CN112834579A - Semiconductor gas sensor, preparation method and application thereof - Google Patents
Semiconductor gas sensor, preparation method and application thereof Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims abstract description 11
- 238000004770 highest occupied molecular orbital Methods 0.000 claims abstract description 9
- 238000012546 transfer Methods 0.000 claims abstract description 7
- 239000004047 hole gas Substances 0.000 claims abstract description 6
- 230000005533 two-dimensional electron gas Effects 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims description 32
- 230000007547 defect Effects 0.000 claims description 23
- 238000001514 detection method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 230000008859 change Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000009832 plasma treatment Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 238000005468 ion implantation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 229910002601 GaN Inorganic materials 0.000 description 23
- 239000000463 material Substances 0.000 description 13
- 230000035945 sensitivity Effects 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 229910002704 AlGaN Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910001872 inorganic gas Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- G01N27/129—Diode type sensors, e.g. gas sensitive Schottky diodes
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Abstract
The invention discloses a semiconductor gas sensor and a preparation method and application thereof. The semiconductor gas sensor comprises a heterojunction, a first electrode and a second electrode, wherein the first electrode and the second electrode are matched with the heterojunction, two-dimensional electron gas or two-dimensional hole gas is formed in the heterojunction, and the first electrode and the second electrode are electrically connected through the two-dimensional electron gas or the two-dimensional hole gas; and a plurality of deep energy level sites are distributed on the surface of the heterojunction, and the energy level of each deep energy level site has enough energy level difference with the LUMO or HOMO energy level of a selected gas molecule, so that when the selected gas molecule is fully contacted with the deep energy level sites, electron or hole transfer can occur between the selected gas molecule and the deep energy level sites, and the channel current of the semiconductor gas sensor is changed. The semiconductor gas sensor provided by the embodiment of the invention has stable chemical property and long service life, and can be suitable for extreme environments.
Description
Technical Field
The invention relates to a semiconductor gas sensor, in particular to a semiconductor gas sensor and a preparation method and application thereof, belonging to the technical field of semiconductors.
Background
At present, the third generation semiconductor material, represented by silicon carbide and gallium nitride, has superior performances such as high frequency, high power, high voltage resistance, high temperature resistance, strong radiation resistance and the like, and is a key electronic component for supporting the new generation of mobile communication, new energy automobiles, high-speed rail trains, display and the like. The third-generation semiconductor material is also applied to the development of the ALGaN/GaN heterojunction-based HEMT device, has the advantages of high voltage resistance, high temperature resistance, strong stability and the like, and can be used for preparing a gallium nitride-based gas sensor which has high chemical stability and high sensitivity and is suitable for working in severe environment. The defect of poor chemical stability of the traditional silicon-based semiconductor sensor is overcome.
Disclosure of Invention
The invention mainly aims to provide a semiconductor gas sensor, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a semiconductor gas sensor which comprises a heterojunction, a first electrode and a second electrode, wherein the first electrode and the second electrode are matched with the heterojunction; and a plurality of deep energy level sites are distributed on the surface of the heterojunction, and the energy level of each deep energy level site has enough energy level difference with the LUMO or HOMO energy level of a selected gas molecule, so that when the selected gas molecule is fully contacted with the deep energy level sites, electron or hole transfer can occur between the selected gas molecule and the deep energy level sites, and the channel current of the semiconductor gas sensor is changed.
The embodiment of the invention also provides a preparation method of the semiconductor gas sensor, which comprises the steps of manufacturing the heterojunction and manufacturing the first electrode and the second electrode which are matched with the heterojunction; the preparation method also comprises the following steps: and arranging a plurality of deep energy level sites on the surface of the heterojunction.
The embodiment of the invention also provides a gas detection method, which comprises the following steps:
providing said semiconductor gas sensor;
and fully contacting selected gas molecules with deep energy level sites on the surface of the heterojunction, and detecting the selected gas molecules by detecting the channel current change of the semiconductor gas sensor.
