CN109786494A - A kind of novel micro-cavity structure ultraviolet detector and preparation method thereof - Google Patents
A kind of novel micro-cavity structure ultraviolet detector and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a kind of novel micro-cavity structure ultraviolet detectors and preparation method thereof, and wherein the preparation process of ultraviolet detector includes substrate cleaning, seed layer growth, micro wire growth, single micro wire two sides metallic film, the preparation of metal Nano structure and the preparation process of metal detector electrode up and down.It is characteristic of the invention that the ultraviolet detector of a kind of high-performance of new construction newly developed, small size, detection cutoff wavelength is less than 380nm, and the raising that the reduction and photoelectricity for solving ultraviolet detector size turn is difficult to the contradictory problems realized simultaneously.In addition, such novel micro-cavity structure UV detector structure is simple, is easy to couple circuit of focal plane readout, it is beneficial to the exploitation of next-generation High Density Integration optical circuit.
Description
Technical field
The invention belongs to technical field of photoelectric detection, and in particular to a kind of compound ultraviolet spy of Fabry-Perot micro-cavity structure
Survey device and preparation method thereof.
Technical background
Ultraviolet detection technology is the important the army and the people of the another item that grows up after Laser Detection Technique and infrared detection technique
Dual-purpose photodetector technology.Currently, the ultraviolet detection technology of modernization is collection ultraviolet detector, optical design, a microcomputer
The multidisciplinary precision detection system being integrated such as tool processing and integrated circuit, due to its, good concealment low with ambient noise etc.
Plurality of advantages is played in numerous areas such as Missile Plume detection, ozone hole monitoring, medicine detection and flame detectings
Huge effect.
Currently, the integrated level with semiconductor devices is improved by mole Law Index, the size of photodetector also exists
Constantly reduce, but therefore the incident photon-to-electron conversion efficiency that the reduction of active region area can reduce device is unfavorable for the inspection of small-signal
Survey and the design of following stage computing circuit, reading circuit.Although being to realize that high photoelectricity turns using metal surface plasma body technique
Rate, an effective way (MRS Bull.2012,37,728-738) for small size photodetector.But due to metal watch
The problems such as face etc. is from the energy match and serious ultraviolet band energy loss of polariton and ultraviolet radioactive, this technology is current
It is applied to visible and infrared band mostly.
Problem in view of the above technology, the present invention propose a kind of novel hybride surface plasma micro-cavity structure ultraviolet detection
Device, such compound micro-cavity structure can integrate optical space layer to the interference modulations of electric field and surface phasmon forward scattering
Double dominant solves ultraviolet detector size to make the extreme value distribution of the main distribution of light intensity of ultraviolet radioactive in active area
Reduce and the raising of device photoelectric transformation efficiency is difficult to the contradiction realized simultaneously.In addition, such device architecture is simple, it is easy to couple
Circuit of focal plane readout is beneficial to the exploitation of next-generation High Density Integration optical circuit.
Summary of the invention
The purpose of the present invention is to provide a kind of ultraviolet spies of novel hybride surface plasma Fabry-Perot micro-cavity structure
Device and preparation method thereof is surveyed, the final operation wavelength that obtains is less than 380nm, the UV photodetector with high-performance, small size.
It is as shown in Fig. 1 that the purpose of the present invention one is to provide a kind of novel micro-cavity structure ultraviolet detector, comprising: metal is anti-
Penetrate layer 1, wide bandgap semiconductor 2, metal electrode 3, metal Nano structure 4.
The purpose of the present invention two is to provide a kind of preparation method of novel micro-cavity structure ultraviolet detector.
The purpose of the present invention is what is be achieved through the following technical solutions, as shown in Fig. 2, include the following steps: 1. in life
5-30 minutes are heated before long seed layer in sulfuric acid, the mixed liquor that hydrochloric acid volume ratio is 3:1 to remove substrate surface attachment
Inorganic matter (outer-lining bottom of sapphire is without this operation), it is clear that substrate is sequentially placed into acetone, ethyl alcohol and deionized water respectively ultrasound
The organic matter for washing removal substrate surface attachment in 5-30 minutes, with being dried with nitrogen after cleaning, and is put into oxygen plasma cleaning machine
Middle processing 5 minutes, completion to be processed is taken out rear spare.
