CN115015331A - WO with hydrogen gas sensitivity x Pd nano-assembly material hydrogen sensor and preparation method thereof - Google Patents

WO with hydrogen gas sensitivity x Pd nano-assembly material hydrogen sensor and preparation method thereof Download PDF

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CN115015331A
CN115015331A CN202210549106.1A CN202210549106A CN115015331A CN 115015331 A CN115015331 A CN 115015331A CN 202210549106 A CN202210549106 A CN 202210549106A CN 115015331 A CN115015331 A CN 115015331A
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hydrogen
nano
sputtering
assembly material
gas
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谢波
肖作旗
胡军
夏盛杰
钱浩宇
毛稀兵
孙健
周兴泉
张澳雪
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Zhejiang University of Technology ZJUT
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    • 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

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Abstract

The invention discloses WO with hydrogen gas sensitivity x Pd nano-assembly material hydrogen sensor and preparation method thereof, WO of the invention x The Pd nano-assembly material is prepared by cluster beam deposition technology, a double-target cluster sputtering source is utilized, and WO is deposited on the surface of an interdigital electrode with an insulating substrate in sequence x Nano particles and Pd nano particles, namely obtaining WO with different mass proportions x a/Pd mixed nanoparticle assembly material; further, a gas sensor device is realized by using the material, and WO x the/Pd mixed nano particle assembly material is deposited on the surface of the interdigital electrode with the insulating substrate, and can be applied to quantitative measurement of hydrogen concentration. Compared with the prior art, the tungsten oxide and palladium mixed nanoparticle assembly material system has larger specific surface area, and has more reaction sites compared with single tungsten oxide due to the catalytic dissociation capability of the Pd nanoparticles to hydrogen, so that the tungsten oxide and palladium mixed nanoparticle assembly material system can be realized at relatively lower temperatureThe hydrogen sensing function with high sensitivity and quick response is realized.

