CN107591457B - A kind of photodetector and preparation method thereof of 3D dendritic structure - Google Patents
A kind of photodetector and preparation method thereof of 3D dendritic structure 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
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- 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 present invention relates to a kind of photodetectors and preparation method thereof of three-dimensional (3D) dendritic structure, belong to field of photodetectors.Photodetector successively has Si substrate, insulation SiO from bottom to top2Layer, 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material and metal electrode.Firstly, preparing 3C-SiC nano wire trunk using the method for hot carbon reduction；Then, layer of ZnO seed layer is deposited in 3C-SiC nanowire surface using the method for deposition；The method of hydro-thermal growing ZnO nano-wire branch in ZnO seed layer is recycled, 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material is formed；Finally, single 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material is transferred to SiO2/ Si substrate plates metal electrode at heterojunction material both ends using photoetching and lift-off technology, both the photodetector.Photodetector of the present invention has bigger extinction area and light absorption range, and more effectively photo-generated carrier separation rate, higher photocurrent gain and faster speed of photoresponse.
Description
Technical field
The present invention relates to a kind of photodetectors and preparation method thereof of three-dimensional (3D) dendritic structure, belong to photodetection
Device field.
Background technique
Photodetector is in light wave communication, imaging technique, photoelectric circuit, the optical storage in future, space exploration, environment prison
The effect in the fields such as survey, biology and medical treatment is most important.One-dimensional (1D) semiconductor nano cable architecture due to its perfect crystallinity,
Biggish specific surface area and higher carrier mobility, it is considered to be construct important basic group of the following high-performance nano device
At unit.However, due to the limited light absorption of 1D semiconductor nanowires and photoelectric conversion efficiency of single component, so that nano wire
Base photodetector is difficult to obtain extensive spectral response, greatly limits them in optoelectronic switch, optical storage and ultraviolet/can
Application in the light-exposed wide spectrum sensitive device of imaging.In order to overcome the problems referred above, the three-dimensional (3D) being made of two kinds of different materials
Dendroid nano material and its application in terms of photoelectricity, photocatalysis, photovoltaic and sensor have received widespread attention.Due to this
Special construction is integrated with two kinds of different materials, can use the different characteristics of two kinds of materials to obtain the integrated of various functions, from
And realize the inaccessiable effect of one-component material institute.In addition, due to the extra specific surface area of its dendritic structure, Ke Yiyou
The contact area for improving absorptivity, increasing material and detecting material of effect.Moreover, the nano wire master relative to larger size
It is dry, the separation and collection that smaller size of nano wire branch can make carrier more efficient.
ZnO and SiC had obtained great pass in field of photodetectors in recent years due to its respective excellent photoelectric characteristic
Note.However the intrinsic defect of Lacking oxygen and zinc calking due to ZnO, the photoelectric current for the photodetector for causing it to prepare are unstable
And the response time is long.And the forbidden bandwidth of ZnO is 3.37eV, can only absorb ultraviolet light, which also limits the spies of zno-based photoelectricity
Survey the application of device in other respects.
Summary of the invention
In order to solve the problems, such as that zno-based ultraviolet detector is showed, the object of the present invention is to provide a kind of 3D branches
The photodetector and preparation method thereof of shape structure, to improve the performance and application range of photodetector.
In order to achieve the goal above, technical solution used by photodetector of the invention is:
A kind of photodetector of 3D dendritic structure, the photodetector include Si substrate, are deposited in Si substrate surface
There is the SiO of insulation2Layer, in SiO2The surface of layer is provided with 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material, in 3C-
SiC/ZnO dendroid heterojunction material both ends are deposited with metal electrode, and form Ohmic contact.
The number of the 3C-SiC/ZnO dendritic structure heterojunction material is 1~20；The metal electrode is
Al, Ti/Au, Cr/Au, Ni/Au, Ti/Al/Ti/Au or Ti/Al/Ni/Au；The metal electrode with a thickness of 100 to 200
Nanometer.
In the 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material, from-inner-to-outer successively has 3C-SiC nano wire
Trunk, ZnO seed layer, ZnO nano-wire branch, 3C-SiC nano wire are the trunk of three-dimensional dendritic structure, ZnO nano-wire three
Tie up the branch of dendritic structure.
The length of the 3C-SiC nano wire trunk is 100 nanometers to 1 millimeter, and diameter is 10 nanometers to 10 microns；Institute
The length for the ZnO nano-wire branch stated is 20 nanometers to 20 microns, and diameter is 10 nanometers to 1 micron.
