CN112510149B - Negative resistance device preparation method based on two-dimensional material - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 19
- 239000010409 thin film Substances 0.000 claims abstract description 18
- -1 transition metal disulfide Chemical class 0.000 claims abstract description 18
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 17
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 42
- 239000010410 layer Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000010408 film Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical group [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 3
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005641 tunneling Effects 0.000 description 4
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H10N80/00—Bulk negative-resistance effect devices
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10N80/00—Bulk negative-resistance effect devices
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Abstract
The invention provides a negative resistance device based on a two-dimensional material, which comprises a substrate, wherein a grid layer, an insulating layer, a transition metal disulfide thin film layer and a surface electrode layer are arranged on the substrate; the grid layer is used as a bottom electrode, and the surface electrode layer is a source electrode and a drain electrode which are respectively electrically connected with the transition metal disulfide thin film layer and are arranged at intervals; the regions of the transition metal disulfide thin film layer connected with the source electrode and the drain electrode are respectively a source electrode region and a drain electrode region, the channel region of the transition metal disulfide thin film layer between the source electrode region and the drain electrode region is a tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction, and the source electrode region and the drain electrode region are both formed by molybdenum disulfide; the invention also provides a preparation method of the negative resistance device based on the two-dimensional material, the whole heterojunction grows by the three-step chemical vapor deposition process, the structure and the implementation mode of the device are simple, the cost is low, the device is compatible with the TMDS process, and the device is suitable for large-scale mass production.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technology of integrated circuit devices, in particular to a method for preparing a negative resistance device based on a two-dimensional material.
[ background of the invention ]
The Negative Differential Resistance (nega) effect, an important property of the electronic field, is mainly represented by the phenomenon that the current decreases with increasing applied voltage. Because the negative resistance device has the advantages of large switching current ratio, low power consumption and the like, the negative resistance device has wide application prospect in the aspects of oscillating circuits, logic devices, wireless communication, neural networks and the like. With the continuous progress of semiconductor process, the "mole law" gradually does not have guiding significance. Before the end of "silicon-based" comes, what materials the latter "silicon-based" era needs to rely on to support has been a subject of continuing research in the semiconductor field.
The negative resistance devices are now mostly based on conventional three-dimensional bulk materials, as shown in fig. 1, showing GaAs/AlGaAs/GaAs negative resistance devices. The existing negative resistance device mainly comprises three parts, wherein GaAs is taken as a source electrode and a drain electrode of the device, a channel region of the device is AlGaAs, and the two materials with different band gaps are spliced into a heterojunction; since the bandgap of the AlGaAs in the middle is smaller than that of the electrodes, band compensation is formed. When a bias voltage is applied to the device and becomes larger, the bias voltage continuously pushes down the energy band of the drain and also causes the energy band of the channel region to be pushed down, and after the fermi level of the intermediate region reaches the conduction band from the forbidden band, since the energy level in the conduction band is discontinuous, the transport capability of electrons from the source is suppressed, and a negative resistance phenomenon occurs. The existing negative resistance devices are built according to three-dimensional materials and are matched with the existing process, but the process is continuously improved and developed, and when the existing process is ended, the existing process of the body materials is eliminated when the two-dimensional materials continue the life of a semiconductor.
Transition-metal dihalides (TMDs), a new class of materials, are receiving wide attention as a large family of two-dimensional materials due to their unique properties. Wherein molybdenum disulfide (MoS) 2 ) And tungsten disulfide (WS) 2 ) The strong stability at normal temperature and the excellent photoelectric characteristics make it the focus of research and study due to the relatively appropriate band gap.
From the two points, the novel two-dimensional material TMDS is used for designing the negative resistance device, when the later silicon-based age comes, the negative resistance device designed based on the TMDS can be well integrated with the TMDS process, and the negative resistance device plays a great role in the field of semiconductors; therefore, a negative resistance device based on a novel two-dimensional material TMDs is urgently needed.
