EP2252728B1 - Procédé d'électrodéposition pour la production de zno nanostructuré - Google Patents

Procédé d'électrodéposition pour la production de zno nanostructuré Download PDF

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Publication number
EP2252728B1
EP2252728B1 EP09711885A EP09711885A EP2252728B1 EP 2252728 B1 EP2252728 B1 EP 2252728B1 EP 09711885 A EP09711885 A EP 09711885A EP 09711885 A EP09711885 A EP 09711885A EP 2252728 B1 EP2252728 B1 EP 2252728B1
Authority
EP
European Patent Office
Prior art keywords
zno
electrode
deposition
solution
hno
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.)
Not-in-force
Application number
EP09711885A
Other languages
German (de)
English (en)
Other versions
EP2252728A2 (fr
Inventor
Jie Chen
Lorenz AÉ
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
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Publication of EP2252728B1 publication Critical patent/EP2252728B1/fr
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    • 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 electrodeposition method for producing nanostructured ZnO, in which in a standard three-electrode reactor, an aqueous solution of a Zn salt and another component used and upon application of a potential and setting a deposition temperature of below 90 ° 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 ° C for the vapor transport method and at about 900 ° C for thermal vapor deposition.
  • the VLS (vapor-liquid-solid) technique uses temperatures above 900 ° C.
  • 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 produced from an aqueous solution, for example from a ZnCl 2 / KCl electrolyte solution saturated with O 2 bubbles (for example described in US Pat 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 in Journal of Electroanalytical Chemistry 517 (2001) 54-62 described.
  • 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.
  • EP 1 420 085 A2 and EP 0 794 270 A1 For example, to form a ZnO film, the method of electrochemical deposition from a solution containing at least Zn 2+ and NO 3 - ions will be described.
  • the ions are available in either an aqueous solution of Zn (NO 3 ) 2 or a mixture of NH 4 NO 3 and ZnSO 4 posed.
  • the solution also contains a carbohydrate.
  • the Zn 2+ and NO 3 - ions in EP 1 420 085 A2 as a further component of the solution polyvalent carboxylic acid and in EP 0 794 270 A1 Carbohydrates are given.
  • a nanostructured ZnO film is deposited from an aqueous solution containing Zn (NO 3 ) 2 .6H 2 O, water and, as a further constituent of the aqueous solution, sodium dodecyl sulfate.
  • IQE internal quantum efficiency
  • the object is achieved by a method of the aforementioned type in that a dopant for the nanostructured ZnO is used as a further constituent of the aqueous solution in order to improve the quality and the optical properties of the ZnO material, and this dopant HNO 3 or NH 4 NO 3 or NH 3 is dissolved in water.
  • 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.
  • ZnO nanorods with an average diameter of 100 to 280 nm by Combination of potentiostatic and galvanostatic processes.
  • 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 -1.2V and -1.8V, preferably between -1.3V and -1.4V.
  • the deposition temperature be set between 60 ° C and 90 ° C and maintained for a period of a few minutes to 20 hours.
  • FTO SnO 2 : F
  • ITO SnO 2 : In
  • Au Au
  • Ag polymer with conductive coating or Si.
  • 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 used. During the deposition, the solution is stirred.
  • a potential of -1.4 V is set against the Pt reference electrode and held for 8,000 s.
  • 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).
  • Fig. 1 shows 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 (NO 3 ) 2 / H 2 O 2 , Zn (NO 3 ) 2 / NaOH, ZnCl ) were used.
  • the strong defect emission is clearly the most important emission and suggests a poor quality of the ZnO nanorods.
  • Fig. 2 shows images of the ZnO nanorods of different shapes produced by the method according to the invention with HNO 3 as a dopant.
  • the different forms are based on different potentials and molarities of the electrolyte solution.
  • ZnO nanorods showed an IQE of approx. 28%, for which in Fig. 4 shown by 23%.
  • Fig. 6 shows the photoluminescence spectra at room temperature for ZnO nanorods with different diameters of about 100 nm to 280 nm. Also, the different diameters were realized by combining potentiostatic and galvanostatic techniques. The position of the intense maximum for the band edge emission in the UV range and only a weak emission in the range of 450 nm to 700 nm can be clearly recognized, 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.
  • Fig. 2 Very similar SEM micrographs were also obtained for this nanostructured ZnO deposited in the second exemplary embodiment.
  • an IQE of approximately 35% was determined.
  • the Fig. 3 coincides with the result in the second embodiment.

