CN101780946A - Method for preparing ZnSe nano wire films by pulsed laser ablation deposition - Google Patents
Method for preparing ZnSe nano wire films by pulsed laser ablation deposition Download PDFInfo
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- CN101780946A CN101780946A CN200910045496A CN200910045496A CN101780946A CN 101780946 A CN101780946 A CN 101780946A CN 200910045496 A CN200910045496 A CN 200910045496A CN 200910045496 A CN200910045496 A CN 200910045496A CN 101780946 A CN101780946 A CN 101780946A
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Abstract
The invention belongs to the technical field of film preparation and particularly relates to a method for preparing ZnSe nano wire films by pulsed laser ablation deposition. In the method, a pulsed laser ablation solid zinc selenide (ZnSe) material with high power is utilized, and the surface of the ZnSe material is quickly ablated and evaporated in a very short time to form a pinniform plasma. The plasma comprises zinc (Zn) and selenium (Se) atoms and ions. The ZnSe plasma has a high temperature and kinetic energy, so the ZnSe nano wire can grow under a lower substrate temperature. The synthesized film consists of uniform ZnSe nanowires, the average size of the ZnSe nano wires is about 20-30 nm, and the length is about 500 nm.
Description
Technical field
The invention belongs to the film preparing technology field, be specifically related to the method that a kind of pulsed laser ablation deposition prepares ZnSe nano wire films.
Background technology
Zinc selenide (ZnSe) can be used for making bluish-green wave band semiconductor laser diode (LD), light emitting diode (LED), photodetector and solar cell etc. as a kind of important broad-band gap II-VI family semi-conducting material.ZnSe has zincblende and two kinds of structures of pricker zinc ore, belongs to face-centered cubic and hex crystal respectively, and fusing point is more than 1500 ℃.ZnSe has the energy gap (2.7ev) of broad, big transparency range (0.5～22 μ m), higher luminous efficiency, low absorption coefficient.
1991, ZnSe has obtained breakthrough in the application of wide band gap semiconducter light source field, Minnesota Mining and Manufacturing Company's growing ZnSe extension on the GaAs substrate has been succeeded in developing first ZnSe base electric pump Pu green blue laser in the world, the wavelength of this device is 490nm, with pulse mode work, caused the great interest of academia in the world under the 77K.1993, people such as Nakayama produced the ZnSe bluish-green laser device that can at room temperature work with continuous wave (CW) again.The ZnSe base semiconductor material provides a new selection for the wide band gap semiconducter light source.At present, the ZnSe base semiconductor material mainly still is at laboratory stage in the exploration of application facet, because the lattice mismatch of ZnSe and GaAs only is 0.27%, so high-quality ZnSe film is mainly grown on the GaAs substrate; From the angle of integrated optoelectronics, growing ZnSe film and then realize that opto-electronic device is integrated and have a more practical meaning on Si substrate commonly used.
The preparation of ZnSe one-dimensional nano structure becomes the new focus of this semi-conducting material research in recent years, and the ZnSe nano wire has tempting prospect aspect the preparation nano photoelectric device.Up to now, reported the synthetic method of multiple ZnSe nano wire,, but yet there are no the report for preparing the ZnSe nano wire with the pulsed laser ablation deposition method as surperficial soft mode method, chemical vapour deposition (CVD), molecular beam epitaxial growth, Thermochemical Decomposition and hydro-thermal method etc.
Summary of the invention
The objective of the invention is to propose the method that a kind of employing pulsed laser ablation deposition prepares zinc selenide (ZnSe) nano wire film, method of the present invention can make the ZnSe nano wire grow on silicon substrate, and underlayer temperature is dropped to below 300 ℃.
The method of the employing pulsed laser ablation deposition that the present invention proposes synthetic ZnSe nano wire film on the silicon substrate below 300 degrees centigrade, be to utilize high-power pulse laser ablation solid zinc selenide material, at the utmost point zinc selenide material surface ablated rapidly and evaporate and formation pinniform plasma.The atom and the ion that comprise zinc (Zn) and selenium (Se) in the plasma.The zinc selenide plasma has very high temperature and kinetic energy, and this makes that ZnSe nano wire can be in lower underlayer temperature (300 degrees centigrade) growth down.
The structure of the impulse laser deposition system that the present invention uses as shown in Figure 1.
This device is made up of pulse laser, thin film deposition chamber, substrate pedestal and vacuum system.Pulse laser and thin film deposition chamber are independent, and laser beam focuses on by condenser lens and incides target material surface by window; Substrate pedestal is in the thin film deposition chamber interior, and its one side that substrate is installed is vertically over against the target platform, and distance between the two is 4 centimetres; Thin film deposition chamber links with vacuum system, and vacuum system is made up of a molecular pump and a mechanical pump.
