes and then the substrates are withdrawn from the solution.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)
  • Silicon Compounds (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé de fabrication de nanofils ancrés sur la surface d'un substrat. Le procédé selon l'invention de fabrication de nanofils ancrés ne comprend pas de phase de dépôt en phase vapeur et comprend au moins les étapes suivantes : a) fourniture d'une surface de substrat avec un agencement géométrique bidimensionnel prédéterminé de nanoparticules ou de nanoamas ; b) contact entre la surface du substrat et les nanoparticules ou nanoamas et au moins une solution du matériau formant les nanofils, le matériau formant les nanofils se déposant sélectivement sur les nanoparticules ou nanoamas et continuant d'y croître. De préférence, le procédé selon l'invention comprend en outre dans l'étape a) l'application d'un matériau germinatif sur les nanoparticules ou nanoamas par contact entre la surface du substrat et une solution du matériau germinatif, si bien que le matériau germinatif se dépose sélectivement sur les nanoparticules ou nanoamas et que, dans l'étape b), le matériau formant les nanofils se dépose sélectivement sur les nanoparticules ou nanoamas ayant reçu le matériau germinatif et continue d'y croître.
PCT/EP2009/008277 2008-11-21 2009-11-20 Nanofils à la surface d'un substrat, leur procédé de fabrication et d'utilisation Ceased WO2010057652A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/130,234 US20110284820A1 (en) 2008-11-21 2009-11-20 Nanowires on substrate surfaces, method for producing same and use thereof
CN200980146632.6A CN102301479B (zh) 2008-11-21 2009-11-20 基底表面上的纳米线、其制造方法及应用
EP09763848A EP2351087A1 (fr) 2008-11-21 2009-11-20 Nanofils à la surface d'un substrat, leur procédé de fabrication et d'utilisation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008058400.2 2008-11-21
DE102008058400A DE102008058400A1 (de) 2008-11-21 2008-11-21 Nanodrähte auf Substratoberflächen, Verfahren zu deren Herstellung sowie deren Verwendung

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WO2010057652A1 true WO2010057652A1 (fr) 2010-05-27
WO2010057652A8 WO2010057652A8 (fr) 2011-06-16

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US (1) US20110284820A1 (fr)
EP (1) EP2351087A1 (fr)
KR (1) KR20110099005A (fr)
CN (1) CN102301479B (fr)
DE (1) DE102008058400A1 (fr)
WO (1) WO2010057652A1 (fr)

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
CN102569034A (zh) * 2012-02-15 2012-07-11 中国科学院半导体研究所 在自然氧化的Si衬底上生长InAs纳米线的方法
CN102618269B (zh) * 2012-03-13 2016-06-29 浙江理工大学 一种CdS/Sn异质结构纳米发光材料的制备方法
CN103794474A (zh) * 2014-01-29 2014-05-14 中国科学院半导体研究所 硅衬底上生长纳米线的衬底处理方法
US9953989B2 (en) 2014-03-31 2018-04-24 Taiwan Semiconductor Manufacturing Company Limited and National Taiwan University Antifuse array and method of forming antifuse using anodic oxidation
US9528194B2 (en) 2014-03-31 2016-12-27 Taiwan Semiconductor Manufacturing Company Limited & National Taiwan University Systems and methods for forming nanowires using anodic oxidation
CN104070178A (zh) * 2014-07-01 2014-10-01 扬州大学 一种粒径可控的单分散铋纳米粒子的制备方法
US10160906B2 (en) 2015-02-24 2018-12-25 Fondazione Istituto Italiano Di Tecnologia Masked cation exchange lithography
DE102017104906A1 (de) * 2017-03-08 2018-09-13 Olav Birlem Anordnung und Verfahren zum Bereitstellen einer Vielzahl von Nanodrähten
FR3103829B1 (fr) * 2019-12-02 2023-06-30 Commissariat Energie Atomique Formation de nanofils
CN114520266B (zh) * 2021-10-22 2024-07-12 中国科学院重庆绿色智能技术研究院 一种硫化铅光电导探测器及其制备方法

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Also Published As

Publication number Publication date
US20110284820A1 (en) 2011-11-24
DE102008058400A1 (de) 2010-05-27
WO2010057652A8 (fr) 2011-06-16
CN102301479B (zh) 2014-08-27
CN102301479A (zh) 2011-12-28
KR20110099005A (ko) 2011-09-05
EP2351087A1 (fr) 2011-08-03

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