CN107808908B - Based on rare earth nickelate-niobium strontium titanate doping heterojunction material and its transducer production method and application - Google Patents
Based on rare earth nickelate-niobium strontium titanate doping heterojunction material and its transducer production method and application Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 63
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 229910003193 Nb:SrTiO3 Inorganic materials 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 239000010931 gold Substances 0.000 claims abstract description 9
- WFPQISQTIVPXNY-UHFFFAOYSA-N niobium strontium Chemical compound [Sr][Nb] WFPQISQTIVPXNY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 19
- 229910002367 SrTiO Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000009702 powder compression Methods 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 210000001367 artery Anatomy 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 210000003462 vein Anatomy 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 239000010408 film Substances 0.000 description 9
- 229910002370 SrTiO3 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- 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 potential barriers, 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
- H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN heterojunction type
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/26—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light
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- H01L31/0264—Inorganic materials
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Abstract
Based on rare earth nickelate-niobium strontium titanate doping heterojunction material and its transducer production method and application, the invention belongs to sensor fields, it does not have in order to which the response speed for solving the problem of existing UV photodetector is slower while having both from driving ultraviolet light photo sensor and position sensitive device material devices.This has p-n junction structure based on rare earth nickelate-niobium strontium titanate doping heterojunction material, there is the p-type nickelate oxide skin(coating) with a thickness of 5~20nm using pulsed laser deposition on N-shaped niobium strontium titanate doping substrate, nickelate oxide therein is nickel acid neodymium, nickel acid samarium or nickel acid gadolinium.Gold electrode is coated on the hetero-junctions surface and prepares sensor, this sensor can be applied to from driving UV photodetector and position sensitive device.The present invention utilizes Nb:SrTiO3Semiconductor is only the characteristics of ultraviolet/black light area responds, and investigative range is close to day-old chick range, and photoelectric response speed is fast.
Description
Technical field
The invention belongs to sensor fields, and in particular to based on hetero-junctions, longitudinally and laterally photovoltaic effect is ultraviolet in driving certainly
Application in photodetector and position sensitive device.
Background technique
UV photodetector with high security, strong antijamming capability, without people operation the advantages that, missile warning with
All there is very important application in terms of the military and civilians such as tracking, Ultraviolet Communication, environmental monitoring, biomedical detection.At present
The disadvantages of UV photodetector used is mainly vacuum photomultiplier tube, but its volume is big, frangible and high power consumption, in reality
The problems such as there is also detectivity and low photoelectric conversion efficiencies in.Mainly divide by working principle semiconductor photo detector
At two major classes: one kind is the heterojunction photoelectric detector to be worked using the photovoltaic effect of hetero-junctions；Another kind of is to utilize half
The photoconductive detector of the photoconductive effect work of conductor.Photoconductive detector is substantially a photo resistance, when no light,
Dark current very little in circuit；When the energy of incident light is greater than material bandwidth, the photo-generate electron-hole pairs of generation are powered on outside
It is collected under pressure effect by two electrode of device, detector resistance strongly reduces, and shows higher luminous sensitivity.Photoconductive detector is most
It is very slow that big disadvantage is in response to speed.By taking wide bandgap semiconductor ZnO nano-wire ultraviolet light detector as an example.Due to ZnO nano
Line surface captures the presence of state, so that the response speed of the ultraviolet light detector based on ZnO nano-wire is very slow --- photoconduction type
Detector photoelectric respone most fast recovery time is 20ms.Y.-Q.Bie etc. assembles n-ZnO nano wire/p-GaN film heterojunction,
The device is 20 μ s to the optical response signal rise time of 367nm wavelength, and recovery time is 219 μ s, what speed ratio was previously reported
Zno-based photoconductive detector improves two orders of magnitude (Advanced Materials, 2011,23,649).Obvious hetero-junctions
The ultraviolet light photo device of type usually has high photoelectric properties, and the photoelectric response speed of device especially can be improved.With existing
For the increasingly developed of optical communication technique, to there is high sensitivity, the photodetector demand of quick photoresponse is also growing.Due to
Powerful built in field energy quick separating photo-generated carrier inside heterojunction semiconductor, therefore, with powerful built in field
Heterojunction photoelectric detector becomes research hotspot.