The laser instrument that uses among the present invention is the model661-10S/N171 of Continuum, and its energisation mode is the light stimulus mode that generally adopts, and the particle that will be in ground state is pumped into excitation state, to form population inversion.This laser instrument adopts xenon flash lamp pumping, generally needs preheating 30 minutes, and is more stable with the output that guarantees laser power.
As active ions, the optical maser wavelength that the Nd:YAG laser instrument produces is 1064nm to the Nd:YAG Q-switched laser, by frequency-doubling crystal, can produce two frequency multiplication 532nm and frequency tripling 355nm with the trivalent neodymium ion.Used in the present invention mainly is the green glow of 532nm, belongs to visible-range, is convenient to the light path adjustment.
Thin film deposition chamber is spherical in shape, can place two targets simultaneously on rotatable target body support, is respectively Au (or Ni target) and ZnSe solid target as catalyst.Regulate one of them target of control and substrate on same straight line, substrate and the parallel placement of target platform, distance is 4cm approximately, and substrate is installed on the substrate.Laser beam focuses on the back through the condenser lens of cavity front and beats on target, consequent action of plasma to the substrate of the parallel placement of target platform on, the realization pulsed laser ablation deposition.In deposition process, can rotate substrate and target platform simultaneously, make film growth comparatively even, obtain the film of better quality.The advantage in this plated film chamber is, can place Au target and ZnSe target simultaneously, behind plating Au, only needs a rotary target body support frame just can change the ZnSe target into like this, changes target and need not to open the plated film chamber.
Vacuum system used in the present invention mainly is made of vacuum coating chamber, mechanical pump, molecular pump, magnetic valve, heating system, digital display control panel.Vacuum chamber is taken out by the side with mechanical pump and is connected; The plated film chamber links to each other by butterfly valve with molecular pump, and molecular pump links to each other by magnetic valve with mechanical pump.At first open the storehouse valve during use, vacuumize the chamber, at this moment butterfly valve and closed electromagnetic valve with mechanical pump; After a few minutes, open magnetic valve, close and close the storehouse valve, allow mechanical pump take out molecular pump, open butterfly valve then and vacuumize the chamber.When air pressure is reduced in the 10Pa by the time, just can start molecular pump.Molecular pump must keep water cooling plant to open when using, otherwise protective device can make the equipment autostop, even damages instrument.
Concrete steps with the pulsed laser ablation deposition ZnSe nano wire films are as follows:
The first step in the coarse surface of silicon of polishing, utilizes the gold of method deposition one deck 20-100nm of pulsed laser deposition or nickel as the intermediate layer.Be deposited in the base vacuum and carry out, vacuum is 2 * 10
-3Handkerchief, the distance of substrate and target are 4 centimetres, and laser power is 0.3 watt, and used pulse laser frequency is 5 hertz, and sedimentation time is 10 minutes, and substrate does not heat in the deposition process; Catalytic action is played in the deposition intermediate layer, is in order to promote the formation of ZnSe nano wire structure.
Second step was heated to 300-400 degree centigrade with the substrate that plated the intermediate layer, can impel the intermediate layer bead of a few to tens of nanometers to form at substrate surface; The size of the diameter of synthetic ZnSe nano wire will be relevant with the size of intermediate layer bead.
In the 3rd step, be heated in temperature on 300-400 degree centigrade the substrate and deposit ZnSe nano wire films.Forward solid zinc selenide target the focus place of pulse laser beam to, utilize the method deposition ZnSe nano wire films of pulsed laser deposition.Be deposited in the base vacuum and carry out, vacuum is 2 * 10
-3Handkerchief, the distance of substrate and target are 4 centimetres, and laser power is 0.3 watt, and used pulse laser frequency is 10 hertz, and sedimentation time is 30 minutes, keep underlayer temperature constant in the deposition process.
The more excellent condition that the pulsed laser ablation deposition method prepares ZnSe nano wire films is as follows:
4 centimetres of the distances of substrate and target
Settling chamber's base vacuum 2 * 10
-3Handkerchief
Underlayer temperature 300-400 degree centigrade
The every pulse of laser intensity 30 millijoules
The main performance index of the ZnSe nano wire films that the pulsed laser ablation deposition method is synthetic is as follows:
Film is made of uniform ZnSe nano wire;
The bottom diameter of ZnSe nano wire is approximately the 20-30 nanometer, and length is about 200 nanometers;
Zinc selenide is a nano thread structure, and the ratio of selenium and zinc was near 1: 1.
