CN102925856A - Method for directly preparing nitrogen-doped zinc oxide film by taking zinc film as base material - Google Patents
Method for directly preparing nitrogen-doped zinc oxide film by taking zinc film as base material Download PDFInfo
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- CN102925856A CN102925856A CN2012104690967A CN201210469096A CN102925856A CN 102925856 A CN102925856 A CN 102925856A CN 2012104690967 A CN2012104690967 A CN 2012104690967A CN 201210469096 A CN201210469096 A CN 201210469096A CN 102925856 A CN102925856 A CN 102925856A
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Abstract
The invention discloses a method for directly preparing a nitrogen-doped zinc oxide film by taking a zinc film as base material. The method comprises the following steps: a clean silicon sheet is selected as a substrate, and metal zinc with purity of 99.99% is taken as sputtering target material; when the vacuum degree in a sputtering chamber reaches 1.0*10<-4> Pa, argon gas is fed to clean the substrate; the substrate is subjected to ion-beam coating after being cleaned; and the zinc film obtained through ion beam deposition is subjected to annealing treatment with mixed gas of nitrogen and oxygen in an atmosphere furnace so as to obtain the nitrogen-doped zinc oxide film directly. According to the invention, argon gas is used as a sputtering gas directly, and other gases are not added, so that the controllability is high; the zinc film is subjected to annealing treatment with mixed gas of nitrogen and oxygen in the atmosphere furnace to obtain the nitrogen-doped zinc oxide film directly, so that the method is simple, the operability is high, and the repeatability is good; and detection data shows that the film crystal has good quality, has a relatively high doping content of nitrogen, is higher in the concentration of hole carriers, and can meet the requirements of a P-type film.
Description
Technical field
The invention belongs to the Application Areas of semiconductor film and device, particularly a kind of preparation method of N doping P type ZnO film.
Background technology
ZnO film is a kind of broad stopband oxide semiconductor material with hexagonal wurtzite structure, its forbidden band is wide to be 3.37eV, exciton bind energy is 60meV, lattice parameter a=0.35nm, c=0.521nm, it has good piezoelectricity and acousto-optic performance, pretend the concern that enjoys people for the candidate material of ultra-violet light-emitting device and Laser Devices, but because the stoichiometric ratio that the ZnO native defect causes is unbalance, making it natural is the N-shaped semiconductor material, and the key of fabricate devices is to obtain P type ZnO film, owing to self compensation effect and the acceptor concentration of the high electron density of ZnO film in preparation process, make the preparation difficult of P type film simultaneously, therefore will prepare high-quality P type film, must again introduce new acceptor impurity to improve acceptor concentration, change simultaneously its conduction type.
Nitrogen is entrained in the successful utilization on the P type ZnSe and is indicating all that based on the theory and technology of ZnO nitrogen is one of optimal acceptor doping element, the ZnO thin film doped preparation method of existing N all is as base material with ZnO, such as a kind of method for preparing P type ZnO film take nitrogen as doped source of patent of invention, publication number is CN1461044A, the P type thin film crystallization of this method preparation is second-rate, optical property is not strong, film is not to grow in the column mode of solid matter, is difficult to satisfy the requirement that the modern optical electricity device is produced.
Summary of the invention
Deficiency for the ZnO thin film doped preparation method's existence of existing N, the object of the invention is to improve the ZnO thin film doped preparation method of N that a kind of method is simple, the parameter controllability is strong, the ZnO thin film doped stable performance of N of preparation, the Study of Defects for ZnO film provides certain theoretical support simultaneously.
