CN112903755A - Carbon dioxide sensor and preparation method thereof - Google Patents

Carbon dioxide sensor and preparation method thereof Download PDF

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CN112903755A
CN112903755A CN202110206629.1A CN202110206629A CN112903755A CN 112903755 A CN112903755 A CN 112903755A CN 202110206629 A CN202110206629 A CN 202110206629A CN 112903755 A CN112903755 A CN 112903755A
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aluminum
gallium nitride
epitaxial wafer
layer
carbon dioxide
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CN112903755B (en
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韩丹
刘琭琭
桑胜波
禚凯
冀健龙
张文栋
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Taiyuan University of Technology
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    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66083—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by variation of the electric current supplied or the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched, e.g. two-terminal devices
    • H01L29/66196—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by variation of the electric current supplied or the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched, e.g. two-terminal devices with an active layer made of a group 13/15 material
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    • H01L29/66212—Schottky diodes
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    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
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Abstract

The invention discloses a carbon dioxide sensor and a preparation method thereof, belongs to the technical field of carbon dioxide sensors, and aims to solve the technical problems that: the improvement of a carbon dioxide sensor hardware structure and a preparation method thereof is provided; the technical scheme for solving the technical problem is as follows: generating a gallium nitride/aluminum gallium nitride epitaxial wafer with high crystal quality on a silicon substrate, depositing an aluminum electrode by utilizing an electrode preparation process after etching one end of the epitaxial wafer, directly photoetching the other end of the epitaxial wafer into a platinum electrode, and coating a mixture of PEI and starch between the two electrodes, thereby obtaining the carbon dioxide sensor with wide detection range, reusability, good stability and high material utilization rate; the carbon dioxide sensor prepared by the invention has the beneficial effects of wide detection range, low price, easy detection, reusability and the like; the invention is applied to a carbon dioxide detection circuit.

Description

Carbon dioxide sensor and preparation method thereof
Technical Field
The invention discloses a carbon dioxide sensor and a preparation method thereof, and belongs to the technical field of carbon dioxide sensors.
Background
With the continuous development of science and technology, the production efficiency is improved by increasing the content of carbon dioxide in the processes of making carbonated beverages, welding, producing fruits and vegetables and the like, and once the carbon dioxide with the concentration of more than 20 percent is absorbed in a human body, carbonic acid is formed in blood to cause acidosis; therefore, the development of a gas sensor for detecting the concentration of carbon dioxide can help to improve the production efficiency and ensure the physical health of operators.
The traditional carbon dioxide sensor detects gas by adopting an infrared detection technology, is expensive, and has the concentration range of only 0-0.5 percent, so that the carbon dioxide sensor with low cost and wide detection range is necessary to be manufactured; when the currently used gallium nitride gas sensor is used for detecting the concentration of carbon dioxide, the detection range can reach 0-50%, and the defect that the detection range of the traditional carbon dioxide sensor is narrow can be well overcome; however, when the gallium nitride is applied to a circuit for detecting carbon dioxide, both ends of the gallium nitride are required to be etched, and then metal is sequentially sputtered to the middle of the gallium nitride and the aluminum gallium nitrogen by a magnetron sputtering method to form an electrode. In summary, a carbon dioxide sensor with a wide detection range, simple manufacturing steps and a long service life needs to be found in the field of the current carbon dioxide sensor.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to solve the technical problems that: an improvement of a carbon dioxide sensor hardware structure and a preparation method thereof are provided.
