CN115064642A - Heterostructure and optoelectronic device and method of making same - Google Patents

Heterostructure and optoelectronic device and method of making same Download PDF

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CN115064642A
CN115064642A CN202210971743.8A CN202210971743A CN115064642A CN 115064642 A CN115064642 A CN 115064642A CN 202210971743 A CN202210971743 A CN 202210971743A CN 115064642 A CN115064642 A CN 115064642A
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layer
heterostructure
substrate
pce10
transition metal
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鄢江兵
陈献龙
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Guangzhou Yuexin Semiconductor Technology Co Ltd
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Guangzhou Yuexin Semiconductor Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene

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Abstract

The invention relates to a heterostructure and a photoelectric device and a preparation method thereof. The above heterostructure includes: a transition metal chalcogenide layer and a PCE10 layer are sequentially stacked on a substrate. According to the heterostructure, the PCE10 layer is laminated on the surface of the transition metal chalcogenide layer to form the heterostructure, the PCE10 organic layer is matched with the transition metal chalcogenide layer, the photoelectric performance of the device can be improved to 2.6 mu A from 7.8nA, and 3 orders of magnitude are improved. Compared with the existing WS-based 2 The photocurrent (only 70 nA) of the photoelectric detector with the Poly-TPD/PCBM heterostructure is improved by about 2 orders of magnitude.

Description

Heterostructure and optoelectronic device and method of making same
Technical Field
The invention relates to the field of photoelectricity, in particular to a heterostructure, a photoelectric device and a preparation method of the heterostructure and the photoelectric device.
Background
Generally, the heterojunction is built by utilizing the two-dimensional thin film, so that interlayer carrier transportation is facilitated, namely, compared with a bulk material, the organic semiconductor material in a two-dimensional scale can effectively reduce potential barrier, and convenience is provided for the transportation of carriers at an interface. In addition, the two-dimensional high-quality organic molecular crystal has a clean interface and high excitation density with high binding energy, and when organic molecules are combined with inorganic materials to form a heterojunction, the organic molecular crystal can interact with an excited state of the inorganic materials so as to realize application of optoelectronic devices.
The transition metal chalcogenide is used as a two-dimensional material and has excellent performances of high electron mobility, adjustable band gap between 1eV and 2eV, changeable band gap types along with the number of layers and the like. However, in the application of two-dimensional materials, the study on the heterojunction formed by the transition metal chalcogenide and the organic material is less, and tungsten disulfide (WS) is used in the prior art 2 ) The prepared device has low photocurrent, resulting in poor device performance and limited application.
Disclosure of Invention
Based on this, there is a need for a heterostructure and a method of fabricating the same that can increase the photocurrent of the device.
In addition, it is necessary to provide a photodetector and a method for manufacturing the same.
A heterostructure, comprising: a transition metal chalcogenide layer and a PCE10 layer are sequentially stacked on a substrate.
In one embodiment, the material of the transition metal chalcogenide layer is selected from any one or more of tungsten disulfide and molybdenum disulfide; and/or the presence of a catalyst in the reaction mixture,
the transition metal chalcogenide layer is a single-layer thin film.
In one embodiment, the thickness of the PCE10 layer is 46nm to 152 nm.
A method of fabricating a heterostructure comprising the steps of:
forming a transition metal chalcogenide layer on a substrate; and
and forming a PCE10 layer on the side of the transition metal chalcogenide layer far away from the substrate to prepare the heterostructure.
In one embodiment, the step of forming a layer of PCE10 on the side of the transition metal chalcogenide layer away from the substrate comprises:
a solution of PCE10 was applied to the side of the transition metal chalcogenide layer remote from the substrate and then dried to form the PCE10 layer.
In one embodiment, the concentration of the PCE10 solution is 8-9 mg/mL; and/or the presence of a catalyst in the reaction mixture,
the solvent used in the PCE10 solution is selected from one or more of chlorobenzene, tetrahydrofuran and chloroform; and/or the presence of a catalyst in the reaction mixture,
the step of laying down a PCE10 solution on the transition metal chalcogenide layer comprises: dropping the PCE solution on one side, far away from the substrate, of the transition metal chalcogenide layer in a protective atmosphere, spin-coating for 6-7 s at the rotating speed of 800-850 rpm, and spin-coating for 35-36 s at the rotating speed of 7000-8000 rpm; and/or the like, and/or,
in the drying process, the temperature is 100-110 ℃, and the time is 18-20 min.
