CN101707231A - New method for realizing efficient electrofluorescence and low threshold laser - Google Patents
New method for realizing efficient electrofluorescence and low threshold laser Download PDFInfo
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- CN101707231A CN101707231A CN200910207830A CN200910207830A CN101707231A CN 101707231 A CN101707231 A CN 101707231A CN 200910207830 A CN200910207830 A CN 200910207830A CN 200910207830 A CN200910207830 A CN 200910207830A CN 101707231 A CN101707231 A CN 101707231A
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Abstract
The invention belongs to the field of semiconductor optoelectronic materials and device technology, and relates to a new method for realizing efficient electrofluorescence and low threshold laser. The method comprises the following steps: utilizing a p-type material and an n-type material which have the same crystal structure and similar lattice constants, and taking the p-type material as a hole source of the n-type material; through the design of an energy band, regulating an energy band structure between the p-type material and the n-type material by adopting a dielectric layer to control the transport property of a current carrier, and accumulating electrons in an n-type material layer to form a hole and injecting electrons to the n-type material layer from the p-type material so as to realize the efficient electrofluorescence and low-threshold later emission in the n-type material. The new method for realizing the efficient electrofluorescence and the low threshold laser is suitable for heterojunction growth and device preparation of II-VI group semiconductor material, III-V group semiconductor material and other semiconductor materials with wide band gap, is a simple and practicable method for realizing semiconductor luminescence, expands the range for preparing high-efficiency luminescent devices greatly, and opens a new way for the research and the preparation of the luminescent devices.
Description
Technical field
The invention belongs to Semiconductor Optoeletronic Materials and device technology technical field, relate to a kind of new method that realizes high efficiency electroluminous and low threshold value laser.
Background technology
Zinc oxide is a kind of important wide bandgap semiconductor materials, and the energy gap width is about 3.37eV under the room temperature, and exciton bind energy is up to 60meV.Because its big exciton bind energy is expected to realize the luminous and low threshold value laser of efficient bluish violet under room temperature even higher temperature, therefore, ZnO becomes the forward position and the focus of international optoelectronic areas research.In addition, compare with other wide bandgap material such as ZnSe, GaN, SiC, ZnO have very high chemistry and thermal stability, better Antiradiation injury ability, lower growth temperature, be fit to do advantage such as long-life device.
At present, though there are indivedual seminar to report the electroluminescence result of ZnO homogeneous pn junction, the p type of ZnO mixes and remains the bottleneck that hinders zno-based material and device application.In order to overcome this bottleneck, the researcher attempts utilizing other existing p section bar material and n-ZnO to form the pn knot.In these p section bar material, GaN receives special concern because of it has identical crystal structure with ZnO with similar lattice constant.But because III-V and II-VI dopant each other, directly the pn knot that GaN and ZnO the are combined formation alms giver that often only demonstrates GaN is subjected to lead luminous to (DAP), and the luminous of ZnO many times do not observe.The advantage of the high exciton bind energy of ZnO does not obtain utilizing fully like this.
ZnO electric pump laser has only several research groups seldom that report is arranged in the world in addition, from results reported, the luminous zone all is to adopt the nanocrystalline or unordered ZnO particle film of ZnO, and the bulk of optical feedback at random of having utilized the ZnO disordered system to produce simultaneously realizes the relevant amplification of light.But all there is very big shortcoming in these devices: at first,, make that the threshold current of device is higher because the optical reflection loss between the particle is bigger; Secondly, because the randomness between the ZnO particle has directly caused the monochromaticjty of optical mode more weak poor with directivity, bring great difficulty to practical application.
Summary of the invention
The purpose of this invention is to provide a kind of new method that realizes high efficiency electroluminous and low threshold value laser, it is simple, has expanded the scope of preparation high efficiency light-emitting device, for new road has been opened up in the research and the preparation of luminescent device.
