CN109269662A - Rare-earth Ni-base perovskite oxide thermistor material applied to infrared acquisition - Google Patents
Rare-earth Ni-base perovskite oxide thermistor material applied to infrared acquisition Download PDFInfo
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- CN109269662A CN109269662A CN201811096534.3A CN201811096534A CN109269662A CN 109269662 A CN109269662 A CN 109269662A CN 201811096534 A CN201811096534 A CN 201811096534A CN 109269662 A CN109269662 A CN 109269662A
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- 239000000463 material Substances 0.000 title claims abstract description 146
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 89
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 65
- 238000001514 detection method Methods 0.000 claims abstract description 34
- 239000012212 insulator Substances 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000007704 transition Effects 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- ZYYBOACWJZNWQT-UHFFFAOYSA-N oxonickel samarium Chemical compound [Sm].[Ni]=O ZYYBOACWJZNWQT-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 8
- 230000035945 sensitivity Effects 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 6
- -1 oxygen rare-earth Chemical class 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- WCYXDPQRKFQCSQ-UHFFFAOYSA-N [Nd].[Sm] Chemical compound [Nd].[Sm] WCYXDPQRKFQCSQ-UHFFFAOYSA-N 0.000 claims description 2
- FLWCYCMGKSKYDB-UHFFFAOYSA-N [Sm].[Pr] Chemical compound [Sm].[Pr] FLWCYCMGKSKYDB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002178 crystalline material Substances 0.000 claims description 2
- RHSKZPGAGXXKCV-UHFFFAOYSA-N europium neodymium Chemical compound [Nd][Eu] RHSKZPGAGXXKCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 description 12
- 230000005855 radiation Effects 0.000 description 12
- 229910052732 germanium Inorganic materials 0.000 description 11
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 11
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 10
- 229910001935 vanadium oxide Inorganic materials 0.000 description 10
- 230000008859 change Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- PWKXVIXDLJPOMA-UHFFFAOYSA-N [Ni]=O.[Nd] Chemical compound [Ni]=O.[Nd] PWKXVIXDLJPOMA-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KBZOVDSCFHXLPB-UHFFFAOYSA-N [O].[Ni].[Eu] Chemical compound [O].[Ni].[Eu] KBZOVDSCFHXLPB-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910002372 SrTiO3(001) Inorganic materials 0.000 description 1
- XBAOPMPPZXHFEX-UHFFFAOYSA-N [Ni]=O.[Pr] Chemical compound [Ni]=O.[Pr] XBAOPMPPZXHFEX-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001595 contractor effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
- G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
- G01J5/20—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using resistors, thermistors or semiconductors sensitive to radiation, e.g. photoconductive devices
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
- Thermistors And Varistors (AREA)
Abstract
A kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared signal detection, belongs to infrared acquisition field.Using the rare-earth Ni-base perovskite oxide insulator phase (or semiconductor phase) with high temperature coefficient of resistance as the thermistor material in infrared detection technique；By adjusting stress suffered by the type of rare earth element in rare-earth Ni-base perovskite oxide material, rare-earth Ni-base material, the metal insulator phase transition temperature of rare-earth Ni-base perovskite oxide thermistor is adjusted in the methods of rare earth element and the stoichiometric ratio of nickel element and oxygen element in rare-earth Ni-base material, thus adjusting of the realization to infrared acquisition temperature range；It is prepared by the combination of rare-earth Ni-base perovskite oxide and different carriers material and integration realization device, to realize the detection realized in 10K-500K temperature range to infrared signal.The present invention is in terms of infrared acquisition, microbolometer heat, temperature sensing and sensing with considerable application value and wide application prospect.
Description
Technical field
The invention belongs to microcell thermal agitation detections, microbolometer heat, infrared acquisition field, are applied to more particularly to one kind
The rare-earth Ni-base perovskite oxide thermistor of infrared acquisition.
Background technique
Develop have high temperature coefficient of resistance (TCR) thermistor material, for precisely characterize microcell thermal agitation to
It further realizes that the microbolometrics such as infrared ray signal detect and has great importance and value [1-25].Applied to room temperature
Neighbouring Uncooled infrared detection technology, which is based primarily upon, is converted into measurable electric signal for sightless infra-red radiation.It is released with heat
Electrical resistivity survey survey, micro-metering bolometer, thermoelectric pile and Gao Laiguan, the mercury meter of the liquid of thermal expansion and cold contraction effect, resonant frequency are to temperature
The technologies such as sensitive quartz resonator Uncooled infrared detection [1-5] compare, the infrared thermistor material based on thermistor
The microbolometer FPA array detection technology of material has without refrigeration, integrated circuit technique, surface micro-fabrication can be achieved
Many advantages, such as combination such as technology and film deposition techniques, low cost, low-power consumption, long-life, miniaturization and reliability [6-
25].Its detection process comprising the following three steps: 1) absorb the infrared light of radiation, and convert light energy into heat；2) due to infrared
The absorption of line increases thermistor temp with fuel factor；3) since temperature change changes the resistivity of thermistor, from
Obtain detectable voltage change signal.Therefore, how to improve the temperature-coefficient of electrical resistance (TCR) of thermistor is high detection spirit living
Sensitivity and the key point for reducing detection noise.