In one embodiment, the transition metal chalcogenide layer is a single layer thin film, and the transition metal chalcogenide layer is formed on the substrate by chemical vapor deposition.
An optoelectronic device, comprising: an electrode in electrical contact with said transition metal chalcogenide layer and/or said PCE10 layer in said heterostructure and a heterostructure as described above or prepared by a method of making a heterostructure as described above.
A method for manufacturing a photoelectric device comprises the following steps:
and sequentially forming an electrode and a heterostructure on the substrate to prepare the photoelectric device, wherein the heterostructure is the heterostructure or the heterostructure prepared by the preparation method of the heterostructure, and the electrode is electrically contacted with the transition metal chalcogenide layer and/or the PCE10 layer in the heterostructure.
In one embodiment, the electrode is a metal material, and the step of sequentially forming the electrode and the heterostructure on the substrate comprises:
forming a metal layer on the substrate;
forming said transition metal chalcogenide layer on a side of said metal layer remote from said substrate, said transition metal chalcogenide layer masking a portion of said metal layer, and then forming said PCE10 layer on a side of said transition metal chalcogenide layer remote from said substrate, said PCE10 layer masking said transition metal chalcogenide layer and said metal layer;
and removing part of the PCE10 layer to expose part of the metal layer to form the photoelectric device with an upper electrode structure and a lower electrode structure.
In one embodiment, the step of forming a metal layer on the substrate comprises:
forming a photoresist layer on the substrate;
exposing and developing the photoresist layer to obtain a photoresist pattern with a groove;
and evaporating metal in the groove, and removing the photoresist layer to obtain the metal layer.
In one embodiment, the exposure process adopts a laser direct writing mode.
In one embodiment, the light intensity is 35% to 38% and the time is 8s to 8.5s in the exposure process.
In one embodiment, the metal layer includes a chromium layer and a gold layer stacked, and in the step of depositing metal in the groove by evaporation, the chromium layer is deposited by evaporation first, and then the gold layer is deposited by evaporation on one side of the chromium layer away from the substrate.
In one embodiment, the thickness of the gold layer is 50 nm-55 nm; and/or the presence of a catalyst in the reaction mixture,
the thickness of the chromium layer is 2 nm-3 nm.
According to the heterostructure, the PCE10 layer is laminated on the surface of the transition metal chalcogenide layer to form the heterostructure, the PCE10 organic layer is matched with the transition metal chalcogenide layer, the photoelectric performance of the device can be improved to 2.6 mu A from 7.8nA, and 3 orders of magnitude are improved. Compared with the existing WS-based 2 The photocurrent (only 70 nA) of the photoelectric detector with the Poly-TPD/PCBM heterostructure is improved by about 2 orders of magnitude.
Drawings
FIG. 1 is a process flow diagram of one embodiment of a process for fabricating an optoelectronic device;
FIG. 2 is a topographical view of a single layer of tungsten disulfide film prepared in example 1;
FIG. 3 is a topographical view of a tungsten disulfide layer prepared in the conventional art;
FIG. 4 is a Raman spectrum of the heterostructure prepared in example 1;
FIG. 5 is an I-V curve of different optical powers of the photoelectric device prepared in comparative example 1 under 635nm laser irradiation;
FIG. 6 is an I-V curve of different optical powers of the photovoltaic device prepared in example 1 under 635nm laser irradiation;
FIG. 7 shows the structure and photoelectric properties of a conventional photodetector based on WS2/Poly-TPD/PCBM heterojunction.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or", "and/or" is used in an alternative range that includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
As used herein, "one or more" means any one, any two, or any two or more of the listed items. Wherein, the 'several' means any two or more than any two.
In this context, the concentrations referred to, unless otherwise indicated, refer to the final concentrations. The final concentration refers to the ratio of the additive component in the system to which the component is added.
