CN115241306B - Bismuth selenium sulfur semiconductor, preparation method and broad-spectrum and ultra-fast polarized photoelectric detector - Google Patents

Bismuth selenium sulfur semiconductor, preparation method and broad-spectrum and ultra-fast polarized photoelectric detector Download PDF

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CN115241306B
CN115241306B CN202210795677.3A CN202210795677A CN115241306B CN 115241306 B CN115241306 B CN 115241306B CN 202210795677 A CN202210795677 A CN 202210795677A CN 115241306 B CN115241306 B CN 115241306B
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钟绵增
莫长勋
束传存
王丹阳
张芬
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Central South University
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Abstract

The invention provides a bismuth selenium sulfur semiconductor, a preparation method and a broad-spectrum and ultra-fast polarized photoelectric detector. The bismuth selenium sulfur semiconductor is crystal, and the chemical structural formula of the bismuth selenium sulfur semiconductor is Bi x Se y S z Wherein x is equal to or greater than 1 and equal to or less than 2, y is equal to or greater than 0 and equal to or less than 3, z is equal to or greater than 0 and equal to or less than 3, and 3x=2y+2z. In the bismuth selenium sulfur semiconductor, bi 2 Se 3 The semiconductor has an orthorhombic structure by doping S to Bi 2 Se 3 In which Bi grows out x Se y S z And a semiconductor. Compared with Bi 2 Se 3 Semiconductor, bi x Se y S z The energy band structure of the semiconductor is optimized and enriched, so that the photoelectric device constructed by the semiconductor has lower dark current and wider detection range, and is beneficial to realizing high performance of the photoelectric device.

Description

Bismuth selenium sulfur semiconductor, preparation method and broad-spectrum and ultra-fast polarized photoelectric detector
Technical Field
The invention relates to the technical field of semiconductors, in particular to a bismuth selenium sulfur semiconductor, a preparation method, a broad spectrum and an ultrafast polarization photoelectric detector.
Background
In recent years, low-dimensional crystals exhibit excellent properties due to their excellent quantum size effect, and thus have been widely studied in the field of optoelectronic devices. Among these low-dimensional crystals, a topology material having low symmetry is considered as one of candidate materials for high-performance photovoltaic devices. However, the topological physical characteristics result in a larger dark state current in the corresponding optoelectronic device, which severely limits its further development in the optoelectronic field. 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 the corresponding photoelectric device.
Bi as a typical representative of V-VI semiconductor materials 2 Se 3 The semiconductor has ultrahigh electron mobility through theoretical and experimental researches, and can be used for constructing electronic devices based on high-performance topological insulators. In particular, high electron mobility contributes to rapid migration of charge carriers, which contributes to achieving an ultrafast photoresponse of the optoelectronic device. However, its high dark current results in large operational noise of the device.
Disclosure of Invention
The invention mainly aims to provide a bismuth-selenium-sulfur semiconductor, a preparation method, a broad-spectrum and ultra-fast polarization photoelectric detector for solving the problem of Bi 2 Se 3 The technical problem of high dark current of the constructed photoelectric device.
In order to achieve the above object, a first aspect of the present invention provides a bismuth-selenium-sulfur semiconductor, wherein the bismuth-selenium-sulfur semiconductor is crystalline and the bismuth-selenium-sulfur semiconductor has a chemical structural formula of Bi x Se y S z Wherein x is more than or equal to 1 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 3, and z is more than or equal to 0 and less than or equal to 3.
Alternatively, in Bi x Se y S z Wherein x=2, 0 < y.ltoreq.3, 0 < z.ltoreq.3.
Alternatively, in Bi x Se y S z In x=2, y=2.15, and 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.
And 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 directly growing the bismuth selenium sulfur semiconductor by chemical vapor transport and hydrothermal-solvothermal synthesis.
Optionally, the step of growing bismuth selenium sulfur crystals directly on the insulating substrate using chemical vapor deposition comprises:
bismuth powder, selenium powder and sulfur powder are arranged at the upper end of the tube furnace in the air flow direction.