The pulsed laser ablation deposition preparation method's of ZnSe nano wire films provided by the present invention advantage is: (1) intense pulse laser bundle can have high power density, can make infusible compound target flash evapn (the component distortion is very little), target temperature tens degree that only raise have been avoided pollution and the undesirable product brought because of the required pyroprocess of chemical reaction in physics or the chemical vapour deposition (CVD); (2) by regulating background gas pressure, can control atom that laser ablation produces or atomic ion at the collision frequency in the substrate flight course, thereby the nanowire size of the film of control deposition (nucleus forms in flight course, collision frequency decision nucleus size); (3) the laser ablation particle and the substrate effect of certain kinetic energy can make the kinetic energy of part particle change the surface migration energy into, help improving synthesis of nano toe-in crystalloid amount under low underlayer temperature, underlayer temperature can be reduced significantly, the adhesive force of film and substrate can also be increased; (4) can control the growth course of nano wire by controlling laser pulse number of times and energy more conveniently; (5) separate lasing light emitter synsedimentary chamber, does not have the problem of homologous ray compatibility, makes device comparatively simple, convenient and economical.
Utilize the ZnSe nano wire films of the pulsed laser ablation deposition preparation method preparation of ZnSe nano wire films provided by the present invention to be made up of uniform ZnSe nano wire, the mean size of nano wire is about the 20-30 nanometer, and length is about 500 nanometers.
Description of drawings
Fig. 1 is a pulsed laser ablation deposition device schematic diagram used in the present invention.
Fig. 2 is the surface topography stereoscan photograph of the ZnSe nano wire films of this method preparation.
Fig. 3 is the transmission electron microscope photo of the ZnSe nano wire films of this method preparation.
Fig. 4 is the X-ray diffractogram of the ZnSe nano wire films of this method preparation.
Fig. 5 is the Raman spectrum of the ZnSe nano wire films of this method preparation.
Specific embodiments
Below in conjunction with specific embodiment, the present invention is further elaborated.Embodiment only is used for the present invention is done explanation rather than limitation of the present invention.
Embodiment 1:
The pulsed laser ablation deposition system that the present invention adopts, its structure as shown in Figure 1, it is made up of laser beam 1, condenser lens 2, zinc selenide target body 4, catalyst nickel target body 5, target body support 6, substrate 7, heater 8, target body turning cylinder 10, dc source 11, vavuum pump 12 and pumped vacuum systems 13.Wherein zinc selenide target body 4 and catalyst nickel target body 5 all are installed on the target body support 6, can rotate by target body turning cylinder 10, make zinc selenide target body 4 or catalyst nickel target body 5 forward laser beam focusing place to, thereby produce plasma 14, like this after having plated catalyst nickel, only need the rotary target body support frame just can change the zinc selenide target into, change target and need not to open the plated film chamber.Silicon substrate is installed on the substrate 7, and substrate is with parallel by the target body of laser ablation, and both distances are 4 centimetres, and the plasma that is produced by the laser ablation target body can be transported on the substrate like this, deposits on substrate, grows nano wire film.By adding dc source 11, can be by 7 heating of 8 pairs of substrates of heater.
Present embodiment need carry out in a vacuum, and vacuum is 2 * 10
-3Handkerchief vacuumizes by pumped vacuum systems 13, reaches the vacuum requirement.
The first step in the coarse surface of silicon of polishing, utilizes the gold of method deposition one deck 50nm of pulsed laser deposition or nickel as the intermediate layer.Be deposited in the base vacuum and carry out, vacuum is 2 * 10
-3Handkerchief, the distance of substrate and target are 4 centimetres, and laser power is 0.3 watt, and used pulse laser frequency is 5 hertz, and sedimentation time is 10 minutes, and substrate does not heat in the deposition process; Catalytic action is played in the deposition intermediate layer, is in order to promote the formation of ZnSe nano wire structure.
Second step was heated to 300 degrees centigrade with the substrate that plated the intermediate layer, impelled the intermediate layer bead of a few to tens of nanometers to form at substrate surface; The size of the diameter of synthetic ZnSe nano wire will be relevant with the size of intermediate layer bead.
In the 3rd step, be heated in temperature on 300 degrees centigrade the substrate and deposit ZnSe nano wire films.Forward solid zinc selenide target the focus place of pulse laser beam to, utilize the method deposition ZnSe nano wire films of pulsed laser deposition.Be deposited in the base vacuum and carry out, vacuum is 2 * 10
-3Handkerchief, the distance of substrate and target are 4 centimetres, and laser power is 0.3 watt, and used pulse laser frequency is 10 hertz, and sedimentation time is 30 minutes, keep underlayer temperature constant in the deposition process.
The constituent structure index of synthetic ZnSe nano wire is as follows:
Film is made of uniform ZnSe nano wire, and nanowire density is about 2 * 10
9Cm
-2
The bottom diameter of ZnSe nano wire is approximately 50 nanometers, and length is about 500 nanometers;
Zinc selenide is a nano thread structure, and the ratio of selenium and zinc was near 1: 1.