In addition, there is also lateral photovoltaic effects in heterojunction semiconductor, and the size and illumination of lateral photovoltaic voltage
There is the linear dependences of height between position, so that lateral photovoltaic effect has important application in position sensitive device.
Up to now, there has been no simultaneously have both from drive ultraviolet light photo sensor and position sensitive device material devices preparation and research,
This is mainly due to the technics comparing of the p-type wide bandgap semiconductor based on p-n junction principle complexity, it is difficult to preparation of industrialization, so
It cannot achieve the device for having both UV photodetector and position sensitive device using wide bandgap semiconductor as core.
Summary of the invention
The present invention is that do not have while having both purple from driving in order to which the response speed for solving existing UV photodetector is slower
The problem of outer photoelectric sensor and position sensitive device material devices, and provide it is a kind of based on wide bandgap semiconductor heterojunction material and
Preparation method and the application in self-driving type UV photodetector and position sensitive device.
The present invention is based on rare earth nickelate-niobium strontium titanate doping heterojunction materials to have p-n junction structure, mixes in N-shaped niobium
Miscellaneous strontium titanates (Nb:SrTiO3) there is the p-type nickelate oxide skin(coating) with a thickness of 5~20nm using pulsed laser deposition on substrate,
Wherein the p-type nickelate oxide is nickel acid neodymium (NdNiO3), nickel acid samarium (SmNiO3) or nickel acid gadolinium (GdNiO3)。
The present invention is based on the transducer production methods of rare earth nickelate-niobium strontium titanate doping heterojunction material to press following step
It is rapid to realize:
One, rare earth oxide and NiO powder are sufficiently mixed for 1: 2 according to stoichiometric ratio, mixed-powder compression molding,
Then pretreatment is sintered at 900~1000 DEG C, then with 1100~1400 DEG C of temperature in high purity oxygen gas (99.9995%) atmosphere
Sintering processes are spent, rare earth nickelate oxide target material is obtained；
Two, by Nb:SrTiO3Substrate is sequentially placed into 10~20min of ultrasonic cleaning in deionized water, acetone and dehydrated alcohol,
Nb:SrTiO after being cleaned3Substrate；
Three, base vacuum is evacuated to 2.5~3.5 × 10-4Pa, with the Nb:SrTiO after cleaning3Substrate as deposition substrate,
Being passed through high pure oxygen (99.9995%) control pressure is 0.01~60Pa, adjusts Nb:SrTiO3The temperature of substrate is 600~650
DEG C, rare earth nickelate oxide target material is irradiated using excimer laser, control single pulse energy is 150~200mJ, pulse frequency
Rate is that 3~8Hz carries out pulse laser deposition of rare-earth nickelate sull, is kept the temperature in situ after deposition, last naturally cold
But room temperature state is arrived, rare earth nickelate-niobium strontium titanate doping heterojunction material is obtained；
Four, sour using rare earth nickel of the magnetron sputtering method respectively in rare earth nickelate-niobium strontium titanate doping heterojunction material
Salt sull surface and Nb:SrTiO3The back side of substrate plates gold electrode, obtains based on rare earth nickelate-niobium doped titanic acid
The sensor of strontium heterojunction material；
Wherein rare earth oxide described in step 1 is Nd2O3、Sm2O3Or Gd2O3。
The present invention using based on rare earth nickelate-niobium strontium titanate doping heterojunction material sensor as sensing element application
In from driving UV photodetector.
The present invention using based on rare earth nickelate-niobium strontium titanate doping heterojunction material sensor as sensing element application
In position sensitive device.