An insulating substrate is placed at the lower end of the tube furnace in the direction of the gas flow.
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 perform chemical vapor deposition to obtain the bismuth selenium sulfur semiconductor.
Optionally, the shielding gas is inert gas, the tube furnace is heated to 700 ℃ at a speed of 20 ℃/min, and the tube furnace is kept for 10 minutes for chemical vapor deposition.
Optionally, the step of directly growing the bismuth selenium sulfur semiconductor by chemical vapor transport comprises:
bismuth powder, selenium powder, sulfur powder and a conveying medium are sealed in a quartz tube, and the interior of the quartz tube is in a vacuum atmosphere.
The quartz tube is placed in a tube furnace with double temperature areas, the temperature of the first temperature area and the second temperature area is set to 780-820 ℃, and the quartz tube is kept for 720-1440 minutes and cooled.
Taking out the quartz tube, uniformly mixing the materials in the quartz tube, putting the quartz tube into a double-temperature-zone tube furnace again, heating the first temperature zone to 680-720 ℃ at a heating rate of 5-20 ℃/min, heating the second temperature zone to 620-660 ℃, and keeping the temperature for 1-7 days; then cooling the mixture to 250-300 ℃ at the speed of 0.6-0.9 ℃/min.
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 put into a double-temperature-zone tube furnace again, the temperature of the first temperature zone is raised to 700 ℃ and the temperature of the second temperature zone is raised to 640 ℃ at a heating rate of 10 ℃/min, and the quartz tube is kept for 6 days; then, the temperature was lowered by 300℃at a rate of 0.8℃per minute, and the mixture was 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 with a shielding gas and annealed at 200 ℃ for 5 hours.
The third aspect of the invention provides a broad-spectrum ultra-fast polarized 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 bismuth selenium sulfur semiconductor, bi 2 Se 3 The semiconductor has an orthorhombic structure by doping S to Bi 2 Se 3 In which Bi grows out x Se y S z And a semiconductor. Compared with Bi 2 Se 3 Semiconductor, bi x Se y S z The energy band structure of the semiconductor is optimized and enriched, so that the photoelectric device constructed by the semiconductor has lower dark current and wider detection range, and is beneficial to realizing high performance of the photoelectric device.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a spectral detection diagram of a photodetector 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 response time plot 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 selenium 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 achievement of the object, functional features and advantages of the present invention will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
It should be noted that all directional indicators (such as upper and lower … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.
In order to achieve the above object, a first aspect of the present invention provides a bismuth-selenium-sulfur semiconductor, wherein the bismuth-selenium-sulfur semiconductor is crystalline and the bismuth-selenium-sulfur semiconductor has a chemical structural formula of Bi x Se y S z Wherein x is equal to or greater than 1 and equal to or less than 2, y is equal to or greater than 0 and equal to or less than 3, z is equal to or greater than 0 and equal to or less than 3, and 3x=2y+2z.
Bismuth selenium sulfur semiconductors are crystals, the structure of which includes but is not limited to bulk crystals, films, nanowires, quantum dots, superlattices, quantum wells, and the like. And crystalline states thereof include, but are not limited to, monocrystalline, polycrystalline, microcrystalline, amorphous, and the like.
The chemical structural formula of the bismuth selenium sulfur semiconductor is Bi x Se y S z Essentially represents a series of Bi 2 Se 3 The semiconductor is doped with S bismuth selenium sulfur semiconductor material. The specific bismuth selenium sulfur semiconductor material is characterized in that x, y and z in the corresponding structural formula are different due to different doping degrees. In other words, in the preparation process, the proportion of bismuth, selenium and sulfur in the raw materials can be changed by changing the proportion of bismuth powder, selenium powder and sulfur powder, so that different bismuth, selenium and sulfur semiconductor materials can be obtained. Therefore, bismuth selenium sulfur semiconductor materials with different band gaps can be obtained, and the corresponding broadband optoelectronic device can be prepared by the bismuth selenium sulfur semiconductor materials, and the bismuth selenium sulfur semiconductor materials can be particularly applied to broadband optoelectronic devices from deep ultraviolet to infrared, namely Yu Anpu and ultra-fast polarized photodetectors.