Most widely used at present Uncooled Infrared Microbolometer thermo-sensitive material is vanadium oxide.Its is with higher
The advantages that TCR (2.0%/K), suitable resistivity, lower thermal conductivity；Furthermore its preparation process can be compatible with silicon technology.This makes
When target scene is infrared to be incident in bolometer, the raising of temperature changes significantly its resistance, to have big
Signal output.Research and development department of western countries headed by Honeywell Corp. USA makes full use of with VO2、V2O5For the mixing of base
Polycrystalline vanadium oxide film develops non-brake method vanadium oxide micro-metering bolometer infrared focus plane, and is applied to uncooled ir
In the practical preparation of radiator.The vanadium oxide film TCR peak realized in report at present is more than 5%K-1[19-25], this
One index means the infrared acquisition sensitivity of material by nearly twice of raising living.In addition to vanadium oxide, polysilicon, polycrystalline germanium
Silicon, Ti and other transition group oxide (such as: Mn, Fe, Co, Ni, Cu) thermistor material answering in terms of infrared acquisition
With having equally caused certain concern [6-11].
However undeniable is that the existing thermistor material applied in terms of infrared acquisition is still asked there are some
Topic.For example, the temperature-coefficient of electrical resistance (TCR) of Ti is relatively low, and polysilicon and poly-SiGe film thermistor are due to formation temperature
It is excessively high, therefore limit it and be applied in monolithic system.In comparison, although vanadium oxide material has been obtained for certain scale
Application how to obtain but since vanadium oxide all has at chemical constituent and the aspect of crystal structure two complexity of height
It obtains high thermistor coefficient and equally exists huge challenge on material preparation process.
Bibliography:
[1] Tang Dingyuan, Mi Zhengyu, photoelectron outline, Shanghai: scientific and technical literature publishing house, 1989:385
[2] Wu Cheng, Su Junhong, Pan Shunchen etc., no-refrigeration infrared focal plane technology review (on), infrared technique, 1999,21
(1): 6
[3] Wu Cheng, Su Junhong, Pan Shunchen etc., no-refrigeration infrared focal plane technology review (under), infrared technique, 1999,21
(2): 1
[4] Yang Yasheng, Bolometer Infrared Focal Plane Arrays, semiconductor technology, 1999,24 (2): 5
[5] Shao Shiping, no-refrigeration infrared focal plane array progress, infrared technique, 1999,18 (2): 1
[6] Chen, Changhong, Yi, Xinj ian, Zhang, Jing, et al., Linear uncooled
Microbolometer array based on VOx thin films, Infrared Physics and Technology,
2001,42 (2): 87
[7] Liu Xi is followed closely, Jiang Meiling, the development of uncooled IR micro bolometer, infrared and millimeter wave journal, and 1997,
16 (6): 459
[8] Tanaka, A., Matsumoto, S., Tsukamoto, N., et al., Infrared Focal Plane
Array Incorporating Silicon IC Process Compatible Bolometer, IEEE Transaction
On Electron Devices, 1996,43 (11): 1844
[9] Wang Yangyuan, polysilicon membrane and its effect in integrated circuits, Beijing: Science Press, 1988:71
[10] Sedky, S., Fiorini, P., Caymax, M., et al., Thermally insulated
structures for IR bolometers,made of polycrystalline sil icon germanium
Alloys, Solid State Sensors and Actuators, 1997,1:237
[11] Rusu, F., Chiriac, H., Urse, M., On temperature dependence of
conductivity and thermopower of co-sputtered Nix-(SiO2)1-x composite thin
Films, Sensors and Actuators A:Physical, 1997,62 (1-3): 687
[12] Gu Wenyun, Pi Defu, the research and development proposal of uncooled IRFPA bolometer, infrared technique, 2000,22 (5): 10
[13] Zhou Shiyuan, Gu Wenyun, the sunykatuib analysis of bolometer performance, infrared technique, 2000,22 (5): 15
[14] Gu Wenyun, Pi Defu, Uncooled microbolometer thermal imaging, infrared and laser engineering, 2000,29 (2):
65
[15] Wang, S.B., Xiong, B.F., Zhou, S.B., et al., Preparation of 128element
of IR detector array based on vanadium oxide thin films obtained by ion beam
Sputtering, Sensors and Actuators A:Physical, 2005,117 (1): 110
[16] Han, Yong-Hee, Choi, In-Hoon, Kang, Ho-Kwan, et al., Fabrication of
vanadium oxide thin film with high-temperature coefficient of resistance
Using V2O5/V/V2O5multi-layers for uncooled microbolometers, Thin Sol id Films,
2003,425 (1-2): 260
