CN111933650B - Molybdenum sulfide thin film imaging array device and preparation method thereof - Google Patents
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000003384 imaging method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010409 thin film Substances 0.000 title claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 2
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- 239000010980 sapphire Substances 0.000 description 3
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- -1 transition metal sulfides Chemical class 0.000 description 3
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14603—Special geometry or disposition of pixel-elements, address-lines or gate-electrodes
- H01L27/14605—Structural or functional details relating to the position of the pixel elements, e.g. smaller pixel elements in the center of the imager compared to pixel elements at the periphery
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2201/00—Specific applications of microelectromechanical systems
- B81B2201/02—Sensors
Abstract
The invention discloses a molybdenum sulfide film imaging array device and a preparation method thereof, belonging to the field of micro-nano manufacturing and optoelectronic devices, wherein the preparation method comprises the following steps: transferring the graphene film to the surface of a substrate, and etching the graphene film into a rectangular array by adopting plasma to obtain a graphene electrode array; sequentially depositing a transverse metal electrode, a dielectric film array and a longitudinal metal electrode on the surface of the graphene film to obtain an initial sample; and transferring the continuous molybdenum sulfide film to the surface of an initial sample and then packaging to obtain the molybdenum sulfide film imaging array device. The preparation method can obviously reduce the damage to the molybdenum sulfide film with atomic-scale thickness in the preparation process of the device, and greatly improves the array density, the yield and the working stability of the imaging device.
Description
Technical Field
The invention belongs to the field of micro-nano manufacturing and optoelectronic devices, and particularly relates to a molybdenum sulfide thin film imaging array device and a preparation method thereof.
Background
The solid-state image sensor is an important branch in a sensing technology device, is an indispensable peripheral device of computer multimedia, and is also a core device in monitoring. The image sensor detects light by means of a photosensitive device, and light carriers are excited by incident light to convert optical signals into electric signals, so that the information such as the existence, strength, position, wave band and the like of the optical signals can be distinguished, and the optical signals are converted into image information. The wavelength of light that can be detected by semiconductor image sensors is determined by the forbidden bandwidth of the semiconductor material, which can detect light in the range from ultraviolet light, visible light, up to the near-infrared and mid-far infrared light bands. Early light detection elements are mainly silicon-based photodiodes, but have the defects of poor high-energy radiation resistance, high cost, easy aging and the like, and are difficult to adapt to the development of flexible devices, so that the research on novel photoelectric materials is emphasized.
In recent years, two-dimensional materials are increasingly used in the field of sensors, in which transition metal sulfides represented by molybdenum sulfide are gaining attention by virtue of their excellent optical and electrical properties. A great number of reports have been reported on photodetector devices based on molybdenum sulfide films, and the photodetector devices show good performance and have wide application prospects. However, the current molybdenum sulfide film-based image sensing array device is rarely reported, and the array device prepared by the fresh part of research is only a simple array of discrete devices, has low integration level and very few device numbers (pixel points), and does not really realize the imaging function.
The main reason for this phenomenon is that the currently prepared continuous molybdenum sulfide thin films all contain a large number of grain boundaries, if the structure and preparation method of the traditional crisscross imaging device are adopted, the molybdenum sulfide thin films are transferred to a target substrate, and then a molybdenum sulfide photosensitive thin film array, a transverse electrode, a dielectric thin film and a longitudinal electrode are sequentially prepared, the steps need to repeatedly use the processes of photoetching, etching, coating, wet stripping and the like, and the grain boundary regions of the molybdenum sulfide thin films are easily damaged in the processes, so that the preparation of the array type device is very difficult, and especially the high-density large-area array device is almost impossible to complete. Furthermore, the performance of the device is also limited by the fact that it is often difficult to form a good ohmic contact when the metal is in direct contact with the molybdenum sulfide film.
Therefore, the technical problems that the grain boundary of the molybdenum sulfide film is damaged, the metal and the molybdenum sulfide film are difficult to form good ohmic contact and the device performance is poor exist in the prior art.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a molybdenum sulfide film imaging array device and a preparation method thereof, so that the technical problems that the grain boundary of the molybdenum sulfide film is damaged, the metal and the molybdenum sulfide film are difficult to form good ohmic contact, and the device performance is poor in the prior art are solved.
To achieve the above object, according to one aspect of the present invention, there is provided a method for manufacturing a molybdenum sulfide thin film imaging array device, comprising the steps of:
(1) Transferring the graphene film to the surface of a substrate, and etching the graphene film into a rectangular array by adopting plasma to obtain a graphene electrode array;
(2) Sequentially depositing a transverse metal electrode, a dielectric film array and a longitudinal metal electrode on the surface of the graphene film to obtain an initial sample;
(3) And transferring the continuous molybdenum sulfide film to the surface of an initial sample and then packaging to obtain the molybdenum sulfide film imaging array device.