The production method of the photodetector of the 3D dendritic structure, includes the following steps:
1) powder of the silica and carbon that take identical molal quantity is uniformly mixed in quartz boat, and mixed powder is put
Enter and heat and keep the temperature in high temperature process furnances, be continually fed into protective gas during heating, obtains 3C-SiC nano wire；
2) layer of ZnO seed layer is uniformly sputtered in the 3C-SiC nanowire surface synthesized using the method for deposition；
3) the hexa crystal of the zinc nitrate hexahydrate of 20~30mM and 20~30mM are put into 80~120ml's
It is sufficiently stirred in water, the solution after stirring is transferred in hydrothermal reaction kettle；Solution is heated and kept the temperature, 3C-SiC/ZnO is obtained
Three-dimensional dendritic structure heterojunction material；
4) obtained 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material is put into tube furnace, at 300~400 DEG C
At a temperature of anneal 0.5~2 hour；
5) using sonic oscillation, the method for spin coating, it is long that 3C-SiC/ZnO dendroid knot heterojunction material is transferred to surface
There is SiO2On the Si substrate of layer；One layer of metal electricity is deposited at the both ends of dendroid dissimilar materials using photoetching process and lift-off technology
Pole forms final 3C-SiC/ZnO dendroid ultraviolet/visible light electric explorer.
The production method of the photodetector of the 3D dendritic structure, in step (1), the heating temperature is
1200~1400 DEG C, soaking time is 0.5~2h.
The production method of the photodetector of the 3D dendritic structure, in step (1), the protective gas is
Argon gas or nitrogen.
The production method of the photodetector of the 3D dendritic structure, in step (2), the method for the deposition is
Magnetron sputtering, electrochemical deposition, molecular beam epitaxy, sol-gel, chemical vapor deposition or atomic layer deposition；The ZnO kind
Sublayer with a thickness of 10~100 nanometers.
The production method of the photodetector of the 3D dendritic structure, in step (3), the time of the stirring is
10~60 minutes；The heating temperature is 70~90 DEG C, and soaking time is 1~8 hour.
The production method of the photodetector of the 3D dendritic structure, in step (5), the SiO2The thickness of layer
It is 100~500 nanometers.
The present invention has the following advantages and beneficial effects:
1) the 3C-SiC nano wire trunk in the present invention and ZnO nano-wire branch lattice match height, thermal mismatching rate are small, have
Conducive to the transfer of growth and photo-generated carrier of the ZnO nano-wire on 3C-SiC nano wire.
2) since the conduction band of ZnO is higher than the conduction band of 3C-SiC, so that the photo-generated carrier of ZnO branch can be shifted more effectively
To 3C-SiC trunk, to be easier to be collected by electrode.Therefore both materials are assembled into three-dimensional dendritic structure will
The performance of photodetector is set to be greatly enhanced.
3) ultraviolet light can be absorbed in the energy band of ZnO larger (3.37eV), and the energy band of 3C-SiC smaller (2.3eV) can be absorbed
Both Material claddings will be widened the application field of photodetector by visible light.
4) three-dimensional block structure of this special 3D dendritic structure of the present invention relative to single component, two-dimensional film knot
Structure, 1-dimention nano cable architecture, the advantages of being not only integrated with two kinds of materials, but also significantly increase the extinction area of material.
Detailed description of the invention
Fig. 1 is preparation flow figure of the invention.
Fig. 2 is the three dimensional structure diagram of 3D dendritic structure photodetector；In figure, 1, Si substrate；2, insulate SiO2
Layer；3,3C-SiC/ZnO three-dimensional dendritic structure heterojunction material；4, metal electrode.
Fig. 3 is the schematic three dimensional views of 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material.In figure, 3,3C-SiC/ZnO
Three-dimensional dendritic structure heterojunction material；5,3C-SiC nano wire trunk；6, ZnO seed layer；7, ZnO nano-wire branch.
Fig. 4 is the SEM image of 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material.
Fig. 5 is IV characteristic curve of the 3D dendritic structure photodetector under Compound eye.
Fig. 6 is 3D dendritic structure photodetector under 370nm illumination condition, the IV characteristic curve of different optical powers.
Fig. 7 is the characteristic curve that opens the light of 3D dendritic structure photodetector.
Specific embodiment:
Hereinafter, narration is of the invention in detail in conjunction with the accompanying drawings and embodiments.
Referring to Fig.1, preparation flow of the invention is as follows:
The production method of the photodetector of 3D dendritic structure of the invention, firstly, the method system restored using hot carbon
Standby 3C-SiC nano wire trunk；Then, layer of ZnO seed layer is deposited in 3C-SiC nanowire surface using the method for deposition；Again
Using the method for hydro-thermal, growing ZnO nano-wire branch, formation 3C-SiC/ZnO three-dimensional dendritic structure are heterogeneous in ZnO seed layer
Tie material；Finally, single 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material is transferred to SiO2/ Si substrate, utilizes light
Carve and lift-off technology at heterojunction material both ends plate metal electrode, both the photodetector.
