CN102181829B - Method for preparing p-type zinc oxide film through K-H co-doping - Google Patents
Method for preparing p-type zinc oxide film through K-H co-doping Download PDFInfo
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- CN102181829B CN102181829B CN 201110102010 CN201110102010A CN102181829B CN 102181829 B CN102181829 B CN 102181829B CN 201110102010 CN201110102010 CN 201110102010 CN 201110102010 A CN201110102010 A CN 201110102010A CN 102181829 B CN102181829 B CN 102181829B
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Abstract
The invention relates to a method for preparing a p-type zinc oxide film through K-H co-doping. At present, the preparation of a K-H co-doped p-ZnO film is not performed by using a pulse laser deposition method. The method provided by the invention comprises the following steps of: firstly, performing ball-mill mixing on potassium hydroxide powder, zinc oxide powder and a caking agent in a ball mill to obtain precursor powder; secondly, performing press forming on the precursor powder, and sintering the precursor powder to obtain a potassium hydroxide doped zinc oxide target material; thirdly, putting the target material and a substrate into a vacuum chamber of a pulse laser deposition device respectively, heating the substrate, introducing a mixed gas of argon and oxygen into the vacuum chamber, and starting a laser source in the pulse laser deposition device to shoot laser beams to the target material so as to grow a film; and finally, when the film grows to the required thickness, turning off the laser source, and performing in situ annealing under an oxygen protected atmosphere. According to the method provided by the invention, the doping concentration is high and is controllable at the same time, gap filling defects can be overcome, and the prepared p-type ZnO film has high electrical properties, repeatability and stability.
Description
Technical field
The present invention relates to a kind of
pPreparing method, the especially K-H of type oxidized form film mix the method for preparing zinc-oxide film altogether, belong to semiconductor optoelectronic thin-film material and device technology field.
Background technology
Zinc oxide (ZnO) particularly up to the exciton bind energy of 60meV, makes it have application potential in ultraviolet/near ultraviolet short-wavelength light field of electronic devices owing to have the desired nearly all excellent specific property of room temperature short-wavelength light electric material.At present, influencing the biggest obstacle that ZnO plays a role in devices field is it
pType doping problem also is not solved.In recent years about
pVA family element is mainly concentrated in the selection of type doping agent, but the VA family solid solubility of element in ZnO is lower, mixes back acceptor impurity ionization difficulty, is difficult for being
pThe type conduction.First principle calculates and shows that IA family element has more shallow acceptor level, is prone to the hole carrier conduction behind the alternative Zn ion.But Li in the IA family or Na more are inclined to because its ionic radius is less and are positioned at the calking position, thereby become alms giver's defective.The K element has bigger ionic radius and has overcome this difficulty, and displacement Zn atom becomes shallow acceptor easily.For increasing the solid solubility of acceptor dopants, receiving master-alms giver's codoped is the method that people use always, and H is positioned at the calking position as involuntary alloying element in the ZnO lattice, plays alms giver's effect, and K has formed with displacement
K Zn -H i Thereby relevant shallow acceptor group presents ZnO
pThe type conduction.
Pulsed laser deposition has advantages such as quality of forming film height, underlayer temperature is low, the target film component is prone to be consistent, and does not carry out in this way also at present that K-H mixes altogether
pThe preparation of-ZnO film.
Summary of the invention
The object of the present invention is to provide a kind of K-H to mix preparation altogether
pThe method of type zinc-oxide film.