Further, the step (1) further comprises:
and etching a graphene electrode channel at the central axis of each rectangle by adopting plasma.
Further, the width of the graphene electrode channel is between 2 and 20 μm.
Further, the graphene film transfer is realized by PMMA-assisted wet transfer or PDMS-assisted dry transfer.
Further, the dielectric film array is m rows and n columns, wherein m and n are integers between 2-500, and the distance between rows or columns is between 5 μm-500 μm.
Further, the dielectric thin film array is Al 2 O 3 、SiO 2 、HfO 2 Or Si 3 N 4 The thickness is between 20nm and 200 nm.
Furthermore, the transverse metal electrode is Ti, ni, cr, au or Ag, and the thickness is between 5nm and 100 nm. The vertical metal electrode is Ti, ni, cr, au or Ag, and the thickness is between 5nm and 100 nm. The substrate material is a silicon wafer, a quartz wafer or a sapphire wafer.
Further, a photoetching alignment process is combined with a coating process and a wet stripping process, a transverse metal electrode, a dielectric film array and a longitudinal metal electrode are sequentially deposited on the surface of the graphene film, and the coating process is magnetron sputtering, electron beam evaporation or atomic layer deposition.
Further, the thickness of the continuous molybdenum sulfide film is between 0.7nm and 20 nm.
Further, the continuous molybdenum sulfide film is prepared by low-pressure chemical vapor deposition, atmospheric-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, metal organic chemical vapor deposition or electrochemical stripping coating.
Further, the continuous molybdenum sulfide film transfer is realized by PMMA-assisted wet transfer or PDMS-assisted dry transfer.
According to another aspect of the present invention, there is provided a molybdenum sulfide thin film imaging array device prepared by the method for preparing a molybdenum sulfide thin film imaging array device of the present invention.
In general, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:
(1) According to the invention, the graphene electrode array is introduced into the device in the preparation process, so that ohmic contact between the photosensitive film and the electrode is realized, and the molybdenum sulfide photosensitive film array which needs to be prepared in the first step is changed into the last step for transfer coverage, so that the problem of crystal boundary damage of the molybdenum sulfide film can be directly solved, the yield and performance of the device are greatly improved, the number and density of rows and columns of the device are increased, and the development and application of a molybdenum sulfide film imaging device are promoted.
(2) The original light detection structure is that positive and negative metal electrodes are directly contacted with molybdenum sulfide, but the metal electrodes and the molybdenum sulfide often form Schottky barriers.
(3) The structure and the material of the dielectric film array enable the dielectric film array to have the best insulation effect as an insulation layer, and the transverse electrode and the longitudinal electrode are insulated and separated through the dielectric film. And the continuous molybdenum sulfide thin film with atomic thickness forms a photosensitive layer, and the molybdenum sulfide thin film with atomic thickness finally covers the surfaces of the layers, so that the graphene electrode channels realize electrical interconnection.
Drawings
FIG. 1 is a flow chart of the fabrication of a molybdenum sulfide thin film imaging array device according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a molybdenum sulfide thin film imaging array device provided by an embodiment of the invention;
FIG. 3 is a cross-sectional view of a molybdenum sulfide thin film imaging array device provided by an embodiment of the invention;
the same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
the array substrate is characterized in that 1 is a substrate, 2 is a graphene electrode array, 3 is a transverse metal electrode, 4 is a dielectric film array, 5 is a longitudinal metal electrode, and 6 is a continuous molybdenum sulfide film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, a method for manufacturing a molybdenum sulfide thin film imaging array device includes the following steps:
(1) Transferring the graphene film to the surface of a substrate, and etching the graphene film into a rectangular array by adopting plasma to obtain a graphene electrode array;
(2) Sequentially depositing a transverse metal electrode, a dielectric film array and a longitudinal metal electrode on the surface of the graphene film to obtain an initial sample;
(3) And transferring the continuous molybdenum sulfide film to the surface of an initial sample and then packaging to obtain the molybdenum sulfide film imaging array device.
Further, the step (1) further comprises:
and etching a graphene electrode channel at the central axis of each rectangle by adopting plasma.
Further, the width of the graphene electrode channel is between 2 and 20 μm.
Further, the graphene film transfer is realized by PMMA-assisted wet transfer or PDMS-assisted dry transfer.
Further, the dielectric film array is m rows and n columns, wherein m and n are integers between 2 and 500, and the distance between the rows or the columns is between 5 and 500 μm.
Further, the dielectric thin film array is Al 2 O 3 、SiO 2 、HfO 2 Or Si 3 N 4 The thickness is between 20nm and 200 nm.
Furthermore, the transverse metal electrode is Ti, ni, cr, au or Ag, and the thickness is between 5nm and 100 nm. The vertical metal electrode is Ti, ni, cr, au, ag, and has a thickness of 5-100 nm. The substrate material is a silicon wafer, a quartz wafer or a sapphire wafer.
