CN104808017B - Probe and preparation method thereof for near-field optical microscope - Google Patents

Probe and preparation method thereof for near-field optical microscope Download PDF

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Publication number
CN104808017B
CN104808017B CN201410036355.6A CN201410036355A CN104808017B CN 104808017 B CN104808017 B CN 104808017B CN 201410036355 A CN201410036355 A CN 201410036355A CN 104808017 B CN104808017 B CN 104808017B
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semiconductor
needle point
metal
layer
cantilever beam
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CN104808017A (en
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徐耿钊
樊英民
刘争晖
钟海舰
黄增立
徐科
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Abstract

The present invention provides a kind of probe for near-field optical microscope, including cantilever beam substrate, semiconductor needle point in the cantilever beam substrate is set, two metal electrodes being arranged on semiconductor needle point, described two metal electrodes are oppositely arranged, the semiconductor needle point and two metal electrodes form the metal-semiconductor-metal photo detector for converting optical signals to electric signal, one of metal electrode with an external dc bias loading device for connecting, another metal electrode is used to collect photoelectric current and photoelectricity is streaming to the controller of near-field optical microscope.It is an advantage of the current invention that near-field optical microscope structurally and operationally complexity can be simplified, its use scope is widened significantly, to facilitate transmission and replacement of the probe in various environment.

Description

Probe and preparation method thereof for near-field optical microscope
Technical field
The present invention relates to technical field of optical test more particularly to a kind of probes and its system for near-field optical microscope Preparation Method.
Background technology
Measure absorption, scattering and luminescence phenomenon of the material to light, be the transition for studying semiconductor carriers, it is compound with And the important laboratory facilities of lattice motor pattern, and sample nondestructive is hindered.And with the development of nanotechnology, people are interested Material and device scale it is smaller and smaller;And common optical detection means are limited by microcobjective diffraction limit, Spatial resolution is generally on the micron order of magnitude.And since the 1980s, with the quick of scanning probe microscopy technology Progress, is combined, the near-field optical microscope developed with optical detector technology, has the optical space more than diffraction limit Resolution ratio, at a kind of important means in important aspect and nanostructure research to solve this problem.
As other scanning probe microscopies, near-field optical microscope is also that a needle point is placed in sample surfaces, is led to Cross detection needle point sample room tunnel current or atomic force interaction come maintain needle point sample interval from it is constant, usually exist On the order of magnitude of 1 nm.And then by needle point in the scanning of sample surfaces, the point-by-point optical signal for acquiring sample surfaces.Near field optic Microscope mainly achieves over the high spatial resolution of optical diffraction limit by two ways:There is hole probe near field optic aobvious Micro mirror and scattering formula near-field optical microscope.
Figure 1A and Figure 1B show the probe schematic diagram of near-field optical microscope in the prior art.Referring to Figure 1A, there is hole spy The aperture 11 that needle near-field optical microscope is opened the optical fiber probe 10 of the metal-plated membrane of aperture 11 using a tip, and opened Diameter is much smaller than optical wavelength, and the near field optic signal on 13 surface of sample is acquired and by fiber optic conduction outside by this aperture 11 The photodetector in portion.Referring to Figure 1B, scattering formula near-field optical microscope uses a metal needle point 12, utilizes metal surface etc. The effects such as antenna effect are shaken by electromagnetism from excimer concussion, " lightning rod " effect of point discharge and metal needle point 12 and dipole Field local includes sample 13 around metal needle point 12, forms the near field optic signal of enhancing, then pass through the optics such as microcobjective System collects these signals and passes to photodetector.Finally, by needle point, collected optical signal turns photodetector point by point It changes electric signal into and passes through computer acquisition and record.
And in practical applications, above-mentioned working method is limited in that photodetector always distant apart from needle point Place, be required for the light signal transduction that needle point is collected by complicated optical facilities to photodetector.For there is hole probe Mode, always connect a long optical fiber behind needle point, from needle point be continuously connected to photodetector before optical fiber coupling Mechanism is closed to pass to optical signal;For scatter formula mode, it is also desirable to it is a set of can be with the optical system of multiple dimension fine adjustments The focus long-time stable of microcobjective is precisely aligned to the position where needle point, has acquired the near field optic letter of needle point enhancing Number and the photodetector that passes to distant place.This all considerably increases the responsible degree of operation.
