EP2252728A2 - Procédé d'électrodéposition pour la production de zno nanostructuré - Google Patents

Procédé d'électrodéposition pour la production de zno nanostructuré

Info

Publication number
EP2252728A2
EP2252728A2 EP09711885A EP09711885A EP2252728A2 EP 2252728 A2 EP2252728 A2 EP 2252728A2 EP 09711885 A EP09711885 A EP 09711885A EP 09711885 A EP09711885 A EP 09711885A EP 2252728 A2 EP2252728 A2 EP 2252728A2
Authority
EP
European Patent Office
Prior art keywords
zno
solution
electrode
electrode position
nanostructured
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.)
Granted
Application number
EP09711885A
Other languages
German (de)
English (en)
Other versions
EP2252728B1 (fr
Inventor
Jie Chen
Lorenz Ae
Christian-Herbert Fischer
Martha Christina Lux-Steiner
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.)
Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH
Original Assignee
Helmholtz Zentrum Berlin fuer Materialien und Energie 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
Priority claimed from DE102008010287A external-priority patent/DE102008010287B3/de
Priority claimed from DE200810029234 external-priority patent/DE102008029234A1/de
Application filed by Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH filed Critical Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH
Publication of EP2252728A2 publication Critical patent/EP2252728A2/fr
Application granted granted Critical
Publication of EP2252728B1 publication Critical patent/EP2252728B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