Compared with the prior art, the invention has the advantages that:
1) according to the preparation method of the semiconductor gas sensor provided by the embodiment of the invention, based on the excellent characteristics of the semiconductor material, a series of deep energy levels are introduced into the surface layer of the heterojunction, so that the sensitivity of a semiconductor device to gas is improved;
2) the semiconductor gas sensor provided by the embodiment of the invention has stable chemical properties and long service life, and can be suitable for extreme environments;
3) the semiconductor gas sensor provided by the embodiment of the invention has stable sensitivity, and the sensitivity cannot be attenuated along with the placement time;
4) the preparation process of the semiconductor gas sensor provided by the embodiment of the invention is mature, simple and controllable, has strong compatibility and is easy to realize mass production.
Drawings
FIG. 1 is a schematic diagram of a semiconductor gas sensor in accordance with an exemplary embodiment of the present invention;
FIG. 2 is a schematic diagram of the electron transfer mechanism between the heterojunction and the gas molecules of a semiconductor gas sensor provided in an exemplary embodiment of the invention;
FIG. 3 is a schematic diagram of the energy band distribution of a semiconductor gas sensor having a plurality of deep energy level sites provided in an exemplary embodiment of the invention;
FIG. 4 shows an organic molecule and Al in accordance with an exemplary embodiment of the present invention0.26Ga0.74Schematic diagram of electron transfer mechanism between N/GaN heterojunction;
FIG. 5 is a graph showing the current response of various semiconductor gas sensors when they are in contact with ethanol gas;
fig. 6 is a graph showing the current response of different semiconductor gas sensors when they were in contact with acetone gas.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the invention provides a method for regulating and controlling the sensitivity of a heterojunction to gas molecules by introducing a deep energy level, belonging to the technical field of introducing a deep energy level physical mechanism into a GaN-based heterojunction material. According to the method, different deep level impurities or defects are introduced to the surface of the heterojunction, the deep level impurities ionize corresponding donor levels or acceptor levels, and when gas molecules are in full contact with deep level sites introduced to the surface of the heterojunction, energy level differences exist between the LUMO levels and the HOMO levels of the gas molecules and the introduced deep levels, so that electron transfer is generated under the driving of the energy level differences, and channel current of the heterojunction is reduced or increased.
According to the method, a series of deep energy level sites are introduced to the surface of the heterojunction by regulating the depth and distribution of the introduced deep energy levels, the distance between the introduced deep energy level sites is controlled, and the single sensitivity of the heterojunction to gas molecules is realized by extracting the difference set of gas molecular species responded by two deep energy level sites.
The embodiment of the invention provides a semiconductor gas sensor which comprises a heterojunction, a first electrode and a second electrode, wherein the first electrode and the second electrode are matched with the heterojunction; and a plurality of deep energy level sites are distributed on the surface of the heterojunction, and the energy level of each deep energy level site has enough energy level difference with the LUMO or HOMO energy level of a selected gas molecule, so that when the selected gas molecule is fully contacted with the deep energy level sites, electron or hole transfer can occur between the selected gas molecule and the deep energy level sites, and the channel current of the semiconductor gas sensor is changed.
Further, the HOMO energy level of the selected gas molecule is higher than the energy level of the deep level site and higher than the fermi energy level of the heterojunction system, such that when the selected gas molecule is brought into sufficient contact with the deep level site, electrons are transferred from the selected gas molecule onto the deep level site and then into the channel, thereby raising the channel current of the semiconductor gas sensor;
alternatively, the LUMO level of the selected gas molecule is lower than the level of the deep level site and lower than the potential well conduction band bottom level, such that when the selected gas molecule is brought into sufficient contact with the deep level site, electrons are transferred from the deep level site to the selected gas molecule, and electrons in the channel compensate to the deep level site, thereby decreasing a channel current of the semiconductor gas sensor.
Further, the plurality of deep energy level sites includes a plurality of deep energy level sites having different energy levels, wherein the energy level difference between any two deep energy level sites satisfies the following condition: when one of the deep energy level sites is brought into contact with m selected gas molecules, and the other deep energy level site is brought into contact with n selected gas molecules, the channel current of the semiconductor gas sensor is changed, wherein the m selected gas molecules comprise the n selected gas molecules, and the number (m-n) ≧ 1.