In order to solve the technical problems, the invention adopts the technical scheme that: the utility model provides a carbon dioxide sensor, includes silicon substrate layer and the epitaxial wafer of deposit on silicon substrate layer, the epitaxial wafer specifically is high crystal quality gallium nitride or aluminium gallium nitride epitaxial wafer, the epitaxial wafer from the bottom up deposits in proper order has: the device comprises an aluminum nitride buffer layer, an aluminum gallium nitride buffer layer, a gallium nitride voltage-resisting layer, a gallium nitride layer, an aluminum nitride buffer layer, an aluminum gallium nitride layer and a gallium nitride cap layer;
etching one end of the epitaxial wafer and depositing an aluminum electrode by adopting magnetron sputtering, and forming a platinum electrode at the other end of the epitaxial wafer by adopting a photoetching mode;
in addition, a mixture consisting of polyethyleneimine and starch is coated on the top of the epitaxial wafer and between the aluminum electrode and the platinum electrode;
and a passivation layer is coated on the tops of the aluminum electrode and the platinum electrode.
The thickness of the silicon substrate layer is 0-2000 um;
the thickness of the aluminum nitride buffer layer is 100-300 nm;
the thickness of the AlGaN buffer layer is 1000-2000 nm;
the thickness of the gallium nitride voltage-proof layer is 1500-;
the thickness of the gallium nitride layer is 200-400 nm;
the thickness of the aluminum nitride buffer layer is 0-2 nm;
the thickness of the aluminum gallium nitride layer is 10-20 nm;
the thickness of the gallium nitride cap layer is 0-2 nm;
the thickness of the aluminum electrode is 120nm-150 nm;
the thickness of the platinum electrode is 20nm-50 nm.
The passivation layer is specifically one or more of silicon nitride, silicon aluminum nitrogen and aluminum oxide;
the thickness of the passivation layer is 10-30 nm;
the passivation layer does not completely cover the aluminum electrode and the platinum electrode, and a groove for circuit wiring is formed in the uncovered part of the passivation layer.
The mixing ratio of the polyethyleneimine to the starch in the mixture is 2: 1.
A preparation method of a carbon dioxide sensor comprises the following preparation steps:
the method comprises the following steps: growing a gallium nitride or aluminum gallium nitride epitaxial wafer with high crystal quality on the silicon substrate layer;
step two: etching the epitaxial wafer by adopting molten sodium hydroxide or potassium hydroxide at one end of the epitaxial wafer to form a cuboid groove, depositing an aluminum electrode with the thickness of 120nm-150nm in the gallium nitride layer at the groove by adopting a magnetron sputtering technology, and forming ohmic contact between the aluminum electrode and the epitaxial wafer;
a platinum electrode with the thickness of 20nm-50nm is manufactured on the surface layer of the other end of the epitaxial wafer by adopting a photoetching technology, so that the platinum electrode and the AlGaN layer form a Schottky diode;
step three: depositing a passivation layer on the surfaces of the aluminum electrode and the platinum electrode;
step four: mixing polyethyleneimine and starch together according to the proportion of 2:1, uniformly mixing the mixture by using a magnetic stirrer, and coating the uniformly mixed mixture solution on an epitaxial wafer and between an aluminum electrode and a platinum electrode;
step five: and (3) putting the whole epitaxial wafer in a drying oven to evaporate the solvent, and forming a stable film on the epitaxial wafer to finish the manufacture of the whole carbon dioxide sensor device.
The specific steps of the first step are as follows: the method comprises the steps of sequentially growing an aluminum nitride buffer layer of 200nm, an aluminum gallium nitride buffer layer of 1600nm, a gallium nitride voltage-withstanding layer of 2200nm, gallium nitride of 300nm, an aluminum nitride buffer layer of 1nm, an aluminum gallium nitride layer of 18nm and a gallium nitride cap layer of 1nm on a silicon substrate layer of 1000 microns, and preparing an epitaxial wafer containing gallium nitride or aluminum gallium nitride with high crystal quality after the growth is finished.
And in the second step, the etching thickness of the epitaxial slice material is 100 nm.
In the second step, the epitaxial wafer with the prepared electrode needs to be split, so that the epitaxial wafer is uniformly divided into epitaxial wafer units of 5mm multiplied by 5 mm;
the specification of the aluminum electrode in the 5mm x 5mm epitaxial wafer is 1mm x 5mm x 150nm, and the specification of the platinum electrode is 1mm x 5mm x 50 nm.