[17] Rajendra Kumar, R.T, Karunagaran, B., Mangalaraj, D., et al., Pulsed
Laser deposited vanadium oxide thin films for uncooled infrared detectors,
Sensors and Actuators A:Physical, 2003,107 (1): 62
[18] Balcerak, R., Jenkins, D.P., Diakides, N.A., Uncooled infrared focal
plane arraysEngineering in Medicine and Biology Society,1996.Bridging
Disciplines for Biomedicine.Proceedings of the 18th Annual International
Conference of the IEEE, 1996, Volume 5:2077
[19] Yin great Chuan, Xu Niankan, the treatment process of high-performance vanadium dioxide film, Northwestern Polytechnical University's journal, 1995,
13 (3): 483
[20] permitted Min, Cui Jingzhong, He Deyan, uncooled infrared focal plane array VO2 membrane structure and performance study, it is fine
Processing technology, 2003 (1): 34
[21] Wu Guangming, Chen Yan, lithium ion are injected to V2O5Film infrared vibration characteristics influences, investigation of materials journal,
2000,14 (2): 210
[22] Wang Zhongchun, Chen Xiaofeng sputter stagnation pressure to the structure of vanadium oxide film and the influence of electrochromism property, silicic acid
Salt journal, 1999,27 (1): 28
[23] Yuan Ningyi, Li Jinhua, the properity of vanadium oxide film and the correlation of technology of preparing, functional material,
2001,32 (6): 572
[24] Wang Hongchen, easily newly-built, Chen Sihai etc., the preparation of non-refrigeration infrared detector vanadium oxide polycrystal film are red
Outside with millimeter wave journal, 2004,23 (1): 64
[25] week is into Ru Guoping, Li Ping Zong etc., the preparation of vanadium oxide thermosensitive film and its property Quality Research are infrared with milli
Metric wave journal, 2001,20 (4): 291
Summary of the invention
The purpose of the present invention is to provide a kind of based on the novel heat of rare-earth Ni-base oxide with distorted perovskite structure
The infrared acquisition method of quick resistance.Compared with traditional vanadium oxide thermistor material, rare-earth Ni-base perovskite oxide has
Higher temperature-coefficient of electrical resistance, so as to realize higher detectivity in the detection such as infrared ray, micro-disturbance thermal signal
With lower detection noise.The present invention further provides the spies that rare-earth Ni-base perovskite oxide is applied to infrared detector
The adjusting of testing temperature range, integrated morphology and integrated approach are realized in 10K-500K temperature range to infrared letter to realize
Number detection.The present invention is in terms of infrared acquisition, microbolometer heat, temperature sensing and sensing with considerable application value and width
Wide application prospect.
Central scope of the invention is: being insulated using the rare-earth Ni-base perovskite oxide with high temperature coefficient of resistance
Body phase (or semiconductor phase) is as the thermistor material in infrared detection technique；By adjusting rare-earth Ni-base perovskite oxide
The type of rare earth element in material, rare earth element and nickel element and oxygen in stress, rare-earth Ni-base material suffered by rare-earth Ni-base material
The methods of stoichiometric ratio of element becomes the temperature and resistance variation coefficient and temperature and resistance of rare-earth Ni-base perovskite oxide
Change the distribution relation of coefficient at different temperatures to be adjusted, to realize to infrared acquisition sensitivity and detection temperature range
It is adjusted；It is prepared eventually by the combination of rare-earth Ni-base perovskite oxide and different carriers material and integration realization device.
A kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared acquisition, which is characterized in that application
In infrared signal detection thermistor material be the rare-earth Ni-base perovskite oxide with distorted perovskite structure.Its chemistry
Group becomes ABO3Distorted perovskite structure ReNiO3: Re (A) combinations for Rare Earth Elements Determination or a variety of rare earth elements,
It is preferred that samarium (Re=Sm), neodymium (Re=Nd), europium (Re=Eu), praseodymium (Re=Pr), samarium neodymium (Re=SmxNd1-x, 0 < x < 1), samarium praseodymium
(Re=SmxPr1-x, 0 < x < 1), europium neodymium (Re=EuxNd1-x, 0 < x < 1)；Europium spreads (Re=EuxPr1-x, 0 < x < 1)；Nickel element (Ni)
Occupy the position B in perovskite structure.
