CN114152652A - Preparation method of integrated MEMS hydrogen sensor - Google Patents

Preparation method of integrated MEMS hydrogen sensor Download PDF

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CN114152652A
CN114152652A CN202111485555.6A CN202111485555A CN114152652A CN 114152652 A CN114152652 A CN 114152652A CN 202111485555 A CN202111485555 A CN 202111485555A CN 114152652 A CN114152652 A CN 114152652A
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mems
ald
sno
deposition
preparation
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胡庆敏
徐甲强
张景韬
王晨
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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

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Abstract

The invention relates to the technical field of gas sensors, in particular to a preparation method of an integrated MEMS hydrogen sensor, which comprises the steps of cleaning and drying an MEMS, transferring the MEMS into an ALD reactor, and depositing SnO by using tetra (dimethylamino) tin (IV) and water as precursors2Thin film, controlled ALD SnO2Cycle number of deposition on MEMS to obtain SnO with different thicknesses2Film, 150 cycles of ALD-SnO deposition in MEMS2NiO is deposited continuously on the surface of the substrate to form nickel cyclopentadienyl (NiCp)2) And O3For precursor, deposition temperature 270 ℃ for NiCp2Varying the cycle number of ALD NiO deposition on MEMS to obtain NiO-SnO with different ratios2Compared with the prior art, the invention accurately controls the size of nanometer or the thickness of a film through atomic layer deposition, and realizes the preparation of the MEMS sensor with high strength, high sensitivity and stability.

