CN108493289A - Based on hexagonal YMnO3Plane ultraviolet light detector of epitaxial film and preparation method thereof - Google Patents
Based on hexagonal YMnO3Plane ultraviolet light detector of epitaxial film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910009567 YMnO3 Inorganic materials 0.000 claims abstract description 67
- 229910009580 YMnO Inorganic materials 0.000 claims abstract description 38
- 238000000137 annealing Methods 0.000 claims abstract description 37
- 230000008021 deposition Effects 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 45
- 239000001301 oxygen Substances 0.000 claims description 45
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- 238000005137 deposition process Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 20
- 238000004549 pulsed laser deposition Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 74
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 38
- 239000011787 zinc oxide Substances 0.000 description 19
- 238000010586 diagram Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000000994 depressogenic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- JXSUUUWRUITOQZ-UHFFFAOYSA-N oxygen(2-);yttrium(3+);zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Y+3].[Y+3].[Zr+4].[Zr+4] JXSUUUWRUITOQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
- H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the PN heterojunction type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero-junctions, X being an element of Group VI of the Periodic System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to one kind being based on hexagonal YMnO3Plane ultraviolet light detector of epitaxial film and preparation method thereof.The plane ultraviolet light detector includes hexagonal YMnO3Epitaxial film and ZnO plane electrodes, the ZnO plane electrodes are deposited on hexagonal YMnO3On epitaxial film, the hexagonal YMnO3The thickness of epitaxial film is 145~155nm, and the thickness of the ZnO plane electrodes is 25~35nm.The preparation method includes：Hexagonal YMnO is first deposited using pulsed laser deposition on substrate3Epitaxial film, and to the hexagonal YMnO of deposition3Epitaxial film is made annealing treatment；Use pulse laser deposition combination mask plate in the hexagonal YMnO again3ZnO plane electrodes are deposited on epitaxial film.Plane ultraviolet light detector obtained there is apparent absorb to be greatly improved with response, photoconductivity switching ratio ultraviolet light through the invention.
Description
Technical field
The present invention relates to opto-electronic conversion and ultraviolet detector, response fields, and hexagonal YMnO is based on more particularly to one kind3
Plane ultraviolet light detector of epitaxial film and preparation method thereof.
Background technology
Detector is that a form of ELECTROMAGNETIC RADIATION SIGNATURE is converted into another biography for being easily received processing signal form
Sensor, photodetector utilize photoelectric effect, optical radiation are converted to electrical signal.
In recent years, ferroelectric material is as a kind of emerging material, in following electronic device, memory device, sensor etc.
Field has a wide range of applications.Ferroelectric material research is all with BiFeO all the time3For mainstream, but BiFeO3Have compared with
Wide energy gap, and then had some limitations in light absorption and photoresponse, and YMnO3As another more iron materials
Expect but to possess very narrow band gap, energy gap about 1.5eV, therefore in terms of photoelectric sensor, detector and solar cell
There is huge application prospect；Zinc oxide ZnO is as a kind of ultraviolet semiconductor photoelectron material, it is converted in piezoelectricity, and photoelectricity is aobvious
Show and integrated-optic device etc. is also widely used, also acts as ultraviolet light detector, luminescent device, sensing in addition
The transparent electrode etc. of device, solar cell, based on probing into above, a kind of purple of the ferroelectricity hexagonal Mn oxide based on narrow band gap
Outer optical detector is used and is given birth to, and there is presently no correlative study reports.
Invention content
Based on this, the object of the present invention is to provide one kind being based on hexagonal YMnO3The plane ultraviolet detector of epitaxial film
Device, and a kind of preparation method is provided, so that its performance is optimized.
The purpose of the present invention is what is be achieved through the following technical solutions：Based on hexagonal YMnO3The plane of epitaxial film is ultraviolet
Optical detector, including hexagonal YMnO3Epitaxial film and ZnO plane electrodes, the ZnO plane electrodes are deposited on hexagonal YMnO3Extension
On film；The hexagonal YMnO3The thickness of epitaxial film is 145~155nm, the thickness of the ZnO plane electrodes is 25~
35nm。
Compared with the existing technology, the present invention is by hexagonal YMnO3Epitaxial film and ZnO plane electrodes are compound, wherein hexagonal
YMnO3It is also electronics generation and transmission channel simultaneously that epitaxial film, which has narrow band gap, ZnO plane electrodes, and the two constitutes hetero-junctions,
There is apparent absorb to be greatly improved with response, photoconductivity switching ratio ultraviolet light as photodetector.
