CN115347075A - Two-dimensional material KP improved by surface doping 15 Method of electrical performance - Google Patents
Two-dimensional material KP improved by surface doping 15 Method of electrical performance Download PDFInfo
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- H—ELECTRICITY
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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
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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
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H01L31/10—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 in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/112—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
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Abstract
A method for improving the electrical property of a two-dimensional material KP15 by surface doping belongs to the field of photoelectric materials and devices. The invention regulates and controls KP by doping organic molecules on the surface of the material 15 The conductivity type and the carrier concentration of the conductive material greatly improve the electrical property of the conductive material. The method is simple, has obvious effect, does not cause damage to the material, has reversibility, and can be popularized and applied to the doping of other two-dimensional materials. In addition, the present invention enhances KP 15 The conductivity of the material lays a foundation for the application of the polarization photoelectric detector.
Description
Technical Field
The invention belongs to the field of photoelectric materials and devices, and particularly relates to a method for improving KP (Kernel Permeability) through surface doping 15 Method of electrical properties of a material.
Background
Polarization is a very important optical information, and for any object in nature, light, after being reflected and transmitted, contains polarization spectrum information determined by the characteristics of the object itself. The detector based on the polarized light has wide application in the fields of remote sensing imaging, environmental monitoring, medical detection, military equipment and the like. From the 20 th century and the 70 th century, the technology of polarized light detectors has been continuously developed and improved, and has undergone various evolutions and improvements, such as a rotating polarizer type, a split-amplitude type, a liquid crystal modulation/acousto-optic tunable filter type, a channel modulation type, a micro-nano device type and the like. Currently, polarization photodetectors are moving toward miniaturization and integration. To achieve miniaturization and integration of polarized light detectors, a directly effective method is to use a semiconductor material that is itself polarization-sensitive as the working medium of the detector. The anisotropic two-dimensional material has the outstanding advantages of sensitivity to polarized light, adjustable band gap, no dangling bond on the surface, contribution to device integration and the like, and is widely applied to the field of photoelectricity in recent years.
KP 15 Is a high-anisotropy sheet material, has rich and non-toxic raw materials, and has single-layer and multi-layer KP (Kernel pressure) proved by experiments and theories 15 Has good stability in atmospheric environment and single-layer KP 15 Has higher theoretical hole mobility (2.46 +/-0.95 multiplied by 10) 3 cm 2 V -1 s -1 ). Based on KP 15 The prepared photoelectric detector has the advantages of high response speed (10 ms) and high detection rate (more than 10) 10 Jones). Furthermore, KP 15 The high anisotropy of light emission and absorption has been experimentally and theoretically demonstrated, KP 15 The method is extremely expected to be applied to the development of the subminiature polarized photoelectric detector. However, KP 15 Has lower conductivity, is not beneficial to the extraction of photon-generated carriers, and influences the responsivity of the photon-generated carriers, thereby limiting the further development of the photon-generated carriers. Improving KP 15 The conductivity of materials is an important issue that needs to be addressed at present.
Doping is a common method to improve the performance of two-dimensional semiconductor materials. The concentration of the current carrier can be improved by doping, and KP is hopeful to be improved 15 Conductivity of the material, promotion of KP 15 The material was further developed. Currently, some researchers have attempted to improve KP by doping other elements during the growth of the material 15 Electrical properties of the material. However, the doping method needs to achieve the expected doping effect by theoretical calculation and prediction and multiple times of adjustment of experimental parameters, and the workload of researchers is greatly increased. In additionIn addition, the method requires a long time period, which is not favorable for KP 15 The rapid development of materials. Aiming at the problems, the KP is adsorbed by organic molecules 15 The material is subjected to surface doping, and KP is realized 15 And the electrical property of the material is improved. The surface doping method can simply and effectively improve KP 15 The electrical property of the material can not affect the crystal structure of the material. In addition, compared with other methods for doping and modifying the surface, the method has a reversible type and is beneficial to the repeated use of materials.
