CN114122192A - Film preparation method and photoelectric detector - Google Patents
Film preparation method and photoelectric detector Download PDFInfo
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- CN114122192A CN114122192A CN202111301989.6A CN202111301989A CN114122192A CN 114122192 A CN114122192 A CN 114122192A CN 202111301989 A CN202111301989 A CN 202111301989A CN 114122192 A CN114122192 A CN 114122192A
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- 229910052711 selenium Inorganic materials 0.000 claims abstract description 19
- 239000011669 selenium Substances 0.000 claims abstract description 19
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02417—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
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Abstract
The application belongs to the technical field of photoelectric detection, and particularly relates to a film preparation method and a photoelectric detector. The film light utilization efficiency on the existing photoelectric detector is low, and the performance of the photoelectric detector is limited. The application provides a film preparation method, which is characterized in that a tin material source and a selenium material source are heated under the condition that the temperature is lower than 250 ℃, so that tin and selenium longitudinally grow on a substrate after being evaporated to form a semiconductor nanosheet array film. SnSe2The vertical V-shaped structure of the two-dimensional thin film material has a very obvious light trapping effect, the light utilization efficiency is greatly enhanced, the absorption of light with the wavelength of 340nm to 650nm exceeds 90 percent, and the light responsivity and the external quantum efficiency of the detector can be effectively improved.
Description
Technical Field
The application belongs to the technical field of photoelectric detection, and particularly relates to a film preparation method and a photoelectric detector.
Background
Photodetectors, also referred to as photosensors, are sensors of light or other electromagnetic radiation that can absorb incident radiation and convert it into electrical signals. And is also an important component of modern integrated and miniaturized electronics. The method is vital to capture, identification and visualization of optical information, and has different applications in the fields of visual imaging, optical communication, remote sensing, photoelectric storage, environmental monitoring, military detection and the like. The two-dimensional layered semiconductor material has made great progress in both basic research and technical development. Such as MoS2、SnSe2、SnS2The two-dimensional layered chalcogenide compounds are receiving more and more attention due to their unique nanoelectronic, optical and optoelectronic properties. The preparation method is simple, feasible and low-cost through molecular beam epitaxy, vapor deposition and other process flows, so that the application of the preparation method in the aspect of photoelectric detectors is expanded.
The film light utilization efficiency on the existing photoelectric detector is low, and the performance of the photoelectric detector is limited.
Disclosure of Invention
1. Technical problem to be solved
The film light utilization efficiency on the existing photoelectric detector is low, and the performance of the photoelectric detector is limited.
2. Technical scheme
In order to solve the technical problem, the application provides a film preparation method, wherein a tin material source and a selenium material source are heated under the condition that the temperature is lower than 250 ℃, so that tin and selenium are evaporated and then longitudinally grow on a substrate to form a semiconductor nanosheet array film.
Another embodiment provided by the present application is: SnSe is grown and formed on the substrate by adopting a molecular beam epitaxy processxA nanosheet array film; the molecular beam epitaxy process comprises adding high-purity selenium material source and high-purity tin material source into molecular beam epitaxy equipment respectively, and passing throughThe molecular beam epitaxy device respectively heats the selenium material source and the tin material source, sprays the selenium material source onto the substrate in the form of molecular beams or atomic beams, and simultaneously sprays the tin material source onto the substrate in the form of molecular beams or atomic beams to form SnSexA nanosheet array film.
Preparation of vertical SnSe by low-temperature ultrahigh vacuum co-evaporation technology2A two-dimensional nanoplate array.
Another embodiment provided by the present application is: rotating the substrate such that the SnSe isxThe nano-sheet array film grows uniformly.
Another embodiment provided by the present application is: the semiconductor nano-sheet array film is SnSe2The two-dimensional film material vertical V-shaped structure.
The application also provides a photoelectric detector, and the film is applied to the photoelectric detector. SnSe2The nano-sheet array has strong light trapping capability, so that the nano-sheet array is used for a photoelectric detector.
Another embodiment provided by the present application is: comprises a substrate and SnSe sequentially laminatedxThe nano-sheet array thin film comprises a nano-sheet array thin film, an insulating layer, an adhesive layer and a first electrode, wherein the substrate comprises a substrate and a second electrode, and the substrate, the second electrode and the SnSe are arranged on the substratexThe nano-sheet array films are sequentially laminated.
