CN104638079B - Ultraviolet LED based on one-dimensional micro-nano structure/gallium nitride film schottky junction - Google Patents
Ultraviolet LED based on one-dimensional micro-nano structure/gallium nitride film schottky junction Download PDFInfo
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- CN104638079B CN104638079B CN201510053998.6A CN201510053998A CN104638079B CN 104638079 B CN104638079 B CN 104638079B CN 201510053998 A CN201510053998 A CN 201510053998A CN 104638079 B CN104638079 B CN 104638079B
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 35
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 27
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 229910052594 sapphire Inorganic materials 0.000 claims description 5
- 239000010980 sapphire Substances 0.000 claims description 5
- 229910002065 alloy metal Inorganic materials 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910001020 Au alloy Inorganic materials 0.000 claims 1
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010931 gold Substances 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
Classifications
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- H01L33/0033—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H01L33/20—
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
- Led Devices (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
The invention discloses a kind of ultraviolet LED based on one-dimensional micro-nano structure/gallium nitride film schottky junction, active light emissive body including negative electrode, anode and jointed anode, also include a micro-nano structure, one end of the micro-nano structure is connected with negative electrode, and the other end contacts to form schottky junction with active light emissive body.The present invention is simple in construction, cost is cheap, emission wavelength is short, wavelength does not raise with electric current to be changed, efficiency is higher, it can be operated under continuous current or pulse current and overcome the problem that emergent light is absorbed and scattered by metal electrode in traditional schottky knot LED using micro-nano structure, the luminous efficiency of device is greatly improved while cheap cost of manufacture is ensured.
Description
Technical field
It is thin based on one-dimensional micro-nano structure/gallium nitride more particularly, to one kind the present invention relates to semiconductor and micro optical element
The ultraviolet LED of film schottky junction.
Background technology
Ultraviolet LED light source has a wide range of applications in industrial production and daily life, such as net for information storage, water
The fields such as change, medical equipment sterilization, ultra-violet curing, medical diagnosis.The structure of ultraviolet LED can be realized at this stage mainly includes amount
Sub- trap, p-n junction, metals-oxides-semiconductor and schottky junction.
For example, the patent application of Application No. 201110063867.8 provides a kind of preparation method of ultraviolet LED, it is used for
Make the ultraviolet LED light source of multi quantum well structure, including step：A substrate is taken, and grows nucleating layer and n successively on substrate
Type layer, then grows multiple quantum well layer in n-layer；Electronic barrier layer and p-type layer are finally grown on multiple quantum well layer, is completed
The growth of structure.
In addition, the patent application of Application No. 201310168605.7 provides a kind of semiconductive ultraviolet light source device, institute
Stating the epitaxial structure of device includes：At least one N-type layer, at least one P-type layer and at least one luminous zone, the luminous zone
Between the N-type layer and the P-type layer and comprising at least one SQW, the SQW is at least built by quantum to be wrapped
Wrap up in, the epitaxial structure of the device also comprises at least a cation area in the luminous zone side；One anion area is in the hair
Light area opposite side, the cation area offset or reduced the polarized electric field in SQW with extra electric field caused by anion area.
In these structures, schottky junction has minimum cost of manufacture because its is simple in construction and requires low to doping.But
It is that the schottky junction LED reported before locks into relatively low external quantum efficiency, this is mainly due to the metal for forming schottky junction
Film can absorb and scatter the emergent light of the overwhelming majority.So how to overcome, this problem cost of implementation is low and luminous efficiency is high
Ultraviolet LED be always industrial quarters demand.
The content of the invention
The cheap and higher luminous efficiency ultraviolet LED it is an object of the invention to provide a kind of cost of manufacture.Metal micro-nano
Structure forms Schottky hetero-junctions by Van der Waals force and gallium nitride film, and the small size of micro-nano structure causes emergent light by very
Few decay, improve the external quantum efficiency of device.Can be with the case of gallium nitride film positive bias, micro-nano structure back bias voltage
Obtain the efficient ultra-violet light-emitting in heterojunction regions.This device obtains 0.9% external quantum efficiency at present, and report before based on Xiao
Special base junction LED best efficiency is only 0.05%.
Concrete technical scheme of the present invention is as follows：
A kind of ultraviolet LED based on one-dimensional micro-nano structure/gallium nitride film schottky junction, including negative electrode, anode and connection
The active light emissive body of anode, in addition to a micro-nano structure, one end of the micro-nano structure are connected with negative electrode, the other end and active hair
Body of light contacts to form schottky junction.
Wherein, described ultraviolet LED also includes the substrate for being coated with active light emissive body, the active light emissive body top subregion
Interior alloy plating metal film is as described anode.Active light emissive body according to LED luminosities determine, the present invention in ultraviolet LED
Corresponding active light emissive body is gallium nitride film.