The specification of the passivation layer deposited in step three was 1mm 4mm 20 nm.
Compared with the prior art, the invention has the beneficial effects that: the invention prepares a novel carbon dioxide sensor by compounding a two-dimensional electronic channel in the middle of gallium nitride/aluminum gallium nitride with Polyethyleneimine (PEI) and starch mixture, aims at the problems of narrow detection range, more complex manufacture of gallium nitride-based electrodes, short service life and the like of the existing carbon dioxide sensor, designs a silicon substrate as a base material by utilizing the two-dimensional electronic channel in the middle of gallium nitride/aluminum gallium nitride and PEI to have the characteristics of high sensitivity, good selectivity, good device stability and the like on carbon dioxide under the action of starch, prepares a gallium nitride/aluminum gallium nitride epitaxial wafer with high crystal quality, manufactures a platinum electrode on the epitaxial wafer by utilizing a photoetching technology to form a Schottky diode to replace a common electrode, and finally finishes the preparation by a passivation layer protective material and the electrode, wherein the detection range of the prepared carbon dioxide sensor can be expanded from 0-0.5 percent to 0-50 percent, meanwhile, the manufacturing cost is reduced, and the service life is long; meanwhile, the manufacturing process is simplified in the preparation process, the etching process of the carbon dioxide sensor manufactured by the invention is reduced, the gallium nitride/aluminum gallium nitride material is fully utilized, and in addition, the epitaxial wafer used in the sensor has good biocompatibility and environmental friendliness.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic structural diagram of an epitaxial wafer of a carbon dioxide sensor according to the present invention;
FIG. 2 is a schematic structural view of an electrode of a carbon dioxide sensor according to the present invention;
FIG. 3 is a schematic structural diagram of a passivation layer of a carbon dioxide sensor according to the present invention;
FIG. 4 is a schematic diagram of a circuit configuration of the carbon dioxide sensor according to the present invention;
in the figure: 11 is an epitaxial wafer, 1 is a silicon substrate layer, 2 is an aluminum nitride buffer layer, 3 is an aluminum gallium nitride buffer layer, 4 is a gallium nitride voltage-resistant layer, 5 is a gallium nitride layer, 6 is an aluminum nitride buffer layer, 7 is an aluminum gallium nitride layer, 8 is a gallium nitride capping layer, 9 is an aluminum electrode, 10 is a platinum electrode, 21 is a mixture, and 22 is a passivation layer.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly and clearly understood, the present invention will be further clearly and completely described below with reference to the embodiments and the accompanying drawings in the present invention; it is to be understood that the specific embodiments described herein are merely illustrative of some, and not restrictive, of the embodiments of the invention; the technical solutions of the present invention are described in detail below with reference to the embodiments and the drawings, but the scope of protection is not limited thereto.
As shown in fig. 1 to 3, the carbon dioxide sensor provided by the present invention belongs to the technical field of gas sensors, and particularly relates to a novel electrode manufacturing step and a carbon dioxide sensor with a wide detection range, which can be applied to a circuit for detecting carbon dioxide, wherein the steps for manufacturing the sensor in the figure include:
firstly, growing a 200nm aluminum nitride buffer layer, a 1600nm aluminum gallium nitride buffer layer, a 2200nm gallium nitride voltage-withstanding layer, 300nm gallium nitride, a 1nm aluminum gallium nitride buffer layer, an 18nm aluminum gallium nitride layer and a 1nm gallium nitride cap layer on a 1000um silicon substrate in sequence, and further generating a high-crystal-quality gallium nitride/aluminum gallium nitride epitaxial wafer as shown in figure 1;
etching one end of the epitaxial wafer by using molten NaOH/KOH to form a groove, and depositing an aluminum electrode with the thickness of 120nm-150nm on the gallium nitride layer at the groove by adopting a magnetron sputtering technology to form ohmic contact between the aluminum electrode and the epitaxial wafer, wherein the ohmic contact is formed between the aluminum electrode and the epitaxial wafer, and the ohmic contact is shown in figure 2;
manufacturing a platinum electrode with the thickness of 20nm-50nm on the surface layer of the epitaxial wafer by adopting a photoetching technology, enabling the platinum electrode and the AlGaN to form a Schottky diode, and splitting the generated epitaxial wafer to uniformly divide the epitaxial wafer with the manufactured electrode into 5mm multiplied by 5mm epitaxial wafers;
fourthly, covering one or more of silicon nitride, silicon aluminum nitrogen and aluminum oxide on the surface of the electrode to be used as a passivation layer, wherein the volume of the passivation layer is 1mm x 4mm x 20 nm;
fifthly, mixing the polyethyleneimine and the starch together according to the ratio of 2:1, uniformly mixing the polyethyleneimine and the starch by using a magnetic stirrer, coating the uniformly mixed solution on an epitaxial wafer and between two electrodes, putting the epitaxial wafer and the electrodes in a drying box to evaporate the solvent, forming a stable film on the epitaxial wafer, and finally finishing the preparation of the gas sensor, wherein the preparation is shown in figure 3.