In this context, the temperature parameters referred to are, if not particularly limited, both for isothermal processing and for processing within a certain temperature interval. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
Tungsten disulfide (WS) was studied in 2019 by researchers 2 ) The metal electrode is prepared by combining with Poly-TPD/PCBM through an evaporation method to form a photoelectric detector, but the method can cause poor interface contact, and the photocurrent of the device is only 70nA, so that the further application of the device is limited. Based on this, the present application provides a heterostructure capable of increasing a photocurrent of a photoelectric device.
Specifically, the heterostructure of an embodiment includes: a transition metal chalcogenide layer and a PCE10 layer are sequentially stacked on a substrate.
PCE10(PTB7-Th, PBDTTT-EFT) is one of new generation OPV donor polymers, belongs to a P-type organic polymer semiconductor type, has a band gap value of about 1.58eV, and can maintain the performance for ten years. The inventor of the application finds that a novel transition metal chalcogenide-PCE 10 inorganic-organic heterojunction device is built based on the transition metal chalcogenide, the photocurrent of the device can be effectively improved, and a reference function is provided for application of organic materials.
In some embodiments, the material of the transition metal chalcogenide layer is selected from at least one of tungsten disulfide and molybdenum disulfide.
In some embodiments, the transition metal chalcogenide layer is a single layer thin film. In one particular example, the transition metal chalcogenide layer is a single layer WS 2 And the thickness of the film is 0.8 nm. Compared with a photoelectric detector made of a block material, the photoelectric detector of the single-layer film has the excellent characteristics of wide wavelength detection, rapidness and high response, and has a better development prospect. Further, the size of the transition metal chalcogenide layer is about 100 nm.
In some embodiments, the PCE10 layer has a thickness of 46nm to 152 nm. In a particular example, the PCE10 layer has a thickness of 46nm, 50nm, 80nm, 90nm, 100nm, 120nm, 150nm, or a range of any two of these values.
In some embodiments, the substrate is silicon and/or silicon dioxide. In one specific example, the substrate is silicon/silicon dioxide and the thickness of the substrate may be 500 μm. It is to be understood that the thickness of the substrate is not limited thereto.
The second aspect of the present invention also provides a method for manufacturing the heterostructure of an embodiment, including the steps of:
forming a transition metal chalcogenide layer on a substrate;
a heterostructure is prepared by forming a layer of PCE10 on the side of the transition metal chalcogenide layer remote from the substrate.
In some embodiments, the method of forming the transition metal chalcogenide layer on the substrate can be chemical vapor deposition. Further, the transition metal compound layer is a single-layer thin film. A method of forming a single layer of a transition metal chalcogenide layer on a substrate may include the steps of: the substrate is placed in a chemical vapor deposition cavity, the deposition surface of the substrate faces the raw material conveying direction, and a preset angle of 15-40 degrees is formed between the deposition surface and the horizontal plane. The chemical vapor deposition cavity comprises a first heating area and a second heating area, the first heating area and the second heating area are sequentially arranged along the conveying direction of raw materials, sulfur powder is placed in the first heating area and heated and gasified to obtain a sulfur source, transition metal oxide powder is placed in the second heating area and heated and gasified to obtain a transition metal source, the reaction temperature is set to be 700-850 ℃, the sulfur source and the transition metal source are made to react, and a single-layer transition metal chalcogenide layer is formed on a deposition surface.
The method can obtain a single-layer transition metal chalcogenide thin film with a larger size. Compared with a photoelectric detector made of a block material, the photoelectric detector of the single-layer film has the excellent characteristics of wide wavelength detection, rapidness and high response, and has a better development prospect.
In one specific example, the transition metal chalcogenide layer is a single layer WS 2 And the thickness of the film is 0.8 nm. Further, the size of the transition metal chalcogenide layer is 100 nm.
In some embodiments, the step of forming a layer of PCE10 on the side of the transition metal chalcogenide layer away from the substrate comprises:
the PCE10 solution was applied to the side of the transition metal chalcogenide layer away from the substrate and then dried to form a PCE10 layer.
Specifically, the concentration of the PCE10 solution is 8-9 mg/mL. In a particular example, the PCE10 solution has a concentration of 8mg/mL, 8.2mg/mL, 8.5mg/mL, 8.8mg/mL, 9mg/mL, or a range of any two of these values.
