CN110581187B - Sub-band flexible optical detector based on ink-jet printing technology and printing method - Google Patents
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- H01L31/00—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
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- H01L31/0248—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0304—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L31/03044—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds comprising a nitride compounds, e.g. GaN
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- H01L31/0248—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
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- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
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Abstract
A sub-band flexible optical detector based on an ink-jet printing technology and a printing method relate to the technical field of semiconductor materials, solve the problems that the existing detector cannot carry out sub-band detection and cannot realize flexible design, and sequentially print MoS on a substrate2A layer, a graphene layer, a BN layer and an Ag layer; printing PtSe on the back of the substrate2A layer and an Ag layer; MoS2Layer, graphene layer, BN layer, Ag layer, and PtSe2The thickness of the layers is 1-10 μm. Further comprises growing Al on the graphene layer, the BN layer and the Ag layer respectively2O3Protective layer of Al2O3The thickness of the protective layer is 2nm-3 nm. The invention adopts the ink-jet printing technology to prepare the semiconductor two-dimensional material and the electrode. According to the provided sub-band flexible photodetector, the structure of a grid is increased, and a boron nitride two-dimensional material is grown below the grid, so that the grid current is increased when molybdenum disulfide generates a photon-generated carrier, the sub-band detection is realized because a transparent substrate is selected, and a platinum diselenide two-dimensional material is grown on the back of a device to realize the response to a mid-infrared band.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a monolithic integrated sub-band detector for a boron nitride ultraviolet band, a molybdenum disulfide visible light band and a platinum diselenide intermediate infrared band.
Background
The ultraviolet detector is taken as a core device of an ultraviolet detection technology, and receives high attention and intensive research at home and abroad for several years. Especially widely applied in the military fields of missile guidance, missile early warning, ultraviolet communication and the like, and further promotes and accelerates the rapid development of ultraviolet detector research. Although the first and second generation semiconductors such as Si and GaAs can be used to fabricate the ultraviolet detector, the characteristics and the usage of the device are greatly limited due to the characteristics of small forbidden band width, large device long-wave cut-off wavelength, low maximum operating temperature, and the like, and the limitation is particularly prominent particularly in severe environments such as high temperature, sunlight irradiation, and the like. The third-generation semiconductor BN with the forbidden bandwidth larger than 2.2eV has the advantages of forbidden bandwidth, high critical breakdown electric field, high electron saturation velocity, high thermal conductivity, strong radiation resistance and the like, well overcomes the defects of the first-generation and second-generation semiconductor ultraviolet detectors, and becomes the main material for manufacturing the ultraviolet detectors at present.
The molybdenum disulfide film is similar to graphene in structure and performance, but different from graphene, the molybdenum disulfide film has a controllable band gap. Bulk crystalline MoS2The band gap of (A) is 1.2eV, and the electron transition mode of the band gap is indirect transition; when the thickness is a single layer, MoS2Can reach 1.82eV, and the electron transition mode is changed into direct transition. Thus, MoS2The unique structure and excellent physical properties of the film and the adjustable energy band gap enable the film to have more application potential than graphene in the field of photoelectric devices.
Platinum diselenide and molybdenum disulfide belong to the same sulfur group compound, and have physical properties similar to those of molybdenum disulfide. Like molybdenum disulfide, the band gap structure of the molybdenum disulfide also changes from an indirect band gap to a direct band gap along with the reduction of the number of layers. The band gap of the single-layer platinum diselenide is 1.2eV theoretically, and the special energy band structure of the single-layer platinum diselenide enables the single-layer platinum diselenide to have a good response degree in the middle infrared band.
For discrete boron nitride BN ultraviolet detector, MoS2For the infrared light detector in the visible light detector PtSe2, the response wavelength band of the BN detector is generally less than 214nm (deep ultraviolet band), while MoS2The response band is typically between 460-500nm (visible band), while PtSe2Has a comparison effect near 1470nm (middle infrared band)A good response. However, for the conventional light detector, a single semiconductor material is usually used for detection, and detection of only a single wavelength band is usually performed. And the substrate is usually a hard substrate, conventional photodetectors generally do not have the properties of flexibility, extensibility, and the like.