Further, be the characteristics of material of the present invention be utilized rare-earth Ni-base perovskite oxide temperature lower than metal it is exhausted
Insulator (or semiconductor) temperature-coefficient of electrical resistance mutually with higher this feature when edge phase transformation temperature, to be made
For thermistor material and it is applied to infrared acquisition.
Further, the rare-earth Ni-base perovskite oxide thermistor for infrared acquisition includes: block materials,
Film, crystal whisker materials, nano wire, nano powder；Its crystal structure includes monocrystal material, polycrystalline material, non-crystalline material.
Further, the present invention is by changing the type of rare earth element in rare-earth Ni-base perovskite oxide material to rare earth
The metal insulator phase transition temperature of Ni-based perovskite oxide thermistor is adjusted, thus to rare-earth Ni-base perovskite oxygen
Temperature range existing for compound material insulator phase (semiconductor phase) is adjusted, and is carried out with realizing to infrared acquisition temperature range
The purpose of adjusting.By reducing the atomic radius of A rare earth elements in rare-earth Ni-base perovskite structure, metal-insulator can be reduced
Phase transformation temperature so that the insulator for preparing rare-earth Ni-base perovskite compound thermistor material mutually exist temperature to
Low temperature range is mobile, and increases in the temperature-coefficient of electrical resistance for being lower than phase transition temperature 100K range.It is made when rare earth element is shirt
The metal insulator phase transition temperature of standby shirt nickel oxygen rare-earth Ni-base material thermistor be 430K, realized to infrared acquisition
Temperature range is 230-420K；When rare earth element is selected as europium in rare-earth Ni-base perovskite oxide material, metal insulator
Phase transition temperature is 460K, and being realized is 280-450K to infrared acquisition temperature range；When rare-earth Ni-base perovskite oxide
When rare earth element is selected as praseodymium in material, metal insulator phase transition temperature be 80K, realized to infrared acquisition temperature range
For 5-70K.
In a preferred example, we using praseodymium of the atomic quantity than 25% and 75% samarium made of praseodymium samarium nickel oxygen calcium
Titanium ore oxide (Pr0.25Sm0.75NiO3) material is as thermistor material.It is compared to and utilizes samarium nickel oxygen perovskite oxide
(SmNiO3) material as thermistor material the case where, by being using the lesser praseodymium doped perovskite structure A of atomic radius,
Realize 200K this at a temperature of infrared acquisition sensitivity raising.
Further, the present invention is by applying stress to rare-earth Ni-base perovskite oxide temperature-sensitive electricity to rare-earth Ni-base material
The metal insulator phase transition temperature of resistance is adjusted, to (partly lead to rare-earth Ni-base perovskite oxide material insulator phase
Body phase) existing for temperature range be adjusted, to realize purpose that infrared acquisition temperature range is adjusted.Wherein, it manufactures
Compressive deformation can make the phase transition temperature of rare-earth Ni-base perovskite compound reduce, to realize so that preparing rare earth nickel
It is mobile to low temperature range mutually to there is temperature in the insulator of based perovskite compound thermistor material, and increases and be lower than phase alternating temperature
The temperature-coefficient of electrical resistance for spending 100K range is aoxidized using with distortion of lattice samarium nickel oxygen perovskite under 1% two-way action of compressive stress
Object (SmNiO3) thin-film material is as thermistor material, compared to the samarium nickel oxygen perovskite oxygen utilized under unstressed induction deformation
The case where compound material is as thermistor material utilizes the SmNiO under bi-directional compression deformation3Gold as thermistor material
Belonging to insulator phase transition temperature reduces 20K, the temperature-coefficient of electrical resistance under room temperature to 130 degrees Celsius is which thereby enhanced, to improve
Infrared acquisition sensitivity at room temperature.
In a preferred example, we aoxidize using with distortion of lattice samarium nickel oxygen perovskite under 1% two-way action of compressive stress
Object (SmNiO3) thin-film material is as thermistor material.Compared to the samarium nickel oxygen perovskite oxygen utilized under unstressed induction deformation
The case where compound material is as thermistor material utilizes the SmNiO under bi-directional compression deformation3It is realized as thermistor material
The raising of infrared acquisition sensitivity at room temperature.