The concrete steps of the inventive method are:
1. step with analytical pure Pottasium Hydroxide powder and analytical pure Zinc oxide powder ball mill mixing 8～10 hours in ball mill, adds sticker in the ball mill mixing process, forms forerunner's powder, and described sticker is the polyvinyl alcohol of purity 99.99%; The quality percentage composition of Pottasium Hydroxide is 0.1～1.0% in composite forerunner's powder, and the quality percentage composition of sticker is 3～10%;
Step is 2. with the compression moulding of forerunner's powder, 500～800 ℃ of following presintering 1～2 hour, 1000～1300 ℃ of following sintering 2～4 hours, makes the zinc oxide target of mixing Pottasium Hydroxide then;
The vacuum chamber that the zinc oxide target of mixing Pottasium Hydroxide that 3. step will make and the substrate behind the cleaning surfaces are put into the pulsed laser deposition device respectively; Distance between target and the substrate is 6～10cm, and the vacuum tightness in the vacuum chamber is 10
-3～10
-4Pa;
Step is heated substrate 4., and temperature remains on 400～600 ℃; The gas mixture that feeds argon gas and oxygen in the vacuum chamber is as film growth atmosphere, and wherein oxygen partial pressure compares 10～40% in the gas mixture;
Step is the laser source in the unbalanced pulse laser deposition device 5., and laser beam is beaten on target, carries out film growth; Laser frequency is 3～5Hz, and energy is 300～500mJ;
After the film that 6. step grows reaches desired thickness, close laser source, under the oxygen protective atmosphere, carry out in-situ annealing, annealing time is 30～90min, and annealing temperature is 300～700 ℃.
Described substrate is silicon single crystal or monocrystalline sapphire polished section.
The purity of the analytical pure Pottasium Hydroxide powder of step described in 1. and analytical pure Zinc oxide powder is more than or equal to 99.99%.
The argon gas of step described in 4. and oxygen purity are more than or equal to 99.999%.
The present invention is through regulating the mass percent of KOH in ZnO, can prepare different levels of doping
pThe type ZnO film, the thickness of growth is by laser energy and growth time decision.
The beneficial effect that the present invention has is:
1. can avoid generating interstitial defect, because the K ionic radius is bigger, its calking forms and can form ability far above displacement, receives major defects thereby be more prone to form.
2. doping content is higher, owing to form
K Zn -H i The donor-acceptor group, help improving the solid solubility of K element in ZnO, thereby improve its doping content.
3. can in the ZnO crystal film growth, realize the real-time codoped of K, H, wherein H is involuntary alloying element.
4. doping content is controlled, through regulating KOH and the ZnO mass ratio in the target, the content of K impurity in the may command ZnO film crystal.
5. prepare
pThe type ZnO film has good electric property, and repeatability is better with stability.
Description of drawings
Fig. 1 makes for one embodiment of the invention
pThe X-ray diffraction of type ZnO film (XRD) collection of illustrative plates.
Embodiment
The present invention is further described through instance below in conjunction with accompanying drawing.
Embodiment 1
With purity is 99.99% 189 gram ZnO powders and 1 gram KOH powder ball mill mixing 9 hours in ball mill, adds 10 gram purity in the ball mill mixing process and be 99.99% polyvinyl alcohol, forms forerunner's powder of 200 grams; With the compression moulding of forerunner's powder,, 1200 ℃ of following sintering 3 hours, make the ZnO target of mixing KOH then 600 ℃ of following presintering 1.5 hours; With the vacuum chamber that the ZnO target of mixing KOH that makes and the monocrystalline substrate behind the cleaning surfaces are put into the pulsed laser deposition device respectively, the distance between target and the substrate is 8cm, and the vacuum tightness in the vacuum chamber is 5 * 10
-4Pa; Feed purity in the heated substrate to 500 ℃, vacuum chamber and be 99.999% the argon gas and the gas mixture of oxygen, the intrinsic standoff ratio of oxygen is 25% in the gas mixture; Laser source in the unbalanced pulse laser deposition device, laser beam is beaten on target, carries out film growth, and laser frequency is 4Hz, and energy is 400mJ; After the film of growth reaches desired thickness, close laser source, in-situ annealing 60min under the oxygen protective atmosphere, annealing temperature is 500 ℃.
The K-H that makes mixes the ZnO crystal film altogether and is
pThe type conduction, and have excellent room temperature electric property, hole concentration reaches 8.96 * 10
17Cm
-3, resistivity is 6.2 Ω .cm, hall mobility is 1.24 cm
2/ V.s.And electric property does not have considerable change after placing several months.