Disclosure of Invention
It is an object of the invention to improve KP 15 The poor conductivity of the material provides a means to increase KP by surface doping 15 A method of conducting electrical properties. The principle of the method is as follows: when the dopant is adsorbed on KP 15 When the surface of the material is coated, the electron affinity of the material and the electron affinity of the material are different, so that charges are transferred. When the electron affinity of the dopant is greater than that of the material, electrons are transferred from the material to the dopant, and the hole concentration of the material increases; when the electron affinity of the dopant is smaller than that of the material, electrons are transferred from the dopant into the material, and the electron concentration of the material increases. The carrier concentration of electrons or holes of the material can be improved by adopting different dopants, the conductivity of the material is improved, and the conductivity type of the material is adjusted. The invention has the advantages of low cost, simple operation, obvious effect and reversibility, is suitable for improving the electrical property of a two-dimensional material and adjusting the conductivity type, and has great effect in the future photoelectron field.
The technical scheme provided by the invention is as follows:
the invention discloses a method for changing KP by doping 15 The method can change KP by controlling the concentration of the dopant (in the range of 2mmol/L-10 mmol/L) and the doping time (in the range of 10min-2 h) 15 The carrier concentration of the material, and further the KP is improved 15 Electrical properties of the field effect transistor. The specific implementation steps are as follows:
(1) Preparation of bulk KP 15 : the raw materials potassium and red phosphorus were weighed in a glove box and sealed in a vacuum quartz tube. Growing acicular KP in low-temperature region by adopting chemical vapor transport method 15 Material, and obtaining KP by crushing quartz tube 15 A material.
(2)KP 15 Preparing a field effect transistor: bonding KP blocks with adhesive tape 15 Performing mechanical stripping and transferring to Si/SiO 2 On a substrate. Adopting ultraviolet exposure machine to make photoetching to obtain proper electrode pattern on the material, adopting electron beam evaporation and metal-stripping (Live-off) process to obtain parallel electrode penetrating through the material on the material so as to obtain KP 15 The field effect transistor of (1).
(3)KP 15 Surface doping of the material: the doping is based on the KP being prepared 15 Field effect transistors. To KP 15 The field effect transistor is soaked in an isopropanol solution of LI-TFSI to realize surface doping of the material.
(4) Measurement of electrical properties: use of B1500A semiconductor parameter analyzer to treat MP before and after doping 15 The electrical properties of the field effect transistor were measured.
Compared with the prior art, the invention has the beneficial effects that:
the invention is based on a two-dimensional material KP 15 A field effect transistor was produced. And a surface doping method is adopted, and the conductivity type and the carrier concentration are adjusted by utilizing charge transfer between the dopant and the material so as to improve the conductivity of the material. The invention has the characteristics of low price, simplicity, effectiveness, reversible doping, no damage to the structure of the material, and popularization and application in the photoelectron field of other two-dimensional materials. Furthermore, KP 15 The improvement of the electrical conductivity of the material will also help the further development of the polarization photodetector.
Drawings
FIG. 1 is a schematic diagram of the preparation of KP by an embodiment of the present invention 15 A field effect transistor schematic diagram (a) and a photoscope photograph (b).
FIG. 2 shows KP according to the present invention 15 Schematic illustration of material doping.
FIG. 3 shows KP before and after doping and after de-doping in an embodiment of the present invention 15 R of the materialand (4) performing aman characterization. KP (Key Performance) 15 The raman peak of (a) is shifted after doping and returns to the original position after removal of the doping, demonstrating the success of the doping and the reversibility of the doping.
FIG. 4 shows KP before and after doping and after de-doping in an embodiment of the present invention 15 I-V plot (a) and transfer plot (b) after doping.
FIG. 5 shows KP after adjusting dopant concentration (a) and doping time (b) in an example of the present invention 15 I-V curve of (a).
Detailed Description
The invention is further described below with reference to the examples of implementation, but the invention is not limited to the scope of this example of implementation.
Example 1
(1)KP 15 Preparation of the Material
Ultrasonically cleaning a quartz tube with the length of 15cm for 15min by using deionized water and alcohol, and drying in a vacuum drying oven for 2h after ultrasonic cleaning. In a glove box, 1.822g of red phosphorus and 0.178g of metal potassium are respectively weighed by a precision balance, put in a dried quartz tube and vacuumized with the vacuum degree less than 10 -5 bar. Putting the packaged quartz tube into a horizontal double-temperature-zone tube furnace, placing one end with materials in a high-temperature zone, wherein the temperature of the high-temperature zone is 650 ℃, placing the other end in a low-temperature zone, wherein the temperature of the low-temperature zone is 400 ℃, keeping the temperature for 12 hours, naturally cooling at room temperature to obtain dark brown crystals in the quartz tube, transferring the quartz tube to a glove box, crushing the quartz tube, and collecting clean crystals without attachments on the surface.