[ summary of the invention ]
According to the preparation method of the negative resistance device based on the two-dimensional material, the two-barrier quantum well is constructed by the aid of the two-dimensional material TMDs and the molybdenum disulfide and the tungsten disulfide, the source electrode and the drain electrode are both made of the molybdenum disulfide, the middle channel region is a tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction, the negative resistance effect is achieved by means of resonance tunneling, and the negative resistance device based on the two-dimensional material is high in stability at normal temperature.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the invention provides a preparation method of a negative resistance device based on a two-dimensional material, which comprises the following steps:
step one, adopting a chemical vapor deposition method, using sulfur powder and tungsten trioxide powder as precursors, adopting a silicon dioxide substrate or a silicon substrate as a substrate, respectively evaporating the sulfur powder and the tungsten trioxide powder during growth, enabling the substrate to face downwards to be placed under the tungsten trioxide precursor, and growing a single crystal tungsten disulfide sheet on the substrate;
continuing to adopt a chemical vapor deposition method, and then growing molybdenum disulfide on the single-crystal tungsten disulfide sheet by taking sulfur powder and molybdenum trioxide powder as precursors;
thirdly, on the basis of the second step, forming a continuous single-layer molybdenum disulfide film on the molybdenum disulfide by prolonging the growth time, then respectively evaporating the sulfur powder and the tungsten trioxide powder on the single-layer molybdenum disulfide film by taking the sulfur powder and the tungsten trioxide powder as precursors, and preparing the tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction by a chemical vapor deposition method;
and fourthly, transferring the tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction onto the substrate, adding a metal electrode to the heterojunction to form a source electrode, a drain electrode and a grid electrode of the negative group device, and finishing the preparation of the negative resistance device. Further, in the first step, the evaporation temperatures of the sulfur powder and the tungsten trioxide powder are respectively 120 ℃ and 900 ℃;
the negative resistance device comprises a substrate, wherein a grid layer, an insulating layer, a transition metal disulfide thin film layer and a surface electrode layer are sequentially and layer-wise superposed on the substrate from bottom to top; the grid layer is used as a bottom electrode, and the surface electrode layer comprises a source electrode and a drain electrode which are respectively and electrically connected with the transition metal disulfide thin film layer and are arranged at intervals; the regions of the transition metal disulfide thin film layer connected with the source electrode and the drain electrode are a source region and a drain region respectively, the channel region of the transition metal disulfide thin film layer between the source region and the drain region is a tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction, and the source region and the drain region are both formed by molybdenum disulfide; the channel region between the source region and the drain region is composed of tungsten disulfide, molybdenum disulfide and tungsten disulfide from left to right in sequence.
Further, in the third step, the evaporation temperatures of the sulfur powder and the molybdenum trioxide powder are 120 ℃ and 900 ℃, respectively.
Further, in the first step, a 300nm silicon dioxide substrate or a silicon substrate is adopted as the substrate.
Further, in the first step, the size of the crystal domain of the single crystal tungsten disulfide sheet grown on the substrate is 60-100 um.
Furthermore, the insulating layer is a hafnium oxide layer using a high-K dielectric, so that the grid control capability is enhanced.
The beneficial effects of the invention are:
in the invention, the middle channel region of the transition metal disulfide thin film layer connected with the source electrode and the drain electrode is a tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction, the negative resistance effect is realized by utilizing a resonant tunneling mode, and the stability is stronger at normal temperature.
And the whole tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction grows by a three-step chemical vapor deposition process, the structure and the implementation mode of the device are simple, the cost is low, the process is simple, the device is compatible with a TMDS process, the device is suitable for large-scale mass production, the cost can be saved by mass production, and the device is beneficial to large-scale integration.
[ description of the drawings ]
FIG. 1 is a schematic structural view of a conventional GaAs/AlGaAs/GaAs negative resistance device;
FIG. 2 is a MoS of the present invention 2 A schematic structure diagram of a negative resistance device;
FIG. 3 shows WS under AFM in the present invention 2 /MoS 2 An image of the heterojunction;
fig. 4 is a working principle diagram of the negative resistance effect in the present invention.
[ detailed description ] embodiments
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather construed as limited to the embodiments set forth herein. Next, the present invention is described in detail by using schematic diagrams, and in the detailed description of the embodiments of the present invention, the cross-sectional views illustrating the device structure are not enlarged partially according to the general scale for convenience of illustration, and the schematic diagrams are only examples, which should not limit the scope of the present invention.