Further, the hexagonal YMnO3The thickness of epitaxial film is 150nm, and the thickness of the ZnO plane electrodes is
30nm.The best performance of plane ultraviolet light detector under this condition, photoconductivity switching ratio reach 300 times or more.
The present invention also provides one kind being based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
Include the following steps：
S1：Deposit hexagonal YMnO on substrate using pulse laser deposition3Epitaxial film, and to the hexagonal YMnO of deposition3
Epitaxial film is made annealing treatment；In deposition process, growth of oxygen pressure is 4.5~5.5Pa, and underlayer temperature is 780~820 DEG C, is sunk
Long-pending hexagonal YMnO3Epitaxial film thickness is 145~155nm；In annealing process, annealing oxygen pressure is 90~110Pa, annealing temperature
It it is 580~620 DEG C, soaking time is 25~35min, and rate of temperature fall is 4~6 DEG C/min；
S2：Using pulse laser deposition combination mask plate hexagonal YMnO made from step S13It is deposited on epitaxial film
ZnO plane electrodes；In deposition process, vacuum degree is less than 5.0 × 10-4The ZnO plane electrode thickness of Pa, deposition are 25~35nm.
Compared with the existing technology, the present invention is prepared by pulse laser deposition by hexagonal YMnO3Epitaxial film is flat with ZnO
The plane ultraviolet light detector that face electrode is combined, and technological parameter is improved, make plane ultraviolet detector obtained
Device there is apparent absorb to be greatly improved with response, photoconductivity switching ratio ultraviolet light.
Further, in the deposition process of the step S1, growth of oxygen pressure is 5Pa, and underlayer temperature is 800 DEG C.Oxygen press and
Underlayer temperature can influence the crystallization of single crystal epitaxial film at phase, at the process conditions, can depositing high-quality on substrate
YMnO3Single crystal epitaxial film.
Further, in the deposition process of the step S1, laser energy density 2J/cm2, frequency 3Hz, target spacing
For 5cm.Laser energy density and frequency can influence deposition rate, and target spacing can influence uniformity of film, at the process conditions,
The good film of uniformity can be obtained.
Further, in the deposition process of the step S1, the hexagonal YMnO of deposition3Epitaxial film thickness is 150nm.
YMnO under the thickness3The photodetection performance of film is best.
Further, in the annealing process of the step S1, annealing oxygen pressure is 100Pa, and annealing temperature is 600 DEG C, heat preservation
Time is 30min, and rate of temperature fall is 5 DEG C/min.At the process conditions, YMnO3The photoconductivity switching of film is than maximum, about
30 times, and response speed is quickly, stability is also high.
Further, the substrate in the step S1 is to mix yttrium zirconia substrate.
Further, in the deposition process of the step S2, laser energy density 1.5J/cm2, frequency 5Hz, between target
Away from for 5cm.
Further, in the deposition process of the step S2, the ZnO plane electrode thickness of deposition is 30nm.
In order to better understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Description of the drawings
Fig. 1 is that different growth of oxygen depress YMnO3The XRD diffraction comparison diagrams of film sample.
Fig. 2 is that 5Pa growth of oxygen depresses YMnO3The Phi scanning figures of film sample.
Fig. 3 is that 5Pa growth of oxygen depresses YMnO3The TEM phenograms of film sample.
Fig. 4 is that different annealing oxygen depress YMnO3I-V diagram of the film sample in no ultraviolet light.
Fig. 5 is that different annealing oxygen depress YMnO3I-V diagram of the film sample when there is ultraviolet light.
Fig. 6 is that different annealing oxygen depress YMnO3The photoresponse figure of film sample.
Fig. 7 is that different annealing oxygen depress YMnO3The photoconductivity switching of film sample is than the relational graph with annealing oxygen pressure.
Fig. 8 is the YMnO of different-thickness3I-V diagram of the film sample in no ultraviolet light.
Fig. 9 is the YMnO of different-thickness3I-V diagram of the film sample when there is ultraviolet light.
