CN115241306A - Bismuth selenium sulfur semiconductor, preparation and broad-spectrum and ultra-fast polarization photoelectric detector - Google Patents
Bismuth selenium sulfur semiconductor, preparation and broad-spectrum and ultra-fast polarization photoelectric detector Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 229910052797 bismuth Inorganic materials 0.000 claims description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 17
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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
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Abstract
The invention provides a bismuth selenium sulfur semiconductor, a preparation method thereof and a broad-spectrum ultrafast polarization photoelectric detector. The bismuth selenium sulfur semiconductor is a crystal, and the chemical structural formula of the bismuth selenium sulfur semiconductor is Bi x Se y S z Wherein x is more than or equal to 1 and less than or equal to 2,0 and more than or equal to y is more than or equal to 3,0 and more than z is less than or equal to 3, and 3x =2y +2z. In the above bismuth-selenium-sulfur semiconductor, bi 2 Se 3 The semiconductor has an orthorhombic structure formed by doping S into Bi 2 Se 3 In the middle, bi grows out x Se y S z A semiconductor. Compare Bi 2 Se 3 Semiconductor, bi x Se y S z The band structure of the semiconductor is optimized and enriched, and therefore, the semiconductor can be used as a semiconductorThe constructed photoelectric device has lower dark current and wider detection range, and is beneficial to realizing the high performance of the photoelectric device.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a bismuth selenium sulfur semiconductor, a preparation method thereof and a broad-spectrum ultrafast polarization photoelectric detector.
Background
In recent years, low dimensional crystals have been widely studied in the field of optoelectronic devices because of their excellent properties exhibited by their excellent quantum size effect. Among these low dimensional crystals, topological materials with low symmetry are considered as one of the candidates for high performance optoelectronic devices. However, the topological physical characteristics lead to larger dark-state current in the corresponding photoelectric device, and the further development of the photoelectric device in the photoelectric field is severely limited. Opening the surface gap is critical to solving these problems. Semiconductor alloying is a good strategy for controlling the electronic energy band structure of the semiconductor, and can widen the photoresponse range of corresponding photoelectric devices.
As a representative of the V-VI semiconductor material, bi 2 Se 3 Theoretical and experimental researches prove that the semiconductor has ultrahigh electron mobility and can be used for constructing electronic devices based on high-performance topological insulators. In particular, high electron mobility facilitates rapid transport of charge carriers, which facilitates ultra-fast optical response of the optoelectronic device. However, its high dark current causes the device to operate noisier.
Disclosure of Invention
The invention mainly aims to provide a bismuth selenium sulfur semiconductor, a preparation method thereof and a broad-spectrum ultrafast polarization photoelectric detector, so as to solve the problem of Bi 2 Se 3 The dark current of the constructed photoelectric device is high.
In order to achieve the above object, the first aspect of the present invention provides a bismuth-selenium-sulfur semiconductor, wherein the bismuth-selenium-sulfur semiconductor is a crystal, and the chemical structural formula of the bismuth-selenium-sulfur semiconductor is Bi x Se y S z Wherein x is more than or equal to 1 and less than or equal to 2,0 and more than or equal to 3,0 and more than z and less than or equal to 3.
Optionally, in Bi x Se y S z Wherein x =2,0 < y ≦ 3,0 < z ≦ 3.
Optionally, in Bi x Se y S z In (1), x =2, y =2.15, z =0.85.
The second aspect of the invention provides a preparation method of a bismuth selenium sulfur semiconductor, which comprises the following steps:
bismuth powder, selenium powder and sulfur powder are provided.
The bismuth-selenium-sulfur semiconductor is directly grown on the insulating substrate by adopting chemical vapor deposition, physical vapor deposition and metal organic source chemical vapor deposition. Or chemical vapor transport and hydrothermal-solvothermal synthesis are adopted to directly grow the bismuth selenium sulfur semiconductor.
Optionally, the step of growing the bismuth selenide sulfide crystal directly on the insulating substrate by chemical vapor deposition comprises:
bismuth powder, selenium powder and sulfur powder are placed at the upper end of the tube furnace in the airflow direction.