Description

Preparation method of integrated MEMS hydrogen sensor
Technical Field
The invention relates to the technical field of gas sensors, in particular to a preparation method of an integrated MEMS hydrogen sensor.
Background
As is well known, H2Is a colorless and odorless gas, and is considered to be an attractive alternative energy source and a sustainable energy carrier due to the relatively low influence on the environment. As the most abundant element in the universe, H2Is a very promising thing on the earth "The fuel is clean because the only by-product of the combustion reaction is water. However H2Leakage of molecules above a certain critical concentration can cause serious explosions and be extremely lethal. Thus, appropriate instrumentation was developed to determine and control H during production, transport, storage and utilization2The content becomes more and more important and urgent.
Various gas-sensitive performance influencing factors such as morphology, crystal face and size have been reported in research. When the particle size of the nano sensitive material is larger than the Debye length, the influence of the particle size change on the sensitive performance is small, and the gas sensitive response is gradually increased along with the reduction of the particle size, so that the reduction of the diameter of the nano particles is one of effective means for improving the sensitive performance.
However, the traditional preparation methods such as a drop coating method and a spin coating method are difficult to prepare uniform films on the MEMS, and the gas sensitive material close to the thickness of the electron depletion layer generally has a small particle size and a high working temperature, so that nanoparticles of the gas sensitive material are easily agglomerated at the working temperature, thereby reducing the response and stability of the gas sensitive material. Meanwhile, the sensitive film (the thickness is usually in micron level) prepared by the traditional dripping method increases the collision probability of gas molecules and sensitive materials due to particle accumulation, Knudsen diffusion and other gas diffusion modes, but the bottom of the sensitive film is difficult to react with the gas molecules.
Therefore, the invention designs an integrated MEMS hydrogen sensor preparation method, and realizes the preparation of an integrated NiO/SnO2 ultrathin heterogeneous gas-sensitive film on an MEMS in situ by ALD (atomic layer deposition), so that the MEMS sensor with high bonding strength, high sensitivity and long-term stability is prepared.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an integrated MEMS hydrogen sensor, which is characterized in that an integrated NiO/SnO2 ultrathin heterogeneous gas-sensitive film is constructed on an MEMS in situ by ALD (atomic layer deposition) to realize the preparation of the MEMS sensor with high bonding strength, high sensitivity and long-term stability.
In order to achieve the above object, the present invention provides a method for manufacturing an integrated MEMS hydrogen sensor, comprising the steps of:
s1: cleaning and drying the MEMS;
s2: transferring the MEMS into an ALD reactor;
s3: deposition of SnO using tetrakis (dimethylamino) tin (IV) and water as precursors2A film;
s4: SnO by controlling ALD2Cycle number of deposition on MEMS to obtain SnO with different thicknesses2A film;
s5: ALD-SnO deposition in MEMS2NiO is continuously deposited on the surface;
s6: with nickel cyclopentadienyl (NiCp)2) And O3For the precursor, the deposition temperature was controlled at 270 ℃;
s7: for NiCp2The pulse, exposure and purging time of the O3 is respectively 0.03-100 seconds, 0.03-300 seconds and 5-1200 seconds, and the pulse, exposure and purging time of the O3 is respectively 0.03-100 seconds, 0.03-300 seconds and 0.03-1200 seconds;
s8: different proportions of NiO-SnO are obtained by changing cycle times of ALD NiO deposition on MEMS2Sensitive material of the interface site.
S9: and aging in situ for 12 hours to obtain the MEMS hydrogen sensor.
The temperature of the precursor in the S3 is 10-120 ℃.
ALD is an atomic layer deposition synthesis preparation technique.
The MEMS is one of semiconductor silicon, germanium, gallium arsenide, niobium metal, and quartz crystal.
Compared with the prior art, the method has the advantages that the size or thickness of the nano particles is accurately controlled at the atomic level through the atomic layer deposition technology, the problems of slow gas diffusion, particle agglomeration and the like in the traditional drop coating method for preparing the sensitive film are effectively solved, the advantages of accurate atomic scale regulation, in-situ integrated structure and the like are shown, the thermodynamic stability and gas sensitivity performance of the gas sensitive film are obviously improved, the integrated NiO/SnO2 ultrathin heterogeneous gas sensitive film is constructed in situ on the MEMS through ALD, and the preparation of the MEMS sensor with high bonding strength, high sensitivity and long-term stability is realized.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings.
Referring to fig. 1, the invention provides a preparation method of an integrated MEMS hydrogen sensor, comprising the following steps:
s1: cleaning and drying the MEMS;
s2: transferring the MEMS into an ALD reactor;
s3: deposition of SnO using tetrakis (dimethylamino) tin (IV) and water as precursors2A film;
s4: ALD SnO control by automated instrumentation2Cycle number of deposition on MEMS to obtain SnO with different thicknesses2A film;
s5: ALD-SnO deposition in MEMS2NiO is continuously deposited on the surface;
s6: with nickel cyclopentadienyl (NiCp)2) And O3For the precursor, the deposition temperature was controlled at 270 ℃;
s7: for NiCp2The pulse, exposure and purging time of the O3 is respectively 0.03-100 seconds, 0.03-300 seconds and 5-1200 seconds, and the pulse, exposure and purging time of the O3 is respectively 0.03-100 seconds, 0.03-300 seconds and 0.03-1200 seconds;
s8: different proportions of NiO-SnO are obtained by changing the cycle number of ALD NiO deposition on MEMS through an automatic control instrument2Sensitive material of the interface site.
S9: and aging in situ for 12 hours to obtain the MEMS hydrogen sensor.
The temperature of the precursor in the S3 is 10-120 ℃.
ALD is an atomic layer deposition synthesis preparation technique.
The MEMS is one of semiconductor silicon, germanium, gallium arsenide, niobium metal, and quartz crystal.
