CN1897236A - Production of manganese-doped zinc oxide thin-film and nano-column by electrochemical deposition - Google Patents
Production of manganese-doped zinc oxide thin-film and nano-column by electrochemical deposition Download PDFInfo
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- CN1897236A CN1897236A CN 200510017068 CN200510017068A CN1897236A CN 1897236 A CN1897236 A CN 1897236A CN 200510017068 CN200510017068 CN 200510017068 CN 200510017068 A CN200510017068 A CN 200510017068A CN 1897236 A CN1897236 A CN 1897236A
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Abstract
The invention is concerned with the flower of zinc thin magnetism semiconductor film and nanometer column growing on the conducting underlay by the electrochemistry deposition growth method, it is: cleans the conducting underlay as the working electrode before deposition; confects the electrolytic liquor by the deionized water and the solutes, namely ZnCl2, Mn(CH3COOH)2 and Zn(CH3COO)2, adds the potassium chloride (KCl) with 0.1mol/L in the electrolytic liquor to form the electrolyte; evaporates the indium film on the working electrode and the counter- electrode, makes to be the evaporating indium working electrode and the vapor indium opposite electrode, and educes the leads from the evaporating indium working electrode and the vapor indium opposite electrode respectively; puts the evaporating indium working electrode and the vapor indium opposite electrode in the electrolyte, uses the constant temperature meter to control the temperature to be invariable, the selected invariable pressure is -0.6--1.0V, the deposition time is 0.5-2 hours.
Description
Technical field:
The invention belongs to the semiconductor material growing field, relate to and adopt zinc oxide diluted semi-conductor thin-film and the nano-pillar that the electrochemical deposition growing method is grown has manganese to mix on conductive substrates.
Background technology:
Zinc oxide ZnO is a kind of broad stopband, direct band gap II-VI semi-conducting material, has wide band-gap energy (3.37eV) and bigger exciton bind energy (60meV), is a kind of ultraviolet semiconductor photoelectric device material with very big potential using value.
The application study of spin dynamic behavior in the condensed state system and spin quantum device is one of common focus of paying close attention to of many ambits such as current Condensed Matter Physics, information science and new material in recent years, develops into a brand-new field-spintronics (Spintronics) at present gradually.Since its multiple futures such as spin quantum computer, spin transistor and spin memory device etc. novel based on the potential using value on the quantum device of spin feature, thereby the extremely concern of scientific circles and electronics industry circle in recent years.In spin electric device research system, ferromagnetic semiconductor (Ferromagnetic Semiconductor) is considered to the next generation and utilizes the electronic spin degree of freedom to make the main material of microelectronic component.What wherein attract most attention is rare magnetic (or half magnetic) semiconductor (diluted magneticsemiconductor), and its practice is with the metal ion in the transition metal substitution material, makes it produce spontaneous magnetic moment.
2000, Dietl has carried out theoretical prediction based on charge carrier and local spin (localizedspins) exchange interaction (exchange interaction) model of Zener, thinks that Mn doped p-type ZnO can form the diluted magnetic semiconductor that Curie temperature is higher than room temperature.After this, each seminar has carried out number of research projects in the research of oxide lanthanon magnetic semiconductor material.
At present, the technology of preparing of the relevant Mn doping ZnO material of report mainly adopts molecular beam epitaxy (MBE) both at home and abroad, method such as magnetron sputtering and chemistry, the problem that these technology mainly exist are complicated operation, cost height, experimental design is dumb, manufacturing cycle is long etc.
Summary of the invention:
In order to solve above-mentioned background technology complicated operation, cost height, to design problems such as dumb, that manufacturing cycle is long, the purpose of this invention is to provide the preparation method who utilizes electrochemical deposition method growth Mn doping ZnO diluted semi-conductor thin-film and nano-pillar.
In order more to be expressly understood the present invention in detail, the preparation process of Mn doping ZnO diluted semi-conductor thin-film and nano-pillar is described in detail below:
(a) before the deposition, at first conductive substrates is cleaned the back as work electrode;
(b) adopting solute is ZnCl
2, Mn (CH
3COOH)
2And Zn (CH
3COO)
2Be mixed with electrolytic solution with deionized water together, the potassium chloride (KCl) that adds 0.1mol/L in above-mentioned electrolytic solution forms electrolyte;
(c) with the indium film respectively evaporation make and steam the indium work electrode and steam indium at the work electrode of step (a) with on electrode to electrode, and will steam the indium work electrode and the steaming indium is drawn lead respectively to electrode;
(d) electrode is placed on steaming indium work electrode in the step (c) and steaming indium in the electrolyte for preparing in the step (b), utilize the temperature-resistant of constant temperature instrument control electrolyte again, and selected steam the indium work electrode and steam indium to the constant deposition voltage at electrode two ends be-0.6V～-1.0V, sedimentation time is 0.5 hour～2 hours, can realize the zinc-oxide film and the nano-pillar of mixing with electrochemical production manganese.