The X-ray diffraction of above-mentioned film (XRD) collection of illustrative plates is seen Fig. 1, and ZnO has only (002) diffraction peak to occur, and shows the K-H codoped that the inventive method makes
pType ZnO crystal film has good crystal property and preferred orientation property.Si among the figure (111) is the diffraction peak of silicon substrate;
Embodiment 2
With purity is 99.99% 196.9 gram ZnO powders and 0.1 gram KOH powder ball mill mixing 8 hours in ball mill, adds 3 gram purity in the ball mill mixing process and be 99.99% polyvinyl alcohol, forms forerunner's powder of 100 grams; With the compression moulding of forerunner's powder,, 1000 ℃ of following sintering 4 hours, make the ZnO target of mixing KOH then 500 ℃ of following presintering 2 hours; With the vacuum chamber that the ZnO target of mixing KOH that makes and the monocrystalline substrate behind the cleaning surfaces are put into the pulsed laser deposition device respectively, the distance between target and the substrate is 6cm, and the vacuum tightness in the vacuum chamber is 10
-4Pa; Feed purity in the heated substrate to 400 ℃, vacuum chamber and be 99.999% the argon gas and the gas mixture of oxygen, the intrinsic standoff ratio of oxygen is 10% in the gas mixture; Laser source in the unbalanced pulse laser deposition device, laser beam is beaten on target, carries out film growth, and laser frequency is 3Hz, and energy is 300mJ; After the film of growth reaches desired thickness, close laser source, in-situ annealing 30min under the oxygen protective atmosphere, annealing temperature is 300 ℃.
The K-H that makes mixes the ZnO crystal film altogether and is
pThe type conduction, and have excellent room temperature electric property, hole concentration reaches 3.19 * 10
17Cm
-3, resistivity is 10.7 Ω .cm, hall mobility is 1.83 cm
2/ V.s.And electric property does not have considerable change after placing several months.
Embodiment 3
With purity is 99.995% 267 gram ZnO powders and 3 gram KOH powder ball mill mixing 10 hours in ball mill, adds 30 gram purity in the ball mill mixing process and be 99.99% polyvinyl alcohol, forms forerunner's powder of 300 grams; With the compression moulding of forerunner's powder,, 1300 ℃ of following sintering 2 hours, make the ZnO target of mixing KOH then 800 ℃ of following presintering 1 hour; The ZnO target of mixing KOH that makes and the monocrystalline sapphire polished section substrate behind the cleaning surfaces are put into the vacuum chamber of pulsed laser deposition device respectively, and the distance between target and the substrate is 10cm, and the vacuum tightness in the vacuum chamber is 10
-3Pa; Feed purity in the heated substrate to 600 ℃, vacuum chamber and be 99.9995% the argon gas and the gas mixture of oxygen, the intrinsic standoff ratio of oxygen is 40% in the gas mixture; Laser source in the unbalanced pulse laser deposition device, laser beam is beaten on target, carries out film growth, and laser frequency is 5Hz, and energy is 500mJ; After the film of growth reaches desired thickness, close laser source, in-situ annealing 90min under the oxygen protective atmosphere, annealing temperature is 700 ℃.
The K-H that makes mixes the ZnO crystal film altogether and is
pThe type conduction, and have excellent room temperature electric property, hole concentration reaches 6.47 * 10
17Cm
-3, resistivity is 4.3 Ω .cm, hall mobility is 2.27 cm
2/ V.s.And electric property does not have considerable change after placing several months.