Example 1:
s1: cleaning and drying the MEMS;
s2: transferring the MEMS into an ALD reactor;
s3: deposition of SnO using tetrakis (dimethylamino) tin (IV) and water as precursors2A film;
s4: ALD SnO control by automated instrumentation2Cycle number of deposition on MEMSObtaining SnO with different thicknesses2A film;
s5: ALD-SnO deposition in MEMS2NiO is continuously deposited on the surface;
s6: with nickel cyclopentadienyl (NiCp)2) And O3For the precursor, the deposition temperature was controlled at 270 ℃;
s7: for NiCp2Respectively for 0.03, and 5 seconds, and for all 0.03 seconds to O3;
s8: different proportions of NiO-SnO are obtained by changing the cycle number of ALD NiO deposition on MEMS through an automatic control instrument2Sensitive material of the interface site.
S9: and aging in situ for 12 hours to obtain the MEMS hydrogen sensor.
The temperature of the precursor in S3 was 10 ℃.
ALD is an atomic layer deposition synthesis preparation technique.
MEMS are semiconductor silicon.
Example 2:
s1: cleaning and drying the MEMS;
s2: transferring the MEMS into an ALD reactor;
s3: deposition of SnO using tetrakis (dimethylamino) tin (IV) and water as precursors2A film;
s4: ALD SnO control by automated instrumentation2Cycle number of deposition on MEMS to obtain SnO with different thicknesses2A film;
s5: ALD-SnO deposition in MEMS2NiO is continuously deposited on the surface;
s6: with nickel cyclopentadienyl (NiCp)2) And O3For the precursor, the deposition temperature was controlled at 270 ℃;
s7: for NiCp2Respectively 100 seconds, 300 seconds, and 1200 seconds, and to O3 for 100 seconds, 300 seconds, and 1200 seconds;
s8: different proportions of NiO-SnO are obtained by changing the cycle number of ALD NiO deposition on MEMS through an automatic control instrument2Sensitive material of the interface site.
S9: and aging in situ for 12 hours to obtain the MEMS hydrogen sensor.
The temperature of the precursor in S3 was 120 ℃.
ALD is an atomic layer deposition synthesis preparation technique.
The MEMS is a quartz crystal.
Example 3:
s1: cleaning and drying the MEMS;
s2: transferring the MEMS into an ALD reactor;
s3: deposition of SnO using tetrakis (dimethylamino) tin (IV) and water as precursors2A film;
s4: ALD SnO control by automated instrumentation2Cycle number of deposition on MEMS to obtain SnO with different thicknesses2A film;
s5: ALD-SnO deposition in MEMS2NiO is continuously deposited on the surface;
s6: with nickel cyclopentadienyl (NiCp)2) And O3For the precursor, the deposition temperature was controlled at 270 ℃;
s7: for NiCp2Respectively 50 seconds, and 600 seconds, and for O3, respectively 50 seconds, 150 seconds, and 600 seconds;
s8: different proportions of NiO-SnO are obtained by changing the cycle number of ALD NiO deposition on MEMS through an automatic control instrument2Sensitive material of the interface site.
S9: and aging in situ for 12 hours to obtain the MEMS hydrogen sensor.
The temperature of the precursor in S3 was 60 ℃.
ALD is an atomic layer deposition synthesis preparation technique.
The MEMS is one of semiconductor silicon, germanium, gallium arsenide, niobium metal, and quartz crystal.
Atomic Layer Deposition (ALD) is a bottom-up synthesis/fabrication technique that allows precise control of nanoparticle size or film thickness at the atomic level due to the self-limiting nature of its surface reactions. The ALD film is a compact film due to the growth characteristics, so that the problems of slow gas diffusion, particle agglomeration and the like in the conventional drop coating method for preparing a sensitive film can be effectively solved. Meanwhile, compared with the traditional dripping coating method, spin coating method or dip coating method, the ALD method has the advantages of accurate atomic scale regulation, in-situ integrated structure and the like, and has obvious advantages of improving the thermodynamic stability and the gas sensitivity performance of the gas sensitive film. Due to the unique advantages of the ALD technology, the ALD technology can be widely applied to the regulation and control of sensing material structures, the surface modification of materials and the construction of new materials. Therefore, it is feasible to build an integrated thin film of zinc oxide using ALD.
In-situ construction of integrated SnO on MEMS (micro-electromechanical system) by ALD (atomic layer deposition)2The gas-sensitive film realizes the preparation of the MEMS sensor with high bonding strength, high sensitivity and long-term stability. The process can effectively improve the consistency of the MEMS sensor.
In-situ construction of integrated NiO/SnO on MEMS (micro-electromechanical system) by ALD (atomic layer deposition)2The ultrathin heterogeneous gas-sensitive film realizes the preparation of the MEMS sensor with high bonding strength, high sensitivity and long-term stability.
Integrated SnO preparation on MEMS wafer by ALD method2And NiO/SnO2The ALD preparation process of the ultrathin heterogeneous gas-sensitive film can realize high-flux, consistent and uniform preparation, and improve the preparation efficiency of the MEMS hydrogen sensor.
The above is only a preferred embodiment of the present invention, and is only used to help understand the method and the core idea of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
The method solves the problems that the prior art is difficult to prepare a uniform film on the MEMS, and nanoparticles of the gas-sensitive material are easy to agglomerate at the working temperature, so that the response and the stability of the gas-sensitive material are reduced, and the integrated NiO/SnO is constructed on the MEMS in situ by utilizing ALD (atomic layer deposition)2The ultra-thin heterogeneous gas-sensitive film realizes the preparation of the MEMS sensor with high bonding strength, high sensitivity and long-term stability, the ALD preparation process can realize the preparation with high flux, consistency and uniformity,the preparation efficiency of the MEMS hydrogen sensor is improved, the ALD integrated film has extremely high mechanical strength, consistency and uniformity, the bonding strength of the ALD integrated film is 140 times that of the ALD integrated film of the common method, the in-situ preparation of MEMS wafers below 8 inches can be realized, and SnO2And NiO/SnO2The ALD integrated film has excellent hydrogen sensing performance, and compared with a traditional method, the MEMS sensor has the characteristics of low resistance, high sensitivity, low power consumption and the like.

