CN108956712B - ZnO nanocrystal enhanced Si nanorod array sensitive material, preparation method thereof and sensor - Google Patents
ZnO nanocrystal enhanced Si nanorod array sensitive material, preparation method thereof and sensor Download PDFInfo
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- CN108956712B CN108956712B CN201810700070.6A CN201810700070A CN108956712B CN 108956712 B CN108956712 B CN 108956712B CN 201810700070 A CN201810700070 A CN 201810700070A CN 108956712 B CN108956712 B CN 108956712B
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 32
- 239000002073 nanorod Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000002061 nanopillar Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910001020 Au alloy Inorganic materials 0.000 claims description 4
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229920002120 photoresistant polymer Polymers 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
The invention discloses a ZnO nanocrystalline reinforced Si nanorod array sensitive material, which comprises a Si substrate, a Si nanorod array, ZnO nanocrystals and an electrode material, wherein the Si substrate is provided with the Si nanorod array, the surface of the Si nanorod array is distributed with the ZnO nanocrystals, and the top of the Si nanorod array is also provided with the electrode material; also discloses a preparation method of the sensitive material and a sensor. The distribution uniformity of ZnO nanocrystals is regulated and controlled by controlling the order and uniformity of the Si nano-column array, and the sensitivity and the overall performance of the sensor are improved by utilizing the special optical characteristics of the Si nano-column array and the local surface sensitivity of the ZnO nanocrystals.
Description
Technical Field
The invention belongs to the technical field of semiconductor sensing, and particularly relates to a ZnO nanocrystal reinforced Si nanorod array sensitive material, a preparation method thereof and a sensor prepared from the sensitive material.
Background
The sensor is widely applied to the fields of smart home, safety production, environmental protection, national defense and the like, and particularly, the Si-based sensor is most widely applied. However, the existing silicon-based sensor is usually made by taking a Si nano array obtained by etching a Si substrate as a sensitive material and further adding Au electrodes and leads, wherein the Si nano array has a significant influence on the detection sensitivity, so that the minimum detection limit of the sensor containing the Si nano array is in the order of 100ppm, which is far inferior to the level of 5-10ppm of other semiconductor sensors, and in addition, the response time is longer, generally 30-50 s.
ZnO is a wide-bandgap metal oxide with a hexagonal wurtzite structure, has the advantages of cheap and easily-obtained raw materials, simple preparation process, excellent photoelectric property, excellent piezoelectricity, gas sensitivity, pressure sensitivity and humidity sensitivity, and is another semiconductor material commonly used for manufacturing sensors besides Si. The ZnO-based sensor has the advantages of high response speed, high integration degree, low power, high sensitivity, good selectivity and the like, and has a long research history and a relatively mature development technology. The minimum detection limit of the existing Au/ZnO nano-column array sensor is 10ppm, which is obviously superior to that of a Si nano-column array sensor, however, the uniformity of the sensor and the distribution uniformity of the nano-column array need to be further improved, the ZnO crystal quality is poor, the full width at half maximum of an X-ray rocking curve is generally more than 200arcsec, and a larger promotion space exists.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a ZnO nanocrystal reinforced Si nanorod array sensitive material, a preparation method thereof and a sensor prepared from the sensitive material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a ZnO nanocrystal enhanced Si nanorod array sensitive material comprises a Si substrate, a Si nanorod array, ZnO nanocrystals and an electrode material, wherein the Si substrate is provided with the Si nanorod array, the surface of the Si nanorod array is distributed with the ZnO nanocrystals, and the top of the Si nanorod array is further provided with the electrode material.
Preferably, the Si substrate is an n-type or p-type Si single crystal wafer, the full width at half maximum of an X-ray rocking curve is less than 50arcsec, and the resistance is less than 5 omega.
Preferably, the particle size of the ZnO nanocrystal is 2-10 nm.
Preferably, the diameter of the Si nano-columns is 50-990nm, the distance between the Si nano-columns is 30-1500nm, and the cross-sectional shape of the Si nano-columns is centrosymmetric, such as a central circle, a square, a regular polygon and the like.
Preferably, the electrode material comprises at least one of Pt, Au, Ni; further, the electrode is Au/Ni alloy or Pt/Au/Ni alloy.
A preparation method of the ZnO nanocrystal reinforced Si nanorod array sensitive material comprises the following steps:
(1) spin-coating photoresist on the surface of the Si substrate, exposing, developing and etching to obtain a Si nano-pillar array;
(2) growing ZnO nanocrystals on the surface of the Si nanorod array;
(3) and protecting the part except the electrode deposition area by using a mask plate, and then evaporating an electrode in the electrode deposition area.