2. preparing one layer of seed layer on the substrate after processed.
3. high-purity wide bandgap semiconductor powder and graphite powder that mass ratio is 1:1 are sufficiently mixed, it is more than hour to grind 2.It will
Above-mentioned mixed-powder is placed in ceramic boat middle position, and the substrate with seed layer is placed on to the surface of mixed-powder, later
Ceramic boat level is put into quartz ampoule again, quartz ampoule is put to the growth indoor growing broad stopband of horizontal high temperature process furnances and is partly led
Body micro-/ nano line 2.
Wide in single quadrangle after 4. growth complete has the quadrangle broad stopband micro-/ nano line of Fabry-Perot micro-cavity structure
The downside of forbidden band micro-/ nano line in the axial direction prepares metallic film 1.
5. preparing absorption peak in metallic film material opposite side (i.e. quadrangle broad stopband micro-/ nano line upside) is located at ultraviolet band
Metal Nano structure 4, pattern include the irregular shape of sphere, spheroid, triangular prism one of which and above structure composition
Looks.
6. finally, in single quadrangle broad stopband micro-/ nano line two of the upper and lower two sides with metallic film and metal nanoparticle
End prepares metal electrode 3.
The preparation of the wide bandgap semiconductor seed layer of the step 2. can be by one in chemistry side's synthetic method, magnetron sputtering method
Kind or two methods realize.
The wide bandgap semiconductor micro-/ nano growing environment of the step 3. is normal pressure, and the carrier gas in growth course is high-purity
Argon gas and high purity oxygen gas.Single quadrangle wide bandgap semiconductor micro-/ nano line geometry parameter can by carrier gas flux, growth temperature with
And growth time is adjusted.Final prepared wide bandgap semiconductor micro-/ nano line is MgO, Ga2O3、ZnO、SnO2、TiO2、
The core-shell structure of one or more of NiO composition.
The preparation method of step metallic film 4. 6. and metal electrode can by vacuum thermal evaporation, magnetron sputtering, from
The methods of son sputtering is realized.
The preparation method of the metal Nano structure of the step 5. can by vacuum thermal evaporation, magnetron sputtering, ion sputtering, move back
One step such as fire, electron beam lithography, ion beam etching or multistep process are realized.
The metal material of step metallic film 4. 5. and metal Nano structure is the materials such as Al, Ag, Pt, Ru, Rn, Pd
One or more of material mixed structure.
The metal electrode layer of the step 6. is single-layer metal or metal composite in Ti, Al, Ni, Pt, Au, Ag and In
Layer.
The present invention compared with the existing technology, has the advantages that
1, the microcavity detector being prepared according to the method described above is a kind of completely new UV photodetector structure (attached drawing 1),
Such structure can be integrated hybridized metal surface phasmon and photodetector by Fabry-Perot microcavity, solution
Metal surface plasma body technique of the having determined problem bad in ultraviolet band reinforcing effect, at the same time, which can subtract
The quantum efficiency that device is improved while small device size, is easy to couple circuit of focal plane readout, is beneficial to next-generation high density
The exploitation in integrated electro circuit.Its working principle (attached drawing 3) is summarized as follows: when extraneous light field is incident on hydridization surface plasma
When the microcavity upper surface Fabry-Perot, since metal Nano structure can overcome optical diffraction limit by the ultraviolet of free space
Radiation light field is limited in nanoscale, later since Fabry-Perot microcavity and downside metal film reflector act on, makes free light
The ultraviolet radioactive of field is limited in wide bandgap semiconductor micro-/ nano with hydridization surface plasma standing wave form, i.e. photodetection
The active area of device, to significantly increase the generation of photo-generated carrier and collect probability.