In some embodiments, a step of formulating a solution of PCE10 is also included. Specifically, PCE10 was mixed with a solvent under a protective atmosphere, and then stirred to completely dissolve PCE 10. In one particular example, the protective atmosphere is nitrogen. The stirring time was 10 h.
In one embodiment, the solvent used in the PCE10 solution is selected from any one or more of chlorobenzene, tetrahydrofuran, and chloroform. It is understood that the solvent used in the PCE10 solution is not limited thereto, and may be other solvents capable of dissolving PCE 10.
In one embodiment, the step of laying down the PCE10 solution over the transition metal chalcogenide layer comprises: under the protective atmosphere, firstly, the PCE solution is dripped on one side of the transition metal chalcogenide layer far away from the substrate, then spin-coating is carried out for 6 s-7 s at the rotating speed of 800 rpm-850 rpm, and then spin-coating is carried out for 35 s-36 s at the rotating speed of 7000 rpm-8000 rpm.
In one specific example, the protective atmosphere is nitrogen, helium, or the like.
The prepared film can be covered more uniformly by two-step spin coating. In addition, in an actual process, the thickness of the prepared thin film can be controlled by controlling the rotation speed of the spin coating. In some embodiments, the PCE10 layer has a thickness of 46nm to 152 nm.
In one embodiment, the temperature is 100-110 ℃ and the time is 18-20 min in the drying process. Under the above-mentioned drying conditions, excess water in the film is removed to form an organic film.
In some embodiments, the process of fabricating the heterostructure includes the steps of:
forming a single-layered transition metal chalcogenide layer on a substrate by a chemical vapor deposition method;
preparing a PCE10 solution with the concentration of 8-9 mg/mL in a protective atmosphere, then coating the PCE10 solution on the surface of one side, far away from the substrate, of the transition metal chalcogenide layer, spin-coating for 6-7 s at the rotating speed of 800-850 rpm, and spin-coating for 35-36 s at the rotating speed of 7000-8000 rpm;
and heating at the temperature of 100-110 ℃ for 18-20 min to obtain the PCE10 layer.
The third aspect of the present invention also provides an optoelectronic device of an embodiment, comprising: an electrode and a heterostructure, the heterostructure being the aforementioned heterostructure or a heterostructure prepared by the aforementioned method of preparation of the heterostructure, the electrode being in electrical contact with the transition metal chalcogenide layer and/or the PCE10 layer in the heterostructure.
The fourth aspect of the present invention also provides a method of manufacturing an optoelectronic device of an embodiment, including the steps of: and sequentially forming an electrode and a heterostructure on the substrate to prepare the photoelectric device. The heterostructure is the heterostructure or the heterostructure prepared by the preparation method of the heterostructure.
In some embodiments, the electrode is made of a metal material, and the process of manufacturing the optoelectronic device includes the following steps S110, S120, and S130.
Step S110: a metal layer is formed on a substrate.
In some embodiments, before the step of forming the metal layer on the substrate, the method further comprises: and cutting the substrate. In one particular example, the substrate is a silicon/silicon oxide substrate. And in the cutting process, the silicon surface is cut in a laser cutting mode. The laser cutting precision is high, errors caused by uneven appearance and size of the silicon wafer in the experimental process can be reduced, and meanwhile damage to the oxidation layer surface can be prevented. In the actual process, the substrate oxide layer was placed face down, positioned with a red light source, and the Si face was cut into 1cm x 1cm blocks with a BLFB-100 laser cutter.
In some embodiments, before the step of forming the metal layer on the substrate, the method further comprises: and cleaning the substrate, in particular cleaning the cut substrate. In a specific example, the substrate is sequentially placed in detergent, acetone, absolute ethyl alcohol and deionized water, ultrasonic cleaning is carried out for 10 minutes respectively to remove organic matters, oily matters and other impurities on the substrate, and finally, an ultra-pure nitrogen gun is used for blow-drying for standby.
In some embodiments, the step of forming a metal layer on the substrate comprises:
forming a photoresist layer on a substrate;
then exposing and developing to obtain a photoresist pattern with a groove;
and evaporating metal in the groove, and removing the photoresist layer to obtain the metal layer.