Figure 10 is the YMnO of different-thickness3The photoresponse figure of film sample.
Figure 11 is the YMnO of different-thickness3The photoconductivity switching of film sample is than the relational graph with annealing oxygen pressure.
Specific implementation mode
Embodiment 1
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, including hexagonal
YMnO3Epitaxial film and ZnO plane electrodes, preparation method includes the following steps：
Step 1：Prepare YMnO3Target.
In the present embodiment, YMnO3The raw material for preparing of target includes：Absolute ethyl alcohol (molecular formula C2H6O, purity >=
99.7wt%), polyvinyl alcohol (is abbreviated as PVA, molecular formula is [CH2CHOH]n, purity >=99.8wt%), yttrium oxide (molecular formula
For Y2O3, purity >=99.9wt%) and manganese sesquioxide managnic oxide (molecular formula Mn2O3, purity 99wt%).Specific preparation process is such as
Under：
(1) by Y2O3And Mn2O3With molar ratio for 1:1 ingredient ratio mixes in agate pot, adds agate of different sizes
Bead is several (playing the role of stirring evenly), and addition absolute ethyl alcohol is as dispersant.
(2) the molten pulp mixture is ground 30 hours in horizontal ball mill.If without absolute ethyl alcohol as dispersant,
One side Y2O3And Mn2O3Mixability is limited；On the other hand in process of lapping, very due to the collision energy of bead and powder
It is high, it would be possible to cause amount of powder directly to react, generate dephasign so that the uniformity, the consistency of final target are not achieved
Standard.
(3) ground molten slurry is placed in clean drying box and is dried, main purpose is to evaporate absolute ethyl alcohol, is left
Uniformly mixed Y2O3And Mn2O3Powder.
(4) by the Y2O3And Mn2O3Powder keeps 850 DEG C of high temperature sinterings 18 hours in Muffle furnace, it is therefore an objective to make mixing equal
Even powder at phase, generates YMnO for the first time3Powder.It summarizes the experience through experiment, YMnO can be all generated at 810 DEG C~900 DEG C3, comprehensive
Optimum efficiency is more stable in 850 DEG C of condition.
(5) YMnO that will tentatively generate3It is first ground with mortar, and is placed again into ball mill ball milling, it is therefore an objective to by grinding
YMnO3Powder further refine to nanometer scale, in case the target of later stage compacting can guarantee higher consistency；Then by ball milling
Molten slurry be put into drying box and dry again, just obtain the YMnO of nanometer scale3Powder.
(6) in YMnO3Suitable a concentration of 4% PVA solution is added in powder, is gently mixed uniformly, places 24 hours,
Purpose is to make PVA diffusions uniform, adhered to one another between powder particle, that is, is granulated.
(7) it will be granulated ripe powder compression moulding in electric tablet machine, then in Hydrostatic Press
Hot pressed sintering is carried out for maximum temperature 25 hours, to obtain, purity is high, consistency is high, ingredient is uniform in System with 1250 DEG C
YMnO3Target.
Step 2：Prepare hexagonal YMnO3Epitaxial film.Specific preparation process is as follows：
(1) YMnO for preparing step 13Target is put on the target position of pulsed laser deposition (PLD) vacuum chamber, is fixed,
It prevents target rotation and falls off when swing.
(2) sample warm table is cleared up with sand paper, alcohol, non-dust cloth wiping is used in combination, after alcohol volatilization, in sample stage center
Silver paste is dripped, is then clamped with tweezers and mixes yttrium zirconium oxide (YSZ) substrate, be slowly placed in silver paste, gently press substrate four
A angle, substrate is adhered on sample stage.
(3) after silver paste solidification, sample warm table is put into vacuum chamber sample stage screens, places, shuts chamber door.
(4) it vacuumizes：Mechanical pump, slide valve are opened, after vacuum degree reaches 5Pa or less, slide valve is closed, before opening
Step valve, molecular pump, then slowly open it is other take out valve, etc. vacuum degrees be extracted into 5.0 × 10-4After Pa or less, heating system is opened, if
Set 20 DEG C/min of the rate of heat addition, 800 DEG C of purpose temperature.