The present invention uses broad-band gap n-type semiconductor Nb:SrTiO3Monocrystalline is as substrate, with p-type semiconductor rare earth nickelate
Oxide forms p-n junction as thin-film material, and preparation drives UV photodetector and position sensitive device certainly.Nb:SrTiO3
Belonging to wide bandgap semiconductor materials, band gap is about 3.2eV, and theoretically only monochromatic light of the wavelength less than 390nm can just respond,
Its investigative range relatively short wavelength regions and may extend into day-old chick range to a certain extent, be conducive in certain circumstances
Detection use.
It is of the present invention to include following advantages from driving UV photodetector and position sensitive device:
1, rare earth nickelate oxide is nontoxic, cheap and easy to get, and chemical property is stablized, resistance to air corrosion；
2, Nb:SrTiO is utilized3Semiconductor only responds in ultraviolet/black light area, the structure theoretically detectable wavelength
Monochromatic light less than 390nm, relatively day-old chick range, the detection be conducive in certain circumstances use investigative range,
Solve the problems, such as that existing UV photodetector is needed using external driving power；
3, two electrode distances have reached position-sensitivity 32mV/mm at 2.0mm, wherein testing the laser power used and being
10mW, optical maser wavelength 266nm, laser spot diameter are about 0.4mm；
4, what the present invention obtained is simple from the structure of driving UV photodetector and position sensitive device, due to Nb:
SrTiO3Semiconductor wide bandgap semiconductor only responds in ultraviolet/black light area, so rare earth nickelate/niobium strontium titanate doping p-
N knot has from driving built in field and can get the sensor of only ultraviolet light photo response.From opening for driving UV photodetector
Road voltage reaches 0.45V, and the rising edge of photoelectric current is 0.8 μ s, and half-peak breadth has reached currently used ultraviolet in 1.8 μ s or so
Photodetector is horizontal.Rising edge from the driving lateral photovoltaic response of ultraviolet light photo position sensor is 1.4 μ s, and half-peak breadth exists
7.4 μ s or so are the most fast ultraviolet light photo position sensitive devices of current photoelectric respone；
5, it since rare earth nickelate/niobium strontium titanate doping all has perovskite structure and lattice constant matches very much, is easy
The epitaxial growth for realizing film, is conducive to the stability of device.It should be from driving UV photodetector and position sensing structure electricity
Pole material is easily combined with existing semiconducter process.
Detailed description of the invention
Fig. 1 is embodiment one in SrTiO3The rare earth nickelate NbNiO grown on substrate3The x-ray diffraction spectra of film；
Fig. 2 is NbNiO under one Compound eye of embodiment and non-illumination condition3/Nb:SrTiO3Longitudinal volt-ampere of p-n junction
Curve graph, wherein ■ represents dark current, ● 365nm laser irradiation is represented, ▲ represent 266nm laser irradiation；
Fig. 3 is the NbNiO under 266nm, 10mW laser of embodiment one3/Nb:SrTiO3The photoelectricity of longitudinal photovoltaic of p-n junction is rung
Answer performance diagram；
Fig. 4 is the lateral relational graph between photovoltaic and facula position under different wave length laser of embodiment one, and wherein △ is represented
266nm laser irradiation, zero represents 365nm laser irradiation, and represents 405nm laser irradiation；
The quick sensing of ultraviolet light current potential that Fig. 5 is made of the thin-film material of different-thickness and the substrate of different Nb doping concentrations
The location sen-sitivity curve graph of device, wherein ■ represents 10nm, ● 5nm is represented, ▲ represent 15nm；
Fig. 6 is to survey the time response for black light current potential dependent sensor lateral photovoltaic when there is load that embodiment one obtains
Curve graph is tried, wherein being in the direction of the arrow respectively to load as 10k Ω, 5k Ω, 4k Ω, 3k Ω, 2k Ω, 1k Ω.
Specific embodiment
Specific embodiment 1: present embodiment is had based on rare earth nickelate-niobium strontium titanate doping heterojunction material
P-n junction structure has the p-type nickelate oxygen with a thickness of 5~20nm using pulsed laser deposition on N-shaped niobium strontium titanate doping substrate
Compound layer, wherein the p-type nickelate oxide is nickel acid neodymium (NdNiO3), nickel acid samarium (SmNiO3) or nickel acid gadolinium
(GdNiO3)。
Specific embodiment 2: the present embodiment is different from the first embodiment in that Nb in niobium strontium titanate doping substrate
The mass concentration of doping is 0.05%~0.5%.