2, micro-cavity structure detector proposed by the present invention has good universality, passes through different active area difference forbidden bandwidths half
Selection (such as MgO, Ga of conductor material2O3、ZnO、SnO2、TiO2, NiO etc.), response cutoff wavelength range can cover UVA-
UVC wave band is with a wide range of applications in numerous areas.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of hydridization surface plasma Fabry-Perot micro-cavity structure ultraviolet detector of the present invention,
Figure label: 1- metallic reflector, 2- wide bandgap semiconductor micro-/ nano line, 3- metal electrode, 4- metal Nano structure；
Fig. 2 is the preparation flow figure of hydridization surface plasma Fabry-Perot micro-cavity structure ultraviolet detector of the present invention,
In figure: 1. substrate cleans, and 2. prepared by seed layer, 3. prepares wide bandgap semiconductor micro-/ nano line, 4. single quadrangle broad stopband half
Downside prepares the preparation of metallic film to conductor micro-/ nano line in the axial direction, 5. single quadrangle wide bandgap semiconductor it is micro-/receive
6. rice noodles prepare metal electrode along the preparation of metal Nano structure on the upside of axis direction；
Fig. 3 a is metal surface etc. from polariton operation schematic diagram, figure label: 1- incident light, 2- metal nano knot
Structure, the standing wave that 3- is formed in Fabry-Perot microcavity, the broad stopband 4- micro/nano structure, 5- metal film reflector layer；Fig. 3 b
To simulate the light field confinement result in hydridization surface plasma Fabry-Perot microcavity using Finite-Difference Time-Domain Method.
Specific embodiment
2 further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this
Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered
Within the protection scope of the present invention.
Embodiment 1
Hydridization surface plasma Fabry-Perot micro-cavity structure ultraviolet detection is prepared according to the following steps in the present embodiment
Device:
Substrate cleaning.It is heated 5-30 minutes in sulfuric acid, the mixed liquor that hydrochloric acid volume ratio is 3:1 before growing seed layer
Remove the inorganic matter (outer-lining bottom of sapphire without this operation) of substrate surface attachment, substrate be sequentially placed into acetone, ethyl alcohol and
Respectively it is cleaned by ultrasonic the organic matter of removal substrate surface attachment in 5-30 minutes in deionized water, with being dried with nitrogen after cleaning,
And be put into oxygen plasma cleaning machine and handle 5 minutes, completion to be processed is taken out rear spare；
The preparation of ZnO seed layer.Zinc acetate (99.99%) without the crystallization water is dissolved in top grade straight alcohol, is configured to dense
Degree is the zinc acetate ethanol solution of 30mg/ml；Zinc acetate ethanol solution is then spin-coated on to the substrate surface handled well, is then put
Enter tube furnace, is sintered 15 minutes for 400 DEG C in air atmosphere, and so on 2~6 times, it is brilliant to obtain ZnO nano in substrate surface.
The growth of broad stopband micro-/ nano line.High-purity ZnO powder and graphite powder that mass ratio is 1:1 are sufficiently mixed, grind 2
It is more than a hour.Above-mentioned mixed-powder is placed in ceramic boat middle position, and the substrate with ZnO nano crystalline substance is placed on mixed powder
The surface at end, ceramic boat level is put into quartz ampoule, quartz ampoule is put to the growth room of horizontal high temperature process furnances again later
Interior growth, growing environment are normal pressure, and the carrier gas in growth course is high-purity argon gas and high purity oxygen gas, single quadrangle obtained
The cross-sectional width of ZnO micro-/ nano line is 10nm~10 μm, and section thickness is 10nm~10 μm, and the length of micro wire is 1mm-
1cm.Specific size can be determined by the comprehensive regulation of growth temperature and growth time.
The preparation of metallic film.Growth complete have Fabry-Perot micro-cavity structure quadrangle broad stopband micro-/ nano line it
Afterwards, 5nm~2 μm metallic film is prepared by magnetron sputtering method in the downside of single quadrangle broad stopband micro-/ nano line, it is prepared
Metallic film include various metals mentioned by claim 3, selected according to required condition difference, thickness can be by splashing
Penetrate time decision.
The preparation of metal Nano structure.In metallic film material opposite side, (i.e. on the upside of quadrangle broad stopband micro-/ nano line) is logical
It crosses vacuum thermal evaporation, magnetron sputtering or ion sputtering and 2 footworks of annealing prepares the metal nano that absorption peak is located at ultraviolet band
Structure, pattern includes the irregular pattern of sphere, spheroid, triangular prism one of which and above structure composition, prepared
Metal Nano structure include various metals mentioned by claim 4, selected according to required condition difference, feature ruler
It is very little to be determined by sputtering current size, sputtering time and annealing temperature.
