CN102162129A - Method for preparing p-type zinc oxide nano rod array - Google Patents
Method for preparing p-type zinc oxide nano rod array Download PDFInfo
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- CN102162129A CN102162129A CN2011100829232A CN201110082923A CN102162129A CN 102162129 A CN102162129 A CN 102162129A CN 2011100829232 A CN2011100829232 A CN 2011100829232A CN 201110082923 A CN201110082923 A CN 201110082923A CN 102162129 A CN102162129 A CN 102162129A
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Abstract
The invention belongs to the technical field of semiconductor photo-electronic devices, and discloses a method for preparing a p-type zinc oxide nano rod array. The method comprises the following steps of: (1) preparing a high-purity zinc oxide film transition layer: [1] preparing a substrate by using quartz, sapphire or silicon, and [2] preparing the high-purity zinc oxide film transition layer; and (2) preparing the p-type zinc oxide nano rod array: [1] putting a zinc-potassium alloy source block and the substrate with the zinc oxide transition layer on a quartz boat together, conveying the quartz boat into a quartz tube of a vacuum annealing furnace and growing the p-type zinc oxide nano rod array, and [2] growing the p-type zinc oxide nano rod array by the following steps of: 1, vacuumizing the vacuum annealing furnace; 2, heating the vacuum annealing furnace; and 3, introducing mixed gas of Ar and O in a ratio of 2:1, growing for 20 minutes, and obtaining the p-type zinc oxide nano rod array. The method has the advantages of effectively solving the problem that the p-type zinc oxide is difficultly prepared and laying a solid foundation for producing zinc oxide-based photo-electronic devices.
Description
Technical field
The invention belongs to the semiconductor photoelectronic device technical field, relate to the method for technology such as utilizing magnetron sputtering plating, vapor transport and prepared p type nanometic zinc oxide rod array.
Background technology
Research to zinc oxide (ZnO) photoelectric information functional material was risen later on from 1997.In 1997, Japan and scientist's reported first in Hong Kong the near ultraviolet Stimulated Light-emission under the zinc-oxide film room temperature, it has caused the repercussion of industry intensive immediately." Science " (science) and " Nature " (nature) magazine have all carried out relevant report and commentary to the research, are called the important development of laser technology, are the work of a greatness.At present, the research of Zinc oxide-base opto-electronic device has been become very popular advanced subject, be subjected to extensive concern and development has rapidly been arranged, it mainly shows two aspects: 1. film light electronics preparation of devices, for example, photodiode, short wavelength laser, ultraviolet detector etc.; 2. the preparation of low-dimensional nano structure and opto-electronic device, for example, zinc oxide nanowire, nano ball shell, nanometer rod etc.Yet, prepare the zinc oxide opto-electronic device, must prepare stable, p type zinc oxide repeatably, because, can p type zinc oxide is related to the Zinc oxide-base opto-electronic device be successfully developed and industrialization, for example, and the development of short wavelength laser and photodiode and production.Theory and practice proves: the stable repeatably p type zinc oxide of preparation is very difficult, and this is a global difficult problem, and everybody is making great efforts to solve this difficult problem.This problem has seriously hindered the development of Zinc oxide-base opto-electronic device.
Though have at present much about preparing the report of p type zinc-oxide film, but, be difficult to find to have the preparation of high quality p type zinc-oxide film in these reports, its reason mainly is: mobility is lower, hole is lower and p type electricity is led the repeated low of feature.Cause the major cause of p type zinc oxide preparation difficulty to have: 1. in p type zinc oxide preparation process, zinc element and oxygen element are difficult to that (Zn:O=1:1) combine formation ZnO according to stoichiometric ratio, zinc element is excessive often, and the excessive meeting of zinc element causes a large amount of alms givers to exist in the zinc oxide, causes zinc oxide to present n type electricity and leads feature.2. be subjected to the master to mix element and be difficult to dissolve in zinc-oxide film, particularly utilize first main group element (for example Li, Na, K) when carrying out acceptor doping, these elements are difficult to be in the case that substitutes Zn, form the alms giver but be in interstitial site, cause film to present n type electricity and lead.3. the zinc-oxide film crystalline quality is not high, causes a large amount of alms giver's defectives to exist in the film, for example, and defectives such as hydrogen interstitial atom, oxygen room, dislocation.