Specific embodiment 3: biography of the present embodiment based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Sensor preparation method follows these steps to implement:
One, rare earth oxide and NiO powder are sufficiently mixed for 1:2 according to stoichiometric ratio, mixed-powder compression molding,
Then pretreatment is sintered at 900~1000 DEG C, then with 1100~1400 DEG C of temperature in high-purity (99.9995%) oxygen atmosphere
Sintering processes are spent, rare earth nickelate oxide target material is obtained；
Two, by Nb:SrTiO3Substrate is sequentially placed into 10~20min of ultrasonic cleaning in deionized water, acetone and dehydrated alcohol,
Nb:SrTiO after being cleaned3Substrate；
Three, base vacuum is evacuated to 2.5~3.5 × 10-4Pa, with the Nb:SrTiO after cleaning3Substrate as deposition substrate,
Being passed through high pure oxygen (99.9995%) control pressure is 0.01~60Pa, adjusts Nb:SrTiO3The temperature of substrate is 600~650
DEG C, rare earth nickelate oxide target material is irradiated using excimer laser, control single pulse energy is 150~200mJ, pulse frequency
Rate is that 3~8Hz carries out pulse laser deposition of rare-earth nickelate sull, is kept the temperature in situ after deposition, last naturally cold
But room temperature state is arrived, rare earth nickelate-niobium strontium titanate doping heterojunction material is obtained；
Four, sour using rare earth nickel of the magnetron sputtering method respectively in rare earth nickelate-niobium strontium titanate doping heterojunction material
Salt sull surface and Nb:SrTiO3The back side of substrate plates gold electrode, obtains based on rare earth nickelate-niobium doped titanic acid
The sensor of strontium heterojunction material；
Wherein rare earth oxide described in step 1 is Nd2O3、Sm2O3Or Gd2O3。
Specific embodiment 4: present embodiment rare earth oxygen described in step 1 unlike specific embodiment three
The partial size of compound powder and NiO powder is 100~200nm.Other steps and parameter are the same as the specific implementation mode 3.
Specific embodiment 5: present embodiment unlike specific embodiment three or four step 1 in high purity oxygen gas
(99.9995%) with 1300~1400 DEG C of 10~14h of temperature sintering processes in atmosphere.Other steps and parameter and specific implementation
Mode three or four is identical.
Specific embodiment 6: step 3 deposition is dilute unlike one of present embodiment and specific embodiment three to five
Native nickelate sull with a thickness of 5~20nm.Other steps and parameter are identical as one of specific embodiment three to five.
Specific embodiment 7: step 3 unlike one of present embodiment and specific embodiment three to six be passed through it is pure
Oxygen control pressure is 0.1~20Pa, adjusts Nb:SrTiO3The temperature of substrate is 650 DEG C.Other steps and parameter and specific implementation
One of mode three to six is identical.
Specific embodiment 8: step 3 is using quasi- unlike one of present embodiment and specific embodiment three to seven
Molecular laser irradiates rare earth nickelate oxide target material, and control single pulse energy is 200mJ, and pulse frequency is that 5Hz carries out arteries and veins
Impulse light deposition rare earth nickelate sull.Other steps and parameter are identical as one of specific embodiment three to seven.
Specific embodiment 9: step 3 deposition is tied unlike one of present embodiment and specific embodiment three to eight
20~30min is kept the temperature after beam in situ.Other steps and parameter are identical as one of specific embodiment three to eight.
Specific embodiment 10: step 4 unlike one of present embodiment and specific embodiment three to nine is divided in advance
Not in rare earth nickelate sull surface and Nb:SrTiO3The back side of substrate is covered with aperture plate, and base vacuum is evacuated to 5 × 10-4Pa, using magnetron sputtering method respectively in rare earth nickelate sull surface and Nb:SrTiO3The back side of substrate plates 10nm
Thick gold electrode.Other steps and parameter are identical as one of specific embodiment three to nine.