Invention content
The technical problem to be solved by the invention is to provide a kind of probe for near-field optical microscope and its preparation sides Method can simplify near-field optical microscope structurally and operationally complexity, widen its use scope significantly, to facilitate probe to exist Transmission in various environment and replacement.
To solve the above-mentioned problems, the present invention provides a kind of probes for near-field optical microscope, including cantilever beam Substrate, the semiconductor needle point being arranged in the cantilever beam substrate, two metal electrodes being arranged on semiconductor needle point are described Two metal electrodes are oppositely arranged, and the semiconductor needle point and two metal electrodes are formed for converting optical signals to electric signal MSM-PD with low, one of metal electrode be used for and an external dc bias loading device connect It connects, another metal electrode is used to collect photoelectric current and photoelectricity is streaming to the controller of near-field optical microscope.
Further, the material of the semiconductor needle point is III- group-III nitrides.
Further, the III- group-III nitrides include gallium nitride, aluminium nitride, indium nitride and its alloy.
A kind of preparation method of the above-mentioned probe for near-field optical microscope, includes the following steps:One cantilever is provided Beam substrate;Semiconductor needle point is formed in the cantilever beam substrate;Formation two is oppositely arranged on the semiconductor needle point Metal electrode;The semiconductor needle point is formed with two metal electrodes and is partly led for converting optical signals to the metal-of electric signal Body-metal photodetector.
Further, described further includes following steps the step of forming semiconductor needle point in the cantilever beam substrate:Institute State in cantilever beam substrate grown semiconductor layer, silicon dioxide layer and metal layer successively;In the layer on surface of metal relative to cantilever The position of making semiconductor needle point is coated with photoresist and is protected in beam substrate;The metal layer of no photoresist protection is removed successively And silicon dioxide layer a so that protrusion is formed on the semiconductor layer, the composition of the protrusion is followed successively by two from semiconductor layer Silicon oxide layer, metal layer and photoresist;The photoresist and metal layer in the protrusion are removed successively, and it only includes silica to be formed The protrusion of layer;The semiconductor layer and silicon dioxide layer are etched, until silicon dioxide layer disappears, semiconductor needle point is formed, in institute It states and exposes cantilever beam substrate except semiconductor needle point position.
Further, it is described on the semiconductor needle point formed two be oppositely arranged metal electrode the step of further include as Lower step:A metallic film is deposited in the semiconductor needle surface;Metallic film etching is oppositely arranged for two Electrode, the semiconductor needle point and two metal electrodes form MSM-PD with low, and the metal-is partly led Body-metal photodetector is for converting optical signals to electric signal.
Further, it in the cantilever beam substrate after grown semiconductor layer, before growing silicon dioxide layer, is partly led described Another semiconductor layer different from the semiconductor layer material of continued growth one on body layer.
Further, the material of the semiconductor needle point is III- group-III nitrides.
A kind of probe for near-field optical microscope, including cantilever beam substrate are formed in the cantilever beam substrate Semiconductor needle point, and two metal electrodes being formed on the semiconductor needle point.
It is an advantage of the current invention that near field optic signal is converted into electric signal output by semiconductor needle point itself, to It is avoided the collected light signal transduction of probe tip near field optic measurement using complicated optical coupling system to far The photodetector at place simplifies near-field optical microscope structurally and operationally complexity, has widened its use scope significantly, to Facilitate probe in various environment(Including ultra-high vacuum environment)In transmission and replacement, and need not expend in an experiment a large amount of Manpower regulation optical system makes it steadily be directed at probe tip.
Description of the drawings
Figure 1A and Figure 1B show the probe schematic diagram of near-field optical microscope in the prior art;
Fig. 2A show side schematic view of the present invention for the probe of near-field optical microscope;
Fig. 2 B show vertical view of the present invention for the probe of near-field optical microscope;
Fig. 3 show the step schematic diagram of the preparation method of the probe for near-field optical microscope;
Fig. 4 A ~ Fig. 4 H and 5A ~ Fig. 5 H show preparation flow figure of the present invention for the probe of near-field optical microscope, In, Fig. 4 A ~ Fig. 4 H are side view, and Fig. 5 A ~ Fig. 5 H are vertical view.