Since it does not distinguish the wavelength band of light and generally due to its large size, the substrate is a rigid substrate and does not have the property of flexibility. Therefore, it is of great value to design a detector which has flexible properties and can respond to different wave bands respectively at the same time. A novel flexible photodetector is prepared which can operate in both extended and non-planar operating environments as compared to conventional microelectronic devices. And the flexible substrate has good light transmission and excellent processing performance, so that the device is more miniaturized and densified, and the device with lighter weight and good compatibility is prepared, so that the device has wider application range. The flexible substrate and the two-dimensional material are combined with excellent performance and complement each other. The size of the prepared light detector can be controlled manually, and the light detector can be even developed into circuits with various integrated components depending on the design scheme of ink-jet printing patterns. Can be used as a microelectronic device and a photosensitive device in the fields of information transmission and storage.
Disclosure of Invention
The invention provides a band-splitting flexible optical detector based on an ink-jet printing technology, aiming at solving the problems that the existing detector cannot carry out band-splitting detection and cannot realize flexible design.
A sub-band flexible photodetector based on ink-jet printing technology comprises MoS printed on a substrate in sequence2Layer, graphene layer, BN layer, and in MoS, respectively2Printing Ag layers serving as electrodes on two sides of the layer and the graphene layer and on the BN layer; printing PtSe on the back of the substrate2Layer, and in PtSe2Printing Ag layers serving as electrodes on two sides of the layer; the MoS2Layer, graphene layer, BN layer, Ag layer, and PtSe2The thickness of the layers is 1-10 μm.
The printing method of the sub-band flexible light detector based on the ink-jet printing technology is realized by the following steps:
step one, preparing BN and MoS2Graphene, Ag and PtSe2Ink-jet printing inks;
step two, adopting an ink-jet printing method to sequentially replace MoS2And graphene ink-jet printing ink, and MoS is sequentially printed on the substrate2A layer and a graphene layer;
step three, replacing the ink box in the ink-jet printer with BN ink-jet printing ink in MoS2-printing a BN layer on the graphene heterojunction;
step four, replacing the ink box in the ink-jet printer with Ag ink-jet printing ink in MoS2Printing Ag metal electrodes on the graphene heterojunction and the BN layer in sequence;
cleaning the back surface of the PC substrate by ultrasonic, and drying by using nitrogen; replacing ink cartridge in ink-jet printer with PtSe2Ink for ink jet printing of PtSe on the back of a PC substrate2Layer, then replacing the cartridge in an ink-jet printer with an Ag ink-jet printing ink, in PtSe2Ag layers were printed on both sides of the layer as electrodes.
The invention has the beneficial effects that: the invention adopts the ink-jet printing technology to prepare the semiconductor two-dimensional material and the electrode. According to the provided sub-band flexible photodetector, in the aspect of device structures, a grid structure is added, and a boron nitride two-dimensional material grows below the grid, so that the grid current is increased when molybdenum disulfide generates a photon-generated carrier, and therefore the sub-band detection is realized. In addition, the light detector adopts a polycarbonate flexible substrate, and the thickness of the other part of the device is less than or equal to 10 μm, so that the flexibility of the device is realized; in terms of the performance of the device,
according to the invention, the graphene-boron nitride heterojunction structure and the nanoparticle dispersion system are adopted, so that the photon-generated carrier density and the response speed of the device are improved; in the aspect of device preparation, the preparation flow is greatly simplified by the transfer of the two-dimensional material or the ink-jet printing, so that the preparation cost is lower, and a wider approach is provided for device preparation.
Compared with the traditional microelectronic device, the light detector can work in an extension and non-planar working environment. And the flexible substrate has good light transmission and excellent processing performance, so that the device is more miniaturized and densified, and the device with lighter weight and good compatibility is prepared, so that the device has wider application range.