Further, the present invention compares rare-earth Ni-base by adjusting the stoichiometry of rare earth element and nickel element and oxygen element
The metal insulator phase transition temperature of perovskite oxide thermistor is adjusted, thus to rare-earth Ni-base perovskite oxide
Temperature range existing for material insulator phase (semiconductor phase) is adjusted, and infrared acquisition temperature range is adjusted with realizing
Purpose.In a preferred example, we are by reducing nickel oxygen stoichiometry ratio, by reducing nickel oxygen stoichiometry ratio by 3.0
To 2.7, realizes and the phase transition temperature for mentioning samarium nickel oxygen perovskite thermistor material is improved to 210 degrees Celsius, improve insulation
Temperature range existing for phase stabilizer is to widen the temperature range of infrared survey.
The present inventor after extensive and in-depth study, by improving preparation process, obtains a kind of based on distortion
The infrared acquisition method of the rare-earth Ni-base oxide thermal resistance of perovskite structure.With traditional vanadium oxide thermistor material
Material is compared, and rare-earth Ni-base perovskite oxide has higher temperature-coefficient of electrical resistance, so as in infrared ray, micro-disturbance heat letter
Higher detectivity and lower detection noise are realized in number equal detection.The present invention further provides by rare-earth Ni-base calcium titanium
Mine oxide applications exist in the adjusting of detection temperature range, integrated morphology and the integrated approach of infrared detector to realize
The detection to infrared signal is realized in 10K-500K temperature range.The central scope of invention is: using with high resistance temperature
The rare-earth Ni-base perovskite oxide insulator phase (or semiconductor phase) of coefficient is as the thermistor material in infrared detection technique
Material；By adjusting stress, rare earth suffered by the type of rare earth element in rare-earth Ni-base perovskite oxide material, rare-earth Ni-base material
The methods of stoichiometric ratio of rare earth element and nickel element and oxygen element is to rare-earth Ni-base perovskite oxide heat in nickel-base material
The metal insulator phase transition temperature of quick resistance is adjusted, to realize the adjusting to infrared acquisition temperature range；By dilute
It is prepared by the combination of the Ni-based perovskite oxide of soil and different carriers material and integration realization device.The present invention is in infrared acquisition, micro-
Surveying radiant heat, temperature sensing and sensing aspect has considerable application value and wide application prospect.
Detailed description of the invention
Fig. 1 is samarium nickel oxygen perovskite oxide (SmNiO3) temperature and relative resistance change relationship.
Fig. 2 is samarium nickel oxygen perovskite oxide (SmNiO3) temperature-coefficient of electrical resistance (TCR) vary with temperature relationship.
Fig. 3 is neodymium nickel oxygen perovskite oxide (NdNiO3) temperature-relative resistance change relationship.
Fig. 4 is neodymium nickel oxygen perovskite oxide (NdNiO3) temperature-coefficient of electrical resistance (TCR) vary with temperature relationship.
Fig. 5 is the infrared detector structure prepared based on rare-earth Ni-base perovskite oxide thermistor material.
Specific embodiment
Embodiment 1:
Using with resistance temperature variation relation shown in Fig. 1, the samarium nickel oxygen perovskite oxygen of TCR temperature change as shown in Figure 2
Compound (SmNiO3) material as thermistor material, is made infrared detector according to device architecture shown in Fig. 5 and is insulated envelope
In germanium window.At room temperature, in SmNiO3Thermistor material leads to an electric current, reads two sections of voltage values.When utilize wavelength
3, SmNiO is irradiated to after 4,5 microns of infrared line focus of long infrared radiation3When thermistor material, due to infrared absorption point office
Domain temperature increases so that VRVariation 3%, after turning off infrared incident light, VROriginal numerical value is returned to, to realize that for wavelength be 3-5
The room temperature detection of the infrared signal of micron.
Embodiment 2:
Using with resistance temperature variation relation shown in Fig. 3, the neodymium nickel oxygen perovskite oxygen of TCR temperature change as shown in Figure 4
Compound (NdNiO3) material as thermistor material, is made infrared detector according to device architecture shown in Fig. 5 and is insulated envelope
In germanium window.150K is cooled the temperature to using liquid nitrogen, in NdNiO3Thermistor material leads to an electric current, reads two sections of electricity
Pressure value.SmNiO is irradiated to after using 3,4,5 microns of infrared line focus of long infrared radiation of wavelength3When thermistor material, by
It increases in infrared absorption point local temperature so that VRVariation 2%, after turning off infrared incident light, VROriginal numerical value is returned to, to realize
The low temperature of infrared signal detects.
