CN103132063A - Method for preparing p-type Cu-Co-codoped zinc oxide film - Google Patents
Method for preparing p-type Cu-Co-codoped zinc oxide film Download PDFInfo
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- CN103132063A CN103132063A CN2011103775728A CN201110377572A CN103132063A CN 103132063 A CN103132063 A CN 103132063A CN 2011103775728 A CN2011103775728 A CN 2011103775728A CN 201110377572 A CN201110377572 A CN 201110377572A CN 103132063 A CN103132063 A CN 103132063A
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Abstract
The invention belongs to the field of preparation of a ZnO-based diluted magnetic semiconductor and discloses a method for preparing a p-type Cu-Co-codoped zinc oxide film by a sol-gel technology. The method comprises the following steps of preparing Zn(NO3)2.6H2O, Cu(CH3COO)2.9H2O, Co(NO3)2.6H2O and polyvinylpyrrolidone (PVP) as raw materials and anhydrous ethanol as an organic solvent into sol according to a certain ratio, wherein a Co<2+> concentration is kept in a range of 0.001 to 0.002mol/l and a Cu<2+> concentration is adjusted in a range of 0.001 to 0.003mol/l, spin-coating the sol on a cleaned substrate at a rotation rate of 2000r/min to obtain a film, putting the film into an oven having a temperature of 100 DEG C, drying for 10min to remove the organic solvent, carrying out thermal treatment on the film in an oxygen atmosphere at a temperature of 300 to 400 DEG C for 20min to remove the organic component in the film, repeating the above processes 3-12 times, and carrying out high-temperature crystallization of the treated film at a temperature of 700 to 900 DEG C for 1h to obtain the p-type Cu-Co-codoped zinc oxide film. The p-type Cu-Co-codoped zinc oxide film has good uniformity and high purity. The method has simple processes, has a flexible design, realizes p-type Cu-Co-codoped zinc oxide film growth, and is suitable for large-scale industrial production.
Description
Technical field:
The invention belongs to the semiconductor material growing field, relate to the copper, the cobalt that adopt sol-gel method to prepare p-type and mix altogether zinc-oxide film.
Background technology:
ZnO is a kind of broad stopband, direct band gap II-VI semiconductor material, has wide band-gap energy (3.37eV) and larger exciton bind energy (60meV), is a kind of ultraviolet semiconductor photoelectric device material with very large potential using value.
The applied research of the Spin dynamics behavior in the condensed state system in recent years and spin quantum device is one of common focuses of paying close attention in subjects field such as current Condensed Matter Physics, information science and novel material, develops into gradually a brand-new field-spintronics at present.Due to 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 fashion, thereby the extremely concern of scientific circles and electronic industry circle in recent years.In the spin electric device Study system, ferromagnetic semiconductor is considered to the main raw that the next generation utilizes the spin degree of freedom making microelectronic device of electronics.What wherein attract most attention is rare magnetic (or half magnetic) semi-conductor, and its practice is with the metal ion in the transition metal equivalent material, makes it produce spontaneous magnetic moment.
2000, Dietl carried out theoretical prediction based on current carrier and the local spin-exchange interaction model of Zener, thought that the p-type ZnO of Mn doping can form Curie temperature higher than the diluted magnetic semiconductor of room temperature.After this, each study group has carried out a large amount of research work in the research of oxide lanthanon magnetic semiconductor material.
At present, relevant Cu, the Co codope ZnO material preparation technology of report mainly adopt molecular beam epitaxy (MBE) both at home and abroad, the methods such as magnetron sputtering and pulse vapour deposition, and prepare p-type seldom.The problem that these technology mainly exist is complicated operation, and cost is high, and experimental design is dumb, and preparation cycle is long etc.
Summary of the invention:
The problems such as in order to solve in the above-mentioned background technology due to complicated operation, cost is high, and experimental design is dumb, and preparation cycle is long.We adopt sol-gel method.The purpose of this invention is to provide the preparation method who utilizes sol-gel method growing p-type Cu, Co codope ZnO diluted semi-conductor thin-film.
In order more clearly to understand the present invention, the below describes the preparation process of p-type Cu, Co codope ZnO diluted semi-conductor thin-film in detail.
(a) Zn (NO
3)
26H
2O, Cu (CH
3COO)
29H
2O, Co (NO
3)
26H
2O and polyvinylpyrrolidone (PVP) raw material take dehydrated alcohol as solvent, is configured to colloidal sol by a certain percentage.Make Co
2+Concentration remains on 0.001～0.002mol/l, regulates Cu
2+The concentration of ion is 0.001～0.003mol/l.
(b) the colloidal sol spin-coating film on the substrate that was cleaning under the rotating speed of 2000 rev/mins that is made into through step (a) is put into the gained film baking oven 10min of 100 ℃, to remove organic solvent.
(c) then the film thermal treatment 20min in 300 ℃～400 ℃ lower oxygen atmospheres through step (b), remove the organic composition in film.Said process can repeat 3～12 times, with the thickness that needing to obtain.
(d) finally by the high temperature crystallization 1h of the film of crossing step (d) at 700 ℃～900 ℃, obtain required sample.
The present invention possesses following advantage: the good uniformity of goods, especially multicomponent system, and its uniformity coefficient can reach molecule or atomic scale; The purity of goods is high, and owing to can use high-purity raw, and solvent easily is removed in processing engineering; Method is simple, is easy to prepare large-area film; The microtexture of reaction process and gel all is easy to control, and greatly reduces side reaction; Selected material system is new, is the focus of studying in the world; Can flexible design and realize that the copper of p-type, cobalt mix growth of zinc oxide thin film altogether; Not only be suitable for scientific research, and be suitable for large-scale commercial production.