Described alloy metal film can be Cr/Au, Pt/Au, Pd/Au, preferably using Ni (20nm)/Au (50nm) alloy
Metal film, low-resistance Ohmic contact can be formed compared to other metal films.
In the present invention, negative electrode has two kinds of embodiments, and the first is：Described negative electrode is to plate on a sapphire substrate
Ito thin film, the substrate for being coated with active light emissive body and Sapphire Substrate are apart from and gap between the two should be not more than
30μm.It is for second：Insulating barrier is coated with another region being coated with the substrate of active light emissive body, the insulating barrier upper surface
Gold-plated film forms described negative electrode.
Negative electrode can be ito thin film, can also use metallic film, such as：Au, Pt, Al etc..
Wherein, described micro-nano structure is to grow obtained wall scroll or a plurality of nano silver wire by hot solvent method.
In addition, described micro-nano structure can also be silver-colored micro-nano array, there is crisscross nano silver wire, and longitudinal direction silver
Nano wire or horizontal nano silver wire one end are connected with negative electrode, and the other end contacts to form schottky junction with active light emissive body.
Micro-nano structure can also use nanowires of gold and copper nano-wire, the advantage of nano silver wire in addition to using nano silver wire
It is that its conductive capability is strong, thermal conductivity is high.Single nano silver wire can be used for the light source of structure micro/nano-scale, its in integrated optics,
There is important application in the fields such as optic communication.Silver-colored micro-nano array can realize the High Efficiency Luminescence of large area, for the neck such as illumination, ultraviolet disinfection
There is application in domain.
In the present invention, the resistivity of the micro-nano structure should be less than 5 μ Ω cm, and resistivity is small to may advantageously facilitate electronics
The diffusion of carrier, radiation recombination is set to carry out in a wider context.
The invention has the advantages that：Simple in construction, cost is cheap, and emission wavelength is short, and wavelength does not raise with electric current
Change, efficiency is higher, can be operated under continuous current or pulse current；Under forward bias, the electronics from silver-colored micro-nano structure
It is directly injected into gallium nitride film and radiation recombination occurs with hole therein；Under low driving current, this device is i.e. luminous, main peak
Position be located at ultraviolet region, full width at half maximum is less than 10nm, and is the FREE EXCITON EMISSION IN FORWARD of gallium nitride；FREE EXCITON EMISSION IN FORWARD is steady
Fixed, peak position does not increase and offset with electric current；It is golden that emergent light in traditional schottky knot LED is overcome using silver-colored micro-nano structure
Belong to the problem that electrode absorbs and scattered, the luminous efficiency of device is greatly improved while cheap cost of manufacture is ensured.
Brief description of the drawings
Fig. 1 is the device architecture schematic diagram in embodiment 1.
Fig. 2 is the device architecture schematic diagram in embodiment 2.
Fig. 3 is the device architecture schematic diagram in embodiment 3.
Fig. 4 is current-voltage characteristic curve of the device between -6V to 6V.
Fig. 5 is the spectrogram that measurement obtains and the luminous photo of CCD shootings.
Fig. 6 is curve of the glow peak position in spectrum with curent change.
Fig. 7 is the output intensity of device with curent change curve.
Embodiment
A kind of effective UV LED based on one-dimensional silver-colored micro-nano structure/gallium nitride film schottky junction, its in general embodiment party
Formula includes：The substrate 1 of gallium nitride 3 is coated with deionized water rinsing and with drying up in a nitrogen environment, then using thermal evaporation
Method plates layer of Ni (20nm)/Au (50nm) alloy metal film 2 on partial nitridation gallium.Device cathodes part both can be
Ito thin film can also be gold thin film.Silver-colored micro-nano structure used herein above can be received by what hot solvent method grew to obtain
Rice noodles can also be the micro-nano array structure obtained by the method for printing.
The structural representation of example 1 such as Fig. 1, negative electrode are the ito thin film 5 plated in Sapphire Substrate 6.This substrate is pressed close into plating
The substrate 1 for having gallium nitride 3 is placed, and gap between the two can be by micro-nano operational control within 30 μm.Then, silver is received
Rice noodles solution is dripped on clean slide, after ethanol volatilization completely, is transferred to nano silver wire 4 by micro-nano operation and has been made
Into substrate on so that the one end of nano silver wire 4 is on ito thin film 5, and the other end is on gallium nitride 3.Nano silver wire 4 passes through model moral
Hua Liyu substrates rigid contact forms schottky junction.
The structural representation of example 2 such as Fig. 2, the method is not required to make cathode substrate in addition, and is coated with nitridation in identical
In the part of substrate 1 of gallium 3 plate insulating barrier 7, and the upper surface gold-plated film 8 of insulating barrier 7 form negative electrode, the one end of nano silver wire 4 with
Negative electrode is connected, and the other end contacts to form schottky junction with gallium nitride 3.