In the step (1), the spin coating process may adopt a method known in the art, the exposure and development process uses a metal plate as a mask plate, the etching process is preferably ICP etching, and the etching depth is 200-. Further, the etching gas is SF6/C4F8 mixed gas.
Preferably, in the step (2), the ZnO nanocrystals are grown by the following process: placing the Si nano-column array prepared in the step (1) in a ZnO sol-gel solution, using a pulling machine to pull for 1-3 times at the speed of 1-3mm/min, naturally drying, then placing the silicon nano-column array in a resistance furnace, and annealing for 30-120min at the temperature of 150-; further, the resistance furnace is a box-type resistance furnace.
More preferably, the ZnO sol-gel solution is a zinc acetate/ethanol mixed solution.
A ZnO nanocrystalline reinforced Si nanometer column array sensor comprises the sensitive material and wires led out from the periphery of the sensitive material; further, the wire is an Au wire.
The invention has the beneficial effects that:
(1) by controlling the order and the uniformity of the Si nano-pillar array, the distribution uniformity of ZnO nanocrystals is regulated and controlled, and the overall performance of the sensor is improved;
(2) ZnO nanocrystals are distributed on the surface of the Si nano-column, and the sensitivity of the sensor is improved by utilizing the special optical characteristics of the Si nano-column array and the local surface sensitivity of the ZnO nanocrystals.
Drawings
Fig. 1 is a schematic top view of an array of Si nanopillars of example 1;
FIG. 2 is a schematic top view of an Si nanocolumn array having ZnO nanocrystals distributed on the surface thereof in example 1;
FIG. 3 is a cross-sectional view of a ZnO nanocrystal enhanced Si nanorod array sensitive material prepared in example 1;
in the figure: the device comprises a 10-Si substrate, a 11-Si nano-column array, 12-ZnO nanocrystals and 13-Au/Ni electrodes.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A preparation method of a ZnO nanocrystal reinforced Si nanorod array sensitive material comprises the following steps:
(1) preparing a Si nano-pillar array 11: selecting a commercially available p-type Si single crystal wafer with an X-ray rocking curve half-height width smaller than 50arcsec and a resistance smaller than 5 omega as a substrate 10, spin-coating photoresist on the surface of the substrate, taking a metal plate as a mask plate for exposure and development, and then carrying out ICP (inductively coupled plasma) etching with the etching depth of 1000nm to obtain a Si nano-pillar array 11 with the diameter of 250nm and the distance of 400nm from each other, as shown in figure 1;
(2) placing the Si nano-pillar array 11 prepared in the step (1) into a zinc acetate/ethanol mixed solution, pulling for 1 time at a speed of 2mm/min by using a pulling machine, naturally drying, then placing into a resistance furnace, and annealing at 500 ℃ for 30min to obtain ZnO nanocrystals 12 with the particle size of 5nm distributed on the surface of the Si nano-pillar array 11, as shown in FIG. 2;
(3) blocking the Si nano-pillar array by using a mask plate to expose an electrode deposition area, and then evaporating an Au/Ni electrode 13 by adopting a thermal evaporation method to prepare the sensitive material shown in figure 3.
Example 2
The ZnO nanocrystal reinforced Si nanorod array sensitive material was prepared according to the method of example 1, except that the p-type Si single crystal wafer in step (1) was replaced with an n-type Si single crystal wafer of the same specification.
The above embodiments are only for illustrating the technical solutions of the present invention and are not limited thereto, and any modification or equivalent replacement without departing from the spirit and scope of the present invention should be covered within the technical solutions of the present invention.
Claims (3)
1. A ZnO nanocrystal reinforced Si nanorod array sensitive material is characterized by comprising a Si substrate, a Si nanorod array, ZnO nanocrystals and an electrode material, wherein the Si substrate is provided with the Si nanorod array, the surface of the Si nanorod array is distributed with the ZnO nanocrystals, and the top of the Si nanorod array is also provided with the electrode material;
the grain size of the ZnO nanocrystal is 2-10 nm;
the diameter of the Si nano-column array is 50-990nm, the distance between the Si nano-column array and the Si nano-column array is 30-1500nm, and the cross section of the Si nano-column array is centrosymmetric;
the electrode material comprises at least one of Pt, Au and Ni;
the Si substrate is an n-type or p-type Si single chip, the full width at half maximum of an X-ray rocking curve is less than 50arcsec, and the resistance is less than 5 omega;
the electrode is an Au/Ni alloy or a Pt/Au/Ni alloy.