Further, the plurality of deep energy level sites are distributed in different regions of the surface of the heterojunction.
Further, the deep level sites include deep level impurities or defects.
Further, the deep level impurity includes any one or a combination of two or more of F, S, C, N, Au, Cr, Mn, Fe, Mg, Zn, and Si elements, but is not limited thereto.
The embodiment of the invention also provides a preparation method of the semiconductor gas sensor, which comprises the steps of manufacturing the heterojunction and manufacturing the first electrode and the second electrode which are matched with the heterojunction; the preparation method also comprises the following steps: and arranging a plurality of deep energy level sites on the surface of the heterojunction.
Further, the preparation method specifically comprises the following steps: and introducing deep energy level sites on the surface of the heterojunction by at least any one of plasma treatment, ion implantation, ion diffusion and epitaxial growth.
The embodiment of the invention also provides a gas detection method, which comprises the following steps:
providing said semiconductor gas sensor;
and fully contacting selected gas molecules with deep energy level sites on the surface of the heterojunction, and detecting the selected gas molecules by detecting the channel current change of the semiconductor gas sensor.
Further, the method further comprises the following steps: and applying a constant voltage between the first electrode and the second electrode, fully contacting selected gas molecules with deep energy level sites on the surface of the heterojunction, and detecting the selected gas molecules by detecting the change of channel current of the sensor.
Further, the method further comprises the following steps:
the method comprises the steps that multiple selected gas molecules are made to be in full contact with a first deep energy level site and a second deep energy level site on the surface of a heterojunction, and the detection of the first deep energy level site on m selected gas molecules and the detection of the second deep energy level site on n selected gas molecules are achieved by detecting the change of channel current of the semiconductor gas sensor;
and detecting a single selected gas molecule by obtaining a difference set of the m selected gas molecules and the n selected gas molecules, wherein the energy levels of the first deep energy level site and the second deep energy level site are different, and the m selected gas molecules comprise the n selected gas molecules, and (m-n) ≧ 1.
Further, the selected gas molecules may be organic gas molecules including ethanol, acetone, acetic acid, acetonitrile, methanol, formic acid, NMP, etc., inorganic gas molecules including ammonia, etc.
The following will further explain the technical solutions, the implementation processes, the principles, etc., in conjunction with the drawings, and if not specifically stated, the preparation methods and the detection methods adopted in the embodiments of the present invention may be known to those skilled in the art.
The embodiment of the invention provides a semiconductor heterojunction sensor with high chemical stability and high sensitivity, which is mainly used for regulating and controlling the sensitivity of a heterojunction material to gas molecules by introducing a series of deep-level impurities or defects.
Specifically, due to the polarization effect of a heterojunction material system (for example, a heterojunction system formed by two semiconductor materials with different forbidden band widths, such as AlGaN/GaN, AlN/GaN, AlGaAs/GaAs and the like), a very strong built-in electric field can be formed in a heterojunction, the energy band structure of a nitride heterojunction is modulated, and a quantum well on the GaN side of a heterojunction becomes deep and narrow, so that free electrons or holes are attracted and accumulated in the well to form two-dimensional electron gas or two-dimensional hole gas, specific metal is evaporated on the surface of the heterojunction to form ohmic contact, a closed loop can be formed, and the value of channel current can be measured and obtained by arranging a current detection device.
Specifically, a high-concentration two-dimensional electron gas or two-dimensional hole gas exists at the heterojunction interface, if a specified impurity or defect is introduced on the surface of the heterojunction, the specified impurity or defect ionizes to form a corresponding deep energy level in the heterojunction body (when the impurity is introduced, the formed deep energy level is an impurity energy level, when the defect is introduced, the formed deep energy level is a defect energy level, the same applies below), an energy level difference exists between the energy level of a gas molecule and the deep energy level of the introduced impurity or defect, and when the gas molecule is effectively contacted with a site corresponding to the impurity or defect, the transfer of electrons or holes can occur, so that channel current of the heterojunction device generates different current signals for the gas molecule.