Summary of the invention
The objective of the invention is, a kind of preparation method of p type nanometic zinc oxide rod array is provided, can prepare stable, p type nano structure of zinc oxide repeatably, lay the first stone for finally preparing the Zinc oxide-base opto-electronic device with it.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of p type nanometic zinc oxide rod array is characterized in that, comprises following preparation process:
(1) preparation high pure zinc oxide film transition layer
1. prepare substrate
Substrate is selected quartz, sapphire or silicon for use, before preparation zinc-oxide film transition layer, earlier substrate is cleaned, and cleaning step comprises:
The first step was with substrate in ethanol ultrasonic 3 to 5 minutes;
In second step, the substrate after the first step cleaning was used acetone ultrasonic 3 to 5 minutes again;
In the 3rd step, the substrate after second step cleaned was with hot salt acid soak 10～20 minutes, and soaking temperature is 70～120 ℃;
2. prepare high pure zinc oxide film transition layer
Adopt d.c. sputtering during growth, target is selected the zinc oxide of purity 〉=99.999% for use, and sputter gas is a high-purity argon gas, vacuum tightness is at 0.1Pa～10Pa during growth, sputtering power is 10～200 watts, and growth temperature is between 100～700 ℃, and the film thickness of employing is between 10～1000 nanometers;
(2) preparation of P type nanometic zinc oxide rod array
1. step (1) substrate preparation, that have the zinc oxide transition layer is placed on the quartz boat, zinc potassium-sodium alloy source piece is placed in the boat under the substrate, the distance of zinc source and substrate is 1～5mm, then, quartz boat is put into the growth of carrying out p type nanometic zinc oxide rod array in the silica tube of vacuum annealing furnace;
2. the growth step of p type nanometic zinc oxide rod array is:
The first step is given the vacuum annealing stove evacuation, and the vacuum tightness of obtaining is between 0.001Pa～0.1Pa;
Second step to the vacuum annealing furnace heating, kept in the heat-processed vacuumizing, and was heated to 400～1400 ℃;
The 3rd step fed gas, and gas is pressed A
r: O ratio mixes the back and feeds in the scope of 1:5～5:1, gas pressure intensity is controlled between 0.1Pa～20Pa, and growth time is 3～50 minutes; Obtain p type nanometic zinc oxide rod array.
The high purity zinc potassium-sodium alloy that contains mass percent 0.005%～5.000% potassium is adopted in the described zinc potassium-sodium alloy of step (2) source.
Positively effect of the present invention is:
(1) uses method of the present invention and can effectively solve the problem that p type zinc oxide is difficult to prepare, lay a solid foundation for producing the Zinc oxide-base opto-electronic device;
(2) current carrier mobility along the zinc oxide growth direction in the one-dimension zinc oxide structure is greater than its mobility in film, and therefore, the transport velocity of hole in the zinc-oxide nano bar structure is greatly improved; In addition, at preparation one deck zinc oxide transition layer of having grown before the nanometer rod, this has just formed p-ZnO nanometer rod/such homostyructure of n-ZnO film, and this kind structure is natural light emitting diode construction, thereby can prepare opto-electronic devices such as zinc oxide luminescent diode.
Embodiment
Below provide the preparation method's of a kind of p type of the present invention nanometic zinc oxide rod array embodiment, but be noted that enforcement of the present invention is not limited to following embodiment.
Why very difficult P type zinc-oxide film system mainly be because self compensation effect, the recipient element of zinc oxide are difficult to mix, the acceptor level position is high and be difficult to reason such as ionization.Theoretical Calculation shows: potassium element can the instead of zinc case, forms acceptor level, still, the adulterated zinc-oxide film of potassium also has the shortcoming of self, mainly be that potassium element forms gap potassium easily and forms the alms giver, therefore, Many researchers is difficult to realize the preparation of potassium doped p type zinc-oxide film.
In enforcement of the present invention, the contriver utilizes the small-size effect of nanostructure, has avoided the existence form of potassium in zinc-oxide film effectively, the preparation of the p type zinc oxide nano rod of the potassium of successfully having realized having mixed; Its technology comprises following several respects: (1) on substrate the high pure zinc oxide of sputter one deck purity 〉=99.999% as transition layer, transition layer is because the stress that lattice parameter difference causes between quartz substrate and the zinc oxide in order to have reduced, thereby reduce the required energy of nanorod growth initial stage forming core, helping zinc oxide nano rod can grow by certain orientation, forms nanometer stick array; (2) adopt zinc potassium-sodium alloy source as the zinc source, can realize effective doping of potassium element, and potassium element is on the zinc case; Simultaneously, because the size little (diameter of nanometer rod is generally 20nm between the 50nm) of nanometer rod makes that potassium is difficult to exist, thereby reduced donor concentration on the zinc oxide interstitial site, help nanometer rod and present p type electricity and lead feature; (3) hole carrier is greatly improved along the mobility of nanorod growth direction; (4) adopt the vacuum annealing furnace apparatus to carry out chemical vapor deposition growth, help adjusting growth temperature and growth atmosphere, thereby reach the control saturated vapor pressure, realize the purpose of preparation nanometer stick array.