Embodiment 3:
Utilize europium nickel oxygen perovskite oxide (EuNiO3) material is as thermistor material, according to device junction shown in Fig. 5
Infrared detector and heat insulating package are configured in germanium window.At room temperature, in EuNiO3Thermistor material leads to an electric current,
Read two sections of voltage values.EuNiO is irradiated to after using 3-5 microns of infrared line focus of long infrared radiation of wavelength3Thermistor
When material, since infrared absorption point local temperature increases so that VRVariation 4%, after turning off infrared incident light, VRReturn to original number
Value detects the room temperature of infrared signal to realize.
Embodiment 4:
Utilize samarium europium nickel oxygen perovskite oxide (Sm0.5Eu0.5NiO3) material is as thermistor material, according to Fig. 5 institute
Show that infrared detector and heat insulating package is made in germanium window in device architecture.At room temperature, in Sm0.5Eu0.5NiO3Thermistor
Material leads to an electric current, reads two sections of voltage values.It is irradiated to after using 3-5 microns of infrared line focus of long infrared radiation of wavelength
Sm0.5Eu0.5NiO3When thermistor material, since infrared absorption point local temperature increases so that VRVariation 3%, turn off it is infrared enter
After penetrating light, VROriginal numerical value is returned to, the room temperature of infrared signal is detected to realize.
Embodiment 5:
Utilize europium nickel oxygen perovskite oxide (EuNiO3) material is as thermistor material, according to device junction shown in Fig. 5
Infrared detector and heat insulating package are configured in germanium window.Temperature is risen to 100 degrees Celsius, in EuNiO3Thermistor material
Expect to lead to an electric current, reads two sections of voltage values.It is irradiated to after using 3-5 microns of infrared line focus of long infrared radiation of wavelength
EuNiO3When thermistor material, since infrared absorption point local temperature increases so that VRVariation 2%, after turning off infrared incident light,
VROriginal numerical value is returned to, to realize the high temperature detection for infrared signal.
Embodiment 6:
By samarium nickel oxygen perovskite oxide (SmNiO3) thin-film material coherent growth is in SrTiO3(001) in single crystalline substrate, by
In SmNiO3Lattice parameter be less than SrTiO3, the SmNiO that is grown3Film is in two-way tensile stress tensional state, to make gold
Belong to insulator phase transition temperature to improve.Infrared detector and heat insulating package is made according to device architecture shown in Fig. 5 using the material
In germanium window.Temperature is risen to 120 degrees Celsius, SmNiO under tensile strain3Thermistor material leads to an electric current, reads
Take two sections of voltage values.SmNiO is irradiated to after using 4 microns of infrared line focus of long infrared radiation of wavelength3Thermistor material
When, since infrared absorption point local temperature increases so that VRVariation 2%, after turning off infrared incident light, VROriginal numerical value is returned to, from
And realize the high temperature detection for infrared signal.
Embodiment 7:
Using chemical means in samarium nickel oxygen perovskite oxide (SmNiO3) in manufacture Lacking oxygen, to make metal insulator
Phase transition temperature improves.Infrared detector and heat insulating package is made in germanium window according to device architecture shown in Fig. 5 using the material
In.Temperature is risen to 100 degrees Celsius, SmNiO under tensile strain3Thermistor material leads to an electric current, reads two sections of electricity
Pressure value.SmNiO is irradiated to after using 5 microns of infrared line focus of long infrared radiation of wavelength3When thermistor material, due to red
Outer absorption point local temperature increases so that VRVariation 2.5%, after turning off infrared incident light, VROriginal numerical value is returned to, thus realization pair
In the high temperature detection of infrared signal.
Embodiment 8:
Utilize praseodymium nickel oxygen perovskite oxide (PrNiO3) material is as thermistor material, according to device junction shown in Fig. 5
Infrared detector and heat insulating package are configured in germanium window.80K is cooled the temperature to using liquid helium, in PrNiO3Thermistor
Material leads to an electric current, reads two sections of voltage values.It is irradiated to after using 5 microns of infrared line focus of long infrared radiation of wavelength
PrNiO3When thermistor material, since infrared absorption point local temperature increases so that VRVariation 2%, after turning off infrared incident light,
VROriginal numerical value is returned to, to realize the low temperature detection of infrared signal.