Referring to fig. 1, deep level impurities or defects introduced into a semiconductor heterojunction material can ionize corresponding donor levels or acceptor levels in the heterojunction, and the introduced impurities or defects are located on the surface of the heterojunction; referring to fig. 2, when a gas molecule collides with a deep level impurity or defect site and the collision time is sufficient, if the HOMO energy level of the gas molecule is higher than the energy level of the impurity or defect and higher than the fermi energy level of the heterojunction system, electrons will be transferred from the gas molecule to the impurity or defect energy level, and then from the impurity or defect energy level to the channel of the heterojunction, which is indicated as a channel current rise of the heterojunction device; if the LUMO energy level of the gas molecule is lower than the impurity or defect energy level and lower than the bottom energy level of the conduction band of the potential well, the impurity or defect energy level transfers electrons to the energy level of the gas molecule, the electrons in the heterojunction channel are supplemented to the impurity or defect energy level, and the channel current of the heterojunction device is reduced when the electrons in the heterojunction channel are outward; therefore, the invention can enable the channel current of the heterojunction device to generate specific response to gas molecules by regulating and controlling the depth of the energy level of ionization of the introduced impurities or defects.
Specifically, in order to improve the resolution of the device to gas molecules, a series of deep energy level impurities or defects, namely various deep energy level sites, are introduced into the heterojunction material based on a specific processing method; when the distance between two adjacent deep energy level sites is small enough (specifically determined according to the energy level difference of specific molecules), single sensitivity of the heterojunction device to gas molecules can be realized by extracting the difference set of multiple gas molecules which can respond to the two adjacent deep energy level sites and the energy level depths of the two adjacent deep energy level sites; for example, referring to fig. 3, assuming that three impurity deep levels A, B, C are respectively introduced into different regions of the heterojunction, the position distributions of the three impurity deep levels are shown in fig. 3, and the LUMO level positions of the gas molecules a, B, and C are shown in fig. 3, where the gas molecules of the region response of the introduced deep level a are a, B, and C, the gas molecules of the region response of the introduced deep level B are B and C, and the gas molecules of the region response of the introduced deep level C are C, it can be known that the difference set of the gas molecule species of the deep level a and the deep level B response is gas a, and the difference set of the gas molecule species of the deep level B and the deep level C is gas B; the impurity elements introduced to form the three impurity deep levels A, B, C may be adjusted as needed, and the introduced impurity elements may be any one or a combination of two or more of F, S, C, N, Au, Cr, Mn, Fe, Mg, Zn, and Si; for example, in a gallium nitride heterojunction system, the excitation energy of Cr is 2.25eV, the excitation energy of Mn is 1.7eV, and the excitation energy of Mg, Si and Zn is 2.7-3.0 eV, and by comparing the difference of the types of response molecules of regions into which two or more elements are introduced, the energy levels of corresponding gas molecules are identified, and selected gas molecules are identified by means of a calibration scheme.
Specifically, in order to improve the range of the device response to gas molecules, the invention can form a heterojunction with a larger forbidden band width by modifying the corresponding semiconductor material, so as to widen the range and the number of impurity energy levels to be introduced, such as: the invention can adopt AlGaN/GaN heterojunction material, the forbidden band width of GaN is about 3.4ev, the aluminum component is 25.9%, the forbidden band width of AlGaN is about 4.12ev, if the AlGaN/GaN heterojunction is replaced by AlN/GaN heterojunction, the forbidden band width of the surface of the heterojunction is about 6.2 ev.
In particular, in order to improve the sensitivity of the device to gas molecules, the invention can also shorten the distance of electron transfer by reducing the distance from the surface of the device to the heterojunction channel, thereby obtaining higher responsivity.
Example 1
Referring to fig. 1, a semiconductor gas sensor according to an embodiment of the present invention includes a sapphire substrate, and Al disposed on the sapphire substrate0.26Ga0.74N/GaN heterojunction and Al0.26Ga0.74The first electrode and the second electrode are matched with the N/GaN heterojunction, and ohmic contact is formed between the first electrode and the heterojunction and the second electrode and the heterojunction is formed by the Al0.26Ga0.74Two-dimensional electron gas-electric connection in N/GaN heterojunction, wherein the Al0.26Ga0.74The surface layer of the N/GaN heterojunction is distributed with a plurality of deep energy level sites (the deep energy level sites are formed by introducing deep energy level impurities), and the energy level of the deep energy level sites has enough energy level difference with the LUMO or HOMO energy level of selected gas molecules, so that when the selected gas molecules are fully contacted with the deep energy level sites, electron or hole transfer can occur between the selected gas molecules and the deep energy level sites, and the channel current of the semiconductor gas sensor is changed.