Specific embodiment 11: present embodiment will be based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Sensor is applied to as sensing element from driving UV photodetector.
Specific embodiment 12: present embodiment will be based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Sensor is applied in position sensitive device as sensing element.
Embodiment one: the present embodiment is pressed based on the sensor of rare earth nickelate-niobium strontium titanate doping heterojunction material
Column step is implemented:
One, by Nd2O3It is stoichiometrically disk through mold tabletting at Φ 13 after 1:2 mixing with NiO powder, then
The sintering pretreatment 12h at 1000 DEG C, then it is sintered 12h under 1200 DEG C of high purity oxygen gas atmosphere, obtain the NdNiO of pure phase3Target；
Two, by Nb:SrTiO3Substrate (mass concentration of Nb doping is 0.05%) is sequentially placed into deionized water, acetone and nothing
It is cleaned by ultrasonic 20min in water-ethanol respectively, the Nb:SrTiO after being cleaned3Substrate；
Three, base vacuum is evacuated to 3 × 10-4Pa, with the Nb:SrTiO after cleaning3Substrate is passed through pure as deposition substrate
Oxygen (purity is greater than 99.99%) control pressure is 5Pa, adjusts Nb:SrTiO3The temperature of substrate is 600 DEG C, is swashed using quasi-molecule
Light device irradiates NdNiO3Target, control single pulse energy are 200mJ, and pulse frequency is that 5Hz progress deposition thickness is 10nm's
NdNiO3Film layer keeps the temperature 30min after deposition in situ, finally naturally cools to room temperature state, obtain NdNiO3-Nb:
SrTiO3P-n junction；
Four, using the magnetron sputtering method film layer table in rare earth nickelate-niobium strontium titanate doping heterojunction material respectively
Face and Nb:SrTiO3The back side of substrate plates the gold electrode of 10nm thickness, and the diameter of electrode is 0.2mm, obtains based on NdNiO3-
Nb:SrTiO3The sensor of heterojunction material.
Nb:SrTiO described in the present embodiment step 23Substrate is commercially available from Shanghai Daheng Optical Fine Mechinery Co., Ltd,
Excimer laser described in step 3 is Germany Compex, KrF gas laser, λ=248nm.
The present embodiment obtain based on NdNiO3-Nb:SrTiO3The sensor of heterojunction material can be using as driving certainly
UV photodetector can be used as position sensitive device again.
Embodiment two: the present embodiment is 5nm's from step 3 pulse laser deposition thickness unlike embodiment one
NdNiO3Layer.
Embodiment three: the present embodiment is 20nm's from step 3 pulse laser deposition thickness unlike embodiment one
NdNiO3Layer.
It is shone by the laser from driving UV photodetector in 266nm wavelength, 10mW power that embodiment one is prepared
It penetrates down, in NdNiO3(10nm)-Nb:SrTiO3Its open-circuit voltage of structure is maximum, has reached 0.45V；In same wavelength and power
Laser under, NdNiO that embodiment two obtains3(5nm)-Nb:SrTiO3The open-circuit voltage of structure is 0.38V；And embodiment three
The NdNiO arrived3(15nm)-Nb:SrTiO3The open-circuit voltage of structure only has 0.3V.
The NdNiO that embodiment one is prepared3(10nm)-Nb:SrTiO3From driving ultraviolet light photo position sensitive device in difference
Lateral photovoltaic value under wavelength laser with facula position variation, as shown in Figure 4.Have between the photovoltaic value and facula position of device
Have a good linear relationship, position-sensitivity maximum 266nm wavelength, 10mW power laser irradiation under, reached 32mV/
mm；In the case where keeping identical laser power, wavelength is that position-sensitivity is respectively 20mV/mm under 365nm and 405nm laser irradiation
And 8mV/mm.It is 10mW in power, wavelength is the NdNiO that embodiment two obtains under 266nm laser irradiation3(5nm)-Nb:
SrTiO3The position-sensitivity of the position sensitive device of device is 24mV/mm；And the NdNiO that embodiment three obtains3(20nm)-Nb:
SrTiO3The position-sensitivity of the position sensitive device of structure only has 16mV/mm.