The insulating substrate is placed at the lower end of the tube furnace in the gas flow direction.
Heating the tube furnace to 680-720 ℃ at the speed of 10-30 ℃/min under the atmosphere of protective gas, and preserving the temperature for 5-20 minutes to carry out chemical vapor deposition to obtain the bismuth selenium sulfur semiconductor.
Optionally, the protective gas is inert gas, the tube furnace is heated to 700 ℃ at the speed of 20 ℃/min, and the temperature is kept for 10 minutes for chemical vapor deposition.
Optionally, the step of directly growing the bismuth selenium sulfide semiconductor by chemical vapor transport comprises:
the bismuth powder, the selenium powder, the sulfur powder and the conveying medium are sealed in a quartz tube, and the quartz tube is in a vacuum atmosphere.
And (3) placing the quartz tube in a double-temperature-zone tube furnace, setting the temperature of the first temperature zone and the second temperature zone to be 780-820 ℃, keeping the temperature for 720-1440 minutes, and cooling.
Taking out the quartz tube, uniformly mixing the materials in the quartz tube, putting the quartz tube into the double-temperature-zone tube furnace again, heating the first temperature zone to 680-720 ℃ and the second temperature zone to 620-660 ℃ at the heating rate of 5-20 ℃/min, and keeping the temperature for 1-7 days; then, the temperature is reduced to 250-300 ℃ at the speed of 0.6-0.9 ℃/min, and the mixture is cooled.
And taking out the growth material in the quartz tube.
And removing the conveying medium in the growth material to obtain the bismuth selenium sulfur semiconductor.
Optionally, the quartz tube is placed into the double-temperature-zone tube furnace again, the first temperature zone is heated to 700 ℃ and the second temperature zone is heated to 640 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 6 days; then, the temperature is reduced by 300 ℃ at the speed of 0.8 ℃/min, and the product is cooled.
Optionally, the transport medium is elemental iodine.
The step of removing the transport medium within the growth material comprises:
the growth material was placed in a tube furnace under protective gas and annealed at 200 ℃ for 5 hours.
The invention provides a broad-spectrum and ultra-fast polarization photoelectric detector, which comprises a substrate and a semiconductor material arranged on the substrate, wherein the semiconductor material is the bismuth selenium sulfur semiconductor or the bismuth selenium sulfur semiconductor prepared by the preparation method.
In the above-mentioned Bi-Se-S semiconductor, bi 2 Se 3 The semiconductor has an orthorhombic structure formed by doping S into Bi 2 Se 3 In the middle, bi grows out x Se y S z A semiconductor. Compare Bi 2 Se 3 Semiconductor, bi x Se y S z The band structure of the semiconductor is optimized and abundant, so that the photoelectric device constructed by the semiconductor is low in dark current and wide in detection range, and the high performance of the photoelectric device is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a diagram of a photodetector spectrum detection according to an embodiment of the present application;
FIG. 2 is an I-V diagram of a photodetector according to an embodiment of the present application;
FIG. 3 is a graph of response time of a photodetector according to an embodiment of the present application;
FIG. 4 is an I-T diagram of a photodetector according to an embodiment of the present application;
FIG. 5 is an EDS spectrum of a bismuth selenide sulfur semiconductor according to an embodiment of the present application;
fig. 6 is a schematic diagram of a photodetector according to an embodiment of the present application.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that all the directional indicators (such as upper and lower … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the figure), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
To realizeIn order to achieve the above object, the first aspect of the present invention provides a bismuth-selenium-sulfur semiconductor, wherein the bismuth-selenium-sulfur semiconductor is a crystal, and the chemical structural formula of the bismuth-selenium-sulfur semiconductor is Bi x Se y S z Wherein x is more than or equal to 1 and less than or equal to 2,0 and more than or equal to y is more than or equal to 3,0 and more than z is less than or equal to 3, and 3x =2y +2z.