Another embodiment provided by the present application is: the insulating layer is Al2O3The adhesive layer is a polymethyl methacrylate layer, an electron beam photoresist positive adhesive layer or an epoxy negative adhesive layer; the first electrode is a titanium electrode, and the second electrode is a titanium electrode.
Another embodiment provided by the present application is: the substrate is a 4 inch silicon wafer or glass.
Another embodiment provided by the present application is: the Al is2O3Layer deposition by atomic layer with said SnSexAnd (3) a nano-sheet array film.
Another embodiment provided by the present application is: the glue layer is arranged by spin coatingIn the presence of Al2O3On the layer.
Firstly preparing a patterned Ti/Au lower electrode on a substrate by an electron beam evaporation technology, and then growing SnSe on the upper surface2Nanosheet array, depositing a layer of Al by atomic deposition2O3，Al2O3For the insulating layer, SnSe can be effectively passivated2The surface defects are reduced; can also be used as an effective water oxygen barrier layer to improve stability. In Al2O3A layer of PMMA is prepared on the layer by spin coating, and the PMMA has two functions: the first is as an isolating layer, because the electrode is plated later, the upper electrode and the lower electrode are easy to be communicated to cause short circuit if the electrode is not directly plated by PMMA; the other is that PMMA is an insulating organic polymer and also acts as a water-oxygen barrier to improve stability. And finally, preparing a patterned Ti/Au upper electrode by an electron beam evaporation technology.
3. Advantageous effects
Compared with the prior art, the thin film preparation method and the photoelectric detector have the advantages that:
the application provides a film preparation method, which is a two-dimensional layered material SnSe with a chip-level large-area vertical structure2A method for preparing a film.
The application provides a photoelectric detector, for based on SnSe2High performance broadband photodetectors and arrays thereof.
The application provides a photoelectric detector, aims at growing vertical two-dimentional laminar material SnSe2And preparing a broadband photodetector based on the material. On the one hand by high quality two-dimensional SnSe2The growth of the film and the light trapping effect of the structure improve the utilization efficiency of light, thereby improving the light responsivity of the photoelectric detector.
The photoelectric detector provided by the application is prepared from Al2O3The layer and the PMMA high polymer layer effectively prevent water and oxygen in the air from corroding, so that the stability of the photoelectric detector is improved.
The photoelectric detector provided by the application is prepared from Al2O3Layer and PMMThe protection of A improves the response time and the stability of the device, thereby opening the application path of the high-performance broadband photoelectric detector based on a large-area uniform two-dimensional material.
Drawings
FIG. 1 is a schematic flow diagram of a photodetector fabrication process of the present application;
FIG. 2 is a schematic diagram of a photodetector structure of the present application;
FIG. 3 is a vertical SnSe of the present application2A schematic view of a film structure;
FIG. 4 is SnSe of the present application2Film SEM image schematic;
FIG. 5 is SnSe of the present application2A film performance result diagram;
FIG. 6 is SnSe of the present application2And (3) a schematic diagram of light trapping characteristics of the film.
Detailed Description
Hereinafter, specific embodiments of the present application will be described in detail with reference to the accompanying drawings, and it will be apparent to those skilled in the art from this detailed description that the present application can be practiced. Features from different embodiments may be combined to yield new embodiments, or certain features may be substituted for certain embodiments to yield yet further preferred embodiments, without departing from the principles of the present application.
The existing broadband photoelectric detectors, such as photoelectric detectors based on field effect transistors, photoelectric detectors based on perovskite structures and the like, have greatly improved detection response intensity. Although the ultraviolet light detectors with various structures realize certain breakthrough in performance, the photoelectric detectors are often poor in stability and cannot be exposed in air and are very easy to oxidize.
Referring to fig. 1 to 6, the application provides a film preparation method, under the condition that the temperature is less than 250 ℃, a tin material source and a selenium material source are heated, so that tin and selenium are evaporated and then longitudinally grow on a substrate to form a semiconductor nanosheet array film.