The preparation of metal electrode.Single quadrangle broad stopband of the upper and lower two sides with Al film and Al nanoparticle it is micro-/
Nano wire both ends prepare metal electrode by magnetron sputtering method or thermal evaporation method, and prepared electrode includes claim 5
Mentioned various electrodes are selected according to the condition difference of required contact.
Embodiment 2
For the present embodiment in addition to following characteristics, other are same as Example 1: step 2) SnCl in the present embodiment4·5H2O
Crystal (molecule formula weight is 350.6) prepares the solution of 0.1g/ml, and ultrasound 2~3 minutes is uniformly mixed it；It is picked up with dropper
The SnCl just prepared4Solution drips on washed silicon wafer, to be paved with SnCl on silicon wafer4Solution is dried, and Muffle is then placed in
It anneals 2 hours at 500 DEG C in baking oven case, obtains SnO2Seed crystal.At the same time, by high-purity SnO of mass ratio 1:12Powder and stone
Ink powder is sufficiently mixed, it is more than hour to grind 2.Above-mentioned mixed-powder is placed in ceramic boat middle position, and SnO will be had2Seed
Brilliant silicon base is placed on the surface of mixed-powder, then ceramic boat level is put into quartz ampoule, and quartz ampoule is put to horizontal high
It is grown under normal pressure in the growth room of warm tube furnace, growing environment is normal pressure, and the carrier gas in growth course is high-purity argon gas and height
Purity oxygen, single quadrangle SnO obtained2The cross-sectional width of micro-/ nano line be 10nm~10 μm, section thickness be 10nm~
10 μm, the length of micro wire is 1mm-1cm.Specific size can be determined by the comprehensive regulation of growth temperature and growth time.
Embodiment 3
For the present embodiment in addition to following characteristics, other are same as Example 1: the substrate that step 2) will be washed in the present embodiment
It is put into the growth room of magnetron sputtering apparatus, sputtering target used in seed crystal film is ZnO ceramic target (99.999%), and sputtering is penetrated
Frequency source power is adjusted to 130W, is continually fed into oxygen (10SCCM) and argon gas (30SCCM) in sputtering in growth room.Growth room is true
Reciprocal of duty cycle remains 1Pa, and substrate revolving speed is 20 turns/min, and base reservoir temperature is 400 DEG C, and growth time is 0.5-1.5 hour, obtains
ZnO seed crystal.At the same time, by high-purity ZnO powder (99.999%) of mass ratio 1:0.1:1, Ga2O3Powder (99.99%) and graphite powder
It is sufficiently mixed, it is more than hour to grind 2.Above-mentioned mixed-powder is placed in ceramic boat middle position, and the lining that will have ZnO seed crystal
Bottom is placed on the surface of mixed-powder, then ceramic boat level is put into quartz ampoule, and quartz ampoule is put to horizontal high temperature process furnances
Growth room in grow under normal pressure, growing environment is normal pressure, the carrier gas in growth course be high-purity argon gas and high purity oxygen gas, institute
The ZnO-Ga of acquisition2O3The cross-sectional width of single quadrangle core-shell structure micro-/ nano line is 10nm~10 μm, and section thickness is
10nm~10 μm, the length of micro wire are 1mm-1cm.Specific size can be determined by the comprehensive regulation of growth temperature and growth time
It is fixed.
Above-described embodiment is only highly preferred embodiment of the present invention, practical range not for the purpose of limiting the invention, it is all according to
It is all the range that the present invention is protected according to the equivalent change that the present invention is made.
Claims (9)
1. a kind of novel micro-cavity structure ultraviolet detector characterized by comprising metallic film, wide bandgap semiconductor micro-/ nano
The metal electrode at line, metal Nano structure and device both ends；Wherein metallic film with a thickness of 5nm~2 μm, single quadrangle
The cross-sectional width of broad stopband micro-/ nano line is 10nm~10 μm, and section thickness is 10nm~10 μm, and the length of micro wire is 1mm-
1cm, the feature size range of metal Nano structure are 10~300nm, the spacing between adjacent metal nanoparticle is 5~
100nm, metal electrode layer with a thickness of 30~500nm.