The bismuth selenide sulfide semiconductor is a crystal, and the structure of the crystal includes but is not limited to bulk crystal, thin film, nanowire, quantum dot, superlattice, quantum well and the like. And crystalline states thereof include, but are not limited to, single crystal, polycrystalline, microcrystalline, amorphous, and the like.
The chemical structural formula of the bismuth selenium sulfur semiconductor is Bi x Se y S z Substantially represents a series of compounds represented by Bi 2 Se 3 The semiconductor is a bismuth selenium sulfur semiconductor material doped with S. The specific bismuth-selenium-sulfur semiconductor material is reflected in different x, y and z in the corresponding structural formula due to different doping degrees. In other words, in the preparation process, the proportions of the bismuth powder, the selenium powder and the sulfur powder in the raw materials can be changed, so that different bismuth-selenium-sulfur semiconductor materials can be obtained by changing the proportions of the bismuth powder, the selenium powder and the sulfur powder. Therefore, bismuth selenium sulfur semiconductor materials with different band gaps can be obtained, and further, corresponding broadband photoelectronic devices can be prepared, and the method can be particularly applied to broadband photoelectronic devices from deep ultraviolet to infrared, and can be applied to broad-spectrum and ultra-fast polarization photodetectors.
In the above bismuth-selenium-sulfur semiconductor, bi 2 Se 3 The semiconductor has an orthorhombic structure formed by doping S into Bi 2 Se 3 In the middle, bi grows out x Se y S z A semiconductor. Compare Bi 2 Se 3 Semiconductor, bi x Se y S z The band structure of the semiconductor is optimized and abundant, so that a photoelectric device (such as a broad-spectrum and ultra-fast polarized photoelectric detector) constructed by the semiconductor has lower dark current and wider detection range, and is beneficial to realizing high performance of the photoelectric device.
Optionally, in Bi x Se y S z Wherein x =2,0 < y ≦ 3,0 < z ≦ 3.
Optionally, in Bi x Se y S z Where x =2,y =2.15,z =0.85. In this case, the bismuth selenium sulfur semiconductor is Bi 2 Se 2.15 S 0.85 And (4) crystals.
The second aspect of the invention provides a preparation method of a bismuth selenium sulfur semiconductor, which comprises the following steps:
s100, providing bismuth powder, selenium powder and sulfur powder.
In step S100, the bismuth powder, the selenium powder and the sulfur powder have high purity, and illustratively, the bismuth powder may be a bismuth powder having a purity of 99.999%, the sulfur powder may be a sulfur powder having a purity of 99.999%, and the selenium powder may be a selenium powder having a purity of 99.999%.
S200, directly growing the bismuth selenium sulfur semiconductor on the insulating substrate by adopting chemical vapor deposition, physical vapor deposition and metal organic source chemical vapor deposition. Or chemical vapor transport and hydrothermal-solvothermal synthesis are adopted to directly grow the bismuth selenium sulfur semiconductor.
In step S200, there are various methods for growing the bi-se-S semiconductor, which are not particularly limited.
In some embodiments, chemical vapor deposition is used to grow bismuth selenium sulfur crystals directly on an insulating substrate, and the specific steps include:
s201, placing bismuth powder, selenium powder and sulfur powder at the upper end of a tube furnace in the airflow direction.
In step S201, bismuth powder, selenium powder, and sulfur powder may be weighed and mixed according to the ratio of each element in the bismuth-selenium-sulfur semiconductor, and then placed in a quartz boat. The quartz boat with the raw materials is placed at the upper end of the airflow of the tube furnace.
S202, placing the insulating substrate at the lower end of the tube furnace in the airflow direction.
In step S202, an insulating substrate is placed at the lower end of the tube furnace in preparation for material growth.
S203, heating the tube furnace to 680-720 ℃ at the speed of 10-30 ℃/min under the atmosphere of protective gas, and preserving the temperature for 5-20 minutes to carry out chemical vapor deposition to obtain the bismuth selenium sulfur semiconductor.