Specifically, an AlN insertion layer of 1-2nm and Al may be arranged between the GaN layer and the AlGaN layer0.26Ga0.74The N layer has a thickness of 25.5nm, the GaN layer has a thickness of 1-3 μm, and the first and second electrodes can be composed of a multilayer metal structure of Ti/Al/Ni/Au, Ti goldThe main layer is directly contacted with a GaN cap layer on the AlGaN layer, the cap layer is made of GaN material with the thickness of 2nm, and the deep energy level point adopts an ICP (Inductively Coupled Plasma, of course, APEXICP (Inductively Coupled Plasma) or RIE (reactive Ion Etching) device) Inductively Coupled Plasma etcher based on CF (CF)4Plasma treatment for introducing F element into Al0.26Ga0.74Formed in an N/GaN heterojunction device.
Specifically, referring to fig. 4, if the conduction band is taken as a zero potential reference point, the ionization energy level depth of the F element is generally below the fermi energy, the ionization energy level depth of the F element is generally-1.8 ev, -2.1ev, -2.8ev, -3.25ev, in the heterojunction energy band system, the deep energy level of the F is mainly the acceptor level, the physical position is on the shallow surface of the heterojunction, when the gas molecule collides with the vicinity of the deep energy level site of the F, because the two (the gas molecule and the deep energy level site of the F) are closer, if the LUMO energy level of the gas molecule is lower than the deep energy level of the F, the electrons on the deep energy level of the F are transferred to the gas molecule, the electrons in the channel are supplemented to the deep energy level of the F, and macroscopically expressed as the reduction of the device channel current.
Specifically, the gas detection method comprises the following steps: CF in FIG. 14The non-grid AlGaN/GaN heterojunction HEMT device processed by the plasma is placed in a closed cavity, selected gas is introduced into the closed cavity, a 5V constant voltage is applied to an electrode of the device, the current value of the device is read, and the detection of selected gas molecules is realized by detecting the change of the channel current of the device.
Specifically, the current change of the device after the ethanol gas is introduced into the sealed chamber is shown in fig. 5, and the current change of the device after the acetone gas is introduced is shown in fig. 6, wherein NP1-1 represents a device which does not adopt plasma treatment to form a deep energy level site, P1-1, P1-2, P1-4 and P2-1 respectively represent devices which have a deep energy level site formed by plasma treatment, and the aspect ratios of the deep energy level sites filled in the P1-1, P1-2, P1-4 and P2-1 devices are respectively 1:1, 1:2, 1:4 and 2: 1.
The inventors also formed the deep level sites with any one or a combination of two or more of S, C, N, Au, Cr, Mn, Fe, Mg, Zn, and Si elements as impurity elements, and detected organic gas molecules including acetone, acetic acid, acetonitrile, methanol, formic acid, NMP, and inorganic gas molecules including ammonia gas by the gas detection method provided by the present invention, and the results showed that the gas detection method provided by the embodiments of the present invention can effectively realize detection of selected gas molecules.