2. micro-cavity structure ultraviolet detector according to claim 1, it is characterised in that the wide bandgap semiconductor micro wire
MgO、Ga2O3、ZnO、SnO2、TiO2, one or more of NiO core-shell structure.
3. micro-cavity structure ultraviolet detector according to claim 1, it is characterised in that the material of the metallic film is suitable
One of Al, Ag, Pt, Ru, Rn, Pd for ultraviolet band or several composite constructions.
4. micro-cavity structure ultraviolet detector according to claim 1, it is characterised in that the metal nanoparticle is to absorb
Peak is located at one or more asymmetric composite structures of the materials such as Al, Ag, Pt, Ru, Rn, Pd of ultraviolet band, and pattern includes
The regular and irregular pattern that sphere, spheroid, triangular prism and above structure form.
5. micro-cavity structure ultraviolet detector according to claim 1, it is characterised in that the metal electrode layer be Ti, Al,
Single-layer metal or metal composite layer in Ni, Pt, Au, Ag and In.
6. micro-cavity structure ultraviolet detector according to claim 1, it is characterised in that the upper surface of described metal electrode layer steams
Plate the Au layer of one layer of 10~500nm thickness.
7. a kind of preparation method based on micro-cavity structure ultraviolet detector as described in claims 1-6, which is characterized in that tool
Body step are as follows:
1. substrate cleans, heats 5-30 minutes and make a return journey in sulfuric acid, the mixed liquor that hydrochloric acid volume ratio is 3:1 before growth seed layer
Except the inorganic matter (outer-lining bottom of sapphire without this operation) of substrate surface attachment, substrate be sequentially placed into acetone, ethyl alcohol with go from
Respectively it is cleaned by ultrasonic the organic matter of removal substrate surface attachment in 5-30 minutes in sub- water, with being dried with nitrogen after cleaning, and puts
Enter in oxygen plasma cleaning machine and handle 5 minutes, completion to be processed is taken out rear spare；
2. prepared by seed layer, according to selected materials difference, corresponding seed layer is prepared by magnetron sputtering or chemical synthesis.
3. broad stopband micro-/ nano line is grown, high-purity wide bandgap semiconductor powder and graphite powder that mass ratio is 1:1 are sufficiently mixed
It closes, grinding 2 is more than hour.Above-mentioned mixed-powder is placed in ceramic boat middle position, and the substrate with seed layer is placed on
The surface of mixed-powder later again puts ceramic boat level into quartz ampoule, and quartz ampoule is put to horizontal high temperature process furnances
Indoor growing is grown, growing environment is normal pressure, and the carrier gas in growth course is high-purity argon gas and high purity oxygen gas.
4. the preparation of metallic film, growth complete have Fabry-Perot micro-cavity structure quadrangle broad stopband micro-/ nano line it
Afterwards, metallic film is prepared by magnetron sputtering method in the downside of single quadrangle broad stopband micro-/ nano line.
5. the preparation of metal Nano structure, in metallic film material opposite side, (i.e. on the upside of quadrangle broad stopband micro-/ nano line) passes through
Vacuum thermal evaporation, ion sputtering or magnetron sputtering and 2 footworks of annealing prepare the metal nano knot that absorption peak is located at ultraviolet band
Structure, pattern include the irregular pattern of sphere, spheroid, triangular prism one of which and above structure composition.
6. the preparation of metal electrode, in single quadrangle broad stopband of the upper and lower two sides with metallic film and metal nanoparticle
Micro-/ nano line both ends prepare metal electrode by magnetron sputtering method or thermal evaporation method.
8. step according to claim 7 2. be used to grow seed layer substrate be sapphire, quartz, diamond, mica,
SiO2The hardness such as/Si or MgO or flexible substrate.
9. step according to claim 7 is 3., it is characterised in that the growth conditions is normal pressure, growth temperature 900
~1300 DEG C, growth time is 20~60 minutes, and the argon gas and 0~25SCCM oxygen of 100~150SCCM are used in growth course
Gas is as carrier gas.
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