Claims (4)

1. A preparation method of an integrated MEMS hydrogen sensor is characterized by comprising the following steps:
s1: cleaning and drying the MEMS;
s2: transferring the MEMS into an ALD reactor;
s3: deposition of SnO using tetrakis (dimethylamino) tin (IV) and water as precursors2A film;
s4: SnO by controlling ALD2Cycle number of deposition on MEMS to obtain SnO with different thicknesses2A film;
s5: ALD-SnO deposition in MEMS2NiO is continuously deposited on the surface;
s6: with nickel cyclopentadienyl (NiCp)2) And O3For the precursor, the deposition temperature was controlled at 270 ℃;
s7: for the NiCp2The pulse, exposure and purging time of the O3 is respectively 0.03-100 seconds, 0.03-300 seconds and 5-1200 seconds, and the pulse, exposure and purging time of the O3 is respectively 0.03-100 seconds, 0.03-300 seconds and 0.03-1200 seconds;
s8: different proportions of NiO-SnO are obtained by changing cycle times of ALD NiO deposition on MEMS2Sensitive material of the interface site.
S9: and aging in situ for 12 hours to obtain the MEMS hydrogen sensor.
2. The preparation method of the integrated MEMS hydrogen sensor according to claim 1, characterized in that: the temperature of the precursor in the S3 is 10-120 ℃.
3. The preparation method of the integrated MEMS hydrogen sensor according to claim 1, characterized in that: the ALD is an atomic layer deposition synthesis preparation technique.
4. The preparation method of the integrated MEMS hydrogen sensor according to claim 1, characterized in that: the MEMS is one of semiconductor silicon, germanium, gallium arsenide, niobium metal and quartz crystal.
CN202111485555.6A 2021-12-07 2021-12-07 Preparation method of integrated MEMS hydrogen sensor Pending CN114152652A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115710695A (en) * 2022-11-08 2023-02-24 上海大学 Integrated wafer-level hydrogen sulfide gas-sensitive film and preparation method of single MEMS hydrogen sulfide gas-sensitive film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100270626A1 (en) * 2009-04-27 2010-10-28 Raisanen Petri I Atomic layer deposition of hafnium lanthanum oxides
CN109709192A (en) * 2018-12-14 2019-05-03 复旦大学 It is a kind of based on tungsten oxide/tin oxide core-shell nano chip architecture air-sensitive nano material, preparation process and its application
CN110579526A (en) * 2019-09-03 2019-12-17 华中科技大学 Field effect transistor gas sensor and array preparation method thereof
CN113702447A (en) * 2020-05-22 2021-11-26 中国科学院苏州纳米技术与纳米仿生研究所 Gallium oxide nano-structure device and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100270626A1 (en) * 2009-04-27 2010-10-28 Raisanen Petri I Atomic layer deposition of hafnium lanthanum oxides
CN109709192A (en) * 2018-12-14 2019-05-03 复旦大学 It is a kind of based on tungsten oxide/tin oxide core-shell nano chip architecture air-sensitive nano material, preparation process and its application
CN110579526A (en) * 2019-09-03 2019-12-17 华中科技大学 Field effect transistor gas sensor and array preparation method thereof
CN113702447A (en) * 2020-05-22 2021-11-26 中国科学院苏州纳米技术与纳米仿生研究所 Gallium oxide nano-structure device and preparation method and application thereof

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Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115710695A (en) * 2022-11-08 2023-02-24 上海大学 Integrated wafer-level hydrogen sulfide gas-sensitive film and preparation method of single MEMS hydrogen sulfide gas-sensitive film

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