In the bismuth selenium sulfur semiconductor, bi 2 Se 3 The semiconductor has an orthorhombic structure by doping S to Bi 2 Se 3 In which Bi grows out x Se y S z And a semiconductor. Compared with Bi 2 Se 3 Semiconductor, bi x Se y S z The energy band structure of the semiconductor is optimized and enriched, so that the 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.
Alternatively, in Bi x Se y S z Wherein x=2, 0 < y.ltoreq.3, 0 < z.ltoreq.3.
Alternatively, in Bi x Se y S z In x=2, y=2.15, and z=0.85. In this case, the bismuth selenium sulfur semiconductor is Bi 2 Se 2.15 S 0.85 And (5) a crystal.
The second aspect of the invention provides a preparation method of a bismuth selenium sulfur semiconductor, which comprises the following steps:
and S100, providing bismuth powder, selenium powder and sulfur powder.
In step S100, the purity of bismuth powder, selenium powder, and sulfur powder is high, and illustratively, the bismuth powder may be bismuth powder having a purity of 99.999%, the sulfur powder may be sulfur powder having a purity of 99.999%, and the selenium powder may be selenium powder having a purity of 99.999%.
And 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 directly growing the bismuth selenium sulfur semiconductor by chemical vapor transport and hydrothermal-solvothermal synthesis.
In step S200, there are various methods for growing the bismuth selenium sulfur semiconductor, and the method is not particularly limited.
In some embodiments, bismuth selenium sulfur crystals are grown directly on an insulating substrate using chemical vapor deposition, the specific steps comprising:
s201, bismuth powder, selenium powder and sulfur powder are placed at the upper end of the tube furnace in the air flow direction.
In step S201, bismuth powder, selenium powder, and sulfur powder may be weighed and mixed in proportion 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 air flow of the tube furnace.
And S202, placing an 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 for material growth.
And S203, heating the tube furnace to 680-720 ℃ at a speed of 10-30 ℃/min in the atmosphere of protective gas, and preserving the temperature for 5-20 minutes to perform chemical vapor deposition to obtain the bismuth selenium sulfur semiconductor.
In step S203, the tube furnace is an atmosphere of a shielding gas. The shielding gas may be argon. High-purity argon can be introduced into the tubular furnace for half an hour at a relatively high flow rate so as to remove air in the tubular furnace, and then argon is continuously introduced into the tubular furnace at a relatively low flow rate. The temperature of the tube furnace is raised to 680-720 ℃ at the speed of 10-30 ℃/min, and the tube furnace is kept for 5-20 minutes. In the process, bismuth powder, selenium powder and sulfur powder which are positioned at the upper end of the air flow of the tubular furnace form corresponding gases, and along with the flowing of argon to the lower end of the tubular furnace, the bismuth powder, the selenium powder and the sulfur powder are deposited on an insulating substrate and grow to form the bismuth selenium sulfur semiconductor. After the growth is finished, naturally cooling the tube furnace to room temperature, and taking out the bismuth selenium sulfur semiconductor.
It should be noted that the number and morphology of the products deposited by the temperature rise too slowly or too fast and the temperature rise of the tube furnace are different, for example, bismuth selenium sulfur crystals are in a nanowire state, nanowires are too thick/too thin or too few in number, the uniformity of the sample is reduced, the structure of an electron energy band is directly influenced, and the performance is influenced.
Optionally, in step S203, the tube furnace is heated to 700 ℃ at a rate of 20 ℃/min and incubated for 10 minutes for chemical vapor deposition. Under the condition, the bismuth selenium sulfur semiconductor has better appearance, good sample uniformity and higher growth efficiency, and the formed bismuth selenium sulfur semiconductor has high quality.
In other embodiments, the bismuth selenium sulfur 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 interior of the quartz tube is in a vacuum atmosphere.
In this step, bismuth powder, selenium powder and sulfur powder may be weighed and mixed in proportion of each element in the bismuth-selenium-sulfur semiconductor and placed in a quartz tube, and then a certain amount of a transport medium is added.