According to the preparation method of the semiconductor gas sensor provided by the embodiment of the invention, based on the excellent characteristics of the semiconductor material, a series of deep energy levels are introduced into the surface layer of the heterojunction, so that the sensitivity of a semiconductor device to gas is improved; the semiconductor gas sensor provided by the embodiment of the invention has stable chemical properties and long service life, and can be suitable for extreme environments; the semiconductor gas sensor provided by the embodiment of the invention has stable sensitivity, and the sensitivity cannot be attenuated along with the placement time; in addition, the preparation process of the semiconductor gas sensor provided by the embodiment of the invention is mature, simple and controllable, has strong compatibility and is easy to realize mass production.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A semiconductor gas sensor comprises a heterojunction, a first electrode and a second electrode, wherein the first electrode and the second electrode are matched with the heterojunction, two-dimensional electron gas or two-dimensional hole gas is formed in the heterojunction, and the first electrode and the second electrode are electrically connected through the two-dimensional electron gas or the two-dimensional hole gas; the method is characterized in that: and a plurality of deep energy level sites are distributed on the surface of the heterojunction, and the energy level of each deep energy level site has enough energy level difference with the LUMO or HOMO energy level of a selected gas molecule, so that when the selected gas molecule is fully contacted with the deep energy level sites, electron or hole transfer can occur between the selected gas molecule and the deep energy level sites, and the channel current of the semiconductor gas sensor is changed.
2. The semiconductor gas sensor according to claim 1, characterized in that: the HOMO energy level of the selected gas molecule is higher than the energy level of the deep energy level site and higher than the Fermi energy level of the heterojunction system, such that when the selected gas molecule is brought into sufficient contact with the deep energy level site, electrons are transferred from the selected gas molecule onto the deep energy level site and then into the channel, thereby raising a channel current of the semiconductor gas sensor;
alternatively, the LUMO level of the selected gas molecule is lower than the level of the deep level site and lower than the potential well conduction band bottom level, such that when the selected gas molecule is brought into sufficient contact with the deep level site, electrons are transferred from the deep level site to the selected gas molecule, and electrons in the channel compensate to the deep level site, thereby decreasing a channel current of the semiconductor gas sensor.
3. The semiconductor gas sensor according to claim 1, characterized in that: the plurality of deep energy level sites comprise a plurality of deep energy level sites with different energy levels, wherein the energy level difference of any two deep energy level sites meets the following condition: when one of the deep energy level sites is brought into contact with m selected gas molecules, and the other deep energy level site is brought into contact with n selected gas molecules, the channel current of the semiconductor gas sensor is changed, wherein the m selected gas molecules comprise the n selected gas molecules, and the number (m-n) ≧ 1.
4. The semiconductor gas sensor according to claim 3, wherein: the multiple deep energy level sites are distributed in different regions of the surface of the heterojunction.
5. The semiconductor gas sensor according to claim 1, characterized in that: the deep energy level sites comprise deep energy level impurities or defects;
preferably, the deep level impurity includes one or a combination of two or more of F, S, C, N, Au, Cr, Mn, Fe, Mg, Zn, and Si elements.
6. A production method for a semiconductor gas sensor according to any one of claims 1 to 5, comprising a step of fabricating a heterojunction and a step of fabricating a first electrode and a second electrode which are mated with the heterojunction; it is characterized by also comprising: and arranging a plurality of deep energy level sites on the surface of the heterojunction.
7. The method according to claim 6, comprising: and introducing deep energy level sites on the surface of the heterojunction by at least any one of plasma treatment, ion implantation, ion diffusion and epitaxial growth.
8. A method of gas detection, comprising:
providing a semiconductor gas sensor according to any one of claims 1 to 5;
and fully contacting selected gas molecules with deep energy level sites on the surface of the heterojunction, and detecting the selected gas molecules by detecting the channel current change of the semiconductor gas sensor.
9. The method of claim 8, further comprising: and applying a constant voltage between the first electrode and the second electrode, fully contacting selected gas molecules with deep energy level sites on the surface of the heterojunction, and detecting the selected gas molecules by detecting the change of channel current of the sensor.
10. The method according to claim 8 or 9, further comprising:
the method comprises the steps that multiple selected gas molecules are made to be in full contact with a first deep energy level site and a second deep energy level site on the surface of a heterojunction, and the detection of the first deep energy level site on m selected gas molecules and the detection of the second deep energy level site on n selected gas molecules are achieved by detecting the change of channel current of the semiconductor gas sensor;
and detecting a single selected gas molecule by obtaining a difference set of the m selected gas molecules and the n selected gas molecules, wherein the energy levels of the first deep energy level site and the second deep energy level site are different, and the m selected gas molecules comprise the n selected gas molecules, and (m-n) ≧ 1.
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