Two-dimensional material SnSe2The traditional preparation method mainly comprises mechanical strippingIonization, physical vapor deposition (high temperature heating SnSe)2Powder) and chemical vapor deposition, resulting in SnSe2The nano-sheets have quite discrete shapes and random positions. And because of the thickness<The 10nm tiled thin film structure has weak light absorption and is not favorable for integration of the photodetector. SnSe prepared by traditional chemical vapor deposition process2The nano-sheet has higher growth temperature (over 600 ℃), so SnSe2Molecules are more likely to laterally stack across the migration energy barrier to form a flat film. But when the growth temperature is lower (<250 c) and the molecular migration energy is insufficient to cross the potential barrier, thereby evolving into a stacked longitudinal growth mode.
Further, SnSe is grown and formed on the substrate by adopting a molecular beam epitaxy processxA nanosheet array film; the molecular beam epitaxy process comprises the steps of adding a high-purity selenium material source and a high-purity tin material source into molecular beam epitaxy equipment respectively, heating the selenium material source and the tin material source through the molecular beam epitaxy equipment respectively, spraying the selenium material source onto a substrate in a molecular beam or atomic beam mode, and spraying the tin material source onto the substrate in a molecular beam or atomic beam mode to form SnSexA nanosheet array film.
The preferred purity of the selenium and tin sources is 99.99%. Wherein the Se, Sn source and substrate have a temperature of 260 deg.C, 1100 deg.C and 240 deg.C, respectively, and a vacuum degree of 2 × 10-5Pa. Formation of SnSex(x is 1.6-2.2) nanosheet array structure, and the growth time is 10-50 min. The thickness of the nano-sheet in the semiconductor nano-sheet array is 5 nm-25 nm, and the height is 1 μm-2 μm.
Further, rotating the substrate such that the SnSe isxThe nano-sheet array film grows uniformly. SnSe prepared by traditional chemical vapor deposition2With discrete films, the present application guarantees SnSe by rotating the deposited substrate2The nanosheets grow uniformly.
Further, the semiconductor nanosheet array thin film is SnSe2The two-dimensional film material vertical V-shaped structure. The thickness of the nanosheet is only about a fewSingle layer of SnSe of nm or tens of nm2About 0.6nm, so it is called two-dimensional layered material.
Referring to FIGS. 5(a) and 6, SnSe2The nano-sheets can be regarded as V-shaped light cavities, and light enters the V-shaped cavities and is reflected in the cavities for multiple times and is subjected to SnSe multiple times2The nanosheets absorb and convert into electrical signals. The absorption efficiency of the traditional tiled nanosheet to light is only 2.3%, and the absorption efficiency of the vertical nanosheet prepared in the application to light exceeds 90%. Therefore, the utilization efficiency of light is greatly improved, and the detection performance of light is improved.
The light trapping structure is a V-shaped structure which is usually obtained by photoetching, and the light trapping SnSe is prepared by using the light trapping structure2The nano-sheet array is formed spontaneously. Since all the vertical surfaces are long upwards, but not completely 90 degrees, but 70 degrees, 80 degrees and the like, the V-shaped cavity structure is formed naturally.
The application also provides a photoelectric detector, and the film is applied to the photoelectric detector.
Further, the film comprises a substrate and SnSe which are sequentially stackedxThe nano-sheet array thin film comprises a nano-sheet array thin film, an insulating layer, an adhesive layer and a first electrode, wherein the substrate comprises a substrate and a second electrode, and the substrate, the second electrode and the SnSe are arranged on the substratexThe nano-sheet array films are sequentially laminated.
Further, the insulating layer is Al2O3The glue layer is a polymethyl methacrylate layer PMMA, an electron beam photoresist positive glue layer RZJ-304 or an epoxy negative glue layer SN-100; the first electrode is a titanium electrode, and the second electrode is a titanium electrode. Al (Al)2O3The layer thickness is about 4 nm.
Further, the substrate is a 4-inch silicon wafer or glass. Preparation of 4-inch chip-scale large-area vertical structure SnSe2A film.
Further, the Al2O3Layer deposition by atomic layer with said SnSexAnd (3) a nano-sheet array film.
Further, the glue layer is arranged on the Al layer by spin coating2O3On the layer.