In one embodiment, the photoresist layer includes a LOR photoresist layer and a S1805 photoresist layer, the LOR photoresist layer being closer to the substrate than the S1805 photoresist layer. And a double-layer photoresist is adopted to form a structure similar to an inverted trapezoid, so that stripping is facilitated.
In some embodiments, the step of forming a photoresist layer on the substrate comprises:
firstly, coating an LOR photoresist on a substrate, and drying to form an LOR photoresist layer;
and coating S1805 photoresist on the surface of one side, far away from the substrate, of the LOR photoresist layer, and drying to form an S1805 photoresist layer so as to obtain the photoresist layer.
In one embodiment, the LOR photoresist is coated on the substrate and dried by spin-coating at 500rpm + -5 rpm for 5s + -0.2 s, spin-coating at 4000rpm + -40 rpm for 40s + -1 s, and drying at 170 deg.C + -5 deg.C for 10min + -1 min.
In one embodiment, in the process of coating and drying the side surface of the LOR photoresist layer away from the substrate with S1805 photoresist, spin-coating at 500rpm +/-5 rpm for 5S +/-0.2S, spin-coating at 2000rpm +/-20 rpm for 25S +/-1S, spin-coating at 3000rpm +/-30 rpm for 3S +/-0.1S, and drying at 100 ℃ -110 ℃ for 10min +/-1 min.
In one embodiment, the exposure process adopts a laser direct writing mode. The laser direct writing mode has higher precision, and the connection between the metal layer and the transition metal chalcogenide layer is better.
Specifically, in the exposure process, the light intensity is 35-38%, and the time is 8-8.5 s.
In one embodiment, the developing solution used in the developing process is AZ300 developing solution. The development time was 60 s.
In some embodiments, the metal layer includes a chromium layer and a gold layer which are stacked, and in the step of evaporating metal in the groove, the chromium layer is evaporated first, and then the gold layer is evaporated on the side of the chromium layer away from the substrate.
In some embodiments, the gold layer has a thickness of 50nm to 60 nm. The thickness of the chromium layer is 2 nm-3 nm. In a specific example, the gold layer has a thickness of 50nm, 52nm, 55nm, 58nm, 60nm, or a range consisting of any two of these values. The chromium metal serves as an adhesion layer between the transition metal chalcogenide layer and the gold layer, and can prevent the gold from falling off from the transition metal chalcogenide layer.
In some embodiments, during the removal of the photoresist layer, the sample is treated with acetone and AZ400, respectively, to remove the photoresist layer. Specifically, the samples were soaked in acetone and AZ400 for 30s, respectively.
Referring to fig. 1, a metal layer is formed on a substrate, and the structure is shown in fig. 1. A metal layer 120 is formed on the substrate 110. The metal layer 120 includes a plurality of spaced apart metal elements. Specifically in fig. 1, metal layer 120 includes three spaced apart metal units. It is to be understood that fig. 1 is an example only, and not limited thereto.
Step S120: and forming a heterostructure on the side of the metal layer far away from the substrate.
Specifically, the step of forming the heterostructure on a side of the metal layer remote from the substrate comprises: the transition metal chalcogenide layer is formed on the side of the metal layer away from the substrate, the transition metal chalcogenide layer shields a portion of the metal layer, and then the PCE10 layer is formed on the side of the transition metal chalcogenide layer away from the substrate, the PCE10 layer shields the transition metal chalcogenide layer and the metal layer.
The specific steps for forming the transition metal chalcogenide layer and forming the PCE10 layer are the same as described above and will not be described herein.
With continued reference to fig. 1, the transition metal chalcogenide layer 130 shields a portion of the metal layer 120. The PCE10 layer shields the transition metal chalcogenide layer 130 and the metal layer 120.
Step S130: a portion of the PCE10 layer is removed to expose a portion of the metal layer to form an optoelectronic device having a top and bottom electrode structure.
Specifically, the sample was placed under a microscope and a tip of the needle was coated with acetone to scrape off a portion of the excess layer of PCE10, leaking the metal layer at the corresponding site.
Continuing to refer to fig. 1, an optoelectronic device having a top and bottom electrode structure is obtained by removing a portion of PCE10 layer 140 to expose a portion of metal layer 120.