Definitions

  • the invention relates to an electrode position method for producing nanostructured ZnO, in which in a standard three-electrode reactor, an aqueous solution of a Zn salt and a further component used and upon application of a potential and setting a deposition temperature of below 90 0 C on a in nanostructured ZnO substrate is deposited on the aqueous solution.
  • Nanostructured ZnO material in the context of the invention is intended to mean ZnO in a morphology with dimensions in the nm range or less.
  • the ZnO may be e.g. be formed in the form of nanorods, nanofilaments or thin layers. Due to its optoelectronic and environmentally friendly properties and its chemical stability, ZnO is promising materials for use in light emitting diodes and in highly structured solar cells.
  • ZnO nanorods or nanofibers are produced by various methods.
  • high deposition temperatures are typical. For instance, they are between 300 and 500 ° C. for the chemical vapor deposition (CVD) and metal organic chemical vapor deposition (MOCVD) processes, and between 400 and 500 ° C. for MOVPE (metal organic vapor phase epitaxy) processes. 600 to 900 0 C for the steam transport method and at about 900 0 C. for thermal vapor deposition.
  • materials are deposited by means of electrodeposition methods and chemical bath deposition at moderate temperatures.
  • the electrodeposition process is carried out at atmospheric pressure and is a low cost process which requires only simple equipment.
  • the film thickness can be determined by means of the consumed charges during the deposition process.
  • ZnO nanorods by means of electrodeposition methods are prepared from an aqueous solution, for example from a ZnCVKCl 2
  • Electrolytic solution saturated with O 2 bubbles (described for example in 13th European Photovoltaic Solar Cell Energy Conference, 23-27 October 1995, Nice, France, pp 1750-1752 or in Appl. Phys. Lett., Vol. 77, No. 16, 16 October 2000, pp 2575-2577) or ZnO films of a ZnCl 2 / H 2 O 2 electrolyte solution as described, for example, in Journal of Electroanalytical Chemistry 517 (2001) 54-62.
  • the nanostructured ZnO materials thus prepared do not have the properties such as high efficiency required for use in photovoltaics because photoluminescence spectra recorded for these materials show a very intense defect emission in the range of 450 to 900 nm as the main emission.
  • IQE internal quantum efficiency
  • the object is achieved by a method of the type mentioned above in that as a further constituent of the aqueous solution, a dopant for the nanostructured ZnO is used to improve the quality and the optical properties of the ZnO material.
  • Zn (NO 3 ) 2 as Zn salt, in particular in a concentration of 1 to 20 mM.
  • HNO 3 is used as a dopant, it is intended to prepare the aqueous solution of Zn (NO 3 ) 2 and HNO 3 in a molar ratio of about 100: 1, this solution having a pH of between 4.5 and 5.8 ,
  • NH 4 NO 3 is used as a dopant, it is intended to prepare the aqueous solution of Zn (NO 3 ) 2 and NH 4 NO 3 in a molar ratio of from 1: 1 to 130: 1, this solution having a pH between 4.2 and 6.4 has.
  • the method according to the invention has succeeded in producing ZnO nanorods with an average diameter of 100 to 280 nm by combining potentiostatic and galvanostatic processes manufacture.
  • the ZnO nanorods show dominant band edge emission as desired and no additional annealing step, and have a high IQE, which is 23% and 28%, respectively, for the first ZnO nanorods deposited by the process.
  • the measured high IQE showed deviations of 20 to 25%.
  • IQE is one of the most important parameters for characterizing the quality of both light emitting and optoelectronic materials. It is defined as the ratio of the number of generated photons to the number of injected carriers. In general, the lower the defects in the material, the higher the IQE.
  • a potential against the Pt reference electrode is set to a value between -1.2 V and -1.8 V, preferably between -1.3 V and -1.4 V.
  • the deposition temperature between 60 0 C and 90 0 C is set and maintained over a period of a few minutes to 20 h.
  • FTO SnO 2 : F
  • ITO SnO 2 Mn
  • Au Au
  • Ag polymer with conductive coating or Si.
  • Figure 1 Photoluminescence spectrum of ZnO nanorods prepared by electrodeposition from Zn (NOs) 2 ZH 2 O 2 , ZnCl or Zn (NO 3 ) 2 / NaOH electrolytes;
  • FIG. 2 shows a scanning electron micrograph of ZnO nanorods produced by means of the method according to the invention with HNO 3 as dopant;
  • FIG. 3 Photoluminescence spectrum of ZnO nanorods acc. Fig. 2; 4: further scanning electron micrograph of ZnO nanorods with altered morphology, produced by means of the method according to the invention with HNO 3 as dopant;
  • FIG. 5 Photoluminescence spectrum of ZnO nanorods acc. Fig. 4;
  • FIG. 6 Photoluminescence spectrum of ZnO nanorods of different diameters, produced by means of the method according to the invention with HNO 3 as doping agent.
  • a glass substrate with a fluorine doped SnO 2 layer (so-called FTO glass), on which an undoped 30 nm thick ZnO layer is arranged, is used as the substrate.
  • the substrate has a size of about 2.5 x 2 cm 2 and is first cleaned in an ultrasonic bath (acetone and ethanol) and then rinsing in distilled water.
  • aqueous solution of 10 mM Zn (NO 3 ) 2 and HNO 3 with a pH of 4.5 is used in a mixing ratio of 100: 1 for the deposition.
  • the solution is stirred.
  • Typical deposition current densities in the process according to the invention are about 0.3 to 0.5 mA / cm 2 .
  • the substrate was washed with the applied ZnO nanorods in distilled water.
  • the morphology of the generated layers of ZnO rods was investigated by a scanning electron microscope (SEM).
  • Photoluminescence measurements were carried out at an excitation wavelength of 325 nm (He-Cd laser).
  • ZnO nanorods show the determined photoluminescence spectra of ZnO nanorods, for their preparation on an FTO glass substrate by means of electrode position method known from the prior art according to known electrolyte solutions (Zn (NOs) 2 ZH 2 O 2 , Zn (NO 3 ) 2 / NaOH, ZnCI) were used.
  • Zn (NOs) 2 ZH 2 O 2 , Zn (NO 3 ) 2 / NaOH, ZnCI electrolyte solutions
  • FIGS. 2 and 4 show images of the ZnO nanorods of different shapes produced by the method according to the invention with HNO 3 as a dopant.
  • the different shapes are based on different potentials and molarities of the electrolyte solution.
  • an IQE of about 28% was determined, for the 23% shown in FIG. 4.
  • Fig. 6 shows the photoluminescence spectra at room temperature for ZnO nanorods with different diameters of about 100 nm to
  • the different diameters were also realized by combining potentiostatic and galvanostatic techniques.
  • the location of the intense maximum for band edge emission in the UV range and only a weak emission in the range of 450 nm to 700 nm, ie. the shape of the ZnO nanorods produced by the method according to the invention has no influence on their defect emission.
  • the intensities of the photoluminescence spectra were indicated in the figures in arbitrary units.
  • 10 mM Zn (NO 3 ) 2 and NH 4 NO 3 with a pH of 4.8 in a mixing ratio of 20: 1 are used as dopants and thus further constituents of the aqueous solution for the purpose of depositing nanostructured ZnO. All other details for carrying out the method according to the invention remain unchanged.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention a pour but de perfectionner un procédé d'électrodéposition pour la production de ZnO nanostructuré, de façon que ce procédé permette la production de ZnO nanostructuré avec une efficacité quantique interne (IQE) élevée, sans étape de recuit supplémentaire. A cet effet, l'invention est caractérisée en ce qu'on utilise, dans le procédé d'électrodéposition, une solution aqueuse d'un sel de Zn, par exemple, Zn(NO3)2, et un élément dopant, par exemple HNO3 ou NH4NO3. Des nanobarres de ZnO ainsi fabriquées présentent, en spectre de photoluminescence, une émission en limite de bande intense dans le domaine UV et seulement une faible émission dans le domaine de 450 nm à 700 nm.
EP09711885A 2008-02-21 2009-02-20 Procédé d'électrodéposition pour la production de zno nanostructuré Not-in-force EP2252728B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102008010287A DE102008010287B3 (de) 2008-02-21 2008-02-21 Elektrodepositionsverfahren zur Herstellung von nanostrukturiertem ZnO
DE200810029234 DE102008029234A1 (de) 2008-06-19 2008-06-19 Elektrodepositionsverfahren zur Herstellung von nanostrukturiertem ZnO
PCT/DE2009/000254 WO2009103286A2 (fr) 2008-02-21 2009-02-20 Procédé d'électrodéposition pour la production de zno nanostructuré

