CN102254997A - Method for preparing p-type ZnO film by using plasma immersion ion implantation technology - Google Patents
Method for preparing p-type ZnO film by using plasma immersion ion implantation technology Download PDFInfo
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- CN102254997A CN102254997A CN2011101973353A CN201110197335A CN102254997A CN 102254997 A CN102254997 A CN 102254997A CN 2011101973353 A CN2011101973353 A CN 2011101973353A CN 201110197335 A CN201110197335 A CN 201110197335A CN 102254997 A CN102254997 A CN 102254997A
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Abstract
The invention belongs to the technical field of preparation of semiconductor light-emitting materials, in particular relates to a method for preparing a p-type ZnO film by using a plasma immersion ion implantation technology. The plasma immersion ion implantation technology is combined with an N-Al codoping method, the advantages of the plasma immersion ion implantation technology and the N-Al codoping method are combined for preparing the p-type ZnO film with excellent performance: on the one hand, solid solubility of an acceptor element N can be enhanced by adopting plasmas immersion ion implantation, and ions to be injected are selectively injected; and on the other hand, the solid solubility of N can be enhanced by Al, and a stable N-Al-N compound is formed so that injected N is fixed, and due to the addition of the Al, electric characteristics of n-type ZnO and p-type ZnO can be simultaneously enhanced, thus a feasible method is provided for preparing an excellent homogeneous ZnOp-n junction, and an important basis is laid for the application of the homogeneous ZnOp-n junction on the aspects of LEDs, LDs (Laser Diodes) and the like.
Description
Technical field
The invention belongs to the semiconductive luminescent materials preparing technical field, be specifically related to a kind of method of utilizing the plasma immersion ion injection technique to prepare p type ZnO film.
Background technology
Photoelectron science and technology and industry development in recent years thereof are swift and violent, and as the basis and the guide of opto-electronics, photoelectric semiconductor material is the research and development emphasis in this field, then are the driving source of photoelectric semiconductor material development to the exploration of novel semiconductor light-emitting material.In the novel semiconductor light-emitting material, that at present of greatest concern is exactly zinc oxide (ZnO).ZnO is a kind of direct band gap wide bandgap semiconductor, and the energy gap under the room temperature is 3.37eV, and especially its exciton binding energy is the present unique a kind of photoelectric semiconductor material that may realize the ultraviolet stimulated emission under the room temperature pumping condition up to 60mV.And ZnO aboundresources, cheap, nontoxic, advantages such as mechanical-electric coupling performance that capability of resistance to radiation is strong and good, thereby be widely used in solar cell, surface acoustic wave device (SAW), liquid crystal display, gas sensor, pressure-sensitive device etc.Particularly after the light at room temperature pumping ultraviolet stimulated emission of ZnO is found, as a kind of novel direct broad-band gap photoelectric semiconductor material, ZnO also has huge application potential in transparency conductive electrode, indigo plant/ultraviolet light-emitting diode (LED) and fields such as laser (LD), ultraviolet detector, spin electric device and transducer.We can say that ZnO has become the another research focus of optoelectronic areas after GaN, caused extensive concern and great attention in the global range.Yet ZnO is natural is the n type, therefore how the processability excellence, repeatably, the high p type ZnO of stability is the main challenge that faces in the present ZnO research.
ZnO film p type modification at present mainly contains two kinds of methods, and a kind of is to mix theory by people such as Yamamoto and Yoshida altogether based on what first principle proposed, i.e. the codoping method of N+Group III element is mixed etc. altogether as N+Al, N+Ga, has been subjected to paying close attention to widely; Another kind of raising N method of solid solubility in ZnO is an ion implantation technique, is about to N
+Be injected in the ZnO sample.Although two kinds of methods all have advantage separately and have also realized p type modification to ZnO film, but have and deficiency that it is very big: the p type ZnO that obtains of the technology of mixing has often sacrificed its mobility when raising is subjected to main solid concentration altogether, and conventional beamline ion implanters injection efficiency is very low.Therefore the even injection technique of large tracts of land of seeking out a kind of practicality will provide very bright prospect for ion injects the p type modification that realizes ZnO.(Plasma Immersion Ion Implantation's plasma immersion ion injection technique PIII) just arises at the historic moment, for ion implantation technique has been opened up the wide new world of a slice.