Further, a photoetching alignment process is combined with a coating process and a wet stripping process, a transverse metal electrode, a dielectric film array and a longitudinal metal electrode are sequentially deposited on the surface of the graphene film, and the coating process is magnetron sputtering, electron beam evaporation or atomic layer deposition.
Further, the thickness of the continuous molybdenum sulfide thin film is between 0.7nm and 20 nm.
Further, the continuous molybdenum sulfide thin film is prepared by low-pressure chemical vapor deposition, atmospheric-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, metal organic chemical vapor deposition or electrochemical lift-off coating.
Further, the continuous molybdenum sulfide film transfer is realized by PMMA-assisted wet transfer or PDMS-assisted dry transfer.
As shown in fig. 2 and 3, the molybdenum sulfide thin film imaging array device prepared by the invention comprises: the device comprises a substrate 1, a graphene electrode array 2, a transverse metal electrode 3, a dielectric film array 4, a longitudinal metal electrode 5 and a continuous molybdenum sulfide film 6.
The graphene electrode array is provided with a graphene electrode channel, a cross-shaped electrode is formed by a transverse metal electrode and a longitudinal metal electrode, a dielectric film array is an insulating layer, a photosensitive layer is formed by a continuous molybdenum sulfide film with atomic-level thickness, the dielectric film array is positioned at the cross part of the transverse metal electrode and the longitudinal metal electrode, and the transverse electrode and the longitudinal electrode are insulated and separated through the dielectric film. And finally, covering the surfaces of the layers with an atomic-level thickness molybdenum sulfide thin film, and realizing electrical interconnection by using the graphene electrode channel.
Example 1
(1) Cutting 5mm multiplied by 5mm graphene grown by a CVD process with a copper foil as a substrate, corroding the copper foil by using 0.74mol/L FeCl3.6H2O solution, and transferring a graphene film to the surface of a silicon substrate containing a 280nm oxide layer by adopting PMMA (polymethyl methacrylate) assisted wet transfer.
(2) And preparing a patterned graphene electrode array and an alignment mark for overlay by combining a photoetching process and a plasma etching process, wherein the width of a graphene electrode channel is 2 microns.
(3) And depositing 20nm Au on the surface of the alignment mark by adopting a thermal evaporation process and a wet stripping process.
(4) And sequentially depositing 7nm Ti and 20nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the transverse metal electrode by combining a wet stripping process.
(5) 40nm Al is deposited on the surface of the cross part of the transverse and longitudinal metal electrodes by adopting a photoetching alignment process and a magnetron sputtering coating process 2 O 3 。
(6) And sequentially depositing 7nm Ti and 20nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the longitudinal metal electrode by combining a wet stripping process.
(7) Using a silicon wafer containing a 280nm oxidation layer as a substrate, and preparing MoO with the thickness of 30nm on a clean substrate by using a thermal evaporation process 3 And putting the layer as a molybdenum source into a tube furnace, and placing another clean silicon wafer above the sample wafer, wherein the two wafers are kept in parallel and the distance between the two wafers is 2mm. Sulfur powder is put in the direction of airflow, argon is taken as a carrier, and MoO is used as a carrier 3 Heating to 650 deg.C, starting heating sulfur powder, moO 3 When the temperature reaches 750 ℃, the sulfur powder reaches 200 ℃, and MoO is continuously heated 3 And keeping the temperature at 800 ℃ for 5 minutes, naturally cooling, and removing the sample to obtain the continuous molybdenum sulfide film.
(8) And transferring the continuous molybdenum sulfide film to the surface of the longitudinal metal electrode by adopting PDMS dry-method assisted transfer.
(9) And carrying out wire bonding and packaging on the sample.
Example 2
(1) And transferring the graphene film to the surface of a quartz plate containing a 280nm oxidation layer by adopting PMMA (polymethyl methacrylate) assisted wet transfer.
(2) And preparing a patterned graphene electrode array and an alignment mark for overlay by combining a photoetching process and a plasma etching process, wherein the width of a graphene electrode channel is 12 micrometers.
(3) And depositing 10nm Au on the surface of the alignment mark by adopting a thermal evaporation process and a wet stripping process.
(4) And sequentially depositing 5nm Ni and 10nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the transverse metal electrode by combining a wet stripping process.
(5) Depositing 20nm SiO on the surface of the cross part of the transverse and longitudinal metal electrodes by adopting a photoetching alignment process combined with a Plasma Enhanced Chemical Vapor Deposition (PECVD) process 2 。
(6) And sequentially depositing 5nm Ni and 10nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the longitudinal metal electrode by combining a wet stripping process.
(7) The continuous molybdenum sulfide film is prepared by a low-pressure chemical vapor deposition process.