In step S203, the tube furnace is in a protective gas atmosphere. The shielding gas may be argon. High purity argon may be introduced at a relatively high flow rate for half an hour to remove air from the tube furnace and then argon may be continuously introduced at a relatively low flow rate. The tube furnace is heated to 680-720 ℃ at the speed of 10-30 ℃/min and is kept warm for 5-20 minutes. In the process, bismuth powder, selenium powder and sulfur powder positioned at the upper end of the airflow of the tubular furnace form corresponding gas, and the gas flows to the lower end of the tubular furnace along with argon gas and is deposited on the insulating substrate to grow and form the bismuth-selenium-sulfur semiconductor. After the growth is finished, the tube furnace is naturally cooled to room temperature, and then the bismuth selenium sulfur semiconductor is taken out.
It should be noted that the quantity and the form of the products deposited at too slow or too fast temperature rise and high or low temperature of the tube furnace are different, for example, the bismuth selenium sulfur crystal is in a nanowire state, the nanowire is too thick/too thin or too small in quantity, and the uniformity of the sample is reduced, which directly affects the electronic band structure and inevitably affects the performance.
Alternatively, in step S203, the tube furnace is heated to 700 ℃ at a rate of 20 ℃/min and held for 10 minutes for chemical vapor deposition. Under the condition, the bismuth-selenium-sulfur semiconductor has good appearance, good sample uniformity and high growth efficiency, and the formed bismuth-selenium-sulfur semiconductor crystal has high quality.
In other embodiments, the bismuth selenide sulfide semiconductor can also be directly grown by chemical vapor transport, and the specific steps include:
s301, sealing bismuth powder, selenium powder, sulfur powder and a conveying medium in a quartz tube, wherein the quartz tube is in a vacuum atmosphere.
In the step, bismuth powder, selenium powder and sulfur powder can be weighed according to the proportion of each element in the bismuth-selenium-sulfur semiconductor, mixed and placed in a quartz tube, and then a certain amount of conveying medium is added.
Pumping the quartz tube mixed with the above substances to vacuum, such as 10 deg.C, by using molecular pump -3 Pa, and sealing the quartz tube containing the substances in vacuum by using a oxyhydrogen machine.
S302, placing the quartz tube in a double-temperature-zone tube furnace, setting the temperature of the first temperature zone and the temperature of the second temperature zone to be 780-820 ℃, keeping the temperature for 720-1440 minutes, and cooling.
The holding time of this step may be 720 to 800 minutes, 820 to 950 minutes, 1020 to 1200 minutes, 1250 to 1330 minutes, 1300 to 1440 minutes. The step has the effects that the source materials are uniformly mixed under the drive of iodine vapor, and a polycrystalline bismuth selenium sulfur semiconductor is generated at high temperature, so that the source materials are provided for the growth of the high-quality bismuth selenium sulfur semiconductor.
S303, taking out the quartz tube, uniformly mixing the materials in the quartz tube, putting the quartz tube into the double-temperature-zone tube furnace again, heating the first temperature zone to 680-720 ℃, heating the second temperature zone to 620-660 ℃ at the heating rate of 5-20 ℃/min, and keeping the temperature for 1-7 days; then, the temperature is reduced to 250-300 ℃ at the speed of 0.6-0.9 ℃/min, and the mixture is cooled.
In this step, the first temperature zone is a high temperature zone (may also be referred to as a source zone), and the second temperature zone is a low temperature zone (may also be referred to as a growth zone). The temperature difference between the low temperature region and the high temperature region is ensured to be between 50 and 100 ℃ in the growth process, and the effective transportation can be realized. The first temperature zone and the second temperature zone have too high temperature to cause uneven crystals, and the first temperature zone and the second temperature zone have too low temperature to cause the growth period of the crystals to be prolonged or even not to grow. Thus, the first temperature zone is heated to 700 ℃ and the second temperature zone is heated to 640 ℃. The holding time, i.e., the heat-retaining time in this step may be 1 to 2 days, 2 to 4 days, 5 to 6 days, 6 to 7 days, or the like.
Illustratively, the first temperature zone is heated to 700 ℃ and the second temperature zone is heated to 640 ℃ at a heating rate of 10 ℃/min and kept for 6 days; then, the temperature is reduced by 300 ℃ at the speed of 0.8 ℃/min, and the product is cooled.