The thickness of the spin coating is regulated and controlled by controlling the rotating speed, and then the thickness of the spin coating is tested by a film thickness meter. The rotating speed is 700-3700 rpm, and the thickness is controlled to be about 1-2 μm.
After the glue homogenizing operation is finished, an electron beam evaporation method is used for carrying out evaporation coating on the electrode, and the Ti-Au electrode is characterized by stability, excellent light transmittance and thickness control between 15nm and 20 nm.
Specifically, (1) preparing a layer of patterned Ti/Au bottom electrode on a glass substrate by an electron beam evaporation technology;
(2) SnSe deposition on glass/Ti/Au substrates by ultra-high vacuum co-evaporation technique2A film;
(3) by atomic layer deposition in SnSe2Al after a layer of about 4nm is deposited on the surface of the nanosheet2O3；
(4) Spin-coating a layer of PMMA as an isolation layer by a spin coating process;
(5) patterned Ti/Au top electrodes were prepared by electron beam evaporation technique.
SnSe2The vertical V-shaped structure of the two-dimensional thin film material has a very obvious light trapping effect, the light utilization efficiency is greatly enhanced, the absorption of light with the wavelength of 340nm to 650nm exceeds 90 percent, and the light responsivity and the external quantum efficiency of the detector can be effectively improved. In addition, compared with the traditional discretization two-dimensional material photoelectric detector, the prepared SnSe2The film has uniform large area and low growth temperature, and can be compatible with CMOS chips. These advantages lead to a two-dimensional material SnSe2The film becomes a core photosensitive material of the next generation of high-performance broadband photoelectric detector, is expected to promote the industrialization process of the next generation of photoelectric detector, and meets the increasing market demand on the high-performance broadband photoelectric detector.
The performance parameters of the photodetector mainly include light responsivity, noise power, response time and the like. The performance of a photodetector based on a two-dimensional material semiconductor is greatly dependent on the growth quality of the two-dimensional layered semiconductor material and the design of a device structure. Group IV-VI semiconductor materials such as selenium disulfide (SnS)2) Tin diselenide (SnSe)2) Etc. canSo as to grow the nanometer film meeting the performance requirement under the substrate of various materials. However, most of the nanosheets prepared by the existing chemical vapor deposition process are too sparse and discrete, and the responsivity and the response time can not meet the actual performance requirements. High-density tin diselenide (SnSe) growth by low-temperature PVD method2) The film is not only uniform but also has higher bonding strength with the substrate.
The electric detector is widely applied to the fields of optical communication, safety monitoring, biomedical imaging, industrial detection and the like.
High performance broadband photodetectors.
FIGS. 2a-b are respectively Ti/Au/SnSe2SnSe of nanosheet and final upright structure2A photodetector.
FIG. 3 is a prepared 4-inch silicon chip substrate large-area vertical structure SnSe2A film.
FIGS. 4a-b SnSe2Top and cross-sectional view SEM images of the nanoplatelets. c-d is SnSe after PMMA spin coating process2Top and cross-sectional view SEM images of the nanoplatelets.
FIG. 5 is SnSe2The absorption of the nano sheet array on electromagnetic waves with wave bands of 400-600 nm is more than 90%. Fig. 5 (b): at 390, 532 and 633nm, according to the formula R ═ Iph/PS, wherein IphFor photocurrent, P is the power density (0.5 mW/cm)2) S is the device area (100 um), SnSe2The responsivity of the photodetector is 31.42A/W, 13.13A/W and 8.98A/W respectively.
FIG. 6 is a V-shaped SnSe2According to the schematic diagram and the simulation result of the light trapping characteristic of the nanosheets, incident electromagnetic waves are reflected for multiple times in the V-shaped cavity, and the maximum electric field intensity is at the bottom of the V-shaped row of nanosheets.
Compared with the traditional tiled two-dimensional material laminated structure, the two-dimensional IV-VI semiconductor material with the vertical array structure shows obvious light trapping effect, the light absorption rate of the material is greatly improved, the absorption coefficient reaches more than 90 percent, and the preliminarily obtained quantum efficiency of the photoelectric detector pair reaches 1.02 multiplied by 104% and response time is less than 400 mu s.