(8) And (3) transferring the continuous molybdenum sulfide film to the surface of the longitudinal metal electrode by adopting PMMA assisted wet transfer.
(9) And carrying out wire bonding and packaging on the sample.
Example 3
(1) And transferring the graphene film to the surface of the sapphire sheet by PDMS (polydimethylsiloxane) assisted dry transfer.
(2) And preparing a patterned graphene electrode array and an alignment mark for overlay by combining a photoetching process and a plasma etching process, wherein the width of a graphene electrode channel is 20 micrometers.
(3) And depositing 10nm Au on the surface of the alignment mark by adopting a thermal evaporation process and a wet stripping process.
(4) And sequentially depositing 15nm Cr and 30nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the transverse metal electrode by combining a wet stripping process.
(5) Depositing 50nm HfO on the surface of the cross part of the transverse and longitudinal metal electrodes by adopting a photoetching alignment process and a magnetron sputtering coating process 2 。
(6) And sequentially depositing 15nm Cr and 30nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the longitudinal metal electrode by combining a wet stripping process.
(7) The continuous molybdenum sulfide film is prepared by a normal pressure chemical vapor deposition process.
(8) And (3) transferring the continuous molybdenum sulfide film to the surface of the longitudinal metal electrode by adopting PMMA assisted wet transfer.
(9) And carrying out wire bonding and packaging on the sample.
Example 4
(1) And transferring the graphene film to the surface of the silicon wafer by PDMS (polydimethylsiloxane) assisted dry transfer.
(2) And preparing a patterned graphene electrode array and an alignment mark for alignment of overlay by combining a photoetching process and a plasma etching process, wherein the width of a graphene electrode channel is 15 mu m.
(3) And depositing 10nm Au on the surface of the alignment mark by adopting a thermal evaporation process and a wet stripping process.
(4) And sequentially depositing 25nm Ag and 100nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the transverse metal electrode by combining a wet stripping process.
(5) Depositing 200nm Si on the surface of the cross part of the transverse and longitudinal metal electrodes by adopting a photoetching alignment process combined with a PECVD (plasma enhanced chemical vapor deposition) process 3 N 4 。
(6) And sequentially depositing 25nm Ti and 100nm Au on the surface of the graphene film by adopting a photoetching alignment process and a thermal evaporation coating process, and preparing the longitudinal metal electrode by combining a wet stripping process.
(7) And preparing the continuous molybdenum sulfide film by a plasma enhanced chemical vapor deposition process.
(8) And (3) transferring the continuous molybdenum sulfide film to the surface of the longitudinal metal electrode by adopting PMMA assisted wet transfer.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a molybdenum sulfide thin film imaging array device is characterized by comprising the following steps:
(1) Transferring the graphene film to the surface of a substrate, etching the graphene film into a rectangular array by adopting plasma, and etching a graphene electrode channel at the central axis of each rectangle by adopting the plasma to obtain a graphene electrode array;
(2) Sequentially depositing a transverse metal electrode, a dielectric film array and a longitudinal metal electrode on the surface of the graphene film to obtain an initial sample;
(3) And transferring the continuous molybdenum sulfide film to the surface of an initial sample and then packaging to obtain the molybdenum sulfide film imaging array device.
2. The method of claim 1, wherein the graphene electrode channel width is between 2 μm and 20 μm.
3. The method for preparing the molybdenum sulfide thin film imaging array device as claimed in claim 1 or 2, wherein the graphene thin film transfer is realized by PMMA assisted wet transfer or PDMS assisted dry transfer.
4. The method of claim 1 or 2, wherein the array of dielectric films is m rows and n columns, wherein m and n are integers between 2-500, and the distance between rows or columns is between 5 μm-500 μm.
5. The method for manufacturing a molybdenum sulfide thin film imaging array device according to claim 1 or 2, wherein the dielectric thin film array is Al 2 O 3 、SiO 2 、HfO 2 Or Si 3 N 4 。
6. The method for manufacturing a molybdenum sulfide thin film imaging array device according to claim 1 or 2, wherein the thickness of the continuous molybdenum sulfide thin film is between 0.7nm and 20 nm.
7. The method for preparing a molybdenum sulfide thin film imaging array device according to claim 1 or 2, wherein the continuous molybdenum sulfide thin film is prepared by low pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, metal organic chemical vapor deposition or electrochemical lift-off coating.
8. The method for preparing a molybdenum sulfide thin film imaging array device according to claim 1 or 2, wherein the continuous molybdenum sulfide thin film transfer is realized by PMMA assisted wet transfer or PDMS assisted dry transfer.
9. A molybdenum sulfide thin film imaging array device, characterized in that the molybdenum sulfide thin film imaging array device is prepared by the preparation method of the molybdenum sulfide thin film imaging array device of any one of claims 1 to 8.
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