Embodiment 9:
Using praseodymium of the atomic quantity than 25% and 75 samarium made of praseodymium samarium nickel oxygen perovskite oxide
(Pr0.25Sm0.75NiO3) material as thermistor material, is made infrared detector according to device architecture shown in Fig. 5 and is insulated
It is encapsulated in germanium window.200K is cooled the temperature to using liquid helium, in Pr0.25Sm0.75NiO3Thermistor material leads to an electric current,
Read two sections of voltage values.PrNiO is irradiated to after using 5 microns of infrared line focus of long infrared radiation of wavelength3Thermistor material
When material, since infrared absorption point local temperature increases so that VRVariation 5%, after turning off infrared incident light, VROriginal numerical value is returned to,
To realize the low temperature detection of infrared signal.It is compared to and utilizes samarium nickel oxygen perovskite oxide (SmNiO3) material is as temperature-sensitive
The case where resistance material, realize 200K this at a temperature of infrared acquisition sensitivity raising.
Embodiment 10:
Using with distortion of lattice samarium nickel oxygen perovskite oxide (SmNiO under 1% two-way action of compressive stress3) thin-film material
As thermistor material, infrared detector and heat insulating package is made in germanium window according to device architecture shown in Fig. 5.Room temperature
It is lower to be irradiated to bi-directional compression deformation SmNiO after utilizing 3,4,5 microns of infrared line focus of long infrared radiation of wavelength3Thermistor
When material, since infrared absorption point local temperature increases so that VRVariation 5%, after turning off infrared incident light, VRReturn to original number
Value, to realize that the room temperature for the infrared signal for being 3-5 microns for wavelength detects.It is compared to and utilizes unstressed induction deformation
Under samarium nickel oxygen perovskite oxide (SmNiO3) material as thermistor material the case where, realize at room temperature infrared
The raising of detectivity.
Embodiment 11:
Utilize the samarium nickel oxygen perovskite oxide (SmNiO with part Lacking oxygen2.97) thin-film material is as thermistor
Infrared detector and heat insulating package is made in germanium window according to device architecture shown in Fig. 5 in material.Environment temperature is increased to
200 degrees Celsius, using being irradiated to the SmNiO with part Lacking oxygen after 5 microns of infrared line focus of long infrared radiation of wavelength3Heat
When quick resistance material, since infrared absorption point local temperature increases so that VRVariation 1.5%, after turning off infrared incident light, VRIt returns to
Originally numerical value, from the room temperature detection for the infrared signal that realization is 5 microns for wavelength at 200 degrees celsius.In comparison, nothing
The samarium nickel oxygen perovskite oxide material of Lacking oxygen is in metal phase at 200 degrees celsius, therefore can not be used as thermistor material
Material realizes infrared acquisition.
Claims (6)
1. a kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared signal detection, which is characterized in that heat
Quick resistance material is the rare-earth Ni-base perovskite oxide with distorted perovskite structure；Chemical composition is ABO3Distortion calcium titanium
Mine structure ReNiO3: Re (A) combinations for Rare Earth Elements Determination or a variety of rare earth elements, including samarium (Re=Sm), neodymium (Re
=Nd), europium (Re=Eu), praseodymium (Re=Pr), samarium neodymium (Re=SmxNd1-x, 0 < x < 1), samarium praseodymium (Re=SmxPr1-x, 0 < x < 1), europium
Neodymium (Re=EuxNd1-x, 0 < x < 1)；Europium praseodymium (Re=EuxPr1-x, 0 < x < 1)；Nickel element (Ni) occupies the position the B in perovskite structure.
2. a kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared signal detection as described in claim 1
Material, which is characterized in that rare-earth Ni-base perovskite oxide material has metal-insulator phase transformation characteristic, below phase transition temperature
Insulator or semiconductor temperature-coefficient of electrical resistance mutually with higher in 100K temperature range, is embodied in its resistance temperature system
Several absolute values is greater than 1%.
3. a kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared signal detection as described in claim 1
Material, which is characterized in that the rare-earth Ni-base perovskite oxide thermistor material for infrared acquisition includes: block material
Material, film, crystal whisker materials, nano wire, nano powder；Its crystal structure includes monocrystal material, polycrystalline material, non-crystalline material.
4. a kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared signal detection as described in claim 1
Material, which is characterized in that by changing the type of rare earth element in rare-earth Ni-base perovskite oxide material to rare-earth Ni-base calcium titanium
The metal insulator phase transition temperature of mine oxide thermosensitive resistor is adjusted, thus to rare-earth Ni-base perovskite oxide material
Temperature range existing for insulator phase (semiconductor phase) is adjusted, to realize the mesh that infrared acquisition temperature range is adjusted
's；By reducing the atomic radius of A rare earth elements in rare-earth Ni-base perovskite structure, metal-insulator phase transformation can be reduced
Temperature, so that the insulator for preparing rare-earth Ni-base perovskite compound thermistor material mutually has temperature to low temperature range
It is mobile, and increase in the temperature-coefficient of electrical resistance for being lower than phase transition temperature 100K range；When rare earth element is shirt, prepared shirt nickel
The metal insulator phase transition temperature of oxygen rare-earth Ni-base material thermistor be 430K, realized to infrared acquisition temperature range
For 230-420K；When rare earth element is selected as europium in rare-earth Ni-base perovskite oxide material, metal-insulator phase transformation temperature
Degree is 460K, and being realized is 280-450K to infrared acquisition temperature range；When dilute in rare-earth Ni-base perovskite oxide material
When earth elements are selected as praseodymium, metal insulator phase transition temperature is 80K, and being realized is 5-70K to infrared acquisition temperature range.