A negative resistance device based on two-dimensional materials is shown in figure 2 and comprises a substrate 1, wherein a grid layer 2, an insulating layer 3, a transition metal disulfide thin film layer 4 and a surface electrode layer are sequentially and layer-wise stacked on the substrate 1 from bottom to top; the gate layer is a metal gate, and the substrate is a 300nm silicon dioxide substrate or a silicon substrate. The grid layer is used as a bottom electrode, and the surface electrode layer comprises a source electrode 5 and a drain electrode 6 which are respectively and electrically connected with the transition metal disulfide thin film layer 4 and are arranged at intervals; the regions of the transition metal disulfide thin film layer connected with the source electrode 5 and the drain electrode 6 are a source region and a drain region respectively, the channel region of the transition metal disulfide thin film layer between the source region and the drain region is a tungsten disulfide 7/molybdenum disulfide 8/tungsten disulfide 9 heterojunction, and the source region and the drain region are both formed by molybdenum disulfide; the insulating layer 3 is a hafnium oxide layer using a high-K dielectric, which is convenient for enhancing the gate control capability.
Wherein, the whole tungsten disulfide 7/molybdenum disulfide 8/tungsten disulfide 9 heterojunction is prepared by growth through a three-step Chemical Vapor Deposition (CVD) process.
The corresponding preparation method of the negative resistance device based on the two-dimensional material comprises the following steps:
step one, adopting a chemical vapor deposition method (CVD), and using sulfur (S) powder and tungsten trioxide (WO) 3 ) The powder was used as a precursor, using a 300nm silicon dioxide Substrate (SiO) 2 ) Or a silicon substrate (Si) as a substrate, and sulfur (S) and tungsten trioxide (WO) during the growth 3 ) Powder evaporation, sulfur (S) and tungsten trioxide (WO) respectively 3 ) The evaporation temperatures of the powders were 120 ℃ and 900 ℃ respectively, with the substrate placed face down on tungsten trioxide (WO) 3 ) Growing a single crystal tungsten disulfide sheet (WS) with a crystal domain size of 60-100um on a substrate under a precursor 2 );
Continuing to adopt a chemical vapor deposition method (CVD), and then applying a tungsten disulfide single crystal (WS) 2 ) Above, with sulfur (S) powder and molybdenum trioxide (MoO) 3 ) Growth of molybdenum disulfide (MoS) from powder as precursor 2 );
Step three, then, on the basis of step two, by prolonging the growth time, in molybdenum disulfide (MoS) 2 ) Form a continuous single-layer molybdenum disulfide film (MoS) 2 ) And then a single layer of molybdenum disulfide film is coated again with sulfur (S) powder and tungsten trioxide (WO) 3 ) The powders are evaporated as precursors, sulphur (S) powder and tungsten trioxide (WO) respectively 3 ) The evaporation temperatures of the powders were 120 ℃ and 900 ℃ respectively; preparing tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction by Chemical Vapor Deposition (CVD); as shown in fig. 3, the prepared tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction structure is shown.
Step four, then, the tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction (WS) 2 /MoS 2 /WS 2 ) And transferring the heterojunction on the substrate, adding a metal electrode on the heterojunction to form a source electrode, a drain electrode and a grid electrode of the negative group device, and finishing the preparation of the negative resistance device.