Publications (2)

Publication Number Publication Date
EP2252728A2 true EP2252728A2 (fr) 2010-11-24
EP2252728B1 EP2252728B1 (fr) 2012-12-12

Family

ID=40941906

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09711885A Not-in-force EP2252728B1 (fr) 2008-02-21 2009-02-20 Procédé d'électrodéposition pour la production de zno nanostructuré

Country Status (3)

Country Link
US (1) US20110048956A1 (fr)
EP (1) EP2252728B1 (fr)
WO (1) WO2009103286A2 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202010018127U1 (de) 2010-04-23 2014-04-04 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Superstrat-Solarzelle mit Nanostrukturen
DE102010017962A1 (de) 2010-04-23 2011-10-27 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Superstrat-Solarzelle mit Nanostrukturen
WO2011135514A2 (fr) * 2010-04-28 2011-11-03 Basf Se Procédé de préparation d'un complexe de zinc en solution
DE102010034904A1 (de) 2010-08-18 2012-02-23 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Zweiseitige Solarzelle
DE102010034901B4 (de) 2010-08-18 2016-06-02 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Solarthermische Anordnung
DE202010017656U1 (de) 2010-08-18 2012-05-02 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Zweiseitige Solarzelle
CN102363893B (zh) * 2011-11-02 2014-03-12 西南交通大学 一种同步合成两种ZnO纳米结构的方法
CN103194784B (zh) * 2013-04-11 2016-03-02 江苏大学 一种以胶体为模板可控电沉积制备纳米ZnO薄膜的方法
DE102013113585A1 (de) 2013-12-06 2015-06-11 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Passivierungsschicht mit Punktkontakten für Dünnschichtsolarzellen
DE102013113590A1 (de) * 2013-12-06 2015-06-11 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Verfahren zur Herstellung von Passivierungsschichten mit Punktkontakten für Dünnschichtsolarzellen
WO2015081927A1 (fr) 2013-12-06 2015-06-11 Helmholtz-Zentrum Für Materialien Und Energie Gmbh Couche de passivation présentant des contacts ponctuels pour cellules solaires à couche mince et procédé pour sa fabrication
CN112903770B (zh) * 2019-12-04 2022-05-17 中国石油化工股份有限公司 一种柔性硫化物产生菌菌量测定传感器及间接法测定污水中srb菌量的方法
CN114558592B (zh) * 2022-03-09 2023-11-14 北方民族大学 一种ZnO/ZnS纳米棒核壳结构光催化剂及其制备方法

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DE69702277T2 (de) 1996-03-06 2001-03-01 Canon Kk Verfahren zur Herstellung einer Dünnzinkoxidfilm und Verfahren zur Herstellung eines Substrats einer Halbleiteranordnung und Verfahren zur Herstellung einer photoelektrischen Umwandlungsvorrichtung unter Verwendung dieser Film
US6106689A (en) * 1997-01-20 2000-08-22 Canon Kabushiki Kaisha Process for forming zinc oxide film and processes for producing semiconductor device substrate and photo-electricity generating device using the film
JP3327811B2 (ja) * 1997-05-13 2002-09-24 キヤノン株式会社 酸化亜鉛薄膜の製造方法、それを用いた光起電力素子及び半導体素子基板の製造方法
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Also Published As

Publication number Publication date
US20110048956A1 (en) 2011-03-03
EP2252728B1 (fr) 2012-12-12
WO2009103286A3 (fr) 2009-10-29
WO2009103286A2 (fr) 2009-08-27

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