The quartz tube mixed with the above substances is pumped to vacuum, such as 10 -3 Pa, the quartz tube containing the substance was vacuum sealed with an oxyhydrogen machine.
S302, 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 780-820 ℃, keeping the temperature for 720-1440 minutes, and cooling.
The holding time for this step may be 720 to 800 minutes, 820 to 950 minutes, 1020 to 1200 minutes, 1250 to 1330, 1300 to 1440 minutes. The step has the functions of uniformly mixing source materials under the drive of iodine steam, generating a polycrystalline bismuth selenium sulfur semiconductor at high temperature and providing the source materials 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 a double-temperature-zone tube furnace again, heating the first temperature zone to 680-720 ℃ at a heating rate of 5-20 ℃/min, heating the second temperature zone to 620-660 ℃, and keeping the temperature for 1-7 days; then cooling the mixture to 250-300 ℃ at the speed of 0.6-0.9 ℃/min.
In this step, the first temperature region is a high temperature region (may also be referred to as a source region), and the second temperature region is a low temperature region (may also be referred to as a growth region). In the growth process, the temperature difference between the low temperature area and the high temperature area is ensured to be 50-100 ℃ so as to realize effective transportation. Too high a temperature in the first and second temperature regions may cause non-uniformity of crystals, and too low a temperature in the first and second temperature regions may lengthen the crystal growth period, even without growth. Thus, the first temperature zone was raised to 700 ℃ and the second temperature zone was raised to 640 ℃. The holding time, i.e., the incubation time, of this step may be 1 to 2 days, 2 to 4 days, 5 to 6 days, 6 to 7 days, etc.
Illustratively, the first temperature zone is warmed to 700℃ and the second temperature zone is warmed to 640℃ at a ramp rate of 10deg.C/min for 6 days; then, the temperature was lowered by 300℃at a rate of 0.8℃per minute, and the mixture was cooled.
And S304, taking out the growth material in the quartz tube.
In this step, the quartz tube may be opened and the grown material removed.
And 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 in an inert blanket gas atmosphere, such as nitrogen or an inert blanket gas, such as argon, and annealed at 200 ℃ for 5 hours.
The third aspect of the invention provides a broad-spectrum ultra-fast polarized 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.
Bismuth selenium sulfur semiconductor can be applied to photoelectric devicesFor example, bi may be used x Se y S z A broad spectrum photovoltaic device covering from deep ultraviolet to infrared was prepared as an absorption region. As another example, bi is used x Se y S z The crystal is used as a working area to prepare a logic device for light regulation.
Example 1: direct growth of bulk Bi by Chemical Vapor Transport (CVT) x Se y S z And a semiconductor.
Bi of a single component is prepared by a Chemical Vapor Transport (CVT) method 2 Se 2.15 S 0.85 The specific preparation method of the semiconductor crystal is as follows:
step 1, selecting Bi powder with purity of 99.999%, sulfur powder with purity of 99.999% and selenium powder with purity of 99.999%, wherein the Bi powder comprises the following components in mole ratio: se: s=2: 2.15: a total of 1 gram of material was mixed and placed in a quartz tube at a ratio of 0.85 while adding 5mg/mL of iodine as a transport medium.
Step 2, pumping the quartz tube mixed with the chemical to 10 by using a molecular pump -3 Pa, the quartz tube containing the material was vacuum sealed using an oxyhydrogen machine.
And 3, placing the quartz tube into a double-temperature-zone tube furnace, setting the temperature at 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 a double-temperature-zone tube furnace again, heating a high-temperature zone (source zone) to 700 ℃ and a low-temperature zone (growth zone) to 640 ℃ at a 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 extracted material in a tube furnace in a nitrogen atmosphere, and annealing at 200 ℃ for 5 hours to remove redundant iodine.
And 7, taking out the annealed material.
Step 8, see FIG. 5, which characterizes it as Bi by EDS (dispersive Spectrometry) spectroscopy 2 Se 2.15 S 0.85 Nanowire sheetAnd (5) crystal.