Specific implementation mode
Below in conjunction with the accompanying drawings to the specific of probe provided by the present invention for near-field optical microscope and preparation method thereof Embodiment elaborates.
Fig. 2A show side schematic view of the present invention for the probe of near-field optical microscope, and Fig. 2 B show the present invention The vertical view of probe for near-field optical microscope.Shown in Fig. 2A and Fig. 2 B, the present invention is used for near-field optical microscope Probe include cantilever beam substrate 20, the semiconductor needle point 21 that is arranged in the cantilever beam substrate 20, be arranged in semiconductor needle Two metal electrodes 22 on point 21.
Monocrystalline silicon preparation may be used in the cantilever beam substrate 20.The nitridation of III- races may be used in the semiconductor needle point 21 Object material preparation, for example, gallium nitride, aluminium nitride, indium nitride and its alloy.According to its different component, energy gap can be covered Lid is from infrared, visible light until ultraviolet band range, and all direct band-gap semicondictors, has excellent opto-electronic conversion Characteristic;And it is good with high thermal conductivity, chemical stability(Hardly by any acid corrosion)Etc. properties and strong Flouride-resistani acid phesphatase energy Power can be applied to various use environments.It is standby that the metal electrode 22 may be used made of metal, for example, aluminium.
Described two metal electrodes 22 are oppositely arranged, and the semiconductor needle point 21 and two metal electrodes 22 are formed for inciting somebody to action Optical signal is converted to the MSM-PD with low of electric signal(MSM photoelectric detector), one of metal electricity Pole 22 is connect with an external dc bias loading device, and another metal electrode 22 collects photoelectric current and photoelectricity is streaming near field The controller of light microscope.Further, between this pair of metal electrodes 22 of the needle point tip of semiconductor needle point 21 have one away from From the distance can be 50 ~ 100 nm.
MSM-PD with low(MSM photoelectric detector)Utilize Xiao near metal-semiconductor contact interface Built in field caused by de- base potential barrier makes photo-generate electron-hole to separation, and is diffused into two metal electrodes, forms photoelectric current. It only needs to prepare two arrays of electrodes in semiconductor the same side, and two electrodes can use the metal of identical material, should not It prepares the electrode of Ohmic contact, semiconductor need not be doped, processing prepares simple.Meanwhile metal-semiconductor-metal Photodetector(MSM photoelectric detector)It is exceedingly fast with response speed, the advantages such as dark current is low.These good characteristics are the present invention To break through the physical basis of typical near-field light microscope limitation.
The present invention is used for the probe use of near-field optical microscope as conventional atomic force microscope.By the present invention's Probe is installed on afm scan head, and semiconductor needle point 21 and sample are made under the control of atomic force microscope controller Product surface contacts, and semiconductor needle point 21 is moved to sample surfaces position to be measured, passes through 21 tip of semiconductor needle point and sample room The interaction of power come maintain semiconductor needle point 21 and sample interval from it is constant.
Detect control sample and semiconductor needle point 21 between interaction force be atomic force microscope basic function it One, typically, the active force between control sample and semiconductor needle point 21 is constant, this means that the distance between the two is not Become.Meanwhile semiconductor needle point 21 and two metal electrodes have collectively constituted MSM-PD with low(MSM light Electric explorer), wherein Dc bias is loaded on a metal electrode 22(MSM-PD with low must be Have and works in the case of bias voltage), when nearby there is optical signal at 21 tip of semiconductor needle point, can be produced in metal electrode 22 Generated photo-current, it is aobvious that the photoelectric current that another metal electrode 22 is collected into is sent near field optic after galvo-preamplifier amplifies Micromirror controller, and finally by control computer acquisition and record, and it is point-by-point in sample surfaces by controlling semiconductor needle point 21 It scans and forms near field optic picture.
The present invention also provides a kind of preparation method of the above-mentioned probe for near-field optical microscope, Fig. 3 A show use In the step schematic diagram of the preparation method of the probe of near-field optical microscope.Referring to Fig. 3, described method includes following steps:Step Rapid S30, a cantilever beam substrate is provided;Step S31, semiconductor needle point is formed in the cantilever beam substrate;Step S32, institute State two metal electrodes being oppositely arranged of formation on semiconductor needle point;The semiconductor needle point and two metal electrodes form gold Category-semiconductor-metal photodetector, the MSM-PD with low is for converting optical signals to telecommunications Number.