It is bioengineering that plasma immersion ion injects (PIII), plasma physics, electronic engineering, the emerging laboratory course of subject crossing such as surface physics, inject to compare with beamline ion implanters and have a lot of advantages, plasma immersion injects and has the characteristics of " comprehensive; high dose ", can carry out comprehensive processing to complex-shaped various parts, can be applicable to Aero-Space, precision optical machinery, shipping industry, zero genus parts of equipment carry out surface treatment in the fields such as petroleum industry, increase substantially the overall performance (hardness of equipment, resistance to wear, anticorrosive and life-span etc.).Can carry out surface modification treatment to pottery, polymer etc., characteristics such as the light of change material surface, magnetic.The plasma immersion ion injection technique can also be applied to biomaterial and semi-conductor industry territory, forms super shallow p-n junction or the like as joint prosthesis, semiconductor doping.This technology has overcome the line-of-sight constraint of traditional beamline ion implanters injection technique, and characteristics such as have that equipment is simple, implantation dosage is high, injection length and object size are irrelevant are the significant innovations of ion implantation technique.And the PIII device simplifies greatly than the CBII device, and cost is low, safeguards and operating ratio is easier to, and is easy to promote and the realization industrialization.And the most important thing is that the plasma immersion ion injection technique has the unique advantage that two other any film-forming methods do not possess: the one, can be by the doping content of control implantation dosage and then control recipient element, the 2nd, can select the kind of the nitrogen ion that injects, promptly optionally inject.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the plasma immersion ion injection technique to prepare p type ZnO film, with the p type ZnO film of obtained performance excellence.
The method for preparing p type ZnO film provided by the invention is that using plasma immersion ion injection technique is aided with the method that N-Al mixes altogether, and the two advantage is combined, and prepares the p type ZnO film of excellent performance.Concrete steps are:
(1) at first mix the n type ZnO film (AZO) of Al by magnetron sputtering technique growth, the magnetron sputtering condition of work is: base vacuum 2 * 10
-4Pa-6 * 10
-4Pa, working gas high-purity Ar, operating pressure 0.1Pa-1Pa, radio-frequency power 100W-550W, constant 200 ℃-500 ℃ of underlayer temperature;
(2) the AZO film that obtains is placed on the sample stage in the PIII device, cavity vacuumizes.Afterwards, in cavity, feed the working gas that contains N, use even, the large volume inductively coupled plasma of 600W radio-frequency power supply generation face.The sample stage bias generator adopts the fast rising edge (1 of 10KW solid-state switching circuits
S) high-voltage pulse power source, pulsewidth and frequency are all adjustable.The injection condition of work is: working gas is NO+O
2Mist, operating air pressure 0.5Pa-1Pa, radio-frequency power 100W-550W, pulse duration 10 μ s-100 μ s, pulse frequency 10Hz-100 Hz, bias voltage size 1kV-30kV.High back bias voltage can interrupt original institutional framework and Cheng Jian again effectively when injecting, N is incorporated in the AZO film, obtain the ZnO that N-Al mixes altogether, the thermal radiation diffusion that causes of ion bombardment in addition, the injection degree of depth of ion can arrive the hundreds of nanometer, and injection composition density distribution can be that the back bias voltage size is controlled by ion energy;
(3) carry out annealing in process at last, by control annealing atmosphere, temperature etc., the N element that further activation has been injected improves crystallization situation and the p type modification situation of injecting rear film.Wherein annealing atmosphere is N
2, annealing temperature is 650 ℃-950 ℃, annealing time is 30min-60min.Promptly obtain presenting the ZnO film of p type characteristic.
Among the present invention, on the one hand plasma immersion ion injects the solid solubility that can improve recipient element N and selects row to inject to the ion that will inject; Al can improve the solid solubility of N and form stable N-Al-N complex on the other hand, thus the fixing N that injects; And the adding of Al can improve the electrology characteristic of n type ZnO and p type ZnO simultaneously, this just provides a kind of practicable method for the homogeneity ZnO p-n junction of preparation high-quality, thereby be homogeneity ZnO p-n junction at LED, important basis is established in the application of aspects such as LD.
Description of drawings
Fig. 1 carries out XRD and SEM sign to the AZO film that magnetron sputtering grows out, and we find that the AZO film of gained is the growth of (002) high preferred orientation, the c axle orientation of height is promptly arranged, and film surface are very even.Al
2O
3In the XRD spectrum, be not observed mutually, this explanation Al in thin film growth process does not have and O
2Reaction generates Al
2O
3
Fig. 2 is ZnO:(Al, N) the optical transmittance rate curve of film before and after the annealing.(before wherein the solid line representative is annealed, after the dotted line representative annealing, and OPPR represents O
2Shared volume ratio in mist is respectively 0% (being pure NO), 25%, 50%, 75%).