(5) target is washed：After temperature rises to 800 DEG C, target rotation and swing, 15 ° of hunting range, angle of oscillation rate are opened
1.5 °/s, wash target technological parameter：Laser energy density 2J/cm2, frequency 5Hz, target spacing 5cm, 2000 pulses.
(6) deposition film：Other pumping valve is turned down, oxygen intake valve, regulating valve control so that growth of oxygen pressure is in vacuum chamber are opened
Then 0.15Pa starts deposition film, the YMnO of deposition3Film thickness is 50nm, deposition process parameters：Laser energy density
2J/cm2, frequency 3Hz, target spacing 5cm, 5000 pulses.
(7) it anneals：After film deposits, room temperature is down to 5 DEG C/min rates.
(8) sample is taken：Closing oxygen inlet valve, valve control, other pumping valve, molecular pump close when molecular pump is out of service successively
Close preceding step valve, mechanical pump；Then, nitrogen intake valve is opened, after intracavitary air pressure reaches standard atmospheric pressure, begins to speak to take out YMnO3
Film sample.
Step 3：Prepare ZnO plane electrodes.Specific preparation process is as follows：
(1) by YMnO3Target takes out, and changes ZnO target material into, then, is taken out step 2 using high temperature single side adhesive tape
YMnO3Film sample is fixed on the back side of plane electrode template, and finally sample is adhered on sample stage using high temperature double faced adhesive tape,
It is put into vacuum chamber sample stage screens, shuts chamber door.
(2) it vacuumizes, wash target：Mechanical pump, slide valve are opened, after vacuum degree reaches 5Pa or less, slide valve is closed, beats
Open preceding step valve, molecular pump, then slowly open it is other take out valve, etc. vacuum degrees be extracted into 5.0 × 10-4Target is directly washed after Pa or less, is washed
Target technological parameter：Laser energy density 2J/cm2, frequency 5Hz, target spacing 5cm, 2000 pulses.
(3) ZnO film plane electrode is deposited：The ZnO film plane electrode thickness of deposition is 30nm, deposition process parameters：
Room temperature, laser energy density 1.5J/cm2, frequency 5Hz, target spacing 5cm, 4000 pulses.
(4) sample is taken.Other pumping valve, molecular pump, when molecular pump is out of service, step valve, mechanical pump before closing are closed successively；
Then, nitrogen intake valve is opened, after intracavitary air pressure reaches standard atmospheric pressure, begins to speak to take out the plane ultraviolet light spy finally obtained
Survey device sample.
Embodiment 2
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 1, difference lies in：In the step of step 2 (6), the growth of oxygen pressure of the present embodiment is 1.5Pa.
Embodiment 3
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 1, difference lies in：In the step of step 2 (6), the growth of oxygen pressure of the present embodiment is 5Pa.
Embodiment 4
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 1, difference lies in：In the step of step 2 (6), the growth of oxygen pressure of the present embodiment is 15Pa.
Embodiment 5
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 3, difference lies in：In the step of step 2 (7), the annealing process of the present embodiment is：Film deposition terminates
Afterwards, in 600 DEG C, 5Pa annealing oxygen pressure heat preservation 30min, room temperature is then down to 5 DEG C/min rates.
Embodiment 6
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 5, difference lies in：In the step of step 2 (7), the annealing oxygen pressure in the annealing process of the present embodiment is
100Pa。
Embodiment 7
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 5, difference lies in：In the step of step 2 (7), the annealing oxygen pressure in the annealing process of the present embodiment is
200Pa。
Embodiment 8
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 5, difference lies in：In the step of step 2 (7), the annealing oxygen pressure in the annealing process of the present embodiment is
300Pa。
Embodiment 9
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 6, difference lies in：In the step of step 2 (6), the YMnO of the present embodiment deposition3Film thickness is
100nm。
Embodiment 10
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 6, difference lies in：In the step of step 2 (6), the YMnO of the present embodiment deposition3Film thickness is
150nm。
Embodiment 11
It present embodiments provides a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, preparation method
It is substantially the same manner as Example 6, difference lies in：In the step of step 2 (6), the YMnO of the present embodiment deposition3Film thickness is
200nm。
Performance test
To being based on hexagonal YMnO made from embodiment 1-113The performance of the plane ultraviolet light detector of epitaxial film is surveyed
Examination, obtains following result：
(1) XRD diffraction comparison diagram
Referring to Fig. 1, it depresses YMnO for different growth of oxygen3The XRD diffraction comparison diagrams of film sample (embodiment 1-4),
The test result is obtained by X-ray diffractometer (X ' Pert PRO, PANalytical) test.It can be seen from the figure that XRD
YMnO is shown in figure3The diffraction maximum (0002) of (being abbreviated as YMO), the diffraction of (0004), (0006), (0008) and YSZ substrates
Peak (111), (222)；It is depressed in 0.15Pa, 1.5Pa growth of oxygen, there is a small amount of dephasign (position of figure culminant star labelled notation) occur；
15Pa growth of oxygen is depressed, and the extension characteristic peak (0004), (0006) and (0008) of YMO almost disappears, and illustrates that oxygen presses through height, film
It has not been extension；It is depressed in 5Pa oxygen, YMnO3Film object is mutually best, and no other dephasigns generate.