S304, taking out the growth material in the quartz tube.
In this step, the quartz tube may be opened and the grown material may be removed.
S305, removing the conveying medium in the growth material to obtain the bismuth selenium sulfur semiconductor.
In this step, for example, when the transport medium is elemental iodine, the growth material may be placed in a tube furnace under an inert gas atmosphere such as nitrogen or an inert gas atmosphere such as argon, and annealed at 200 ℃ for 5 hours.
The invention provides a broad-spectrum and ultra-fast polarization photoelectric detector, which comprises a substrate and a semiconductor material arranged on the substrate, wherein the semiconductor material is the bismuth selenium sulfur semiconductor or the bismuth selenium sulfur semiconductor prepared by the preparation method.
The bismuth selenide sulfide semiconductor can be applied to photoelectric devices, for example, bi can be used x Se y S z A broad spectrum of photovoltaic devices covering from deep ultraviolet to infrared was prepared as the absorbing region. As another example, use Bi x Se y S z The crystal is used as a working area to prepare a light-regulated logic device.
Example 1: direct growth of bulk Bi by Chemical Vapor Transport (CVT) x Se y S z A semiconductor.
Single-component Bi is prepared by adopting a Chemical Vapor Transport (CVT) method 2 Se 2.15 S 0.85 The semiconductor crystal is prepared by the following specific preparation method:
And 3, placing the quartz tube into a double-temperature-zone tube furnace, setting the temperature of two ends to 800 ℃, keeping for 1440 minutes, and naturally cooling.
And 4, taking out the quartz tube, uniformly mixing the materials, putting the quartz tube into the double-temperature-zone tube furnace again, heating the high-temperature zone (source zone) to 700 ℃ and the low-temperature zone (growth zone) to 640 ℃ at the heating rate of 10 ℃ per minute, and keeping the temperature for 6 days. Then, the temperature is reduced by 300 ℃ at the rate of 0.8 ℃ per minute, and finally, the temperature is naturally reduced to the room temperature.
And 5, opening the quartz tube and taking out the grown material.
And 6, placing the taken-out material in a tube furnace in a nitrogen atmosphere, and annealing for 5 hours at 200 ℃ to remove redundant iodine.
And 7, taking out the annealed material.
Step 8, see FIG. 5, characterize it as Bi by EDS (dispersive Spectroscopy) Spectroscopy 2 Se 2.15 S 0.85 A nanowire single crystal.
Example 2
The difference from example 1 lies in:
in the step 1, bi powder, sulfur powder and selenium powder are mixed according to a molar ratio of Bi: se: s =2:2.46: 0.54A total of 1 gram of material was mixed into a quartz tube while 5mg/mL iodine was added as a transport medium.
And 3, placing the quartz tube into a double-temperature-zone tube furnace, setting the temperature of two ends to 780 ℃, keeping the temperature for 720 minutes, and naturally cooling.
And step 4, taking out the quartz tube, uniformly mixing the materials, putting the quartz tube into the double-temperature-zone tube furnace again, heating the high-temperature zone (source zone) to 680 ℃ and the low-temperature zone (growth zone) to 620 ℃ at the heating rate of 5 ℃ per minute, and keeping the temperature for 7 days. Then, the temperature is reduced to 250 ℃ at the rate of 0.5 ℃ per minute, and finally, the temperature is naturally reduced to the room temperature.
Step 8, which is Bi after correlation characterization 2 Se 2.46 S 0.54 A nanowire single crystal.
The rest of the procedure was the same as in example 1
Example 3
The difference from example 1 lies in:
in the step 1, bi powder, sulfur powder and selenium powder are mixed according to a molar ratio of Bi: se: s =2:2.73: a total of 1 gram of the material was mixed in a quartz tube at a ratio of 0.27, and 5mg/mL of iodine was added as a transport medium.
And 3, placing the quartz tube into a double-temperature-zone tube furnace, setting the temperature of two ends to 820 ℃, keeping for 1200 minutes, and naturally cooling.