(2)KP 15 Mechanical stripping and transfer of materials
First, KP of a block body 15 The material was placed on tape, folded in half, torn open and this operation repeated 6 times. Then, the Polydimethylsiloxane (PDMS) is tightly attached to the belt with KP 15 The adhesive tape of (1) transfers the sample to the PDMS by means of adhesion between the two. Will then carry KP 15 PDMS of the sample clinging to Si/SiO 2 Placing the substrate on a constant temperature heating table at 70 deg.C, taking off PDMS and KP after 2min 15 Is transferred to Si/SiO 2 On a substrate. Before use of the substrateUltrasonic treating with deionized water, alcohol and acetone, and cleaning with plasma.
(3)KP 15 Preparation of field effect transistor
KP 15 The field effect transistor is prepared by adopting a negative glue process. Will carry KP 15 The silicon chip is placed on a spin coater for coating, photoresist is firstly spread at a low rotating speed of 500r/min (the time is 10 s), and then the rotating speed of 4000r/min is used for spin coating for 50s to spin off the redundant photoresist. And (3) placing the sample after the photoresist is homogenized on a heating table to be heated for 3min, then selecting parallel electrode masks, and modifying the photoresist by adopting an ultraviolet lithography method. And then, quickly putting the sample subjected to ultraviolet exposure into a developing solution, removing unexposed photoresist, obtaining a photoetching parallel electrode pattern on the sample, controlling the developing time to be 35s, cleaning the sample with deionized water after the developing is finished, drying the sample with nitrogen, and baking the sample on a heating table for 2min. And depositing a metal electrode by adopting an electron beam evaporation method. The thickness of the metal electrode is 5nm and 80nm respectively. After the deposition was completed, the sample was put into an acetone solution for ultrasonic treatment at an ultrasonic power of 40W. After sonication, the excess metal film was removed, revealing parallel metal electrodes that penetrated the sample. The device fabrication process is now complete.
(4) Surface charge transfer doping
The weighed LI-TFSI powder was poured into the isopropanol solvent and stirred uniformly using a magnetic stirrer to obtain a 2mmol/L isopropanol solution of LI-TFSI. KP prepared by the method 15 And putting the field effect transistor into the prepared isopropanol solution of 2mmol/L LI-TFSI, keeping one surface of the electrode upward, taking out after 10min, drying, and oven drying. LI-TFSI physical adsorption on KP 15 And the surface of the material realizes surface charge transfer doping. And, after doping, KP 15 Soaking the field effect transistor in isopropanol solution for 3h, and adsorbing on KP 15 The LI-TFSI on the material will re-dissolve in the isopropanol solvent to effect removal of the dope.
(5)KP 15 Field effect transistor performance testing
Testing KP before and after doping using B1500A semiconductor parameter analyzer 15 An output curve and a transfer curve of the field effect transistor.
Example 2
The specific conditions and parameters of this example were the same as those of example 1 except that the doping time was changed to 30min, 1h, 2h, and 3h, respectively, in step (4), and the experimental results were as shown in fig. 5 (b).
Example 3
This example was carried out under the same conditions and parameters as in example 1 except that in step (4), the doping time was changed to 2 hours and the doping concentration was changed to 4mmol/L, 6mmol/L, 8mmol/L and 10mmol/L, respectively, and the experimental results were shown in FIG. 5 (a).
It will be appreciated that this embodiment is disclosed to further aid in the understanding of the invention. Embodiments of the invention are not limited in this regard. Any changes and modifications are possible without departing from the scope of the idea of the invention and the appended claims. Therefore, the protection scope of the present invention is defined by the claims.