Example 2
The difference from example 1 is that:
in the step 1, bi powder sulfur powder and selenium powder are prepared from the following components in percentage by mole: se: s=2: 2.46:0.54 a total of 1 gram of material was mixed into a quartz tube while adding 5mg/mL iodine as a transport medium.
In the step 3, the quartz tube is placed into a tube furnace with a double temperature area, the temperature of the two ends is set to 780 ℃, the quartz tube is kept for 720 minutes, and the temperature is naturally reduced.
And 4, taking out the quartz tube, uniformly mixing the materials, putting the quartz tube into a double-temperature-zone tube furnace again, heating a high-temperature zone (source zone) to 680 ℃ and a low-temperature zone (growth zone) to 620 ℃ at a heating rate of 5 ℃ per minute, and keeping the temperature for 7 days. Then cooling to 250 ℃ at the rate of 0.5 ℃ per minute, and finally naturally cooling to room temperature.
Step 8, after the related characterization, it is Bi 2 Se 2.46 S 0.54 A nanowire single crystal.
The rest of the procedure is as in example 1
Example 3
The difference from example 1 is that:
in the step 1, bi powder sulfur powder and selenium powder are prepared from the following components in percentage by mole: se: s=2: 2.73: 0.27A total of 1 gram of material was mixed and placed in a quartz tube while adding 5mg/mL of iodine as a transport medium.
And 3, placing the quartz tube into a double-temperature-zone tube furnace, setting the temperature at two ends to 820 ℃, keeping for 1200 minutes, and naturally cooling.
And 4, taking out the quartz tube, uniformly mixing the materials, putting the quartz tube into a double-temperature-zone tube furnace again, heating a high-temperature zone (source zone) to 700 ℃ and a low-temperature zone (growth zone) to 650 ℃ at a 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, after the related characterization, it is Bi 2 Se 2.73 S 0.27 A nanowire single crystal.
The rest of the procedure is the same as in example 1.
Example 4: bi (Bi) 2 Se 2.15 S 0.85 The specific preparation method of the base photoelectric detector (namely the broad-spectrum and ultra-fast polarized photoelectric detector) comprises the following steps:
step 1, bi to be grown 2 Se 2.15 S 0.85 The nanowire is directly transferred to SiO by pressing and dragging 2 And sapphire, etc.
Step 2, exposing an electrode area through the processes of coating photoresist, exposing, developing, fixing and the like by the traditional manufacturing process of the semiconductor device, wherein Bi is formed in the electrode area 2 Se 2.15 S 0.85 The area corresponding to the nanowire is a photosensitive area of the photodetector.
Step 3, electrode evaporation and photoresist removal to obtain Bi 2 Se 2.15 S 0.85 See fig. 6 for a base photovoltaic device.
Example 5: preparation of Bi by Chemical Vapor Deposition (CVD) method x Se y S z The specific preparation method of the semiconductor comprises the following steps:
step 1, weighing 1 gram of Bi powder with the purity of 99.999 percent, sulfur powder with the purity of 99.999 percent and selenium powder with the purity of 99.999 percent, wherein the molar ratio of Bi: se: s=2: 2.96: a ratio of 0.04 was placed in a quartz boat.
And 2, placing the quartz boat at the upper end of the air flow of the tubular 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.
Step 5, heating to 700 ℃ at a rate of 20 ℃ per minute with a smaller argon flow, and keeping the temperature for 10 minutes.
And 6, after the growth is finished, naturally cooling to room temperature.
Step 7, obtaining Bi 2 Se 2.96 S 0.04 And a semiconductor.
Example 6: by chemical vapour deposition(CVD) method for producing Bi x Se y S z The specific preparation method of the semiconductor comprises the following steps:
the difference from example 5 is that:
in the step 1, bi powder sulfur powder and selenium powder are prepared from the following components in percentage by mole: se: s=2: 2.32: a ratio of 0.68 was placed in a quartz boat.