Embodiment
Method that the invention is further illustrated by the following examples, concrete steps are:
(1) mix the n type ZnO film (AZO) of Al by magnetron sputtering technique growth, the magnetron sputtering condition of work is: base vacuum 4 * 10
-4Pa, working gas high-purity Ar, operating pressure 0.5Pa, radio-frequency power 250W, constant 300 ℃ of underlayer temperature;
(2) the AZO film that obtains is placed on the sample stage in the PIII device, cavity vacuumizes.Afterwards, in cavity, feed the working gas that contains N, use even, the large volume inductively coupled plasma of 600W radio-frequency power supply generation face.The parameter of plasma is diagnosed by equipment such as youth Miu Shuan probe, multi-channel spectrometer baseds.What the sample stage bias generator adopted is the fast rising edge (1 of 10KW solid-state switching circuits
S) high-voltage pulse power source, pulsewidth and frequency are all adjustable, the highlyest can load back bias voltage up to 60KV to substrate.The injection condition of work is: operating air pressure 1Pa, radio-frequency power 100W, pulse duration 20 μ s, pulse frequency 50Hz, bias voltage size 20kV;
(3) carry out annealing in process at last, annealing atmosphere is N
2, annealing temperature is 650 ℃-950 ℃, annealing time is 30min-60min.Promptly obtain presenting the ZnO of p type characteristic.
Table 1 has provided the comparison of the electrology characteristic of the p type ZnO film that p type ZnO film that method that we adopt PIII+N-Al to mix altogether prepares and other method prepare.As can be seen, to mix the performance of the p type ZnO film that makes altogether good relatively for PIII+N-Al.Under the close situation of carrier concentration, the resistivity that PIII+N-Al mixes the p type ZnO that makes altogether than ion injection method obtain low, and mobility than the high magnitude of the method for mixing altogether about.
Fig. 2 has provided annealing front and back ZnO:(Al, N) the optical transmittance rate curve of film.As can be seen, the transmitance of most of sample all has in visible-range about 80%, especially up to 100%, and very steep ABSORPTION EDGE is arranged in the absorptivity of ultraviolet region.And the fluctuation of transmission spectrum visible region mainly causes owing to interfering.And find, all ZnO:(Al of annealing back, N) the UV absorption border of film is all to the skew of shortwave direction, and this oxygen room, phenomenon explanation annealing back is occupied by nitrogen-atoms or molecule, and the thin film crystallization degree improves.
Table one
Claims (1)
1. method of utilizing the plasma immersion ion injection technique to prepare p type ZnO film is characterized in that concrete steps are:
(1) at first mix the n type ZnO film of Al by magnetron sputtering technique growth, be designated as AZO, the magnetron sputtering condition of work is: base vacuum 2 * 10
-4Pa-6 * 10
-4Pa, working gas high-purity Ar, operating pressure 0.1Pa-1Pa, radio-frequency power 100W-550W, constant 200 ℃-500 ℃ of underlayer temperature;
(2) the AZO film that obtains is placed on the sample stage in the PIII device, cavity vacuumizes; Then, in cavity, feed the working gas that contains N, use even, the large volume inductively coupled plasma of 600W radio-frequency power supply generation face; The sample stage bias generator adopts the fast rising edge high-voltage pulse power source of 10KW solid-state switching circuits, and pulsewidth and frequency are all adjustable; The injection condition of work is: working gas is NO+O
2Mist, operating air pressure 0.5Pa-1Pa, radio-frequency power 100W-550W, pulse duration 10 μ s-100 μ s, pulse frequency 10Hz-100 Hz, bias voltage size 1kV-30kV;
(3) carry out annealing in process at last, annealing atmosphere is N
2, annealing temperature is 650 ℃-950 ℃, annealing time is 30min-60min, promptly obtains the ZnO film of p type characteristic.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610765A (en) * | 2012-04-06 | 2012-07-25 | 复旦大学 | Surface modifying method for improving surface power function of indium tin oxide transparent conductive film |
| CN110364592A (en) * | 2018-04-10 | 2019-10-22 | Tcl集团股份有限公司 | Zinc oxide homojunction and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544685A (en) * | 2003-11-27 | 2004-11-10 | 四川大学 | Preparation of low-resistance / high-resistance composite film through plasma technology |
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- 2011-07-14 CN CN2011101973353A patent/CN102254997A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544685A (en) * | 2003-11-27 | 2004-11-10 | 四川大学 | Preparation of low-resistance / high-resistance composite film through plasma technology |
Non-Patent Citations (1)
| Title |
|---|
| 张树宇: "等离子体浸没离子注入方法制备P型ZnO薄膜的研究", 《硕士学位论文》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610765A (en) * | 2012-04-06 | 2012-07-25 | 复旦大学 | Surface modifying method for improving surface power function of indium tin oxide transparent conductive film |
| CN110364592A (en) * | 2018-04-10 | 2019-10-22 | Tcl集团股份有限公司 | Zinc oxide homojunction and preparation method thereof |
| CN110364592B (en) * | 2018-04-10 | 2021-09-17 | Tcl科技集团股份有限公司 | Zinc oxide homojunction and preparation method thereof |
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Application publication date: 20111123 |