The photodetector provided by the invention integrates three semiconductor materials of BN, MoS2 and PtSe2 to realize the sub-band detection of ultraviolet light, visible light and intermediate infrared light. In addition, the flexibility of the substrate is combined with the semiconductor material with the thinner thickness, so that the invention has better flexibility and ductility, and has wider application.
Drawings
FIG. 1 shows a MoS printed on a PC substrate in a sub-band flexible photodetector based on ink-jet printing technology according to the present invention2Schematic of layer and graphene layer structures;
FIG. 2 shows MoS on PC substrate in a sub-band flexible photodetector based on inkjet printing technology according to the present invention2Schematic diagram of layer, graphene layer, and BN layer structures;
FIG. 3 is a diagram illustrating the structure of a device after printing Ag electrodes in a sub-band flexible photo-detector based on ink-jet printing technology according to the present invention;
FIG. 4 is a schematic diagram illustrating Al deposition by ALD in a sub-band flexible photodetector based on inkjet printing technology according to the present invention2O3A device structure diagram behind the protective layer;
fig. 5 is a schematic structural diagram of a sub-band flexible photo-detector based on inkjet printing technology according to the present invention.
Detailed Description
First, the present embodiment is described with reference to fig. 1 to 5, and provides a flexible device of a light detector with a response in a sub-band on a flexible substrate. And (3) performing process processing on two sides of the substrate by taking the flexible substrate as a process center. Polycarbonate (PC) flexible substrates, i.e. flexible materials that can be bent by external forces to accommodate a variety of extreme conditions, have insulating properties.
The flexible device, i.e., the device also has flexibility, and the semiconductor materials BN and MoS selected in this embodiment mode2All are single-layer materials, so the material has good bending performance. Alumina (Al)2O3) The light-transmitting film is used for protecting devices, has good light transmission, cannot cause too much influence on the performance of a light detector, and ensures the flexibility of the devices due to the thickness of 20 nm. Ag electrode, graphene and MoS2Ohmic contacts are formed as a source, a drain, and a gate. The detector response band of BN is generally less than 214nm (deep ultraviolet band) due to the band gap of 5.9eV, and the single-layer MoS2Has a band gap of 1.82eV and a response band of less than 680nm (ultraviolet band and visible band). Therefore, the detector can respond to different wave bands simultaneously, namely the same bias voltage is applied to the source electrode and the drain electrode, and if light with the wavelength less than 214nm is radiated to enable BN to generate photon-generated carriers, the current is larger; similarly, the same bias is applied to the source and the gate, and the MoS is caused if light with a wavelength less than 680nm is radiated2The generated photogenerated carriers have larger current, thus playing the role of sub-band photoresponse. In order to enhance the absorption of deep ultraviolet light by BN,
the device in the embodiment adopts a graphene-BN heterojunction structure; in addition, by permeating nano silver particles into the material, free electrons of the nano silver are distributed on the surfaces of the particles to form a certain charge motion potential barrier and adjust the distribution of an electric field, and finally, the concentration of a photon-generated carrier is enhanced, so that the high-performance waveband light detector with strong light response capability can be prepared.
Specifically including MoS printing sequentially on a substrate2A layer, a graphene layer, a BN layer and an Ag layer; printing PtSe on the back of the substrate2A layer and an Ag layer; the MoS2Layer, graphene layer, BN layer, Ag layer, and PtSe2The thickness of the layers is 1-10 μm. Further comprises growing Al on the graphene layer, the BN layer and the Ag layer respectively2O3Protective layer of Al2O3The thickness of the protective layer is 2nm-3 nm.
In this embodiment, BN is used、MoS2Graphene, Ag and PtSe2MoS is respectively printed by ink-jet printing ink2Layer, graphene layer, BN layer, Ag layer and PtSe2A layer; the ink for ink-jet printing is prepared by soaking in polyethylene glycol (PEG) for surface modification, and then modifying BN and MoS2Graphene, Ag and PtSe2And respectively dissolving the nano particles in an ammonia water solvent to respectively prepare the ink-jet printing ink.
The substrate described in this embodiment is polycarbonate, polyimide, polyethylene terephthalate, or polyethersulfone. Tungsten sulfide, zinc oxide, and black phosphorus may be used in place of platinum diselenide, molybdenum disulfide, and boron nitride.