According to the preparation method of the photoelectric device, the metal layer is prepared through the laser direct writing technology, the single-layer transition metal chalcogenide layer is generated through the chemical vapor deposition method, and the PCE10 layer is formed through the spin coating method, so that the prepared photoelectric device is excellent in photocurrent and better in performance.
In order to make the objects and advantages of the present invention clearer, the following detailed description of the optoelectronic device and its effects is made with reference to specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the present invention and should not be used to limit the present invention.
Example 1
The preparation process of the photoelectric device of the embodiment is specifically as follows:
1. preparation of metal layer
(1) Mix 4 inch SiO 2 SiO of (300nm)/Si substrate (total thickness 500 μm) 2 The Si face was cut into several 1cm by 1cm areas by placing the face down, positioning with a red light source, and cutting the Si face with a BLFB-100 laser cutter.
(2) And sequentially placing the substrate in a yellow light ultra-clean room, ultrasonically cleaning the substrate in detergent, acetone, absolute ethyl alcohol and deionized water for 10 minutes respectively, and finally blowing the substrate by using an ultra-pure nitrogen gun for later use.
(3) SiO in substrate 2 An LOR photoresist was coated on the side, spin-coated at 500rpm for 5s, then at 4000rpm for 40s, and then dried at 170 ℃ for 10min to form an LOR photoresist layer on the substrate.
(4) And coating S1805 photoresist on the surface of the LOR photoresist layer on the side away from the substrate, spin-coating at 500rpm for 5S, spin-coating at 2000rpm for 25S, spin-coating at 3000rpm for 3S, and drying at 100 ℃ for 10min to form the S1805 photoresist layer.
(5) The exposure is carried out by adopting a laser direct writing mode, the light intensity is adjusted to 35 percent, and the time is 8 s.
(6) Develop for 60s with AZ300 developer.
(7) A magnetron sputtering mode is adopted to evaporate a 2nm chromium layer firstly and then evaporate a 50nm gold layer secondly.
(8) And respectively soaking acetone and AZ400 for 30s to strip the photoresist layer to obtain a metal layer formed on the substrate.
2. Preparation of a monolayer of tungsten disulfide layer
A single-layer tungsten disulfide layer is formed on one side, far away from a substrate, of a metal layer in a chemical vapor deposition mode, and the specific method is as follows:
the substrate is placed in a quartz tube of a chemical vapor deposition cavity, so that the deposition surface of the substrate faces the raw material conveying direction, and a preset angle of 30 degrees is formed between the deposition surface and the horizontal plane. The quartz tube comprises a first heating area and a second heating area, the first heating area and the second heating area are sequentially arranged along the raw material conveying direction, sulfur powder is placed in the first heating area and heated and gasified to obtain a sulfur source, transition metal oxide tungsten oxide powder is placed in the second heating area and heated and gasified to obtain a transition metal tungsten source, the reaction temperature is set to be 800 ℃, the sulfur source and the tungsten source are made to react, and a single-layer tungsten disulfide layer is formed on a deposition surface.
3. Preparation of PCE10 layer
(1) In a glove box filled with nitrogen atmosphere, 8mg of PCE10 is weighed and dissolved in 10mL of chlorobenzene solution which is an organic solvent to prepare 8mg/mL PCE10 solution, a sample vial is placed on a magnetic stirrer at room temperature to be stirred for 10 hours, and the PCE10 solution is shaken up after being completely dissolved.
(2) In a glove box filled with nitrogen atmosphere, a substrate containing a single-layer tungsten disulfide film is placed in the center of a spin coater, 4 drops of PCE10 solution are dropped to cover the substrate, a vacuum pump is started to suck the substrate tightly, then the spin coater is started, parameters of the spin coater are set, the first step is 800-rotation spin coating for 6 seconds, and the second step is 7500-rotation spin coating for 35 seconds.
(3) The vacuum pump was turned off and the sample was taken out and placed on a 100 ℃ hot plate for annealing for 18 minutes to obtain a PCE10 layer.
(4) Placing the sample under a microscope, coating acetone on the needle point to scrape off part of the redundant PCE10 layer, and leaking the metal layer at the corresponding position to obtain WS with upper and lower electrode structures 2 PCE10 optoelectronic device.