As shown in fig. 4, the operating principle of the negative resistance device is as follows: due to tungsten disulfide (WS) 2 ) Possesses specific molybdenum disulfide (MoS) 2 ) Larger band gap, tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction (WS) in channel region 2 /MoS 2 /WS 2 ) A quantum well is formed. Molybdenum disulfide (MoS) intermediate to heterojunction 2 ) Discrete energy levels are formed under the action of local action, as shown in part a of fig. 4, when a bias voltage is applied to the negative resistance device, the bias voltage presses down the fermi level of the drain of the negative resistance device, and simultaneously, the fermi level of the quantum well is reduced, and as the applied bias voltage continues to increase, the energy of the discrete energy levels in the quantum well is consistent with the energy of the fermi level of the source region of the negative resistance device. At the moment, the requirement of resonant tunneling is met, a large amount of electrons in the source region penetrate through the channel region to reach the drain electrode of the device, so that the negative resistance device can show large channel current, then when the applied voltage is continuously increased, the Fermi level of the quantum well is further reduced, the energy of discrete energy levels in the quantum well is not matched with the Fermi level of the source region, the free electrons are greatly hindered from being transported due to the existence of the quantum well, the current of the negative resistance device is sharply reduced, and the negative resistance phenomenon can occur。
In the embodiment, the middle channel region of the transition metal disulfide thin film layer connected with the source electrode and the drain electrode is a tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction, the negative resistance effect is realized by utilizing a resonant tunneling mode, and the stability is high at normal temperature. And the whole tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction grows by a two-step chemical vapor deposition process, the structure and the implementation mode of the device are simple, the cost is low, the process is simple, the device is compatible with a TMDS process, the device is suitable for large-scale mass production, the cost can be saved by mass production, and the device is beneficial to large-scale integration.
The above-mentioned embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, except for the cases listed in the specific embodiments; all equivalent changes in the shape, structure and principle of the invention should be covered by the protection scope of the invention.
Claims (6)
1. A preparation method of a negative resistance device based on a two-dimensional material is characterized by comprising the following steps:
firstly, adopting a chemical vapor deposition method, using sulfur powder and tungsten trioxide powder as precursors, adopting a silicon dioxide substrate or a silicon substrate as a substrate, respectively evaporating the sulfur powder and the tungsten trioxide powder during growth, enabling the substrate to be placed under a tungsten trioxide precursor in a face-down mode, and growing a single-crystal tungsten disulfide sheet on the substrate;
continuing to adopt a chemical vapor deposition method, and then growing molybdenum disulfide on the single-crystal tungsten disulfide sheet by taking sulfur powder and molybdenum trioxide powder as precursors;
thirdly, on the basis of the second step, forming a continuous single-layer molybdenum disulfide film on the molybdenum disulfide by prolonging the growth time, then respectively evaporating the sulfur powder and the tungsten trioxide powder on the single-layer molybdenum disulfide film by taking the sulfur powder and the tungsten trioxide powder as precursors, and preparing the tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction by a chemical vapor deposition method;
transferring the tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction to the substrate, adding a metal electrode to the heterojunction to form a source electrode, a drain electrode and a grid electrode of the negative group device, and finishing the preparation of the negative resistance device;
the negative resistance device comprises a substrate, wherein a grid layer, an insulating layer, a transition metal disulfide thin film layer and a surface electrode layer are sequentially and layer-wise superposed on the substrate from bottom to top; the grid layer is used as a bottom electrode, and the surface electrode layer comprises a source electrode and a drain electrode which are respectively and electrically connected with the transition metal disulfide thin film layer and are arranged at intervals; the regions of the transition metal disulfide thin film layer connected with the source electrode and the drain electrode are a source region and a drain region respectively, the channel region of the transition metal disulfide thin film layer between the source region and the drain region is a tungsten disulfide/molybdenum disulfide/tungsten disulfide heterojunction, and the source region and the drain region are both formed by molybdenum disulfide; the channel region between the source region and the drain region is composed of tungsten disulfide, molybdenum disulfide and tungsten disulfide from left to right in sequence.
2. The method for preparing a negative resistance device based on a two-dimensional material as claimed in claim 1, wherein in the first step, the evaporation temperatures of the sulfur powder and the tungsten trioxide powder are 120 ℃ and 900 ℃, respectively.
3. The method for preparing a negative resistance device based on two-dimensional material as claimed in claim 1, wherein in said third step, the evaporation temperature of the sulfur powder and the molybdenum trioxide powder is 120 ℃ and 900 ℃ respectively.
4. The method for preparing a negative resistance device based on a two-dimensional material as claimed in claim 1, wherein in said first step, said substrate is a 300nm silicon dioxide substrate or a silicon substrate.
5. The method for preparing a negative resistance device based on a two-dimensional material as claimed in claim 1, wherein in said step one, the size of the crystal domain of the single crystal tungsten disulfide sheet grown on the substrate is 60-100 um.
6. The method as claimed in claim 1, wherein the insulating layer is a hafnium oxide layer using a high-K dielectric.
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