EmbodimentA kind of preparation method of p type nanometic zinc oxide rod array the steps include:
(1) the high pure zinc oxide film transition layer of preparation purity 〉=99.999%
1. prepare substrate
Select for use quartz, sapphire or silicon to make substrate, earlier substrate is cleaned, cleaning step comprises:
The first step was with substrate in ethanol ultrasonic 3 to 5 minutes;
In second step, the substrate after the first step cleaning was used acetone ultrasonic 3 to 5 minutes again;
In the 3rd step, the substrate after second step cleaned was with hot salt acid soak 10～20 minutes, and soaking temperature is 70～120 ℃;
2. prepare high pure zinc oxide film transition layer
At first, utilize magnetron sputtering technique on quartz substrate, to prepare the high pure zinc oxide film of thickness for about 100 nanometers, target is selected the zinc oxide of purity 〉=99.999% for use, adopt d.c. sputtering, sputtering power is 30 watts, and sputter gas is an argon gas, and vacuum tightness is 3.0Pa during growth, growth temperature is 300 ℃, and growth time is 10 minutes;
(2) preparation of P type nanometic zinc oxide rod array
1. substrate step (1) preparation, that have the zinc oxide transition layer is placed on the quartz boat, zinc potassium-sodium alloy source piece is placed in the boat under the substrate, the distance of zinc source and substrate is 3mm; Then, quartz boat is put into the growth of carrying out p type nanometic zinc oxide rod array in the silica tube of vacuum annealing furnace; The high purity zinc potassium-sodium alloy that contains quality percentage composition 1.000% potassium is adopted in described zinc potassium-sodium alloy source;
2. the growth step of p type nanometic zinc oxide rod array is:
At first, give the vacuum annealing stove evacuation, being extracted into vacuum tightness is 0.001Pa; Secondly, give the vacuum annealing furnace heat temperature raising, keep in the heat-processed vacuumizing, be heated to 500 ℃ always; The 3rd, feed gas, gas is pressed A
r: O ratio=2:1 mixes the back and feeds, and gas pressure intensity is controlled at 3.0Pa, growth time 20 minutes; Obtain p type nanometic zinc oxide rod array.
Claims (2)
1. the preparation method of a p type nanometic zinc oxide rod array is characterized in that, comprises following preparation process:
(1) preparation high pure zinc oxide film transition layer
1. prepare substrate
Substrate is selected quartz, sapphire or silicon for use, before preparation zinc-oxide film transition layer, earlier substrate is cleaned, and cleaning step comprises:
The first step was with substrate in ethanol ultrasonic 3 to 5 minutes;
In second step, the substrate after the first step cleaning was used acetone ultrasonic 3 to 5 minutes again;
In the 3rd step, the substrate after second step cleaned was with hot salt acid soak 10～20 minutes, and soaking temperature is 70～120 ℃;
2. prepare high pure zinc oxide film transition layer
Adopt d.c. sputtering during growth, target is selected the zinc oxide of purity 〉=99.999% for use, and sputter gas is a high-purity argon gas, vacuum tightness is at 0.1Pa～10Pa during growth, sputtering power is 10～200 watts, and growth temperature is between 100～700 ℃, and the film thickness of employing is between 10～1000 nanometers;
(2) preparation of P type nanometic zinc oxide rod array
1. step (1) substrate preparation, that have the zinc oxide transition layer is placed on the quartz boat, zinc potassium-sodium alloy source piece is placed in the boat under the substrate, the distance of zinc source and substrate is 1～5mm, then, quartz boat is put into the growth of carrying out p type nanometic zinc oxide rod array in the silica tube of vacuum annealing furnace;
2. the growth step of p type nanometic zinc oxide rod array is:
The first step is given the vacuum annealing stove evacuation, and the vacuum tightness of obtaining is between 0.001Pa～0.1Pa;
Second step to the vacuum annealing furnace heating, kept in the heat-processed vacuumizing, and was heated to 400～1400 ℃;
The 3rd step fed gas, and gas is pressed A
r: O ratio mixes the back and feeds in the scope of 1:5～5:1, gas pressure intensity is controlled between 0.1Pa～20Pa, and growth time is 3～50 minutes; Obtain p type nanometic zinc oxide rod array.
2. the preparation method of a kind of p type nanometic zinc oxide rod array according to claim 1 is characterized in that, the high purity zinc potassium-sodium alloy that contains mass percent 0.005%～5.000% potassium is adopted in the described zinc potassium-sodium alloy of step (2) source.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970097A (en) * | 2019-04-11 | 2019-07-05 | 唐山学院 | A kind of preparation method of nano zine oxide and prepared nano zine oxide and application thereof |
| RU2737506C1 (en) * | 2020-03-10 | 2020-12-02 | Федеральное государственное учреждение "Федеральный научно-исследовательский центр "Кристаллография и фотоника" Российской академии наук" | Method of manufacturing scintillator for detectors of ionizing radiation, device for implementation thereof and scintillator for detectors of ionizing radiation |
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2011
- 2011-04-02 CN CN2011100829232A patent/CN102162129A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970097A (en) * | 2019-04-11 | 2019-07-05 | 唐山学院 | A kind of preparation method of nano zine oxide and prepared nano zine oxide and application thereof |
| CN109970097B (en) * | 2019-04-11 | 2021-03-23 | 唐山学院 | Preparation method of nano zinc oxide, prepared nano zinc oxide and application thereof |
| RU2737506C1 (en) * | 2020-03-10 | 2020-12-02 | Федеральное государственное учреждение "Федеральный научно-исследовательский центр "Кристаллография и фотоника" Российской академии наук" | Method of manufacturing scintillator for detectors of ionizing radiation, device for implementation thereof and scintillator for detectors of ionizing radiation |
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Application publication date: 20110824 |