Compared with the traditional discrete thin-layer structure, the two-dimensional IV-VI semiconductor with large area and uniformity (10cm multiplied by 10cm, 4 inch silicon chip) can more easily realize the preparation of the photoelectric detector array, and can have the opportunity to promote the industrialization process of the novel ultrahigh-performance broadband photoelectric detector.
Preparation of Al by ALD2O3And the passivation layer and other technologies regulate and control the surface defect state of the material so as to further improve the response time of the broadband detector.
The application provides a process for directly growing a detector absorption material on a CMOS chip (Si chip) to prepare a two-dimensional imaging chip integrated with CMOS equipment.
Although the present application has been described above with reference to specific embodiments, those skilled in the art will recognize that many changes may be made in the configuration and details of the present application within the principles and scope of the present application. The scope of protection of the application is determined by the appended claims, and all changes that come within the meaning and range of equivalency of the technical features are intended to be embraced therein.
Claims (10)
1. A method for preparing a film, which is characterized by comprising the following steps: and under the condition that the temperature is lower than 250 ℃, the tin material source and the selenium material source are heated, so that the tin and the selenium are longitudinally grown on the substrate after being evaporated to form the semiconductor nanosheet array film.
2. The method for preparing a thin film according to claim 1, wherein: SnSe is grown and formed on the substrate by adopting a molecular beam epitaxy processxA nanosheet array film; the molecular beam epitaxy process comprises the steps of adding a high-purity selenium material source and a high-purity tin material source into molecular beam epitaxy equipment respectively, heating the selenium material source and the tin material source through the molecular beam epitaxy equipment respectively, spraying the selenium material source onto a substrate in a molecular beam or atomic beam mode, and spraying the tin material source onto the substrate in a molecular beam or atomic beam mode to form SnSexA nanosheet array film.
3. The method for preparing a thin film according to claim 2, wherein: rotating the substrate such that the SnSe isxThe nano-sheet array film grows uniformly.
4. A method for producing a film according to any one of claims 1 to 3, wherein: the semiconductor nano-sheet array film is SnSe2The two-dimensional film material vertical V-shaped structure.
5. A photodetector, characterized by: use of the film of any one of claims 1 to 4 in a photodetector.
6. The photodetector of claim 5, wherein: comprises a substrate and SnSe sequentially laminatedxThe nano-sheet array thin film comprises a nano-sheet array thin film, an insulating layer, an adhesive layer and a first electrode, wherein the substrate comprises a substrate and a second electrode, and the substrate, the second electrode and the SnSe are arranged on the substratexThe nano-sheet array films are sequentially laminated.
7. The photodetector of claim 6, wherein: the insulating layer is Al2O3The adhesive layer is a polymethyl methacrylate layer, an electron beam photoresist positive adhesive layer or an epoxy negative adhesive layer; the first electrode is a titanium electrode, and the second electrode is a titanium electrode.
8. The photodetector of claim 6, wherein: the substrate is a 4 inch silicon wafer or glass.
9. The photodetector of claim 7, wherein: the Al is2O3Layer deposited on the SnSe by atomic layerxAnd (3) a nano-sheet array film.
10. The photodetector of claim 7, wherein: the glue layer is formed by spin coatingIs provided on the Al2O3On the layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111301989.6A CN114122192A (en) | 2021-11-04 | 2021-11-04 | Film preparation method and photoelectric detector |
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| CN112820787A (en) * | 2021-01-27 | 2021-05-18 | 深圳先进技术研究院 | Photoelectric detector based on vertical two-dimensional thin film material and preparation method thereof |
| CN113292042A (en) * | 2021-04-22 | 2021-08-24 | 江苏度微光学科技有限公司 | Ultra-wide spectrum absorber, preparation method and application of absorber in spectrometer |
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| CN112820787A (en) * | 2021-01-27 | 2021-05-18 | 深圳先进技术研究院 | Photoelectric detector based on vertical two-dimensional thin film material and preparation method thereof |
| CN113292042A (en) * | 2021-04-22 | 2021-08-24 | 江苏度微光学科技有限公司 | Ultra-wide spectrum absorber, preparation method and application of absorber in spectrometer |
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| WO2024087338A1 (en) * | 2022-10-25 | 2024-05-02 | 深圳先进技术研究院 | Thermosensitive thin film, infrared detector, and manufacturing method for infrared detector |
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