The step S31 forms semiconductor needle point step in the cantilever beam substrate and further comprises following steps: Referring to Fig. 3 B, grown semiconductor layer, silicon dioxide layer and metal layer successively step S310, in the cantilever beam substrate;Step S311, it is coated with photoresist relative to the position for making semiconductor needle point in cantilever beam substrate in the layer on surface of metal and is protected Shield;Step S312, the metal layer and silicon dioxide layer of no photoresist protection are removed successively so that the shape on the semiconductor layer At a protrusion, the composition of the protrusion is followed successively by silicon dioxide layer, metal layer and photoresist from semiconductor layer;Step S313, according to Photoresist and metal layer in the secondary removal protrusion, form the protrusion for only including silicon dioxide layer;Step S314, described in etching Semiconductor layer and silicon dioxide layer form semiconductor needle point until silicon dioxide layer disappears.
The step S32 is further gone back the step of forming two metal electrodes being oppositely arranged on the semiconductor needle point Include the following steps:Referring to Fig. 3 C, step S320, a metallic film is deposited in the semiconductor needle surface;Step S321, will The metallic film etching is two electrodes being oppositely arranged, and the semiconductor needle point and two metal electrodes are formed and are used for light Signal is converted to the MSM-PD with low of electric signal.
Fig. 4 A ~ Fig. 4 H and 5A ~ Fig. 5 H show preparation flow figure of the present invention for the probe of near-field optical microscope, In, Fig. 4 A ~ Fig. 4 H are side view, and Fig. 5 A ~ Fig. 5 H are vertical view.
Referring to Fig. 4 A and Fig. 5 A a cantilever beam substrate 401 is provided with reference to step S30.The cantilever beam substrate 401 can be with It is prepared using monocrystalline silicon.
Referring to Fig. 4 B and Fig. 5 B, with reference to step S301, in the cantilever beam substrate 401 successively grown semiconductor layer 402, Silicon dioxide layer 403 and metal layer 404.
The method of the grown semiconductor layer 402 can be metallo-organic compound chemical gaseous phase deposition method(MOCVD), Metallo-organic compound chemical gaseous phase deposition method is the prior art, and this will not be repeated here.The thickness of the semiconductor layer 402 can be with It is 1 ~ 4 micron.The preparation of III- group nitride materials may be used in the semiconductor layer 402, for example, gallium nitride, aluminium nitride, nitridation Indium and its alloy.According to its different component, energy gap can be covered from infrared, visible light until ultraviolet band range, And all direct band-gap semicondictors have excellent light transfer characteristic;And with high thermal conductivity, chemical stability It is good(Hardly by any acid corrosion)Etc. properties and strong Radiation hardness, can be applied to various use environments.
Further, the wavelength of the light detected for the probe of near-field optical microscope according to the present invention, may be used also when necessary The other III- group nitride materials of 10 ~ 100 nm of regrowth on semiconductive thin film.
The method of the growth silicon dioxide layer 403 is plasma enhanced chemical vapor deposition method(PECVD), plasma It is the prior art that body, which enhances chemical vapour deposition technique, and this will not be repeated here.
The method of the growth metal layer 404 is electron beam evaporation method, and electron beam evaporation method is the prior art, herein It does not repeat.In this embodiment, the material of the metal layer 404 is nickel, in other embodiment of the present invention, Can be other metals such as gold.
Referring to Fig. 4 C and Fig. 5 C, with reference to step S311, on 404 surface of the metal layer relative to being made in cantilever beam substrate The position of semiconductor needle point is coated with photoresist 405 and is protected.The photoresist 405 can be PMMA photoresists.It is specific at this In embodiment, only light is coated with relative to the position for making semiconductor needle point in cantilever beam substrate on 404 surface of the metal layer Photoresist 405 is protected.And in other specific implementation modes of the invention, the photoresist 405 is coated in the complete of metal layer 404 Portion surface then needs the photoresist 405 for further removing 404 surface of metal layer except the position for making semiconductor needle point, makes Only 404 surface of the metal layer relative in cantilever beam substrate make semiconductor needle point position be coated with photoresist 405 into Row protection.The method of the removal photoresist 405 is ultraviolet lithography.