5. a kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared signal detection as described in claim 1
Material, which is characterized in that the stoichiometry by adjusting rare earth element and nickel element and oxygen element compares rare-earth Ni-base perovskite oxygen
The metal insulator phase transition temperature of compound thermistor is adjusted, to insulate to rare-earth Ni-base perovskite oxide material
Temperature range existing for body phase (semiconductor phase) is adjusted, to realize the purpose that infrared acquisition temperature range is adjusted；
Using with distortion of lattice samarium nickel oxygen perovskite oxide (SmNiO under 1% two-way action of compressive stress3) thin-film material is as temperature-sensitive
Resistance material, compared to using the samarium nickel oxygen perovskite oxide material under unstressed induction deformation as thermistor material
Situation utilizes the SmNiO under bi-directional compression deformation3Metal insulator phase transformation temperature as thermistor material reduces 20K, by
This improves the temperature-coefficient of electrical resistance under room temperature to 130 degrees Celsius, to improve infrared acquisition sensitivity at room temperature.
6. a kind of rare-earth Ni-base perovskite oxide thermistor material applied to infrared signal detection as described in claim 1
Material, which is characterized in that the stoichiometry by adjusting rare earth element and nickel element and oxygen element compares rare-earth Ni-base perovskite oxygen
The metal insulator phase transition temperature of compound thermistor is adjusted, to realize to infrared acquisition temperature range and not
The adjusting of synthermal lower detectivity；Nickel oxygen stoichiometry ratio is reduced to 2.7 by 3.0, is realized to mentioning samarium nickel oxygen calcium titanium
The phase transition temperature of mine thermistor material improve improved to 210 degrees Celsius temperature range that insulator is mutually stabilized to
The temperature range of infrared survey is widened.
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| CN109490381A (en) * | 2018-11-19 | 2019-03-19 | 北京科技大学 | Energy perturbation based on rare-earth Ni-base perovskite compound intersects bi-directional probing method |
| CN110146199A (en) * | 2019-05-09 | 2019-08-20 | 北京科技大学 | A Pressure Detection Method Based on Metastable Rare Earth Ni-based Oxide |
| CN110716086A (en) * | 2019-09-30 | 2020-01-21 | 北京科技大学 | Frequency detection and filtering method based on rare earth nickel-based perovskite compound |
| CN111180151A (en) * | 2020-01-03 | 2020-05-19 | 北京科技大学 | Active Switching Method of Positive, Negative and Delta Temperature Coefficient Thermistor Based on Alternating Frequency |
| CN113340356A (en) * | 2021-06-29 | 2021-09-03 | 北京科技大学 | Array type temperature and pressure cooperative sensor and application method |
| CN113698205A (en) * | 2021-08-30 | 2021-11-26 | 华北电力大学 | Composite thermistor material based on rare earth nickel-based oxide and preparation method and application thereof |
| CN114544023A (en) * | 2022-01-25 | 2022-05-27 | 北京科技大学 | Array type rare earth nickel-based oxide precise temperature measurement system and use method |
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| CN110146199A (en) * | 2019-05-09 | 2019-08-20 | 北京科技大学 | A Pressure Detection Method Based on Metastable Rare Earth Ni-based Oxide |
| CN110716086A (en) * | 2019-09-30 | 2020-01-21 | 北京科技大学 | Frequency detection and filtering method based on rare earth nickel-based perovskite compound |
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| CN111180151B (en) * | 2020-01-03 | 2021-08-03 | 北京科技大学 | Active Switching Method of Positive, Negative and Delta Temperature Coefficient Thermistor Based on Alternating Frequency |
| CN113340356A (en) * | 2021-06-29 | 2021-09-03 | 北京科技大学 | Array type temperature and pressure cooperative sensor and application method |
| CN113698205A (en) * | 2021-08-30 | 2021-11-26 | 华北电力大学 | Composite thermistor material based on rare earth nickel-based oxide and preparation method and application thereof |
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