The structural representation of example 3 such as Fig. 3, cathode construction in example 2 with using identical preparation method.Use silver-colored micro-nano
Array 9 replaces the single nano silver wire 4 in example 2, and micro-nano array here is made for the method for printing or micro- manipulation or miniflow
The methods of control, is arranged, the morphology controllable of array.Micro-nano array 9 is predominantly located in the surface of gallium nitride film, at the same also with
Cathode portion is connected.
By taking the device in example 1 as an example, Fig. 4 is the current-voltage characteristic curve of device, it can be seen that under a reverse bias
Basic do not have an electric current, and electric current rises quickly under forward bias, shows good rectification characteristic.Fig. 5 is the luminous CCD of device
The spectrum that photo and measurement obtain.Lighted it can be seen that the Schottky interface generation of nano silver wire and gallium nitride formation is strong,
Spectroscopic data illustrates that main peak is located at dark purple outskirt 362.5nm.Fig. 6 further illustrates device stable luminescence, and peak wavelength is not with electricity
The rise change of stream.Fig. 7 explanations are with intensifying current, the luminous constantly enhancing, and being obtained under 25 μ A driving current of device
Report at present based on schottky junction LED highest external quantum efficiencys.
Claims (9)
1. a kind of ultraviolet LED based on one-dimensional micro-nano structure/gallium nitride film schottky junction, including negative electrode, anode and connection sun
The active light emissive body of pole, it is characterised in that also including a metal micro-nanostructure, one end and the negative electrode phase of the metal micro-nanostructure
Even, the other end contacts to form schottky junction with active light emissive body；
Described ultraviolet LED also includes being coated with the substrate of active light emissive body, alloy plating in the active light emissive body top subregion
Metal film is as described anode.
2. the ultraviolet LED as claimed in claim 1 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature exist
In, ito thin film of the described negative electrode for plating on a sapphire substrate, the substrate and Sapphire Substrate for being coated with active light emissive body
Apart from, and gap between the two should be not more than 30 μm.
3. the ultraviolet LED as claimed in claim 1 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature exist
In being coated with insulating barrier in another region being coated with the substrate of active light emissive body, insulating barrier upper surface gold-plated film is formed
Described negative electrode.
4. the ultraviolet LED as claimed in claim 2 or claim 3 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature
It is, described metal micro-nanostructure is wall scroll or a plurality of nano silver wire.
5. the ultraviolet LED as claimed in claim 4 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature exist
In described nano silver wire grows to obtain by hot solvent method.
6. the ultraviolet LED as claimed in claim 5 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature exist
In described metal micro-nanostructure is silver-colored micro-nano array, has crisscross nano silver wire, and longitudinal nano silver wire or transverse direction
Nano silver wire one end is connected with negative electrode, and the other end contacts to form schottky junction with active light emissive body.
7. the ultraviolet LED as claimed in claim 1 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature exist
In described active light emissive body is gallium nitride film.
8. the ultraviolet LED as claimed in claim 1 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature exist
In described alloy metal film is Ni/Au alloy metal films.
9. the ultraviolet LED as claimed in claim 1 based on one-dimensional micro-nano structure/gallium nitride film schottky junction, its feature exist
In the resistivity of the metal micro-nanostructure should be less than 5 μ Ω cm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510053998.6A CN104638079B (en) | 2015-02-02 | 2015-02-02 | Ultraviolet LED based on one-dimensional micro-nano structure/gallium nitride film schottky junction |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510053998.6A CN104638079B (en) | 2015-02-02 | 2015-02-02 | Ultraviolet LED based on one-dimensional micro-nano structure/gallium nitride film schottky junction |
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| CN104638079B true CN104638079B (en) | 2018-03-23 |
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| CN108400207B (en) * | 2018-02-28 | 2019-11-19 | 浙江大学 | A kind of CdS nano-ribbons silicon based hetero-junction light emitting diode and its manufacturing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1745468A (en) * | 2002-09-30 | 2006-03-08 | 纳米系统公司 | Large-area nanoenabled macroelectronic substrates and uses therefor |
| CN103311388A (en) * | 2013-05-09 | 2013-09-18 | 青岛杰生电气有限公司 | Semiconductor ultraviolet source device |
| CN103746056A (en) * | 2013-12-28 | 2014-04-23 | 华中科技大学 | Wave length-adjustable light-emitting diode based on gallium-doped zinc oxide nanowire array and manufacturing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1745468A (en) * | 2002-09-30 | 2006-03-08 | 纳米系统公司 | Large-area nanoenabled macroelectronic substrates and uses therefor |
| CN103311388A (en) * | 2013-05-09 | 2013-09-18 | 青岛杰生电气有限公司 | Semiconductor ultraviolet source device |
| CN103746056A (en) * | 2013-12-28 | 2014-04-23 | 华中科技大学 | Wave length-adjustable light-emitting diode based on gallium-doped zinc oxide nanowire array and manufacturing method thereof |
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