The test of heterojunction photovoltaic transient response characteristic:
It is converged in using the ps pulsed laser and ns pulsed laser spot of 266nm wavelength, 10mW power from driving UV photodetector
On membrane electrode on the point of a diameter about 1mm, two gold electrodes are prepared respectively in film surface and substrate bottom, electrode diameter
For 0.2mm, two electrodes are connected to the input terminal of lock-in amplifier by conducting wire, and output end connects model Tektronix
5054 digital oscilloscope of DPO, in NdNiO3-Nb:SrTiO3A upper resistance value in parallel is 1k Ω resistance, tests NdNiO3-Nb:
SrTiO3The time resolution characteristics of structure longitudinal direction photovoltaic.
The rising edge of photovoltaic response measured by the UV photodetector of driving certainly obtained to embodiment one is about 0.8 μ
S, half-peak breadth are 1.8 μ s, as shown in Figure 3.
Drive the photovoltaic time resolution characteristics of position sensitive device certainly using the test of same laser system.Two gold electrodes are existed
Preparation is about 0.4mm in film surface, electrode distance 2mm, electrode diameter 0.2mm, spot diameter, and two electrodes are by leading
Line is connected to the input terminal of lock-in amplifier, and output end connects 5054 digital oscilloscope of model Tektronix DPO,
NdNiO3Tunable load resistance in parallel, tests NdNiO on two electrode of surface3-Nb:SrTiO3The time response of the lateral photovoltaic of structure
Characteristic.
The rising edge of photovoltaic response measured by ultraviolet position sensitive device that drives certainly obtained to embodiment one is about 1.4 μ
S, half-peak breadth are 7.4 μ s, and the time response test curve of black light current potential dependent sensor lateral photovoltaic when there is load is such as
Shown in Fig. 6.
266nm wavelength, 10mW power laser irradiation under, the substrate of different Nb doping concentrations and the film of different-thickness
The location sen-sitivity curve graph of the ultraviolet light photo position sensitive device that material is constituted is as shown in figure 5,10nm as we know from the figure
NdNiO3The position-sensitivity highest of the constituted p-n junction of film, and with Nb:SrTiO3The mass concentration that Nb is adulterated in substrate
Increase and be gradually reduced.The Nb:SrTiO for being 0.1% in the mass concentration of Nb doping3The maximum position spirit of constituted p-n junction
Sensitivity is 21mV/mm, the Nb:SrTiO for being 0.5% in the mass concentration of Nb doping3The maximum position sensitivity of constituted p-n junction
For 14mV/mm.
Claims (10)
1. based on rare earth nickelate-niobium strontium titanate doping heterojunction material, it is characterised in that should be mixed based on rare earth nickelate-niobium
The heterojunction material of miscellaneous strontium titanates has p-n junction structure, has thickness using pulsed laser deposition on N-shaped niobium strontium titanate doping substrate
Degree is the p-type nickelate oxide skin(coating) of 5~20nm, wherein the p-type nickelate oxide is nickel acid neodymium, nickel acid samarium or nickel acid
Gadolinium.
2. according to claim 1 based on rare earth nickelate-niobium strontium titanate doping heterojunction material, it is characterised in that niobium
The mass concentration that Nb is adulterated in strontium titanate doping substrate is 0.05%~0.5%.