Second embodiment, the present embodiment is described with reference to fig. 1 to 5, and the present embodiment is a printing method of a sub-band flexible photo-detector based on an inkjet printing technology, which is implemented by the following steps:
firstly, preparing a Polycarbonate (PC) substrate with the thickness of 100 mu m, cleaning the substrate in organic solvents such as acetone, ethanol and the like and deionized water by ultrasound in sequence, and finally drying the substrate by nitrogen. In addition to PC, polyimide, polyethylene terephthalate, polyethersulfone, or the like can be selected.
Preparation of BN, MoS2Graphene, Ag and PtSe2In order to avoid agglomeration of particles in ink due to too high surface energy and influence on ink-jet printing effect, the ink-jet printing ink is soaked in surfactants such as polyethylene glycol (PEG) for surface modification so as to ensure particle dispersion. Subsequently, the modified BN, MoS2Graphene, Ag and PtSe2The nano particles are respectively dissolved in solvents with high solubility and easy volatility, such as ammonia water, and the like, and are respectively prepared into the ink-jet printing ink.
Step two, as shown in figure 1, the ink is replaced in sequence by the ink-jet printing technology, and MoS is printed on the PC substrate in sequence2And sintering the layer and the graphene layer at 200 ℃, evaporating the solvent, and providing energy for the nano particles to form a continuous film.
Step three, as shown in figure 2, replacing the ink box in the ink-jet printer with a BN ink-jetAnd printing the ink. By ink-jet printing techniques, in MoS2-printing a BN layer on the graphene heterojunction, sintering at 200 ℃, evaporating the solvent and providing energy to the nanoparticles to form a continuous film.
And step four, as shown in figure 3, replacing the ink box in the ink-jet printer with Ag ink-jet printing ink. By ink-jet printing techniques, in MoS2Printing Ag metal electrodes on the graphene heterojunction and the BN layer in sequence, sintering at 200 ℃, evaporating the solvent, and providing energy for the nano particles to form a continuous film.
Referring to fig. 4, in this embodiment, a layer of 2nm to 3nm Al is grown on each of the graphene layer, the BN layer and the Ag layer by Atomic Layer Deposition (ALD)2O3Film to protect the surface of the structure, except Al2O3The film can also be made of other materials with high light transmittance of 1nm-5nm, such as Si3N4And the thickness of the protective layer material should not be too thick to ensure the flexibility of the device.
And step five, as shown in fig. 5, soaking the device in fig. 4 in acetone, ethanol and deionized water to ultrasonically clean the back surface of the PC substrate, and finally drying the PC substrate by using nitrogen. Replacing ink cartridge in ink-jet printer with PtSe2Ink for ink jet printing. Printing PtSe on the back of a PC substrate by ink-jet printing2And (3) a layer. Subsequent replacement of the cartridge in the ink jet printer with an Ag ink jet printing ink, similarly in PtSe2Ag nano-particles are printed at two ends of the layer to be used as electrodes. And finally sintering at 200 ℃, evaporating the solvent, and providing energy for the nano particles to form a continuous film.
In this embodiment, in order to form a continuous film while maintaining the flexibility of the device, the number of printing layers of any material in the above-described inkjet printing step is 5, and similarly, the number of printing times may be changed so that the material has a different thickness, which is about 1 μm to 10 μm.
The detector of the embodiment is combined with an ink-jet printing technology to realize a deep ultraviolet, visible light and intermediate infrared sub-band flexible optical detector, and the realization of high performance, such as high photon-generated carrier density, high response speed and the like, is realized by forming a graphene-boron nitride heterojunction and regulating and controlling electric field distribution, such as surface plasma resonance and the like, by nano silver particles. In order to realize the response of different wave bands, platinum diselenide, molybdenum disulfide and boron nitride in the device can be replaced by other two-dimensional materials with different photon absorption, such as tungsten disulfide, zinc oxide, black phosphorus and the like, so as to achieve the required response wave band range.