Comparative example 1
Comparative example 1 provides a method for fabricating an opto-electric device, which is different from example 1 in that the fabrication of the PCE10 layer of step 3 was not performed.
The following are test sections:
1. the morphology of the single layer tungsten disulfide film prepared in example 1 was tested to obtain the SEM image shown in fig. 2 below. Figure 3 is an SEM image of a tungsten disulfide layer obtained during fabrication of photovoltaic devices using tungsten disulfide in combination with Poly-TPD/PCBM in a conventional process, which is small in size and mostly not a single layer.
2. A raman test was performed on the heterostructure in the photoelectric device prepared in example 1 to obtain a raman spectrum as shown in fig. 4. The graph shows several strong Raman peaks and WS of PCE10 polymer 2 The simultaneous appearance of Raman peaks of (A) confirms WS 2 Successful formation of PCE10 heterostructure.
3. Photoelectric performance test
FIG. 5 shows WS prepared in comparative example 1 with Vgs =0V 2 I-V curve of Field Effect Transistor (FET), lower right insert shows the I-V curve at SiO 2 WS on (300nm)/Si substrate 2 The field effect transistor has a structure schematic diagram of Cu, Si/SiO in sequence from bottom to top 2 (300nm), Cr/Au and WS 2 . By introducing into WS of comparative example 1 2 When the field effect transistor was irradiated with laser light having a wavelength of 635nm, it was easily observed that the response current linearly increased as the laser power increased at Vbg = 0V. This is due to WS after the light source is applied 2 The channel can absorb photon energy, and electron-hole pairs in the material are increased along with the increase of the laser power, so that the quantity of carriers in the unit volume in the material is changed. When the laser power density is 10.39mW/mm 2 When Vds is 3V, the device photocurrent value is about 7.8 nA.
Fig. 6 is an I-V curve corresponding to the photovoltaic device prepared in example 1, and the experiment takes the laser power as a variable, and the research shows that the photocurrent of the photovoltaic device increases with the increase of the laser power. When the laser power density is 10.39mW/mm 2 When Vds is 3V, the light current value of the device can reach 2.6 muA, and is improved by about three orders of magnitude compared with the photoelectric device prepared in comparative example 1 under the same condition.
FIG. 7 is a WS-based representation of the prior art 2 The structure and photoelectric performance of the photoelectric detector of the/Poly-TPD/PCBM heterojunction. In FIG. 7, (a) is a chemical vapor deposition method on SiO 2 Two-dimensional WS on/Si surface 2 A film; (b) is based on WS 2 -a schematic structural view of a photovoltaic device of a Poly-TPD/PCBM heterojunction; (c) a graph of drain current (ID) versus drain Voltage (VD) is shown, wherein the upper curve is in the bright state and the lower curve is in the dark state; (d)the light intensity is 0.14mW/cm 2 I-T curve under 450nm laser dark irradiation (VG =0V, VD = 10V). As can be seen in FIG. 7, WS 2 The photoelectric device of the-Poly-TPD/PCBM heterojunction has a photocurrent of only 70nA, which is much less than that of the photoelectric device prepared in example 1.
From the data, the PCE10 layer is laminated on the surface of the transition metal chalcogenide layer to form a heterostructure, and the photoelectric performance of the device is improved from 7.8nA to 2.6 muA and is improved by 3 orders of magnitude by the introduction of the novel organic layer. Compared with the existing WS-based 2 The photocurrent (only 70 nA) of the photoelectric detector with the Poly-TPD/PCBM heterostructure is improved by about 2 orders of magnitude. The improvement of the photocurrent is beneficial to improving the device sensitivity of the device, and has great application prospect in the field of photoelectric detection.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.

Claims (15)

1. A heterostructure, comprising: a transition metal chalcogenide layer and a PCE10 layer are sequentially stacked on a substrate.
2. The heterostructure of claim 1, wherein the transition metal chalcogenide layer is made of a material selected from one or more of tungsten disulfide and molybdenum disulfide; and/or the presence of a catalyst in the reaction mixture,
the transition metal chalcogenide layer is a single-layer thin film.