In step 5, the argon flow is reduced, and the temperature is raised to 680 degrees celsius at a rate of 10 degrees celsius per minute and maintained at that temperature for 20 minutes.
Step 7, obtaining Bi 2 Se 2.32 S 0.68 And a semiconductor.
The rest of the procedure is the same as in example 5.
Example 7: preparation of Bi by Chemical Vapor Deposition (CVD) method x Se y S z The specific preparation method of the semiconductor comprises the following steps:
the difference from example 5 is that:
in the step 1, bi powder sulfur powder and selenium powder are prepared from the following components in percentage by mole: se: s=2: 2.16: a ratio of 0.84 was placed in a quartz boat.
In step 5, the argon flow is reduced, and the temperature is raised to 720 ℃ at a rate of 30 ℃ per minute, and maintained at that temperature for 5 minutes.
Step 7, obtaining Bi 2 Se 2.16 S 0.84 And a semiconductor.
The rest of the procedure is the same as in example 5.
Test examples
Bi of example 4 was taken 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 nanowire, the magnitude of photocurrent is tested under the irradiation of lasers with different wavelengths, and the photoresponse range is 254nm-1310nm, and the result is shown in figure 1.
The output power of the semiconductor laser is regulated by a 685nm semiconductor laser, and the current-voltage relationship is tested under a probe station. As shown in FIG. 2, the current-voltage curve is a symmetrical linear relationship, and it can be seen that the photodetector is in ohmic contact and has high light responsivity.
The pulse with continuous change is input to the photodetector through the waveform generator (de technology, 33612A), so as to test the change rule of the response voltage, and the test result is shown in fig. 3, and the response time is 170ns.
The change in current versus time of the photodetector was tested using a chopper (model MC 2000B-EC), and likewise under the 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 changed after one year in the air, and it was seen that it was stable in the air.
It can be seen that Bi 2 Se 2.15 S 0.85 The base photovoltaic device exhibits excellent photovoltaic properties in the deep ultraviolet to near infrared region.
In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and therefore, the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the description of the present invention and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims (5)

1. A bismuth selenium sulfur semiconductor is characterized in that 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=2; y=2.15; z=0.85.
2. A method for preparing the bismuth selenium sulfur semiconductor as claimed in claim 1, comprising the steps of:
providing bismuth powder, selenium powder and sulfur powder;
the bismuth selenium sulfur semiconductor is directly grown by adopting chemical vapor transport, and the step of directly growing the bismuth selenium sulfur semiconductor by adopting chemical vapor transport comprises the following steps:
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 temperatures of a first temperature zone and a second temperature zone to 780-820 ℃, keeping the temperatures for 720-1440 minutes, and cooling;
taking out the quartz tube, uniformly mixing the materials in the quartz tube, putting the quartz tube into a double-temperature-zone tube furnace again, heating the first temperature zone to 680-720 ℃ at a heating rate of 5-20 ℃/min, heating the second temperature zone to 620-660 ℃, and keeping the temperature for 1-7 days; wherein the temperature difference between the first temperature area and the second temperature area is 50-100 ℃; then cooling the mixture to 250-300 ℃ at a speed of 0.6-0.9 ℃/min;
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.
3. The method for producing bismuth selenium sulfur semiconductor according to claim 2, wherein the quartz tube is put into a double-temperature zone tube furnace again, the first temperature zone is raised to 700 ℃ and the second temperature zone is raised to 640 ℃ at a temperature raising rate of 10 ℃/min, and the quartz tube is maintained for 6 days; then, the temperature was lowered by 300℃at a rate of 0.8℃per minute, and the mixture was cooled.
4. The method for preparing bismuth selenium sulfur semiconductor according to claim 2, wherein 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 in a protective gas atmosphere and annealed at 200 ℃ for 5 hours.
5. The broad-spectrum ultrafast polarized photoelectric detector is characterized by comprising a substrate and a semiconductor material arranged on the substrate, wherein the semiconductor material is the bismuth selenium sulfur semiconductor disclosed in claim 1 or the bismuth selenium sulfur semiconductor manufactured by the manufacturing method disclosed in any one of claims 2-4.
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