Referring to Fig. 2,3D dendritic structure photodetector of the invention, the structure of the device is metal-semiconductor-metal
Contact-type, from bottom to top successively are as follows: Si substrate 1, insulation SiO2Layer 2,3C-SiC/ZnO three-dimensional dendritic structure heterojunction material
The both ends of 3,3C-SiC/ZnO three-dimensional dendritic structure heterojunction materials 3 are metal electrode 4.Metal electrode 4 is respectively overlay in 3C-
The both ends of SiC/ZnO three-dimensional dendritic structure heterojunction material 3, and form Ohmic contact.
Referring to Fig. 3,3C-SiC/ZnO three-dimensional dendritic structure heterojunction material 3 of the invention, from-inner-to-outer successively has 3C-
SiC nanowire trunk 5, ZnO seed layer 6, ZnO nano-wire branch 7.
Embodiment:
1) high-purity (99.99wt%) SiO of 0.1mol is taken2It is uniformly mixed in quartz boat with the powder of C, then will mix
Powder after conjunction is put into high temperature process furnances, is heated to 1400 DEG C and constant temperature 30 minutes.It is continually fed into flow during heating
For the Ar gas of 100ml/min.At high temperature, the carbonization of silicon steam will generate a large amount of 3C-SiC nano wire, and diameter is about
200nm, length are about tens microns.
2) 3C-SiC nano wire is put into the reaction chamber of magnetron sputtering depositing device, selects ZnO ceramic target as target,
Adjusting sputtering power is 80W, sputtering time 10min, Ar throughput is 8sccm, using the method for rf magnetron sputtering
3C-SiC nanowire surface uniform sputter a layer thickness of synthesis is the ZnO seed layer of 50nm.
3) zinc nitrate hexahydrate of 25mM and hexa crystal are put into the water of 100ml and are stirred 30 minutes.So
The solution after stirring is transferred in hydrothermal reaction kettle afterwards, solution is heated to 90 DEG C and keeps the temperature 4 hours, obtains 3C-SiC/ZnO
Three-dimensional dendritic structure heterojunction material, wherein the length of ZnO nano-wire branch is about 300nm, diameter is about 50nm.
4) obtained 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material is put into tube furnace, in 350 DEG C of temperature
Degree lower annealing 1 hour, to improve the crystalline quality of material.
5) with surface with a thickness of 100 Nano-meter SiO_2s2The Si piece of layer is as insulating substrate, respectively in deionized water, third
It is cleaned by ultrasonic 10 minutes in ketone, dehydrated alcohol, and with being dried with nitrogen.Use alcohol as dispersion liquid, by 3C-SiC/ZnO dendroid
Dispersion liquid is added in structure heterojunction material, and sonic oscillation is uniformly suspended in heterojunction material in dispersion liquid.3C-SiC/ will be contained
The dispersant liquid drop of ZnO dendritic structure heterojunction material is in SiO2In/Si insulating substrate, using the method for spin coating, drop is made to exist
SiO2Every 3C-SiC/ZnO dendritic structure in/Si substrate is disconnected from each other.Select a wherein dendritic structure hetero-junctions
Material deposits one layer of Ti/Au gold at the both ends of dendritic structure heterojunction material using traditional photoetching process and lift-off technology
Belong to electrode, forms final 3C-SiC/ZnO3D dendritic structure photodetector.
Referring to Fig. 4, the present invention can be seen that from the SEM image of 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material
3C-SiC/ZnO heterojunction material have a dendritic structure, 3C-SiC nano wire is the trunk of dendritic structure, ZnO nanorod
For the branch of dendritic structure.Also, ZnO nanorod branch is covered on 3C-SiC nano wire trunk surface well.Material ruler
Very little uniform, pattern is neat, repeatability is high.
Referring to Fig. 5, can be seen that from IV characteristic curve of the 3D dendritic structure photodetector under Compound eye
Photodetector of the invention shows the dark current of very little, 0.68nA under conditions of no illumination (under 3V bias condition).
When having illumination and photon energy is greater than 3C-SiC (2.3eV) or ZnO (3.37eV) energy band, photodetector produces very strong
Photoelectric current.Meanwhile with the reduction of lambda1-wavelength, photoelectric current is gradually increased.Under 3V bias, 350nm illumination condition, this
The photoelectric current of the photodetector of invention can reach 127.7nA, show the biggish photocurrent gain of detector and very excellent
Different wavelength selectivity and response characteristics to light.
Referring to Fig. 6, the increase with incident light (350nm) power never can be seen that with the IV characteristic curve of optical power
Photoelectric current also gradually increases, and shows the very outstanding light intensity sensitivity characteristic of photodetector of the invention.