Referring to Fig. 4 D and Fig. 5 D, with reference to step S312, the metal layer 404 and two of the protection of no photoresist 405 is removed successively Silicon oxide layer 403 so that form a protrusion on the semiconductor layer 402, the composition of the protrusion from semiconductor layer 402 successively For silicon dioxide layer 403, metal layer 404 and photoresist 405.
The method for removing the metal layer 404 is different and different according to the material of metal layer 404, for example, metal layer 404 is When nickel, liquor ferri trichloridi wet etching nickel layer can be used.It is using the advantages of material of the nickel as metal layer 404, at this When step removes metal layer 404, it is only necessary to corrode nickel with liquor ferri trichloridi, method is simple, safe, at low cost.Removal institute The method for stating silicon dioxide layer 403 is the method for reactive ion etching(RIE).The liquor ferri trichloridi wet etching metal film And the method for reactive ion etching is the prior art, this will not be repeated here.
Referring to Fig. 4 E and Fig. 5 E, with reference to step S313, the photoresist 405 and metal layer 404 in the protrusion are removed successively, Form the protrusion for only including silicon dioxide layer 403.The method for removing the photoresist 405 is using acetone soak.Described in removal The method of metal layer 404 is using liquor ferri trichloridi wet etching metal film.
The semiconductor layer 402 and silicon dioxide layer 403 are etched, until dioxy with reference to step S314 referring to Fig. 4 F and Fig. 5 F SiClx layer 403 disappears, and forms semiconductor needle point 406, exposes cantilever beam substrate except 406 position of semiconductor needle point 401.In this embodiment, the method for the etching semiconductor layer 402 and silicon dioxide layer 403 be inductively etc. from Daughter method(ICP), the method is the prior art, and this will not be repeated here.It is partly led using inductively coupled plasma method etching When body layer 402 and silicon dioxide layer 403,403 etching speed of silicon dioxide layer is slower than semiconductor layer 402, so in silica Taper is gradually formed under the regions of 403 covering of layer, until silicon dioxide layer 403 disappears, forms semiconductor needle point 406, at this time half Conductor layer 402 is not etched completely away.
Referring to Fig. 4 G and Fig. 5 G, with reference to step S320, a metallic film 407 is deposited on 406 surface of semiconductor needle point. The material of the method for the method electron beam evaporation of the deposited metal film 407, the metallic film 407 can be metallic aluminium.
Referring to Fig. 4 H and Fig. 5 H, with reference to step S321, it is two metals being oppositely arranged that the metallic film 407, which is etched, Electrode 408, the semiconductor needle point 406 and two metal electrodes 408 form the metal-for converting optical signals to electric signal Semiconductor-metal photodetector.The method of the etching metal electrode 408 is the method for focused ion beam.Further, half There is a distance, the distance can be 50 ~ 100 nm between this pair of metal electrodes 408 of the needle point tip of conductor needle point 406.
The present invention is set forth below in the embodiment of the preparation method of the probe of near-field optical microscope.
(a)The semiconductor layer for using MOCVD methods to grow 1 ~ 4 μm in the cantilever beam substrate of single crystalline Si, for example, GaN is thin Film layer.This growing method belongs to existing known technology, herein no longer narration in detail.It is necessary according to the wavelength of the light detected When also on GaN film layer the other III- group nitride materials of 10 ~ 100 nm of regrowth.
(b)In the semiconductor layer surface 300nm silicon dioxide layers are grown using PECVD methods.
(c)The nickel layer of 10 ~ 100 nm thickness is deposited using electron beam evaporation method in the silica layer surface.
(d)In the nickel layer surface spin coating PMMA photoresists.
(e)Major part PMMA photoresists are removed by ultraviolet lithography, retain the discoid PMMA light of 0.5 ~ 1 μm of diameter Photoresist.
(f)The wet etching nickel layer in liquor ferri trichloridi removes other other than having PMMA photoresists protection zone Partial nickel layer.
(g)RIE methods etch away the silicon dioxide layer of the other parts other than the region that nickel layer is protected.