In order to achieve the above object, technical scheme of the present invention is as follows:
A kind of new method that realizes high efficiency electroluminous and low threshold value laser comprises the steps: to utilize p section bar material and n section bar material with same crystal structure and similar lattice constant, the hole source of p section bar material as the n section bar bed of material; By the design that can be with, the employing dielectric layer is regulated the band structure between p section bar material and the n section bar material, transport property to charge carrier is controlled, electronics is accumulated and the hole is injected to the n section bar bed of material from p section bar material in the n section bar bed of material, thereby be implemented in the Laser emission of high efficiency electroluminous and low threshold value in the n section bar material.
Method of the present invention is applicable to utilizes dielectric layer to regulate transporting of charge carrier in homogeneity or the heterostructure, makes the unidirectional injection in electronics or hole, thereby realizes the situation of high efficiency electroluminescence or low threshold value Laser emission.Above-mentioned p section bar material includes but not limited to p-Si, p-GaAs, p-GaN, p-ZnO, p-SiC, p-InP, p-GaP, and described dielectric layer includes but not limited to MgO, SiO
2, described n section bar material includes but not limited to ZnO, GaN, GaAs, Si, SiC.
The present invention utilizes the high exciton bind energy 60meV of zinc oxide (ZnO) to prepare ultraviolet light-emitting diode and low threshold laser; The design of cutting out by energy band engineering, and transporting of charge carrier controlled, electroluminescence among the ZnO is significantly strengthened, and realized low threshold value stimulated emission. specifically adopt MgO dielectric insert layer to regulate band structure between p-GaN and the n-ZnO, the high optical gain of having realized continuous electric pumping ZnO vertical surface Laser emission .ZnO first at ambient temperature makes the threshold value of laser reach 0.8mA with the micro-resonant cavity that becomes voluntarily, compares threshold current with similar GaN based laser diode and has reduced 1-2 magnitude.
The present invention has made full use of p-GaN commercialization, and it has the characteristics of identical crystal structure and similar lattice constant with ZnO, the hole source of p-GaN as the ZnO layer.By the design that can be with, adopt the MgO dielectric layer to regulate band structure between p-GaN and the n-ZnO dexterously, electronics is accumulated and the hole can be from the injection of p-GaN to the ZnO layer in the ZnO layer, thereby realized the Laser emission of efficient ultra-violet light-emitting and low threshold value in ZnO.
On element manufacturing, the present invention utilizes plasma assisted molecular beam epitaxy (P-MBE) equipment, adopts high-purity zinc, magnesium and high-purity O
2Make reaction source, growth MgO electronic barrier layer and high-quality non-Doped n-ZnO luminescent layer on the substrate of p-GaN.Optics and electrology characteristic to device characterize, and find that device has rectification characteristic preferably.At ambient temperature device is carried out the dc electroluminescence test, when finding not have the MgO dielectric layer, the luminous of structure is subjected to the master to the dark defect luminescence among luminous and the ZnO based on the alms giver among the GaN; And had after the MgO layer, under same current drove, the luminous intensity of device had improved two magnitudes nearly, and the stimulated emission phenomenon occurred, and analyzing the threshold current that draws Laser emission is 0.8mA.
Beneficial effect of the present invention is: the present invention is suitable for broad-band gap II-VI family, III-V family and the growth of other semi-conducting material heterojunction and device preparation, is a kind of simple method that realizes semiconductor light emitting and Laser Devices; Greatly expanded the scope of preparation high efficiency light-emitting device, for new road has been opened up in the research and the preparation of luminescent device.
Embodiment
Below in conjunction with embodiment the present invention is done description in further detail:
The present invention realizes that the implementation process of high efficiency electroluminous and low threshold value laser new method is as follows:
(1), device architecture design and energy band engineering cutting
Design during device in order to overcome the shortcoming of ZnO Random Laser, we adopt the resonant cavity of ZnO hexagon prism upper and lower surfaces as optics, can make the recombination luminescence among the ZnO in such hexagonal microcavity, well be excited to amplify, it is the c axle of hexagonal structure that this resonant cavity of while makes the resonance directions of laser, can obtain Laser emission, make device have good directivity perpendicular to substrate surface.