The difference of the present invention and forefathers' report is that we utilize electrochemical production ZnMnO film and nano-pillar, its advantage is to utilize electrochemical production to go out ZnO film and nano-pillar that Mn mixes, owing to adopting electrochemical method to make the present invention have that equipment is simple, cost is low, deposition rate is high, the material growth temperature is low, can operate, be adapted at complicated advantages such as substrate growth material at normal temperatures and pressures; The present invention can flexible design and is realized the ZnO film that Mn mixes and the growth of nano-pillar; Not only be suitable for scientific research, and be suitable for large-scale industrial production.
In embodiment 1, X-ray diffraction (XRD) stave of deposition nano-pillar of the present invention is bright: except deriving from the diffraction maximum of Si substrate, remaining diffraction maximum all belongs to buergerite ZnO structure, and the position of all diffraction maximums is compared with the peak position of pure ZnO, all is offset to low-angle.The stereoscan photograph of deposited samples shows: sample is a columnar nano-structure, and these nano-pillar are about 500-600nm, and diameter has 200-300nm approximately.
The present invention has summed up solution concentration in experiment, growth temperature, conditions such as sedimentation potential and sedimentation time have obtained ZnO nano-pillar and film that high-quality Mn mixes to the influence of sample deposition.
Embodiment
Embodiment 1
The ZnO nano-pillar that growth Mn mixes on P type (111) Si substrate.
At first, before deposition, the Si substrate is cleaned, adopt the RCA treatment process of standard as follows: to adopt CCl
4Ultrasonic, the Si substrate was cleaned 10 minutes, the acetone ultrasonic cleaning is 10 minutes again, washes repeatedly 10 minutes with deionized water again; Then the Si substrate that cleans being put into proportioning is NH
4OH: H
2O
2: H
2O=1: 1: 5 first solution is 80 ℃ to the first solution heating-up temperature, and be 10 minutes heating time, and the Si substrate that cleans is cleaned with deionized water; Clean with deionized water after 1 minute with the 1.5%HF immersion again; Putting into proportioning again is HCl: H
2O
2: H
2O=1: 1: 5 second solution is 80 ℃ to the second solution heating-up temperature, and be that deionized water is cleaned after 10 minutes heating time; Be that 0.5%HF soaked 1 minute with concentration at last, deionized water is cleaned and is formed work electrode after the back dries up the Si substrate with nitrogen.
Then with the indium film respectively the above-mentioned Si work electrode of evaporation and adopt that platinized platinum makes on the electrode, draw lead again.The electrolyte that uses is 0.005mol/L ZnCl
2, 0.00025mol/L Mn (CH
3COOH)
2, 0.00025mol/L Zn (CH
3COO)
2The aqueous solution, the KCl that adds 0.1mol/L in this aqueous solution is as auxiliary electrolyte.Be deposited under the constant voltage and carry out, deposition voltage is-0.8V that in deposition process, temperature is controlled at 60 ℃ by the water-bath temperature regulating device.Sedimentation time is 1 hour.
Embodiment 2
Present embodiment only changes deposition voltage and sedimentation time, and sample of the present invention is grown.
Other conditions are the same, and just changing deposition voltage is-0.6V that sedimentation time is 0.5h.The ZnO nano-pillar length that the Mn that grow this moment mixes is about 300nm, and diameter is about 200nm.
Embodiment 3
On the ito glass substrate, the grow film of ZnMnO of present embodiment.
Other condition is with embodiment 1, and just work electrode is changed to ito glass, and deposition voltage is-1V that sedimentation time is 2h.At first work electrode is cleaned, the cleaning of ito glass ultrasonic cleaning 10 minutes in acetone and ethanol is respectively cleaned and is dried up with deionized water then.The photo of the X-ray diffraction of deposited samples (XRD) spectrum result and ESEM shows that we have obtained high-quality ZnMnO film.