Claims (6)
1. Two-dimensional material KP improved by surface doping 15 A method of electrical performance, characterized by the steps of:
step 1) preparation of KP by using chemical vapor transport method 15 A material;
step 2) KP 15 Mechanical peeling and transferring of materials;
step 3) preparing KP by using photoetching, electron beam evaporation and Live-off processes 15 A field effect transistor;
step 4) KP 15 Surface doping of (2);
the doping in the step 4) is to use a dip-coating mode to dope KP 15 Immersing the field effect transistor into an LI-TFSI organic solution, wherein the concentration range of the LI-TFSI organic solution is 2mmol/L-10mmol/L, fishing out and drying after 10min-2h, and drying on a heating table, wherein LI-TFSI is adsorbed on the surface of the material to realize surface doping; doped KP 15 And soaking the field effect transistor in an organic solvent for 30min, fishing out and drying to realize doping removal.
2. Method according to claim 1 for improving KP in two-dimensional materials by surface doping 15 A method of electrical performance, characterized by: KP in step 1) 15 The preparation of the composite material adopts a chemical vapor transport method, the temperature of a high-temperature area of a tubular furnace is 650 ℃, the temperature of a low-temperature area of the tubular furnace is 400 ℃, and the tubular furnace is cooled along with the furnace after heat preservation for 12 hours.
3. Method according to claim 1 for improving KP in two-dimensional materials by surface doping 15 A method of electrical performance, characterized by: KP in step 2) 15 The mechanical peeling and transfer of the material is to make KP of the block 15 The material is put on the adhesive tape and is repeatedly folded and torn for 6 to 7 times; then attaching polydimethylsiloxane PDMS tightly with KP 15 The sample is transferred to the PDMS by means of the adhesion force between the two on the adhesive tape; will then carry KP 15 PDMS of the sample clinging to Si/SiO 2 Placing the substrate on a constant temperature heating table at 70 deg.C, taking off PDMS and KP after 2min 15 Is transferred to Si/SiO 2 On a substrate.
4. The method of claim 1, wherein KP is increased by surface doping 15 A method of electrical performance characterized by: in the step 3), the photoetching adopts a negative photoresist process, and the photoresist coating parameters are as follows: 500r/min 10s,4000r/min 50s. Heating on a heating table for 3min after the glue is homogenized, wherein the developing time is 35s; the electrode of the field effect transistor adopts an Au/Ti composite layer, and the thicknesses of the Au/Ti composite layer and the Au/Ti composite layer are respectively 80nm and 5nm; and removing redundant electrodes by adopting an acetone solution ultrasonic method, wherein the ultrasonic power is 40W.
5. Method according to claim 1 for improving KP in two-dimensional materials by surface doping 15 A method of electrical performance, characterized by: the dopant can be based on KP 15 The difference of the electron affinity of the materials is selected, the electron affinity of the dopant is larger than that of the materials to realize P-type doping, and the electron affinity of the dopant is smaller than that of the materials to realize N-type doping.
6. According to the claimsOne method described in claim 1 for improving KP of two-dimensional material by surface doping 15 A method of electrical performance, characterized by: KP (Key Performance) 15 By conversion to NaP 15 A material.
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| US4732659A (en) * | 1984-06-11 | 1988-03-22 | Stauffer Chemical Company | Sputtering method for making thin film field effect transistor utilizing a polypnictide semiconductor |
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| JP2020021828A (en) * | 2018-08-01 | 2020-02-06 | 国立研究開発法人物質・材料研究機構 | Semiconductor device and manufacturing method thereof |
| CN111490166A (en) * | 2020-04-24 | 2020-08-04 | 电子科技大学 | Flexible perovskite photoelectric detector based on novel polymer hole transport layer and preparation method thereof |
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Patent Citations (4)
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|---|---|---|---|---|
| US4732659A (en) * | 1984-06-11 | 1988-03-22 | Stauffer Chemical Company | Sputtering method for making thin film field effect transistor utilizing a polypnictide semiconductor |
| CN105439084A (en) * | 2015-12-06 | 2016-03-30 | 北京工业大学 | Novel semiconductor KP15 nanowire and preparation technology thereof |
| JP2020021828A (en) * | 2018-08-01 | 2020-02-06 | 国立研究開発法人物質・材料研究機構 | Semiconductor device and manufacturing method thereof |
| CN111490166A (en) * | 2020-04-24 | 2020-08-04 | 电子科技大学 | Flexible perovskite photoelectric detector based on novel polymer hole transport layer and preparation method thereof |
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