Claims (12)

  1. Procédé de positionnement d'électrode pour produire du ZnO nanostructuré, dans lequel dans un réacteur à trois électrodes standard une solution aqueuse composée d'un sel Zn et d'un autre composant est employée et lors de l'application d'un potentiel et du réglage d'une température de dépôt inférieure à 90°C, un matériau ZnO nanostructuré est déposé sur un substrat électriquement conducteur se trouvant dans la solution aqueuse,
    caractérisé en ce que
    comme autre composant de la solution aqueuse, un moyen de dopage du ZnO nanostructuré est employé et ce moyen de dopage est du HNO3 ou du NH4NO3 ou du NH3 dissous dans l'eau.
  2. Procédé de positionnement d'électrode selon la revendication 1,
    caractérisé en ce que
    comme sel Zn, on emploie du Zn(NO3)2.
  3. Procédé de positionnement d'électrode selon la revendication 2,
    caractérisé en ce que
    du Zn(NO3)2 est employé dans une concentration de 1 à 20 mM.
  4. Procédé de positionnement d'électrode selon au moins une des revendications précédentes,
    caractérisé en ce qu'
    une solution composée de Zn(NO3)2 et HNO3 dans un rapport molaire d'environ 100:1 est employée.
  5. Procédé de positionnement d'électrode selon la revendication 4,
    caractérisé en ce que
    la solution composée de Zn(NO3)2 et HNO3 présente une valeur de pH comprise entre 4,5 et 5,8.
  6. Procédé de positionnement d'électrode selon au moins une des revendications 1 à 3,
    caractérisé en ce qu'
    une solution composée de Zn(NO3)2 et NH4NO3 dans un rapport molaire de 1:1 à 130:1 est employée.
  7. Procédé de positionnement d'électrode selon la revendication 6,
    caractérisé en ce que
    la solution composée de de Zn(NO3)2 et NH4NO3 présente une valeur de pH comprise entre 4,2 et 6,4.
  8. Procédé selon la revendication 1,
    caractérisé en ce qu'
    un potentiel contre l'électrode de référence Pt est réglé à une valeur comprise entre -1,2V et -1,8V.
  9. Procédé selon la revendication 1,
    caractérisé en ce que
    la température de dépôt est réglée entre 60°C et 90°C.
  10. Procédé selon la revendication 1,
    caractérisé en ce que
    la température de dépôt est maintenue sur une durée de quelques minutes à 20 heures.
  11. Procédé selon la revendication 1,
    caractérisé en ce que
    la solution est agitée pendant le dépôt.
  12. Procédé selon la revendication 1,
    caractérisé ce que
    comme substrat FTO, ITO, Au, Ag, un polymère avec un revêtement conducteur ou Si est employé.
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 EP2252728A2 (fr) 2010-11-24
EP2252728B1 true EP2252728B1 (fr) 2012-12-12

Family

ID=40941906

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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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE102013113585A1 (de) 2013-12-06 2015-06-11 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Passivierungsschicht mit Punktkontakten für Dünnschichtsolarzellen

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DE102010017962A1 (de) 2010-04-23 2011-10-27 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Superstrat-Solarzelle mit Nanostrukturen
DE202010018127U1 (de) 2010-04-23 2014-04-04 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Superstrat-Solarzelle mit Nanostrukturen
JP2013525250A (ja) * 2010-04-28 2013-06-20 ビーエーエスエフ ソシエタス・ヨーロピア 溶液中で亜鉛錯体を調製する方法
DE202010017656U1 (de) 2010-08-18 2012-05-02 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
DE102010034904A1 (de) 2010-08-18 2012-02-23 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
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
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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US5804466A (en) * 1996-03-06 1998-09-08 Canon Kabushiki Kaisha Process for production of zinc oxide thin film, and process for production of semiconductor device substrate and process for production of photoelectric conversion device using the same film
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE102013113585A1 (de) 2013-12-06 2015-06-11 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Passivierungsschicht mit Punktkontakten für Dünnschichtsolarzellen

Also Published As

Publication number Publication date
US20110048956A1 (en) 2011-03-03
WO2009103286A3 (fr) 2009-10-29
EP2252728A2 (fr) 2010-11-24
WO2009103286A2 (fr) 2009-08-27

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