3. The heterostructure of claim 1 or 2, wherein the PCE10 layer has a thickness of 46nm to 152 nm.
4. A method for preparing a heterostructure, comprising the steps of:
forming a transition metal chalcogenide layer on a substrate; and
and forming a PCE10 layer on the side of the transition metal chalcogenide layer far away from the substrate to prepare the heterostructure.
5. Method for fabricating a heterostructure according to claim 4, characterized in that the step of forming a layer of PCE10 on the side of the layer of transition metal chalcogenides facing away from the substrate comprises:
a solution of PCE10 was applied to the side of the transition metal chalcogenide layer remote from the substrate and then dried to form the PCE10 layer.
6. The method for preparing the heterostructure according to claim 5, wherein the concentration of the PCE10 solution is 8-9 mg/mL; and/or the presence of a catalyst in the reaction mixture,
the solvent used in the PCE10 solution is selected from one or more of chlorobenzene, tetrahydrofuran and chloroform; and/or the presence of a catalyst in the reaction mixture,
the step of laying down a PCE10 solution on the transition metal chalcogenide layer comprises: dropping the PCE solution on one side of the transition metal chalcogenide layer far away from the substrate in a protective atmosphere, spin-coating for 6-7 ss at the rotating speed of 800-850 rpm, and spin-coating for 35-36 s at the rotating speed of 7000-8000 rpm; and/or the like, and/or,
in the drying process, the temperature is 100-110 ℃, and the time is 18-20 min.
7. A method according to any one of claims 4 to 6, wherein the transition metal chalcogenide layer is a single layer thin film and is formed on the substrate by chemical vapor deposition.
8. An optoelectronic device, comprising: an electrode and the heterostructure of any one of claims 1 to 3 or prepared by the method of preparing the heterostructure of any one of claims 4 to 7, the electrode being in electrical contact with the transition metal chalcogenide layer and/or the PCE10 layer in the heterostructure.
9. A method for manufacturing a photoelectric device is characterized by comprising the following steps:
forming an electrode and a heterostructure in sequence on a substrate to produce an optoelectronic device, the heterostructure being as defined in any one of claims 1 to 3 or produced by a method of producing a heterostructure as defined in any one of claims 4 to 7, the electrode being in electrical contact with the transition metal chalcogenide layer and/or the PCE10 layer in the heterostructure.
10. The method of fabricating an optoelectronic device according to claim 9, wherein the electrode is a metallic material, and the step of sequentially forming the electrode and the heterostructure on the substrate comprises:
forming a metal layer on the substrate;
forming said transition metal chalcogenide layer on a side of said metal layer remote from said substrate, said transition metal chalcogenide layer masking a portion of said metal layer, and then forming said PCE10 layer on a side of said transition metal chalcogenide layer remote from said substrate, said PCE10 layer masking said transition metal chalcogenide layer and said metal layer;
and removing part of the PCE10 layer to expose part of the metal layer to form the photoelectric device with an upper electrode structure and a lower electrode structure.
11. The method of fabricating an optoelectronic device according to claim 10, wherein the step of forming a metal layer on the substrate comprises:
forming a photoresist layer on the substrate;
exposing and developing the photoresist layer to obtain a photoresist pattern with a groove;
and evaporating metal in the groove, and removing the photoresist layer to obtain the metal layer.
12. The method for manufacturing an optoelectronic device according to claim 11, wherein the exposure process is performed by direct laser writing.
13. The method for manufacturing the photoelectric device according to claim 12, wherein the light intensity is 35% to 38% and the time is 8s to 8.5s during the exposure process.
14. The method for manufacturing an optoelectronic device according to claim 11, wherein the metal layer comprises a chromium layer and a gold layer stacked on each other, and in the step of depositing metal in the groove, the chromium layer is deposited by evaporation, and then the gold layer is deposited by evaporation on a side of the chromium layer away from the substrate.
15. The method for manufacturing an optoelectronic device according to claim 14, wherein the thickness of the gold layer is 50nm to 55 nm; and/or the presence of a catalyst in the reaction mixture,
the thickness of the chromium layer is 2 nm-3 nm.
CN202210971743.8A 2022-08-15 2022-08-15 Heterostructure and optoelectronic device and method of making same Pending CN115064642A (en)

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