The objective of the invention is to be achieved by the following technical programs, a kind of ZnO thin film doped method of N that directly prepares take the Zn film as base material may further comprise the steps:
(1) select cleaning Si sheet as substrate material, take the metallic zinc of purity as 99.99% as sputtering target material;
(2) substrate material is put into the ion beam sputtering chamber, and vacuum tightness reaches 1.0 * 10 in chamber
-4During Pa, pass into the sputter gas argon gas, start cleaning device, substrate material is cleaned;
(3) after substrate material cleans and finishes, open sputter gun, carry out ion beam deposition, line voltage is 700～800V, acceleration voltage 210～230V, and line 20～30mA, sparking voltage are 50～70V;
(4) the Zn film that obtains through ion beam depositing carries out N in atmosphere furnace
2, O
2It is ZnO thin film doped that mixed gas anneal directly obtains N, and Hall effect detection display, obtained film are N doping P type ZnO film.
For further improving effect of the present invention, technical scheme also possesses following characteristics:
Pass into N in step (4) atmosphere furnace
2And O
2Volume ratio be 1.5:1.
The temperature of step (4) anneal is 600～700 ℃, and the time is 2 hours.
Beneficial effect: the present invention utilizes the ion beam depositing technology, directly take argon gas as sputter gas, does not add other gases, and controllability is strong, and by changing electric current, the parameters such as voltage prepare high quality Zn film, then take the Zn film as base material, carry out N in atmosphere furnace
2, O
2It is ZnO thin film doped that mixed gas anneal directly obtains N, and method is simple, and is workable, good reproducibility; Sample is detected, related data shows that all the ZnO thin film doped crystal mass of N is fine, the N doping is more, hole is higher, satisfy the requirement of P type film, through repeatedly detecting, its stability is higher, can satisfy the needs of various different components, the simultaneously defect theory research for the preparation of P type film and ZnO film provides certain technical support.Compare with the P type film of existing method preparation, the thin film crystallization quality of present method preparation is good, optical property is strong, owing to directly having carried out anneal in the preparation process, the rete difficult drop-off, the bonding force of film is very good, and film is the columnar growth of solid matter, can satisfy the Production requirement of device in the modern industry fully.
Embodiment
Embodiment 1:
,, at first according to ordinary method the Si sheet is cleaned take the Si sheet as substrate material as sputtering target material take the metallic zinc of purity as 99.99%, to remove surperficial grease and dirt, then it is put into the ion beam sputtering chamber, vacuum tightness reaches 1.0 * 10 in chamber
-4During Pa, pass into the sputter gas argon gas, start cleaning device, sample was cleaned 5 minutes, then open sputter gun, making its line voltage is 750V, acceleration voltage 220V, line 25mA, sparking voltage are that 60V carries out ion beam deposition, obtain high-quality Zn film after 30 minutes, the high quality Zn film that obtains through ion beam depositing is carried out N in atmosphere furnace
2, O
2Mixed gas the high temperature anneal, 600 ℃ of annealing temperatures, annealing time 2 hours, N
2, O
2Flow is respectively 15sccm and 10sccm, obtains at last N ZnO thin film doped.Be N doping P type ZnO film through Hall effect detection display film, resistivity is 7.28 * 10
2Ohm. centimetre, hole is 1.3 * 10
16/ cm
3
Embodiment 2:
The sputter gun filming parameter is: line voltage is 800V, acceleration voltage 210V, and line 20mA, sparking voltage are 70V, 650 ℃ of annealing temperatures, annealing time 2 hours, N
2, O
2Flow is respectively 12sccm and 8sccm, and step is with embodiment 1.Detected result shows that the thin film crystallization quality is very good, and is N doping P type ZnO film, and resistivity is 6.37 * 10 ohm. centimetre, hole is 2.7 * 10
17/ cm
3
Embodiment 3:
The sputter gun filming parameter is: line voltage is 700V, acceleration voltage 230V, and line 30mA, sparking voltage are 55V, 700 ℃ of annealing temperatures, annealing time 2 hours, N
2, O
2Flow is respectively 18sccm and 12sccm, and step is with embodiment 1.Detected result shows that the thin film crystallization quality is very good, and is N doping P type ZnO film, and resistivity is 5.28 ohm. centimetre, hole is 1.32 * 10
17/ cm
3
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Any those of ordinary skill in the art, do not breaking away from the technical solution of the present invention scope situation, all can utilize method and the technology contents of above-mentioned announcement that technical solution of the present invention is made many possible changes and modification, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention, any simple modification of above embodiment being done according to technical spirit of the present invention, be equal to replacements, equivalence changes and modify, all still belong in the scope that technical solution of the present invention protects.