In the design of heterojunction band structure, needed high carrier concentration when considering conduction band and the valence band step that ZnO and GaN are less and realizing Laser emission, simultaneously in conjunction with concrete test result in the experiment, ZnO/GaN heterojunction device that directly mates and the device of introducing MgO dielectric insert layer are compared, analyze the effect that draws the MgO dielectric layer and mainly contain 2 points:
1. can avoid high density of defects on the direct contact interface of ZnO/GaN to luminous cancellation effect, improve crystalline quality at the interface.
The heterogeneous interface place introduce the MgO dielectric layer can be to the ZnO layer in electronics well limit, obtain high electron concentration, thereby and do not influence charge carrier has been realized in unidirectional injection from hole among the p-GaN to the injection of ZnO layer, acquisition comes from the efficient recombination luminescence among the ZnO, for the efficient luminous and low threshold value Laser emission that realizes device is laid a good foundation.
(2), high-quality thin film material growth
By P-MBE equipment, (20～40nm), the growth temperature of non-Doped n-ZnO film is controlled at 700～850 ℃ to the MgO dielectric layer of growth different-thickness, and the oxygen flow of growth is controlled at 0.6～1.0sccm. on the p-GaN substrate
(3), the electrode preparation of device
The electrode of p-GaN adopts the Ni/Au alloy, metal Ni and Au adopt the vacuum coating equipment thermal evaporation method, realize the Ni/Au alloying by annealing in air, and annealing temperature is controlled at 400～500 ℃, annealing time was at 3～8 minutes, and the Hall test shows obtains good Ohmic contact.Sintering high pure metal In is as ohmic contact under vacuum condition in the electrode employing of n-ZnO, and current-voltage (I-V) curve table funerary objects spare has good rectification characteristic, and cut-in voltage is 7V.
Below by specific embodiment application of the present invention and effect are described:
Embodiment 1, under fixing growth room's vacuum and gas flow condition, seeks best underlayer temperature interval, the growing high-quality ZnO film.
The ZnO heterojunction device structure of utilizing the present invention to design, by P-MBE equipment, growth MgO dielectric layer 30nm on the p-GaN substrate, non-Doped n-ZnO film 300nm.With the p-GaN substrate specimen holder of packing into, radio-frequency power is 300W, and 245 ℃ of Zn source temperatures, Mg source temperature are 280 ℃, and the flow of oxygen is 0.8sccm.Through the 30min growth, obtained high-quality MgO film, the ZnO film of then growing 2 hours.
Adopt different growth temperature A-700 ℃, B-800 ℃, C-850 ℃, prepared three different samples.Utilize X-ray diffraction spectrum (XRD) that crystal structure is characterized, the peak value halfwidth B＜C＜A of diffraction maximum (002).Wherein the peak value halfwidth of B sample the narrowest (＜0.2 °) illustrates that the ZnO film of growth has tangible c axle preferrel orientation and good crystalline quality, and the optimum temperature of ZnO film growth is 800 ℃.
Electron concentration is 2.5 * 10 in the Hall test shows B sample
17Cm
-3, electron mobility is 5cm
2V
-1S
-1Hole concentration is 3 * 10 among the p-GaN
17Cm
-3, hole mobility is 10cm
2V
-1S
-1
Photoluminescence spectrum (PL) is pointed out the luminous free exciton recombination luminescence that mainly comes among the ZnO, deep energy level defect is luminous almost survey less than.Utilize field emission microscope (SEM) that the surface topography of sample is characterized, sample has good crystalline quality.ZnO film is arranged closely by the hexagon prism of a lot of surfacings and is formed.Thereby each hexagon prism can play the relevant amplification that the effect of a good optical resonator realizes radioluminescence among the ZnO.
Embodiment 2, under fixing growth room's vacuum and temperature conditions, adopt different gas flows, carry out the growth of high quality ZnO film.
Adopt P-MBE equipment, under fixing growth room's vacuum and temperature conditions, adopt different oxygen flows, three the sample A-0.6sccm that grow, B-0.8sccm, C-1.0sccm, growth time are 120 minutes.