After the detector described in this embodiment is printed, light is emitted from Al2O3Surface incidence, absorption of photons with wavelength less than 214nm by BN deep ultraviolet detector to detect photocurrent, and absorption of photons with wavelength of 470nm to 500nm by MoS2Absorbed and detected, photons with wavelength near 1470nm are PtSe2And the absorption is carried out for detection, and the sub-band absorption detection of the photons is finally realized.
Claims (8)
1. A sub-band flexible optical detector based on ink-jet printing technology is characterized in that: including MoS printed in sequence on a substrate2Layer, graphene layer, BN layer, and in MoS, respectively2Printing Ag layers serving as electrodes on two sides of the layer and the graphene layer and on the BN layer; printing PtSe on the back of the substrate2Layer, and in PtSe2Printing Ag layers serving as electrodes on two sides of the layer; the MoS2Layer, graphene layer, BN layer, Ag layer, and PtSe2The thickness of the layers is 1-10 μm;
further comprises growing Al on the graphene layer, the BN layer and the Ag layer respectively2O3Protective layer of Al2O3The thickness of the protective layer is 2nm-3 nm;
using BN, MoS2Graphene, Ag and PtSe2MoS is respectively printed by ink-jet printing ink2Layer, graphene layer, BN layer, Ag layer and PtSe2A layer; the ink for ink-jet printing is prepared by soaking in polyethylene glycol (PEG) for surface modification, and then modifying BN and MoS2Graphene, Ag and PtSe2And respectively dissolving the nano particles in an ammonia water solvent to respectively prepare the ink-jet printing ink.
2. The flexible optical detector of claim 1, wherein: the substrate is polycarbonate, polyimide, polyethylene terephthalate or polyether sulfone.
3. The flexible optical detector of claim 1, wherein: tungsten sulfide, zinc oxide and black phosphorus are used to replace platinum diselenide, molybdenum disulfide and boron nitride.
4. The method for printing the sub-band flexible photo-detector based on the ink-jet printing technology as claimed in claim 1, wherein: the method is realized by the following steps:
step one, preparing BN and MoS2Graphene, Ag and PtSe2Ink-jet printing inks;
step two, adopting an ink-jet printing method to sequentially replace MoS2And graphene ink-jet printing ink, and MoS is sequentially printed on the substrate2A layer and a graphene layer;
step three, replacing the ink box in the ink-jet printer with BN ink-jet printing ink in MoS2-printing a BN layer on the graphene heterojunction;
step four, replacing the ink box in the ink-jet printer with Ag ink-jet printing ink in MoS2Printing Ag metal electrodes on the graphene heterojunction and the BN layer in sequence;
cleaning the back surface of the PC substrate by ultrasonic, and drying by using nitrogen; replacing ink cartridge in ink-jet printer with PtSe2Ink for ink jet printing of PtSe on the back of a PC substrate2Layer, then replacing the cartridge in an ink-jet printer with an Ag ink-jet printing ink, in PtSe2Ag layers were printed on both sides of the layer as electrodes.
5. The printing method according to claim 4, wherein: using BN, MoS2Graphene, Ag and PtSe2MoS is respectively printed by ink-jet printing ink2Layer, graphene layer, BN layer, Ag layer and PtSe2A layer; the ink for ink-jet printing is prepared by soaking in polyethylene glycol (PEG)) Surface modification is carried out, and then modified BN and MoS are added2Graphene, Ag and PtSe2And respectively dissolving the nano particles in an ammonia water solvent to respectively prepare the ink-jet printing ink.
6. The printing method according to claim 4, wherein: in the fourth step, an atomic layer deposition method is utilized to grow a layer of 2nm-3nm Al on the surface of the graphene, the BN layer and the Ag layer2O3And a protective layer.
7. The printing method according to claim 4, wherein: the MoS2Layer, graphene layer, BN layer, Ag layer and PtSe2Each layer may vary in thickness from the corresponding layer by the number of prints.
8. The printing method according to claim 4, wherein: the MoS2Layer, graphene layer, BN layer, Ag layer and PtSe2The thickness of the layers is 1-10 μm.
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