Claims (4)
1.K-H mix preparation altogether
pThe method of type zinc-oxide film is characterized in that the concrete steps of this method are:
1. step with analytical pure Pottasium Hydroxide powder and analytical pure Zinc oxide powder ball mill mixing 8～10 hours in ball mill, adds sticker in the ball mill mixing process, forms forerunner's powder, and described sticker is the Z 150PH of purity 99.99%; The quality percentage composition of Pottasium Hydroxide is 0.1～1.0% in composite forerunner's powder, and the quality percentage composition of sticker is 3～10%;
Step is 2. with the compression moulding of forerunner's powder, 500～800 ℃ of following presintering 1～2 hour, 1000～1300 ℃ of following sintering 2～4 hours, makes the zinc oxide target of mixing Pottasium Hydroxide then;
The vacuum chamber that the zinc oxide target of mixing Pottasium Hydroxide that 3. step will make and the substrate behind the cleaning surfaces are put into the pulsed laser deposition device respectively; Distance between target and the substrate is 6～10cm, and the vacuum tightness in the vacuum chamber is 10
-3～10
-4Pa;
Step is heated substrate 4., and temperature remains on 400～600 ℃; The gas mixture that feeds argon gas and oxygen in the vacuum chamber is as film growth atmosphere, and wherein oxygen partial pressure compares 10～40% in the gas mixture;
Step is the laser source in the unbalanced pulse laser deposition device 5., and laser beam is beaten on target, carries out film growth; Laser frequency is 3～5Hz, and energy is 300～500mJ;
After the film that 6. step grows reaches desired thickness, close laser source, under the oxygen protective atmosphere, carry out in-situ annealing, annealing time is 30～90min, and annealing temperature is 300～700 ℃.
2. K-H according to claim 1 mixes preparation altogether
pThe method of type zinc-oxide film is characterized in that described substrate is silicon single crystal or monocrystalline sapphire polished section.
3. K-H according to claim 1 mixes preparation altogether
pThe method of type zinc-oxide film, the purity that it is characterized in that analytical pure Pottasium Hydroxide powder described in step 1. and analytical pure Zinc oxide powder is more than or equal to 99.99%.
4. K-H according to claim 1 mixes preparation altogether
pThe method of type zinc-oxide film is characterized in that argon gas described in step 4. and oxygen purity are more than or equal to 99.999%.
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| CN 201110102010 CN102181829B (en) | 2011-04-22 | 2011-04-22 | Method for preparing p-type zinc oxide film through K-H co-doping |
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| CN102181829B true CN102181829B (en) | 2012-12-26 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492928B (en) * | 2011-12-23 | 2013-09-04 | 杭州电子科技大学 | Double-acceptor co-doping method for growing p-(K-N):ZnO thin film |
| CN103103478B (en) * | 2013-01-16 | 2014-12-17 | 浙江工业大学 | Ag-S co-doped p-type ZnO film and preparation method thereof |
| CN108570643A (en) * | 2018-05-18 | 2018-09-25 | 华南师范大学 | A kind of preparation method of Er doping ZnO transparent conductive thin film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800299A (en) * | 2005-11-25 | 2006-07-12 | 浙江大学 | Method for preparing near-infrared light-emitting ZnO film doped with lithium and erbium |
| CN101037795A (en) * | 2007-01-29 | 2007-09-19 | 浙江大学 | Sb doped P-type ZnO crystal film and preparation method thereof |
| CN101603199A (en) * | 2009-06-11 | 2009-12-16 | 浙江大学 | The method of Li, Na growing p-type ZnO crystal film by codoping |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800299A (en) * | 2005-11-25 | 2006-07-12 | 浙江大学 | Method for preparing near-infrared light-emitting ZnO film doped with lithium and erbium |
| CN101037795A (en) * | 2007-01-29 | 2007-09-19 | 浙江大学 | Sb doped P-type ZnO crystal film and preparation method thereof |
| CN101603199A (en) * | 2009-06-11 | 2009-12-16 | 浙江大学 | The method of Li, Na growing p-type ZnO crystal film by codoping |
Non-Patent Citations (1)
| Title |
|---|
| Wu Jun et al.,.Fabrication and characterization of K-H co-doped p-ZnO thin films.《Proceedings of The Fifth International Conference on Physical and Numerical Simulation of Materials Processing》.2007,第1969页第1-31行. * |
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