3. the transducer production method based on rare earth nickelate-niobium strontium titanate doping heterojunction material, it is characterised in that the party
Method is to follow these steps to realize:
One, RE oxide powder and NiO powder are sufficiently mixed for 1:2 according to stoichiometric ratio, mixed-powder compression molding,
Then pretreatment is sintered at 900~1000 DEG C, then with 1100~1400 DEG C of temperature sintering processes in high purity oxygen gas atmosphere,
Obtain rare earth nickelate oxide target material；
Two, by Nb:SrTiO3Substrate is sequentially placed into 10~20min of ultrasonic cleaning in deionized water, acetone and dehydrated alcohol, obtains
Nb:SrTiO after cleaning3Substrate；
Three, base vacuum is evacuated to 2.5~3.5 × 10-4Pa, with the Nb:SrTiO after cleaning3Substrate is passed through as deposition substrate
High pure oxygen control pressure is 0.01~60Pa, adjusts Nb:SrTiO3The temperature of substrate is 600~650 DEG C, using excimer laser
Device irradiates rare earth nickelate oxide target material, and control single pulse energy is 150~200mJ, and pulse frequency is that 3~8Hz carries out arteries and veins
Impulse light deposition rare earth nickelate sull keeps the temperature after deposition in situ, finally naturally cools to room temperature state, obtain
Rare earth nickelate-niobium strontium titanate doping heterojunction material；
Four, using the magnetron sputtering method rare earth nickelate oxygen in rare earth nickelate-niobium strontium titanate doping heterojunction material respectively
Compound film surface and Nb:SrTiO3The back side of substrate plates gold electrode, obtains different based on rare earth nickelate-niobium strontium titanate doping
The sensor of matter knot material；
Wherein rare earth oxide described in step 1 is Nd2O3、Sm2O3Or Gd2O3。
4. the sensor preparation according to claim 3 based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Method, it is characterised in that the partial size of RE oxide powder and NiO powder described in step 1 is 100~200nm.
5. the sensor preparation according to claim 3 based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Method, it is characterised in that step 1 is in high purity oxygen gas atmosphere with 1300~1400 DEG C of 10~14h of temperature sintering processes.
6. the sensor preparation according to claim 3 based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Method, it is characterised in that step 3 deposition of rare-earth nickelate sull with a thickness of 5~20nm.
7. the sensor preparation according to claim 3 based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Method, it is characterised in that step 3 irradiates rare earth nickelate oxide target material using excimer laser, controls single pulse energy
For 200mJ, pulse frequency is that 5Hz carries out pulse laser deposition of rare-earth nickelate sull.
8. the sensor preparation according to claim 3 based on rare earth nickelate-niobium strontium titanate doping heterojunction material
Method, it is characterised in that step 4 is in advance respectively in rare earth nickelate sull surface and Nb:SrTiO3The back side of substrate
It is covered with aperture plate, base vacuum is evacuated to 5 × 10-4Pa, using magnetron sputtering method respectively on rare earth nickelate sull surface
And Nb:SrTiO3The back side of substrate plates the gold electrode of 10nm thickness.
9. such as the application of the sensor based on rare earth nickelate-niobium strontium titanate doping heterojunction material prepared by claim 3,
It is characterized in that being applied to based on rare earth nickelate-niobium strontium titanate doping heterojunction material sensor certainly as sensing element
It drives in UV photodetector.
10. the sensor based on rare earth nickelate-niobium strontium titanate doping heterojunction material prepared by such as claim 3 is answered
With, it is characterised in that using based on rare earth nickelate-niobium strontium titanate doping heterojunction material sensor as sensing element application
In position sensitive device.
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| CN106356421A (en) * | 2016-10-20 | 2017-01-25 | 吉林大学 | Ultraviolet detector of optical controlled transmission channel formed by TiO2-NiO P-N heterojunction based on vertical conductive direction and preparation method thereof |
| CN106480413A (en) * | 2016-12-12 | 2017-03-08 | 北京科技大学 | A kind of preparation method of rare-earth Ni-base oxide polycrystal film material |
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| CN106356421A (en) * | 2016-10-20 | 2017-01-25 | 吉林大学 | Ultraviolet detector of optical controlled transmission channel formed by TiO2-NiO P-N heterojunction based on vertical conductive direction and preparation method thereof |
| CN106480413A (en) * | 2016-12-12 | 2017-03-08 | 北京科技大学 | A kind of preparation method of rare-earth Ni-base oxide polycrystal film material |
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