As shown in figure 4, when the sensor prepared by the invention is used, the prepared carbon dioxide sensor is connected with a power supply, an ammeter and a single chip microcomputer, the single chip microcomputer is used for simultaneously controlling a buzzer and a display, the buzzer is controlled to act by compiling an if else statement in a c language, when the concentration of carbon dioxide corresponding to the ammeter exceeds 10%, the single chip microcomputer sends out a signal to control the buzzer to sound for alarming, and a user is reminded to wear a protection tool or ventilate a corresponding closed space when entering the space.
In the use, still can add data storage module to the singlechip, store the measuring data, realize that the carbon dioxide concentration data in the time quantum that the user did not carry out real-time observation also can keep, conveniently later carry out data calling, analysis, generate the report.
The above description is only for illustrating the technical concept and features of the present invention, and it is not deemed that the specific embodiments of the present invention are limited thereto, and it will be apparent to those skilled in the art of the present invention that several simple deductions or substitutions can be made without departing from the present invention, for example, to fully utilize gallium nitride/aluminum gallium nitride material, directly eliminate the etching of both ends, place the electrodes on both sides of the epitaxial wafer, and cover the passivation layer around the electrodes, etc., and all equivalent changes or modifications made according to the spirit of the present invention should be considered as belonging to the scope of patent protection defined by the claims filed.

Claims (9)

1. A carbon dioxide sensor comprising a silicon substrate layer (1) and an epitaxial wafer (11) deposited on the silicon substrate layer (1), characterized in that: epitaxial wafer (11) are high crystal quality gallium nitride or aluminium gallium nitride epitaxial wafer specifically, epitaxial wafer (11) from the bottom up deposits in proper order has: the device comprises an aluminum nitride buffer layer (2), an aluminum gallium nitride buffer layer (3), a gallium nitride voltage-withstanding layer (4), a gallium nitride layer (5), an aluminum nitride buffer layer (6), an aluminum gallium nitride layer (7) and a gallium nitride cap layer (8);
etching one end of the epitaxial wafer (11) and depositing an aluminum electrode (9) by adopting magnetron sputtering, and forming a platinum electrode (10) at the other end of the epitaxial wafer (11) by adopting a photoetching mode;
in addition, a mixture (21) consisting of polyethyleneimine and starch is coated on the top of the epitaxial wafer (11) and between the aluminum electrode (9) and the platinum electrode (10);
the aluminum electrode (9) and the platinum electrode (10) are also coated with a passivation layer (22) on top.
2. A carbon dioxide sensor according to claim 1, wherein: the thickness of the silicon substrate layer (1) is 0-2000 um;
the thickness of the aluminum nitride buffer layer (2) is 100-300 nm;
the thickness of the AlGaN buffer layer (3) is 1000-2000 nm;
the thickness of the gallium nitride voltage-proof layer (4) is 1500-3000 nm;
the thickness of the gallium nitride layer (5) is 200-400 nm;
the thickness of the aluminum nitride buffer layer (6) is 0-2 nm;
the thickness of the aluminum gallium nitride layer (7) is 10-20 nm;
the thickness of the gallium nitride cap layer (8) is 0-2 nm;
the thickness of the aluminum electrode (9) is 120nm-150 nm;
the thickness of the platinum electrode (10) is 20nm-50 nm.