(h)It impregnates in acetone and removes PMMA photoresist disks, then impregnate and remove originally in liquor ferri trichloridi again Nickel layer below photoresist.
(i)ICP method etching semiconductor layers, silicon dioxide layer disk can also be etched, but etching speed is slower than and partly leads Body layer can gradually form taper below the region for having silicon dioxide layer disk to cover.
(j)It is etched to the disappearance of semiconductor layer disk, forms semiconductor needle point.
(k)The Al films of 50 ~ 100 nm are plated using electron beam evaporation method in semiconductor needle surface.
(l)Al films are portrayed as a pair of metal electrodes in semiconductor needle surface with the method for focused-ion-beam lithography, Spacing between this pair of metal electrodes of semiconductor needle point tip is 50 ~ 100 nm.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as Protection scope of the present invention.

Claims (6)

1. a kind of probe for near-field optical microscope, which is characterized in that including cantilever beam substrate, be arranged in the cantilever beam Semiconductor needle point in substrate, two metal electrodes being arranged on semiconductor needle point, described two metal electrodes are oppositely arranged, The semiconductor needle point and two metal electrodes form the metal-semiconductor-metal light for converting optical signals to electric signal Electric explorer, one of metal electrode with an external dc bias loading device for connecting, and another metal electrode is for receiving The material of collection photoelectric current and the controller that photoelectricity is streaming to near-field optical microscope, the semiconductor needle point is III- races nitrogen Compound, the III- group-III nitrides include gallium nitride, aluminium nitride, indium nitride and its alloy.
2. a kind of preparation method of the probe described in claim 1 for near-field optical microscope, which is characterized in that including such as Lower step:
One cantilever beam substrate is provided;
Semiconductor needle point is formed in the cantilever beam substrate;
Two metal electrodes being oppositely arranged are formed on the semiconductor needle point;
The semiconductor needle point and two metal electrodes form metal-semiconductor-gold for converting optical signals to electric signal Belong to photodetector, the material of the semiconductor needle point is III- group-III nitrides, and the III- group-III nitrides include gallium nitride, nitrogen Change aluminium, indium nitride and its alloy.
3. the preparation method of the probe according to claim 2 for near-field optical microscope, which is characterized in that it is described The step of semiconductor needle point is formed in the cantilever beam substrate further comprises following steps:
Grown semiconductor layer, silicon dioxide layer and metal layer successively in the cantilever beam substrate;
It is protected relative to the position coating photoresist for making semiconductor needle point in cantilever beam substrate in the layer on surface of metal;
The metal layer and silicon dioxide layer of no photoresist protection are removed successively so that it is convex that one is formed on the semiconductor layer It rises, the composition of the protrusion is followed successively by silicon dioxide layer, metal layer and photoresist from semiconductor layer;
The photoresist and metal layer in the protrusion are removed successively, form the protrusion for only including silicon dioxide layer;
The semiconductor layer and silicon dioxide layer are etched, until silicon dioxide layer disappears, semiconductor needle point is formed, is partly led described Body acupuncture point exposes cantilever beam substrate except position.
4. the preparation method of the probe according to claim 2 for near-field optical microscope, which is characterized in that it is described The step of two metal electrodes being oppositely arranged are formed on the semiconductor needle point further comprises following steps:
A metallic film is deposited in the semiconductor needle surface;
It is two electrodes being oppositely arranged by metallic film etching, the semiconductor needle point and two metal electrodes form gold Category-semiconductor-metal photodetector, the MSM-PD with low is for converting optical signals to telecommunications Number.
5. the preparation method of the probe according to claim 3 for near-field optical microscope, which is characterized in that described In cantilever beam substrate after grown semiconductor layer, before growing silicon dioxide layer, the further continued growth on the semiconductor layer The one another semiconductor layer different from the semiconductor layer material.
6. a kind of probe for near-field optical microscope, which is characterized in that including cantilever beam substrate, be formed in the cantilever beam Semiconductor needle point in substrate, and two metal electrodes being formed on the semiconductor needle point, the semiconductor needle point Material is III- group-III nitrides, and the III- group-III nitrides include gallium nitride, aluminium nitride, indium nitride and its alloy.
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