Claims (3)
1. one kind directly prepares the ZnO thin film doped method of N take the Zn film as base material, it is characterized in that, may further comprise the steps:
(1) select cleaning Si sheet as substrate material, take the metallic zinc of purity as 99.99% as sputtering target material;
(2) substrate material is put into the ion beam sputtering chamber, and vacuum tightness reaches 1.0 * 10 in chamber
-4During Pa, pass into the sputter gas argon gas, start cleaning device, substrate material is cleaned;
(3) after substrate material cleans and finishes, open sputter gun, carry out ion beam deposition, line voltage is 700～800V, acceleration voltage 210～230V, and line 20～30mA, sparking voltage are 50～70V;
(4) the Zn film that obtains through ion beam depositing carries out N in atmosphere furnace
2, O
2It is ZnO thin film doped that mixed gas anneal directly obtains N, and Hall effect detection display gained film is N doping P type ZnO film.
2. a kind of ZnO thin film doped method of N that directly prepares take the Zn film as base material according to claim 1 is characterized in that, passes into N in step (4) atmosphere furnace
2And O
2Volume ratio be 1.5:1.
3. a kind of ZnO thin film doped method of N that directly prepares take the Zn film as base material according to claim 1 is characterized in that, the temperature of step (4) anneal is 600～700 ℃, and the time is 2 hours.
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| CN2012104690967A CN102925856A (en) | 2012-11-20 | 2012-11-20 | Method for directly preparing nitrogen-doped zinc oxide film by taking zinc film as base material |
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| CN2012104690967A CN102925856A (en) | 2012-11-20 | 2012-11-20 | Method for directly preparing nitrogen-doped zinc oxide film by taking zinc film as base material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754443A (en) * | 2018-06-04 | 2018-11-06 | 中建材蚌埠玻璃工业设计研究院有限公司 | A method of improving the ZnO thin film doped fluorescent characteristics of N |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030126742A1 (en) * | 2001-12-25 | 2003-07-10 | Jyh-Ming Ting | Method of fabrication of ZnO nanowires |
| CN1461044A (en) * | 2003-06-11 | 2003-12-10 | 浙江大学 | Method for preparing p-type zinc oxide film |
| CN102212792A (en) * | 2011-06-15 | 2011-10-12 | 蚌埠玻璃工业设计研究院 | Method for preparing nitrogen-doped P-type zinc oxide film in one step by using nitrogen as doping source |
-
2012
- 2012-11-20 CN CN2012104690967A patent/CN102925856A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030126742A1 (en) * | 2001-12-25 | 2003-07-10 | Jyh-Ming Ting | Method of fabrication of ZnO nanowires |
| CN1461044A (en) * | 2003-06-11 | 2003-12-10 | 浙江大学 | Method for preparing p-type zinc oxide film |
| CN102212792A (en) * | 2011-06-15 | 2011-10-12 | 蚌埠玻璃工业设计研究院 | Method for preparing nitrogen-doped P-type zinc oxide film in one step by using nitrogen as doping source |
Non-Patent Citations (2)
| Title |
|---|
| N. Y. GARCES ET AL.: "Production of nitrogen acceptors in ZnO by thermal annealing", 《APPLIED PHYSICS LETTERS》 * |
| 顾金宝: "ZnO薄膜的制备与性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅱ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754443A (en) * | 2018-06-04 | 2018-11-06 | 中建材蚌埠玻璃工业设计研究院有限公司 | A method of improving the ZnO thin film doped fluorescent characteristics of N |
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Application publication date: 20130213 |