Claims (1)
1, prepare the zinc-oxide film of manganese doping and the method for nano-pillar with electrochemical deposition, it is characterized in that preparation process is as follows:
(a) before the deposition, at first conductive substrates is cleaned the back as work electrode;
(b) adopting solute is ZnCl
2, Mn (CH
3COOH)
2And Zn (CH
3COO)
2Be mixed with electrolytic solution with deionized water together, the potassium chloride (KCl) that adds 0.1mol/L in above-mentioned electrolytic solution forms electrolyte;
(c) with the indium film respectively evaporation make and steam the indium work electrode and steam indium at the work electrode of step (a) with on electrode to electrode, and will steam the indium work electrode and the steaming indium is drawn lead respectively to electrode;
(d) electrode is placed on steaming indium work electrode in the step (c) and steaming indium in the electrolyte for preparing in the step (b), utilize the temperature-resistant of constant temperature instrument control electrolyte again, and selected steam the indium work electrode and steam indium to the constant deposition voltage at electrode two ends be-0.6V～-1.0V, sedimentation time is 0.5 hour～2 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100170681A CN100428429C (en) | 2005-08-22 | 2005-08-22 | Production of manganese-doped zinc oxide thin-film and nano-column by electrochemical deposition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100170681A CN100428429C (en) | 2005-08-22 | 2005-08-22 | Production of manganese-doped zinc oxide thin-film and nano-column by electrochemical deposition |
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|---|---|
| CN1897236A true CN1897236A (en) | 2007-01-17 |
| CN100428429C CN100428429C (en) | 2008-10-22 |
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ID=37609698
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100552099C (en) * | 2007-08-17 | 2009-10-21 | 中国科学院上海硅酸盐研究所 | Improved electrochemical deposition process prepares the single c-axle oriented zinc oxide film method |
| CN101845672B (en) * | 2009-03-28 | 2012-09-26 | 中国科学院合肥物质科学研究院 | Zinc oxide nanocone array with controllable sharpness and preparation method thereof |
| CN103469273A (en) * | 2013-08-29 | 2013-12-25 | 长春工程学院 | Method for preparing nano-zinc oxide |
| CN105369201A (en) * | 2015-11-12 | 2016-03-02 | 天津大学 | Method for preparing manganese-doped zinc oxide-bismuth ferrite epitaxial heterostructure having indoor-temperature electric-control magnetic property |
| CN109608219A (en) * | 2018-12-06 | 2019-04-12 | 五邑大学 | A kind of preparation method of the porous oxide film of weak acid resistant corrosion |
| CN114171734A (en) * | 2020-09-10 | 2022-03-11 | 比亚迪股份有限公司 | Positive active material, positive pole piece, manufacturing method of positive pole piece and battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4089858B2 (en) * | 2000-09-01 | 2008-05-28 | 国立大学法人東北大学 | Semiconductor device |
| JP3826755B2 (en) * | 2001-09-28 | 2006-09-27 | 株式会社村田製作所 | ZnO film, method for producing the same, and light emitting device |
| US7061014B2 (en) * | 2001-11-05 | 2006-06-13 | Japan Science And Technology Agency | Natural-superlattice homologous single crystal thin film, method for preparation thereof, and device using said single crystal thin film |
| CN1186786C (en) * | 2002-05-31 | 2005-01-26 | 南京大学 | Diluted magnetic ZnO-base semiconductor prepared by sol-gel method |
| JP2004347717A (en) * | 2003-05-20 | 2004-12-09 | Seiko Epson Corp | Photomask, its manufacturing method, photomask manufacturing apparatus, and method for forming pattern |
-
2005
- 2005-08-22 CN CNB2005100170681A patent/CN100428429C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100552099C (en) * | 2007-08-17 | 2009-10-21 | 中国科学院上海硅酸盐研究所 | Improved electrochemical deposition process prepares the single c-axle oriented zinc oxide film method |
| CN101845672B (en) * | 2009-03-28 | 2012-09-26 | 中国科学院合肥物质科学研究院 | Zinc oxide nanocone array with controllable sharpness and preparation method thereof |
| CN103469273A (en) * | 2013-08-29 | 2013-12-25 | 长春工程学院 | Method for preparing nano-zinc oxide |
| CN105369201A (en) * | 2015-11-12 | 2016-03-02 | 天津大学 | Method for preparing manganese-doped zinc oxide-bismuth ferrite epitaxial heterostructure having indoor-temperature electric-control magnetic property |
| CN105369201B (en) * | 2015-11-12 | 2018-06-08 | 天津大学 | Manganese with the automatically controlled magnetic characteristic of room temperature mixes the preparation method of zinc oxide-bismuth ferrite epitaxial heterostructures |
| CN109608219A (en) * | 2018-12-06 | 2019-04-12 | 五邑大学 | A kind of preparation method of the porous oxide film of weak acid resistant corrosion |
| CN114171734A (en) * | 2020-09-10 | 2022-03-11 | 比亚迪股份有限公司 | Positive active material, positive pole piece, manufacturing method of positive pole piece and battery |
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| Publication number | Publication date |
|---|---|
| CN100428429C (en) | 2008-10-22 |
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