(2) Phi scanning figures
Referring to Fig. 2, it depresses YMnO for 5Pa growth of oxygen3The Phi scanning figures of film sample.For clear sample structure
Epitaxy on lattice c-axis direction has carried out Phi scannings to sample substrate YSZ (002), YMO (111) crystal face, and the result is logical
X-ray diffractometer (X ' Pert PRO, PANalytical) test is crossed to obtain.YMnO can be clearly found out from figure3Six refer to peak,
Illustrate YMnO3Film has very high epitaxy, does not have more the lattice arrangement of other orientations, meets the period of long-range order
Property.
(3) sections TEM phenogram
Referring to Fig. 3, it depresses YMnO for 5Pa growth of oxygen3The sections the TEM phenogram of film sample.The test result is logical
Cross high-resolution-ration transmission electric-lens (High Resolution Transmission Electron Microscopy-HRTEM) test
It obtains.The interfacial structure of YMO/YSZ, YMnO can be clearly found out from figure3Thin-film surface is smooth；From selective electron diffraction
As a result lattice diffraction pattern can be obtained, it can be seen that YMnO3Film is grown in hexagonal.
(4) different annealing oxygen depress YMnO3Photoconduction, the photoresponse phenogram of film sample
Please refer to Fig. 4,5,6,7, YMnO is depressed for different annealing oxygen3The photoelectricity of film sample (embodiment 5-8)
It leads, photoresponse phenogram, wherein the I-V diagram of sample when Fig. 4 is no ultraviolet light, Fig. 5 are sample when having ultraviolet light
I-V diagram, Fig. 6 be sample photoresponse figure, Fig. 7 be sample photoconductivity switching than with annealing oxygen pressure relational graph.The test
Be by introducing a branch of ultraviolet light (wavelength 365nm) on sample stage, using external impressed current source table (Keithley 6430) into
Row test, and programmed by LabVIEW (Laboratory Virtual Instrument Engineering Workbench)
Realize relevant operation.It can be obtained according to test result, in 100Pa annealing oxygen pressures, the photoconductivity switching ratio (I of sampleon/
Ioff) 30 times are about, and response speed is quickly, stability is also high.
(5) YMnO of different-thickness3Photoconduction, the photoresponse phenogram of film sample.
It is the YMnO of different-thickness please refer to Fig. 8,9,10,113The photoelectricity of film sample (embodiment 6,9-11)
It leads, photoresponse phenogram, wherein the I-V diagram of sample when Fig. 8 is no ultraviolet light, Fig. 9 are sample when having ultraviolet light
I-V diagram, Figure 10 be sample photoresponse figure, Figure 11 be sample photoconductivity switching than the relational graph with thickness.The test is
By introducing a branch of ultraviolet light (wavelength 365nm) on sample stage, carried out using external impressed current source table (Keithley 6430)
Test, and programmed in fact by LabVIEW (Laboratory Virtual Instrument Engineering Workbench)
Existing relevant operation.It can be obtained according to test result, the properties of sample of 150nm thickness is best, photoconductivity switching ratio (Ion/Ioff)
Reach 300 times or more.