Embodiment
Embodiment 1
The copper, the cobalt that prepare p-type with sol-gel method are mixed zinc-oxide film altogether.
At first with Zn (NO3)
26H
2O, Cu (CH
3COO)
29H
2O, Co (NO
3)
26H
2O and polyvinylpyrrolidone (PVP) are raw material, take dehydrated alcohol as solvent, are configured to by a certain percentage colloidal sol.Make Co
2+Concentration remains on 0.001mol/l, regulates Cu
2+The concentration of ion is 0.001mol/l, then spin-coating film on the substrate that was cleaning under the rotating speed of 2000 rev/mins, put into the gained film baking oven 10min of 100 ℃, to remove organic solvent, and in 300 ℃ of lower oxygen atmospheres thermal treatment 20min, remove the organic composition in film.Said process can be repeatedly, and the thickness needing to obtain at the high temperature crystallization 1h of 700 ℃, obtains required sample at last.
X-ray diffraction (XRD) stave of growth sample is bright: all diffraction peaks all belong to hexagonal wurtzite ZnO structure, and doping does not cause obvious structural changes; X one X-ray photoelectron spectroscopy X (XPS) of sample shows that the Co ion is+divalent, shows that the Cu ion in sample is+1 valency; The electrical properties measurement shows that film is p-type, and its carrier concentration is 2.83 * 10
16cm
-3
Embodiment 2
The copper, the cobalt that prepare p-type with sol-gel method are mixed zinc-oxide film altogether.
Other condition of the present embodiment is with embodiment 1, just with Co
2+Concentration remains on 0.0015mol/l, regulates Cu
2+The concentration of ion is 0.002mol/l, at the high temperature crystallization 1h of 800 ℃, obtains required sample at last.The sample conduction type that obtains is p-type, and carrier concentration is 3.7 * 10
17cm
-3, do not produce phase-splitting.
Embodiment 3
The copper, the cobalt that prepare p-type with sol-gel method are mixed zinc-oxide film altogether.
Other condition of the present embodiment is with embodiment 1, just with Co
2+Concentration remains on 0.002mol/l, regulates Cu
2+The concentration of ion is 0.003mol/l, at the high temperature crystallization 1h of 900 ℃, obtains required sample at last.The sample conduction type that obtains is p-type, and carrier concentration is 4.4 * 10
18cm
-3, do not produce phase-splitting.
Embodiment 4
The copper, the cobalt that prepare p-type with sol-gel method are mixed zinc-oxide film altogether.
Other condition of the present embodiment with embodiment 3, is thermal treatment 20min in 400 ℃ of lower oxygen atmospheres, and the organic composition of removing in film obtains required sample.The sample conduction type that obtains is p-type, and carrier concentration is 3.5 * 10
18cm
-3, do not produce phase-splitting.
Claims (1)
1. one kind prepares the method that p-type copper, cobalt are mixed zinc-oxide film altogether, it is characterized in that being realized by following processing step:
(a) with Zn (NO
3)
26H
2O, Cu (CH
3COO)
29H
2O, Co (NO
3)
26H
2O and polyvinylpyrrolidone are raw material, take dehydrated alcohol as solvent, are configured to by a certain percentage colloidal sol, make Co
2+Concentration remains on 0.001～0.002mol/l, regulates Cu
2+The concentration of ion is 0.001～0.003mol/l;
(b) the colloidal sol spin-coating film on the substrate that was cleaning under the rotating speed of 2000 rev/mins that is made into through step (a) is put into the gained film baking oven 10min of 100 ℃, to remove organic solvent;
(c) then the film thermal treatment 20min in 300 ℃～400 ℃ lower oxygen atmospheres through step (b), remove the organic composition in film, repeat 3～12 times, with the thickness that needing to obtain;
(d) finally by the high temperature crystallization 1h of the film of crossing step (c) at 700 ℃～900 ℃, obtain required sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103775728A CN103132063A (en) | 2011-11-24 | 2011-11-24 | Method for preparing p-type Cu-Co-codoped zinc oxide film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103775728A CN103132063A (en) | 2011-11-24 | 2011-11-24 | Method for preparing p-type Cu-Co-codoped zinc oxide film |
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| Publication Number | Publication Date |
|---|---|
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Family
ID=48492494
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383161A (en) * | 2002-05-31 | 2002-12-04 | 南京大学 | Diluted magnetic ZnO-base semiconductor prepared by sol-gel method |
| CN1948221A (en) * | 2006-09-26 | 2007-04-18 | 中国科学院上海硅酸盐研究所 | Method of preparing high temperature ferromagnetism ZnO:(Co,Al) nano-material using sol-gel method |
-
2011
- 2011-11-24 CN CN2011103775728A patent/CN103132063A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383161A (en) * | 2002-05-31 | 2002-12-04 | 南京大学 | Diluted magnetic ZnO-base semiconductor prepared by sol-gel method |
| CN1948221A (en) * | 2006-09-26 | 2007-04-18 | 中国科学院上海硅酸盐研究所 | Method of preparing high temperature ferromagnetism ZnO:(Co,Al) nano-material using sol-gel method |
Non-Patent Citations (2)
| Title |
|---|
| T. RATANAA 等: "The wide band gap of highly oriented nanocrystalline Al doped ZnO thin films from sol–gel dip coating", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 吴定才 等: "Co与Cu掺杂ZnO薄膜的制备与光致发光研究", 《物理学报》 * |
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Application publication date: 20130605 |