Referring to Fig. 7, it can be seen that photoelectricity of the invention from the characteristic curve that opens the light of 3D dendritic structure photodetector and visit
Light, dark current stabilization, the switch repeatability height of device are surveyed, and the response time is fast (about 40ms), shows very excellent photoelectricity
Signal transfer characteristic and switching characteristic.
Embodiment the result shows that, compared to traditional photodetector, the present invention is this by special 3D dendritic structure
The photodetector of production has bigger an extinction area and light absorption range, and more effectively photo-generated carrier separation rate, more
High photocurrent gain and faster speed of photoresponse.Its manufacture craft is simple, at low cost, is conducive to be widely applied.
The above, the only specific embodiment in the present invention, but scope of protection of the present invention is not limited thereto, appoints
What is familiar with the people of the technology within the technical scope disclosed by the invention, and what can be readily occurred in transforms or replaces, and should all cover
In scope of the invention.Therefore, the scope of protection of the invention shall be subject to the scope of protection specified in the patent claim.
Claims (9)
1. a kind of photodetector of 3D dendritic structure, it is characterised in that: the photodetector includes Si substrate, in Si substrate
Surface is deposited with the SiO of insulation2Layer, in SiO2The surface of layer is provided with 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material,
It is deposited with metal electrode at 3C-SiC/ZnO dendroid heterojunction material both ends, and forms Ohmic contact；
The production method of the photodetector of the 3D dendritic structure, includes the following steps:
1) powder of the silica and carbon that take identical molal quantity is uniformly mixed in quartz boat, and mixed powder is put into height
It heats and keeps the temperature in warm tube furnace, be continually fed into protective gas during heating, obtain 3C-SiC nano wire；
2) layer of ZnO seed layer is uniformly sputtered in the 3C-SiC nanowire surface synthesized using the method for deposition；
3) the hexa crystal of the zinc nitrate hexahydrate of 20~30mM and 20~30mM are put into the water of 80~120ml
It is sufficiently stirred, the solution after stirring is transferred in hydrothermal reaction kettle；Solution is heated and kept the temperature, 3C-SiC/ZnO three-dimensional is obtained
Dendritic structure heterojunction material；
4) obtained 3C-SiC/ZnO three-dimensional dendritic structure heterojunction material is put into tube furnace, in 300~400 DEG C of temperature
Degree lower annealing 0.5~2 hour；
5) using sonic oscillation, the method for spin coating, 3C-SiC/ZnO dendroid knot heterojunction material is transferred to surface with SiO2
On the Si substrate of layer；One layer of metal electrode, shape are deposited at the both ends of dendroid dissimilar materials using photoetching process and lift-off technology
At final 3C-SiC/ZnO dendroid ultraviolet/visible light electric explorer.
2. the photodetector of 3D dendritic structure according to claim 1, it is characterised in that: the 3C-SiC/ZnO
The number of dendritic structure heterojunction material is 1~20；The metal electrode is Al, Ti/Au, Cr/Au, Ni/Au, Ti/
Al/Ti/Au or Ti/Al/Ni/Au；The metal electrode with a thickness of 100 to 200 nanometers.
3. the photodetector of 3D dendritic structure according to claim 1, it is characterised in that: the 3C-SiC/ZnO
In three-dimensional dendritic structure heterojunction material, from-inner-to-outer successively has 3C-SiC nano wire trunk, ZnO seed layer, ZnO nano-wire
Branch, 3C-SiC nano wire are the trunk of three-dimensional dendritic structure, the branch that ZnO nano-wire is three-dimensional dendritic structure.
4. the photodetector of 3D dendritic structure according to claim 3, it is characterised in that: the 3C-SiC nanometer
The length of line trunk is 100 nanometers to 1 millimeter, and diameter is 10 nanometers to 10 microns；The length of the ZnO nano-wire branch is
20 nanometers to 20 microns, diameter is 10 nanometers to 1 micron.
5. the photodetector of 3D dendritic structure according to claim 1, it is characterised in that: described in step (1)
Heating temperature is 1200~1400 DEG C, and soaking time is 0.5~2h.
6. the photodetector of 3D dendritic structure according to claim 1, it is characterised in that: described in step (1)
Protective gas is argon gas or nitrogen.
7. the photodetector of 3D dendritic structure according to claim 1, it is characterised in that: described in step (2)
The method of deposition is magnetron sputtering, electrochemical deposition, molecular beam epitaxy, sol-gel, chemical vapor deposition or atomic layer deposition
Product；The ZnO seed layer with a thickness of 10~100 nanometers.
8. the photodetector of 3D dendritic structure according to claim 7, it is characterised in that: described in step (3)
The time of stirring is 10~60 minutes；The heating temperature is 70~90 DEG C, and soaking time is 1~8 hour.
9. the photodetector of 3D dendritic structure according to claim 7, it is characterised in that: described in step (5)
SiO2Layer with a thickness of 100~500 nanometers.
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