And step 4, taking out the quartz tube, uniformly mixing the materials, putting the quartz tube into the double-temperature-zone tube furnace again, heating the high-temperature zone (source zone) to 700 ℃ and the low-temperature zone (growth zone) to 650 ℃ at the heating rate of 5 ℃ per minute, and keeping the temperature for 1 day. Then, the temperature is reduced by 280 ℃ at the rate of 0.9 ℃ per minute, and finally, the temperature is naturally reduced to the room temperature.
Step 8, which is Bi after correlation characterization 2 Se 2.73 S 0.27 A nanowire single crystal.
The rest of the procedure was the same as in example 1.
Example 4: bi 2 Se 2.15 S 0.85 The specific preparation method of the base photoelectric detector (namely, the broad-spectrum and ultra-fast polarization photoelectric detector) comprises the following steps:
Example 5: preparation of Bi by Chemical Vapor Deposition (CVD) x Se y S z The specific preparation method of the semiconductor comprises the following steps:
And 2, placing the quartz boat at the upper end of the airflow of the tube furnace.
And 3, placing an insulating substrate at the lower end of the tube furnace for material growth.
And 4, introducing high-purity argon for half an hour to remove air in the tube furnace.
And 6, finishing growth and naturally cooling to room temperature.
Step 7, obtaining Bi 2 Se 2.96 S 0.04 A semiconductor.
Example 6: preparation of Bi by Chemical Vapor Deposition (CVD) x Se y S z The specific preparation method of the semiconductor comprises the following steps:
the difference from example 5 lies in:
in the step 1, bi powder, sulfur powder and selenium powder are mixed according to a molar ratio of Bi: se: s =2:2.32: a ratio of 0.68 was placed in a quartz boat.
In step 5, the temperature is raised to 680 ℃ at a rate of 10 ℃ per minute with a small argon flow, and the temperature is maintained for 20 minutes.
Step 7, obtaining Bi 2 Se 2.32 S 0.68 A semiconductor.
The rest of the procedure was the same as in example 5.
Example 7: preparation of Bi by Chemical Vapor Deposition (CVD) x Se y S z The specific preparation method of the semiconductor comprises the following steps:
the difference from example 5 lies in:
in the step 1, bi powder, sulfur powder and selenium powder are mixed according to a molar ratio of Bi: se: s =2:2.16: a ratio of 0.84 was placed in a quartz boat.
In step 5, the temperature was raised to 720 ℃ at 30 ℃ per minute with a smaller argon flow, and held at this temperature for 5 minutes.
Step 7, obtaining Bi 2 Se 2.16 S 0.84 A semiconductor.
The rest of the procedure was the same as in example 5.
Test examples
Taking Bi of example 4 2 Se 2.15 S 0.85 The base photodetector was tested.
The photoelectric detector is placed in a self-built probe station, probes are respectively arranged on two electrodes contacted with the nanowires, the magnitude of photocurrent is tested under the irradiation of lasers with different wavelengths, the photoresponse range is 254nm-1310nm, and the result is shown in figure 1.
The 685nm semiconductor laser is used for adjusting the output power of the laser and the current-voltage relation tested under a probe station. The test result is shown in fig. 2, the current-voltage curve is a symmetrical linear relation, and it can be seen that the photodetector is ohmic contact and has a large photoresponse.
By a waveform generator (german technology, 33612A), a continuously changing pulse is input to the photodetector, and then the change rule of the response voltage is tested, and the test result is shown in fig. 3, and the obtained response time is 170ns.
The change relation of the current of the photoelectric detector and the time is tested by using a chopper (thorlabs model: MC 2000B-EC), and the test can be carried out under a probe station. As a result of the test, as shown in fig. 4, the current of the photodetector was about 52.5nA, and the current of the photodetector after one year was about 52.0 nA. The photodetector hardly changes in air after one year, and is seen to be stable in air.
It can be seen that Bi 2 Se 2.15 S 0.85 The photoelectric device shows excellent photoelectric performance in the deep ultraviolet to near infrared region.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.