3. A carbon dioxide sensor according to claim 1, wherein: the passivation layer (22) is specifically one or more of silicon nitride, silicon aluminum nitrogen and aluminum oxide;
the thickness of the passivation layer (22) is 10-30 nm;
the passivation layer (22) does not completely cover the aluminum electrode (9) and the platinum electrode (10), and a groove for circuit wiring is formed in the uncovered part of the passivation layer (22).
4. A carbon dioxide sensor according to claim 1, wherein: the mixing ratio of the polyethyleneimine to the starch in the mixture (21) is 2: 1.
5. A preparation method of a carbon dioxide sensor is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
the method comprises the following steps: growing a gallium nitride or aluminum gallium nitride epitaxial wafer (11) with high crystal quality on the silicon substrate layer (1);
step two: etching the epitaxial wafer (11) by adopting molten sodium hydroxide or potassium hydroxide at one end of the epitaxial wafer (11) to form a cuboid groove, depositing an aluminum electrode (9) with the thickness of 120nm-150nm in the gallium nitride layer (5) at the groove by adopting a magnetron sputtering technology, and forming ohmic contact between the aluminum electrode (9) and the epitaxial wafer (11);
manufacturing a platinum electrode (10) with the thickness of 20nm-50nm on the surface layer at the other end of the epitaxial wafer (11) by adopting a photoetching technology, and enabling the platinum electrode (10) and the aluminum gallium nitride layer (7) to form a Schottky diode;
step three: depositing a passivation layer (22) on the surfaces of the aluminum electrode (9) and the platinum electrode (10);
step four: mixing polyethyleneimine and starch together according to the ratio of 2:1, uniformly mixing by using a magnetic stirrer, and coating a uniformly mixed mixture (21) solution on an epitaxial wafer (11) and between an aluminum electrode (9) and a platinum electrode (10);
step five: and (3) putting the whole epitaxial wafer (11) in a drying oven to evaporate the solvent, and forming a stable film on the epitaxial wafer (11) to finish the manufacture of the whole carbon dioxide sensor device.
6. The method for manufacturing a carbon dioxide sensor according to claim 5, wherein: the specific steps of the first step are as follows: the method comprises the steps of sequentially growing an aluminum nitride buffer layer (2) of 200nm, an aluminum gallium nitride buffer layer (3) of 1600nm, a gallium nitride voltage-withstanding layer (4) of 2200nm, gallium nitride (5) of 300nm, an aluminum nitride buffer layer (6) of 1nm, an aluminum gallium nitride layer (7) of 18nm and a gallium nitride cap layer (8) of 1nm on a silicon substrate layer (1) of 1000 microns, and preparing an epitaxial wafer (11) containing gallium nitride or gallium aluminum nitride with high crystal quality after the growth is finished.
7. The method for manufacturing a carbon dioxide sensor according to claim 6, wherein: and in the second step, the etching thickness of the epitaxial wafer (11) material is 100 nm.
8. The method for manufacturing a carbon dioxide sensor according to claim 7, wherein: in the second step, the epitaxial wafer (11) with the prepared electrodes needs to be split, so that the epitaxial wafer (11) is uniformly divided into epitaxial wafer units of 5mm multiplied by 5 mm;
the specification of the aluminum electrode (9) in the 5mm x 5mm epitaxial wafer (11) is 1mm x 5mm x 150nm, and the specification of the platinum electrode (10) is 1mm x 5mm x 50 nm.
9. The method for manufacturing a carbon dioxide sensor according to claim 8, wherein: the passivation layer (22) deposited in step three has a specification of 1mm 4mm 20 nm.
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