Embodiment 2:
Pulsed laser ablation deposition system and preparation process are with embodiment 1, and the parameter of preparation process is as follows:
The distance of substrate and target: 4 centimetres, settling chamber's base vacuum: 2 * 10
-3Handkerchief, intermediate layer thickness: 100 nanometers, underlayer temperature: 400 degrees centigrade, laser intensity: the every pulse of 30 millijoules
The constituent structure index of synthetic ZnSe nano wire is as follows:
Film is made of uniform ZnSe nano wire; Nanowire density is 2.5 * 10
9Cm
-2
The diameter of ZnSe nano wire is approximately 20 nanometers, and length is about 500 nanometers;
Zinc selenide is a nano thread structure, and the ratio of selenium and zinc was near 1: 1.
Embodiment 3:
Pulsed laser ablation deposition system and preparation process are with embodiment 1, and the parameter of preparation process is as follows:
The distance of substrate and target: 4 centimetres, settling chamber's base vacuum: 2 * 10
-3Handkerchief, intermediate layer thickness: 100 nanometers, underlayer temperature: 300 degrees centigrade, laser intensity: the every pulse of 30 millijoules
The constituent structure index of synthetic ZnSe nano wire is as follows:
Film is made of uniform ZnSe nano wire; Nanowire density is 8 * 10
9Cm
-2
The diameter of ZnSe nano wire is approximately 50 nanometers, and length is about 200 nanometers;
Zinc selenide is a nano thread structure, and the ratio of selenium and zinc was near 1: 1.
Embodiment 4:
Pulsed laser ablation deposition system and preparation process are with embodiment 1, and the parameter of preparation process is as follows:
The distance of substrate and target: 4 centimetres, settling chamber's base vacuum: 2 * 10
-3Handkerchief, intermediate layer thickness: 100 nanometers, underlayer temperature: 300 degrees centigrade, laser intensity: the every pulse of 20 millijoules
The constituent structure index of synthetic ZnSe nano wire is as follows:
Only there is nano wire to generate at regional area;
The diameter of ZnSe nano wire is approximately 20 nanometers, and length is about 400 nanometers;
Zinc selenide is a nano thread structure, and the ratio of selenium and zinc was near 1: 1.
Claims (6)
1. the pulsed laser ablation deposition preparation method of a ZnSe nano wire films, it is characterized in that by following step: at first at the catalyst nickel of substrate material surface deposition 50-100 nanometer or gold as the intermediate layer, then with the substrate heating, again with pulsed laser ablation deposition method deposition zinc selenide layer.
2. preparation method according to claim 1 is to carry out in base vacuum when it is characterized in that described deposited catalyst intermediate layer, and substrate does not heat in the deposition process.
3. preparation method according to claim 1, when it is characterized in that described usefulness pulsed laser ablation deposition method deposits the zinc selenide layer, deposition is to carry out in a vacuum.
4. preparation method according to claim 1, when it is characterized in that described usefulness pulsed laser ablation deposition method deposits the zinc selenide layer, sedimentation time is 30-60 minute.
5. preparation method according to claim 1 is characterized in that the substrate behind the intact intermediate layer of described deposition is heated to 300-400 degree centigrade.
6. preparation method according to claim 1 is characterized in that the catalyst of described substrate material surface deposition is a nickel.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088422A (en) * | 2013-01-18 | 2013-05-08 | 南京理工大学 | Preparation method of molybdenum trioxide nanorod |
| CN110344110A (en) * | 2019-06-24 | 2019-10-18 | 江苏守航实业有限公司 | A kind of preparation method of nitrogenous semiconductor nano material |
| CN111446358A (en) * | 2020-05-22 | 2020-07-24 | 北京航空航天大学杭州创新研究院 | High-precision rapid thin-film thermoelectric device based on pulse laser ablation and preparation method thereof |
-
2009
- 2009-01-16 CN CN200910045496A patent/CN101780946A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088422A (en) * | 2013-01-18 | 2013-05-08 | 南京理工大学 | Preparation method of molybdenum trioxide nanorod |
| CN103088422B (en) * | 2013-01-18 | 2015-05-13 | 南京理工大学 | Preparation method of molybdenum trioxide nanorod |
| CN110344110A (en) * | 2019-06-24 | 2019-10-18 | 江苏守航实业有限公司 | A kind of preparation method of nitrogenous semiconductor nano material |
| CN111446358A (en) * | 2020-05-22 | 2020-07-24 | 北京航空航天大学杭州创新研究院 | High-precision rapid thin-film thermoelectric device based on pulse laser ablation and preparation method thereof |
| CN111446358B (en) * | 2020-05-22 | 2022-08-05 | 北京航空航天大学杭州创新研究院 | High-precision rapid thin-film thermoelectric device based on pulse laser ablation and preparation method thereof |
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Application publication date: 20100721 |