Utilize X-ray diffraction spectrum (XRD) that crystal structure is characterized, the peak value halfwidth B＜C＜A of diffraction maximum (002).Wherein the peak value halfwidth of B sample diffraction maximum (002) narrower (＜0.2 °) illustrates that the ZnO film of growing has tangible c axle preferrel orientation and good crystalline quality under the 0.8sccm condition.
Utilize field emission microscope (SEM) that the surface topography of sample is characterized, sample has good crystalline quality.The surfacing of B sample thin film, crystalline quality is higher, and the evenness on surface is the highest.
Utilize the present invention, on the p-GaN substrate, adopt the different oxygen flows high-quality ZnO film of having grown, illustrate that the ZnO film of growing has good crystalline quality under the 0.8sccm condition.
Embodiment 3, under fixed pressure, oxygen flow and temperature conditions, adopt the MgO dielectric layer (20-50nm) of different-thickness, carry out the preparation of heterojunction device.
Adopt P-MBE equipment, under fixing growth room's vacuum, oxygen flow and temperature conditions, adopt different MgO medium thicknesses, prepare three sample A-20nm, B-30nm, C-40nm.
Utilize the Hall tester that three samples are characterized, wherein reverse leakage current minimum, the rectification characteristic of B sample are best, and cut-in voltage is that the 7V. explanation adopts the effect of the thick MgO film of 30nm best, and device has best P-N knot effect.
The B sample has obtained very strong ultra-violet light-emitting under forward current drives, and main peak has been realized good ultraviolet light-emitting diode about 390nm.Simultaneously device is carried out the time-dependent current test, obtained the Ultra-Violet Laser emission, threshold current is 0.8mA.
The present invention has avoided dexterously and has prepared the difficulty that high-quality is stablized p-ZnO, utilize the hole source of commercial p-GaN as it, and realized electronics is limited among the ZnO by the MgO dielectric layer, and the hole can be from GaN be injected to ZnO, thereby has realized among the ZnO electroluminescent device and low threshold laser spare efficiently.This structure is compared with common realization semiconductor light emitting or laser diode, and is very simple, and very tangible potential application is being arranged aspect semiconductor light emitting and the Laser Devices.
Embodiment 4, under fixing temperature conditions, adopt different annealing times, carry out the preparation of low resistance ohmic electrode contact.
Adopt homemade vacuum coating machine equipment, at first select the ohmic contact material of high-purity metal nickel gold (Ni/Au) as p-GaN for use, evaporation is on the sample of p-GaN.
Utilize the present invention, under fixing air and temperature conditions, adopt three different annealing times 3 minutes (A), 5 minutes (B), 8 minutes (C) carries out the preparation of low resistance ohmic electrode contact.Under 450 ℃ of conditions, three sample Metal Contact resistivity A＞C＞B.Characterize by Hall, the B sample is the contact of desired metallic Ohmic electrode.Obtained good n-ZnO ohmic contact by vacuum evaporation technology evaporation metal indium (In) equally, current-voltage (I-V) curve table funerary objects spare has good rectification characteristic.By above result, low-resistance p-GaN material metal Ohmic electrode contact optimum annealing temperature is described at 450 ℃, annealing time 5 minutes.
Claims (3)
1. a new method that realizes high efficiency electroluminous and low threshold value laser is characterized in that this method comprises the steps: to utilize p section bar material and the n section bar material with same crystal structure and similar lattice constant, the hole source of p section bar material as n section bar material; By the design that can be with, the employing dielectric layer is regulated the band structure between p section bar material and the n section bar material, transport property to charge carrier is controlled, electronics is accumulated and the hole is injected to the n section bar bed of material from p section bar material in the n section bar bed of material, thereby be implemented in the Laser emission of high efficiency electroluminous and low threshold value in the n section bar material.
2. a kind of new method that realizes high efficiency electroluminous and low threshold value laser as claimed in claim 1, it is characterized in that, described p section bar material package is drawn together p-Si, p-GaAs, p-GaN, p-ZnO, p-SiC, p-InP, p-GaP, and described dielectric layer comprises MgO, SiO
2, described n section bar material package is drawn together ZnO, GaN, GaAs, Si, SiC.