2. A method for preparing the ZnO nanocrystal reinforced Si nanorod array sensitive material as claimed in claim 1, which is characterized by comprising the following steps:
(1) spin-coating photoresist on the surface of the Si substrate, exposing, developing and etching to obtain a Si nano-pillar array;
(2) growing ZnO nanocrystals on the surface of the Si nanorod array;
(3) protecting the part outside the electrode deposition area by using a mask plate, and then evaporating an electrode in the electrode deposition area;
in the step (1), exposing and developing are carried out by taking a metal plate as a mask plate, the etching process is ICP etching, and the etching depth is 200-2000 nm;
in the step (2), the ZnO nanocrystal is obtained by growing the following process: and (2) placing the Si nano-column array prepared in the step (1) in a ZnO sol-gel solution, using a pulling machine to pull for 1-3 times at the speed of 1-3mm/min, naturally drying, then placing in a resistance furnace, and annealing at the temperature of 150-600 ℃ for 30-120 min.
3. A ZnO nanocrystal reinforced Si nanorod array sensor is characterized by comprising the sensitive material of claim 1 and wires led out from the periphery of the sensitive material.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2408573Y (en) * | 1999-12-06 | 2000-11-29 | 中国科学院长春光学精密机械研究所 | Low temperature (normal temperature) field effect gas sensitive element |
| CN101158662A (en) * | 2007-11-02 | 2008-04-09 | 华南理工大学 | Thin film material used for hydrogen gas sensor and preparation method thereof |
| CN102965622A (en) * | 2012-12-19 | 2013-03-13 | 中国科学院微电子研究所 | Preparation method of sensitive film doped with Au or Pt nanocrystals on surface |
| CN104614413A (en) * | 2015-02-09 | 2015-05-13 | 华中科技大学 | Electrodeless semiconductor gas sensor and preparation method thereof |
| CN104713914A (en) * | 2015-02-02 | 2015-06-17 | 华中科技大学 | Semiconductor resistance gas sensor and production method thereof |
| CN105866187A (en) * | 2016-03-25 | 2016-08-17 | 中国科学院高能物理研究所 | Semiconductor gas-sensitive sensor and making method thereof |
| CN107867714A (en) * | 2017-10-26 | 2018-04-03 | 中国工程物理研究院化工材料研究所 | Nanocrystalline SnO2/ graphene composite air-sensitive material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100946701B1 (en) * | 2007-12-10 | 2010-03-12 | 한국전자통신연구원 | Nano-crystalline Composite Oxides Thin Films, Enviromental Gas Sensors Using the Film and Method for Preparing the Sensors |
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- 2018-06-29 CN CN201810700070.6A patent/CN108956712B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2408573Y (en) * | 1999-12-06 | 2000-11-29 | 中国科学院长春光学精密机械研究所 | Low temperature (normal temperature) field effect gas sensitive element |
| CN101158662A (en) * | 2007-11-02 | 2008-04-09 | 华南理工大学 | Thin film material used for hydrogen gas sensor and preparation method thereof |
| CN102965622A (en) * | 2012-12-19 | 2013-03-13 | 中国科学院微电子研究所 | Preparation method of sensitive film doped with Au or Pt nanocrystals on surface |
| CN104713914A (en) * | 2015-02-02 | 2015-06-17 | 华中科技大学 | Semiconductor resistance gas sensor and production method thereof |
| CN104614413A (en) * | 2015-02-09 | 2015-05-13 | 华中科技大学 | Electrodeless semiconductor gas sensor and preparation method thereof |
| CN105866187A (en) * | 2016-03-25 | 2016-08-17 | 中国科学院高能物理研究所 | Semiconductor gas-sensitive sensor and making method thereof |
| CN107867714A (en) * | 2017-10-26 | 2018-04-03 | 中国工程物理研究院化工材料研究所 | Nanocrystalline SnO2/ graphene composite air-sensitive material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 掺杂Sb3+的ZnO纳米晶敏感材料的性能;张丽华 等;《材料研究学报》;19940831;第8卷(第4期);第348-351页 * |
| 花状ZnO纳米晶的合成及其气敏性能研究;张健 等;《黑龙江大学自然科学学报》;20120430;第29卷(第2期);第225-228页 * |
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