Claims (10)
1. The bismuth-selenium-sulfur semiconductor is characterized by being a crystal, and the chemical structural formula of the bismuth-selenium-sulfur semiconductor is Bi x Se y S z Wherein x is more than or equal to 1 and less than or equal to 2,0 and more than or equal to 3,0 and more than or equal to z and less than or equal to 3.
2. The Bi-Se-S semiconductor of claim 1, wherein Bi is present in x Se y S z Wherein x =2,0 < y ≦ 3,0 < z ≦ 3.
3. The Bi-Se-S semiconductor of claim 2, wherein Bi is present in x Se y S z Wherein, x =2; y =2.15; z =0.85.
4. The preparation method of the bismuth selenium sulfur semiconductor is characterized by comprising the following steps of:
providing bismuth powder, selenium powder and sulfur powder;
directly growing the bismuth-selenium-sulfur semiconductor on an insulating substrate by adopting chemical vapor deposition, physical vapor deposition and metal organic source chemical vapor deposition; or the bismuth selenium sulfur semiconductor is directly grown by adopting chemical vapor transport and hydrothermal-solvothermal synthesis.
5. The method for preparing a bismuth selenide sulfide semiconductor according to claim 4, wherein the step of growing the bismuth selenide sulfide crystal directly on the insulating substrate by chemical vapor deposition comprises:
placing the bismuth powder, the selenium powder and the sulfur powder at the upper end of a tube furnace in the airflow direction;
placing an insulating substrate at the lower end of the tube furnace in the gas flow direction;
and under the atmosphere of protective gas, heating the tube furnace to 680-720 ℃ at the speed of 10-30 ℃/min, and preserving the temperature for 5-20 minutes to carry out chemical vapor deposition to obtain the bismuth selenium sulfur semiconductor.
6. The method for preparing a Bi-Se-S semiconductor according to claim 5, wherein the protective gas is an inert gas, the tube furnace is heated to 700 ℃ at a rate of 20 ℃/min, and the temperature is maintained for 10 minutes for chemical vapor deposition.
7. The method for preparing a bismuth selenide sulfur semiconductor according to claim 4, wherein the step of directly growing the bismuth selenide sulfur semiconductor by chemical vapor transport comprises:
sealing the bismuth powder, the selenium powder, the sulfur powder and a conveying medium in a quartz tube, wherein the quartz tube is in a vacuum atmosphere;
placing the quartz tube in a double-temperature-zone tube furnace, setting the temperature of the first temperature zone and the second temperature zone to be 780-820 ℃, keeping the temperature for 720-1440 minutes, and cooling;
taking out the quartz tube, uniformly mixing the materials in the quartz tube, putting the quartz tube into the double-temperature-zone tube furnace again, heating the first temperature zone to 680-720 ℃ and the second temperature zone to 620-660 ℃ at the heating rate of 5-20 ℃/min, and keeping the temperature for 1-7 days; then, cooling at the rate of 0.6-0.9 ℃/min to 250-300 ℃, and cooling;
taking out the growth material in the quartz tube;
and removing the conveying medium in the growth material to obtain the bismuth selenium sulfur semiconductor.
8. The method for preparing a bismuth selenium sulfide semiconductor according to claim 7, wherein the quartz tube is placed in a two-temperature zone tube furnace again, and the first temperature zone is heated to 700 ℃ and the second temperature zone is heated to 640 ℃ at a heating rate of 10 ℃/min and is kept for 6 days; then, the temperature is reduced by 300 ℃ at the speed of 0.8 ℃/min, and the product is cooled.
9. The method of claim 7, wherein the transport medium is elemental iodine;
the step of removing the transport medium within the growth material comprises:
and (3) placing the growth material in a tube furnace in a protective gas atmosphere, and annealing for 5 hours at 200 ℃.
10. A broad-spectrum ultrafast polarization photodetector, comprising a substrate and a semiconductor material disposed on the substrate, wherein the semiconductor material is the bi-se-s semiconductor of any one of claims 1 to 3 or the bi-se-s semiconductor prepared by the preparation method of any one of claims 4 to 9.
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