The setting of the technological parameter of embodiment 1-11 embodies the process modification method of the present invention, includes mainly following several
Step：1, YMnO has been deposited under different growth oxygen pressure conditions3Film sample is mutually tested by object and finds optimum growh oxygen pressure；
2, the sample that object is mutually best in the 1st step is chosen, is made annealing treatment, is found by performance test best in the pressure of different annealing oxygen
Annealing oxygen pressure；3, the best sample of the 2nd step performance is chosen, different-thickness is deposited, optimum thickness is found by performance test.
By process modification, the best technological parameter of the present invention is：1, YMnO is prepared3Film layer：800 DEG C of underlayer temperature,
Growth of oxygen presses 5Pa, laser energy density 2J/cm2, frequency 3Hz, target spacing 5cm, thickness 150nm, after deposition 600 DEG C,
100Pa annealing oxygen pressure heat preservation 30min, are then down to room temperature with the rate of 5 DEG C/min；2, ZnO electrode layer is prepared：Room temperature is high
Vacuum (5.0 × 10-4Pa or less), laser energy density 1.5J/cm2, frequency 5Hz, target spacing 5cm, thickness 30nm.
Compared with the existing technology, the present invention is by narrow band gap P-type semiconductor ferroelectric material YMnO3With N-type semiconductor electronics material
Expect that ZnO constitutes hetero-junctions, forms a kind of based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, passes through technique
It improves so that the performance of detector is optimal, photoconductivity switching ratio reaches 300 times or more, and there is presently no relevant researchs for this
Report.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.
Claims (10)
1. being based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, it is characterised in that：Including hexagonal YMnO3Epitaxial film
With ZnO plane electrodes, the ZnO plane electrodes are deposited on hexagonal YMnO3On epitaxial film；The hexagonal YMnO3Epitaxial film
Thickness is 145~155nm, and the thickness of the ZnO plane electrodes is 25~35nm.
2. according to claim 1 be based on hexagonal YMnO3The plane ultraviolet light detector of epitaxial film, it is characterised in that：Institute
State hexagonal YMnO3The thickness of epitaxial film is 150nm, and the thickness of the ZnO plane electrodes is 30nm.
3. being based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film, it is characterised in that：Including following step
Suddenly：
S1：Deposit hexagonal YMnO on substrate using pulse laser deposition3Epitaxial film, and to the hexagonal YMnO of deposition3Extension
Film is made annealing treatment；In deposition process, growth of oxygen pressure is 4.5~5.5Pa, and underlayer temperature is 780~820 DEG C, deposition
Hexagonal YMnO3Epitaxial film thickness is 145~155nm；In annealing process, annealing oxygen pressure is 90~110Pa, and annealing temperature is
580~620 DEG C, soaking time is 25~35min, and rate of temperature fall is 4~6 DEG C/min；
S2：Using pulse laser deposition combination mask plate hexagonal YMnO made from step S13It is flat that ZnO is deposited on epitaxial film
Face electrode；In deposition process, vacuum degree is less than 5.0 × 10-4The ZnO plane electrode thickness of Pa, deposition are 25~35nm.
4. according to claim 3 be based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
It is characterized in that：In the deposition process of the step S1, growth of oxygen pressure is 5Pa, and underlayer temperature is 800 DEG C.
5. according to claim 3 or 4 be based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
It is characterized in that：In the deposition process of the step S1, laser energy density 2J/cm2, frequency 3Hz, target spacing is 5cm.
6. according to claim 5 be based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
It is characterized in that：In the deposition process of the step S1, the hexagonal YMnO of deposition3Epitaxial film thickness is 150nm.
7. according to claim 6 be based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
It is characterized in that：In the annealing process of the step S1, annealing oxygen pressure is 100Pa, and annealing temperature is 600 DEG C, and soaking time is
30min, rate of temperature fall are 5 DEG C/min.
8. according to claim 3 or 4 be based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
It is characterized in that：Substrate in the step S1 is to mix yttrium zirconia substrate.
9. according to claim 7 be based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
It is characterized in that：In the deposition process of the step S2, laser energy density 1.5J/cm2, frequency 5Hz, target spacing is 5cm.
10. according to claim 9 be based on hexagonal YMnO3The preparation method of the plane ultraviolet light detector of epitaxial film,
It is characterized in that：In the deposition process of the step S2, the ZnO plane electrode thickness of deposition is 30nm.
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