3. a kind of new method that realizes high efficiency electroluminous and low threshold value laser as claimed in claim 1 is characterized in that, utilizes p-GaN and ZnO to have the characteristics of identical crystal structure and similar lattice constant, the hole source of p-GaN as the ZnO layer; By the design that can be with, employing MgO dielectric insert layer is regulated the band structure between p-GaN and the n-ZnO, transport property to charge carrier is controlled, electronics is accumulated in the ZnO layer and the hole from the injection of p-GaN to the ZnO layer, thereby be implemented in the Laser emission of high efficiency electroluminous and low threshold value among the ZnO.
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Cited By (7)
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| CN101958376A (en) * | 2010-05-26 | 2011-01-26 | 中国科学院物理研究所 | Method for preparing positive-intrinsic-negative (PIN) heterostructure-based short-wavelength ultraviolet luminescent material |
| CN102610724A (en) * | 2012-04-01 | 2012-07-25 | 浙江大学 | Electroluminescent device based on CdZnO thin film and preparation method of electroluminescent device |
| CN106601864A (en) * | 2016-05-25 | 2017-04-26 | 北京纳米能源与系统研究所 | Ultraviolet detector, preparation method thereof, and method for modulating sensitivity by stress |
| CN107425098A (en) * | 2017-07-19 | 2017-12-01 | 东南大学 | The zno-based heterojunction light-emitting diode and preparation method of pure ultra-violet light-emitting can be achieved |
| CN107611229A (en) * | 2017-08-24 | 2018-01-19 | 南京大学 | A kind of method for exchanging driving and improving silicon based hetero-junction electroluminescent device stability of photoluminescence |
| CN107611230A (en) * | 2017-08-24 | 2018-01-19 | 南京大学 | A kind of perovskite/silicon heterogenous electroluminescent device and preparation method |
| CN116632134A (en) * | 2023-07-24 | 2023-08-22 | 江西乾照光电有限公司 | Electronic barrier layer, preparation method thereof, epitaxial wafer and light-emitting diode |
-
2009
- 2009-10-30 CN CN200910207830A patent/CN101707231A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958376A (en) * | 2010-05-26 | 2011-01-26 | 中国科学院物理研究所 | Method for preparing positive-intrinsic-negative (PIN) heterostructure-based short-wavelength ultraviolet luminescent material |
| CN102610724A (en) * | 2012-04-01 | 2012-07-25 | 浙江大学 | Electroluminescent device based on CdZnO thin film and preparation method of electroluminescent device |
| CN102610724B (en) * | 2012-04-01 | 2014-12-17 | 浙江大学 | Electroluminescent device based on CdZnO thin film and preparation method of electroluminescent device |
| CN106601864A (en) * | 2016-05-25 | 2017-04-26 | 北京纳米能源与系统研究所 | Ultraviolet detector, preparation method thereof, and method for modulating sensitivity by stress |
| CN106601864B (en) * | 2016-05-25 | 2018-06-26 | 北京纳米能源与系统研究所 | Ultraviolet light detector and preparation method thereof and the method for stress modulation sensitivity |
| CN107425098A (en) * | 2017-07-19 | 2017-12-01 | 东南大学 | The zno-based heterojunction light-emitting diode and preparation method of pure ultra-violet light-emitting can be achieved |
| CN107611229A (en) * | 2017-08-24 | 2018-01-19 | 南京大学 | A kind of method for exchanging driving and improving silicon based hetero-junction electroluminescent device stability of photoluminescence |
| CN107611230A (en) * | 2017-08-24 | 2018-01-19 | 南京大学 | A kind of perovskite/silicon heterogenous electroluminescent device and preparation method |
| CN116632134A (en) * | 2023-07-24 | 2023-08-22 | 江西乾照光电有限公司 | Electronic barrier layer, preparation method thereof, epitaxial wafer and light-emitting diode |
| CN116632134B (en) * | 2023-07-24 | 2023-10-10 | 江西乾照光电有限公司 | Electronic barrier layer, preparation method thereof, epitaxial wafer and light-emitting diode |
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Open date: 20100512 |