Description

WO with hydrogen gas sensitivity x Pd nano-assembly material hydrogen sensor and preparation method thereof
Technical Field
The invention relates to the field of gas sensing, in particular to WO with hydrogen gas sensitivity x A Pd nano-assembly material hydrogen sensor and a preparation method thereof.
Background
Hydrogen is a clean energy with wide application prospect, and as a renewable energy source capable of replacing fossil fuel, the hydrogen has been widely applied to a plurality of industrial fields, but the hydrogen is a colorless, tasteless, flammable and explosive gas, the explosion range in the air is 4% -75%, but because the molecular size of the hydrogen is ultra-small, leakage is easy to occur in the processes of production, storage, transportation and use, how to rapidly detect the leakage in a large range is important for the safe utilization of hydrogen energy.
The metal oxide semiconductor gas sensor is a classical chemical gas sensor, and has the advantages of high sensitivity, high response speed, long service life, simple preparation, low cost and the like, so that the metal oxide semiconductor gas sensor is developed into the gas sensor with the highest practical degree and the widest application range at present. Tungsten oxide is an important semiconductor material, the excellent gas sensing characteristic of the tungsten oxide is widely reported to be applied to the field of gas sensors, the traditional tungsten oxide bulk and continuous film have poor gas-sensitive response capability to hydrogen, and the response temperature is often above 250 ℃, so that the application of the tungsten oxide bulk and continuous film in the field of hydrogen sensing is limited.
The invention is proposed to be used in WO x Pd nanoparticles are deposited on the surfaces of the nanoparticles to form a composite assembly material, so that a high-performance hydrogen sensing technology is realized. In this material WO x Nanoparticle hydrogen generationThe Pd nano particles play a role in concerted catalysis to enhance the gas-sensitive performance of hydrogen, the working temperature of the device is reduced to 150 ℃, and the power consumption of the device is obviously reduced.
Disclosure of Invention
The invention aims to solve the problems of high working temperature and poor response performance of the traditional tungsten oxide hydrogen sensing material at present, and the invention aims to provide a hydrogen-sensitive WO x A Pd nano-assembly material hydrogen sensor and a preparation method thereof. The invention provides a method for preparing WO by cluster beam deposition technology by utilizing physical vapor deposition technology x The Pd nano particle assembly material can realize hydrogen sensing, greatly improve the hydrogen sensing performance of tungsten oxide and reduce the working temperature to 150 ℃.
The WO with hydrogen gas sensitivity x The Pd nano-assembly material hydrogen sensor comprises an interdigital electrode with an insulating substrate and tungsten oxide WO deposited on the surface of the interdigital electrode in sequence x Nanoparticles and Pd nanoparticles, tungsten oxide WO x The nano particles and the Pd nano particles are combined into a disordered and uniform mixed structure to form WO x the/Pd mixed nano particle assembly material.
Further, the WO x In the/Pd mixed nano particle assembly material, the mass ratio of the Pd nano particles is 0.5-10%.
The invention also provides the WO with hydrogen gas sensitivity x The preparation method of the Pd nano-assembly material hydrogen sensor comprises the following steps: high purity WO 3 Respectively placing the target material and the high-purity Pd target material on two sputtering guns of cluster beam deposition equipment, placing an interdigital electrode with an insulating substrate in a deposition chamber of a cluster beam deposition system, vacuumizing the whole device, respectively introducing high-purity argon as sputtering gas and buffer gas into the two sputtering guns after the vacuum degree reaches a standard, introducing voltage, and sequentially placing WO (tungsten trioxide) on the two sputtering guns 3 Gasifying the target and Pd target into gaseous molecules or atoms, colliding buffer gas with the gaseous molecules or atoms to form nano particles, forming a nano particle beam by a differential pumping method, and guiding the beam to a deposition chamber of cluster beam deposition equipmentDeposited on the surface of the placed interdigital electrode to obtain WO 3 The Pd nano particle assembly material. After the preparation is finished, the interdigital electrode is taken out and placed in a test cavity, a Gilberi digital source meter is used for connecting stable and unchangeable voltage to the interdigital electrode, and after hydrogen is introduced, the hydrogen reacts with adsorbed oxygen on the surface of a material to change the resistance of the material, so that the current displayed on the source meter changes according to a formula:
Figure DEST_PATH_IMAGE002
whereinI 0 The current values shown on the hydrogen gas supply table were obtained,I 1 the response performance of the material to hydrogen can be calculated by the current value displayed on the source table after hydrogen is introduced.
Further, the WO x In the preparation method of the/Pd nano-assembly material hydrogen sensor, the air pressure in a sputtering cavity is kept at 40-120 Pa.
Further, the WO x In the preparation method of the Pd nano-assembly material hydrogen sensor, WO is added 3 The sputtering power of the target material is set to be 20-25W, the sputtering current is 0.045-0.05A, the sputtering voltage is 450-500V, and the sputtering time is 180-250 s.
Further, the WO x In the preparation method of the/Pd nano-assembly material hydrogen sensor, the sputtering power of the Pd target material is set to be 10-15W, the sputtering current is 0.035-0.042A, and the sputtering voltage is 300-360V.
The beneficial effects obtained by the invention are as follows: the invention uses vapor deposition technology to deposit the nano particle assembly material, compared with the traditional wet chemical method, the prepared material is purer and can be compatible with the existing microelectronic process. The nano particle assembly material formed by sputtering has a higher specific surface area than a film, so that the contact chance with hydrogen can be greatly improved, more reaction sites can be created, the selectivity and sensitivity to the hydrogen are enhanced by taking Pd loaded on the surface as a catalyst, and the working temperature is greatly reduced.
Drawings
FIG. 1 is a schematic structural diagram of a nanoparticle assembly material prepared according to the present invention.
FIG. 2a is a response curve of the nanoparticle assembly material prepared by the present invention for different hydrogen concentrations.
FIG. 2b is a linear fitting relationship between responsivity and hydrogen concentration when the nano particle assembly material prepared by the invention is tested for hydrogen with different concentrations.
In fig. 1: 1 is an interdigital electrode, 2 is WO X Nanoparticles, 3 are Pd nanoparticles.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
WO with hydrogen gas sensitivity x The preparation of the/Pd nano particle assembly material and the sensing device thereof comprises the following steps:
（1）WO x preparation of Pd nanoparticle assembly material: mixing high-purity WO 3 The target material and the high-purity Pd target material are respectively placed on two sputtering guns of cluster beam deposition equipment, the interdigital electrode is placed in a deposition chamber of a cluster beam deposition system, and the whole device is vacuumized to ensure that the vacuum of the deposition chamber reaches 2 x 10 -4 Pa。
To the WO 3 Introducing 70 sccm sputtering gas into a sputtering gun of the target material, introducing 100 sccm buffer gas into the sputtering cavity, wherein the gas pressure in the sputtering cavity is 110 Pa, and then filling WO 3 The sputtering gun of the target is powered on with 22W, the sputtering current is 0.048A, and the sputtering voltage is 465V. The sputtering time was 200 s. The sputtering gas and power supply are turned off.
And then, introducing 70 sccm of sputtering gas into a sputtering gun provided with the Pd target, wherein the gas pressure in the sputtering cavity is 110 Pa, introducing 12W of power, wherein the sputtering current is 0.036A, the sputtering voltage is 323V, and the deposition time is 10 s. To obtain WO x The Pd nano particle assembly material comprises 2% of Pd nano particles by mass.
（2）To the WO obtained above x Performing hydrogen sensitivity performance test on the/Pd nanoparticle assembly material:
will deposit WO x The interdigital electrode of the/Pd nano particle assembly material is placed in the test cavity, and the temperature in the test cavity is heated to 150 ℃ by utilizing the ceramic heating plate. Two ends of the electrode are connected with a Gishili digital source meter, the source meter is used for giving a stable voltage of 1V to two ends of the interdigital electrode, and the current at two ends of the assembly material is read through the source meter.
Controlling hydrogen flow and air flow through a flowmeter, introducing mixed gas (mixed gas pressure is normal pressure) containing hydrogen with certain concentration into a testing cavity, recording current values before and after ventilation, and utilizing:
Figure DEST_PATH_IMAGE004
whereinI 0 The current values shown on the hydrogen gas supply table were obtained,I 1 the current values shown on the source table after hydrogen gas introduction were used. To obtain WO x Quantitative response of/Pd nanoparticle assembly materials to hydrogen. The results are shown in FIG. 2a (kpa in the graph of FIG. 2a, representing H) 2 Units of partial pressure in the mixed gas) and fig. 2 b. It can be seen from the figure that the detection range is 0-100000 ppm, and the response time T 90 Less than 40s, and the responsiveness is 0% -1766%.
The WOx film prepared by the traditional chemical method has the optimal response temperature of 250 ℃ for hydrogen, the response time of 180 s and the maximum response of 87 percent when the hydrogen concentration is 100 ppm. For example, the literature: rhashesh Godbole, Sadia Ameren, Umesh T. Nakate, M. Shaheer Akhtar, Hyung-Shik Shin, Low temperature HFCVD synthesis of a long step oxide film for high pressure hydrogen sensor application, Materials Letters, Volume 254, 2019, Pages 398-.
In conclusion, it can be seen that the present invention is based on WO, compared to the gas sensitive response effect of the tungsten oxide continuous film of the prior art on hydrogen x The sensor made of Pd nano particle assembly material can greatly improve hydrogen sensingThe performance, response temperature of the test can be as low as 150 ℃, and the selectivity and sensitivity to hydrogen are greatly enhanced.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims (6)

1. WO with hydrogen gas sensitivity x The Pd nano-assembly material hydrogen sensor is characterized by comprising interdigital electrodes with an insulating substrate and tungsten oxide WO deposited on the surfaces of the interdigital electrodes in sequence x Nanoparticles and Pd nanoparticles, tungsten oxide WO x The nano particles and the Pd nano particles are combined into a disordered and uniform mixed structure to form WO x the/Pd mixed nano particle assembly material.
2. WO sensitive to hydrogen as claimed in claim 1 x The hydrogen sensor is characterized in that the WO is x In the Pd mixed nano particle assembly material, the mass ratio of the Pd nano particles is 0.5-10%.
3. WO gas-sensitive to hydrogen as claimed in claim 1 x The preparation method of the/Pd nano-assembly material hydrogen sensor is characterized by comprising the following steps:
(1) mixing high-purity WO 3 The Pd target materials are respectively placed on two sputtering guns of the cluster beam deposition equipment, the interdigital electrodes are placed in a deposition chamber of the cluster beam deposition system, and the whole device is vacuumized;
(2) sputtering gas is introduced into the two sputtering guns, and buffer gas is introduced into a sputtering cavity of the cluster beam deposition system;
(3) successively sputtering WO separately 3 And a Pd target, and WOx and Pd nano-particles are deposited on the surface of the interdigital electrode.
4. WO gas-sensitive to hydrogen as claimed in claim 3 x A method for preparing a Pd nano-assembly material hydrogen sensor,the method is characterized in that in the step (2), high-purity argon with the purity of more than 99.99% is used as sputtering gas and buffer gas, and the air pressure in a sputtering cavity is kept at 40-120 Pa.
5. WO gas-sensitive to hydrogen as claimed in claim 3 x The preparation method of the hydrogen sensor of the Pd nano-assembly material is characterized in that in the step (3), WO is added 3 The sputtering power of the target material is set to be 20-25W, the sputtering current is 0.045-0.05A, the sputtering voltage is 450-500V, and the sputtering time is 180-250 s.
6. WO gas-sensitive to hydrogen as claimed in claim 3 x The preparation method of the/Pd nano-assembly material hydrogen sensor is characterized in that in the step (3), the sputtering power of the Pd target material is set to be 10-15W, the sputtering current is 0.035-0.042A, and the sputtering voltage is 300-360V.
CN202210549106.1A 2022-05-20 2022-05-20 WO with hydrogen gas sensitivity x Pd nano-assembly material hydrogen sensor and preparation method thereof Pending CN115015331A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116425200A (en) * 2023-03-06 2023-07-14 江苏大学 Hydrogen gas-sensitive material resistant to humidity interference, semiconductor resistance type hydrogen sensor, intelligent hydrogen sensing system, preparation and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116425200A (en) * 2023-03-06 2023-07-14 江苏大学 Hydrogen gas-sensitive material resistant to humidity interference, semiconductor resistance type hydrogen sensor, intelligent hydrogen sensing system, preparation and application

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