CN111822013B - Single-cell PN junction and accurate construction method thereof - Google Patents

Single-cell PN junction and accurate construction method thereof Download PDF

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CN111822013B
CN111822013B CN202010640549.2A CN202010640549A CN111822013B CN 111822013 B CN111822013 B CN 111822013B CN 202010640549 A CN202010640549 A CN 202010640549A CN 111822013 B CN111822013 B CN 111822013B
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unit cell
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zinc
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CN111822013A (en
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王煜
张慧娟
吴俣
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Chongqing University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
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    • B01J35/40—
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention belongs to the technical field of PN junctions, and provides a single-cell PN junction which is constructed in a single cell by using a semiconductor material. The invention also provides an accurate construction method of the single-cell PN junction. The single-cell PN junction is uniform and neat, has transparent feeling and has the size of micron level; the thickness of the single-cell PN junction of the invention is completely consistent with the thickness and the number of atomic layers of a single-cell semiconductor material; the construction method has accurate controllability, is widely applicable to various semiconductor materials, and has great significance for exerting the properties of the materials and further improving the photoelectrochemical performance.

Description

Single-cell PN junction and accurate construction method thereof
Technical Field
The invention relates to the technical field of PN junctions, in particular to a single-cell PN junction and an accurate construction method thereof.
Background
The photoelectrochemistry hydrogen production by decomposing water is a method which can effectively solve the problems of energy crisis, environmental pollution and the like and has good prospect. However, the photoactivity of the common semiconductor is limited by the problems of few catalytic active sites, serious recombination of photon-generated carriers and the like. The two-dimensional material with the unit cell thickness can not only expose almost all atoms to provide abundant catalytic active sites, but also greatly shorten the distance from a bulk phase to the surface, thereby accelerating the separation and transmission of photon-generated carriers and further reducing the bulk phase recombination.
Because of the huge specific surface area of the two-dimensional material with unit cell thickness, a single material still suffers from the serious influence of the problems of surface photon-generated carrier recombination, photo-corrosion and the like. The PN junction is reasonably constructed, so that the advantages can be fully integrated, and the defect of a single material can be relieved. It is possible not only to reduce the unproductive consumption of photo-generated electrons to maximize the hydrogen production efficiency, but also to suppress the material photo-corrosion self-decomposition by minimizing the uptake of photo-generated holes.
At present, the limit size is achieved for conventional PN junctions, i.e., the junction is composed of two layers of unit cell material, and van der waals interfaces are between the layers. However, such conventional PN junctions are made of different semiconductors, and the realization of ideal PN junctions is not only dependent on their energy band arrangements, but also significantly affected by other characteristics such as crystal structure and crystal parameters, so that the conventional PN junctions are difficult to realize in practical applications. However, the PN junction in the unit cell performs very well in the above-mentioned respect. Furthermore, covalent bonds between atoms within the unit cell are very advantageous for structural stability, charge transfer and carrier separation. Therefore, further exploration of PN junctions in unit cells will deepen understanding of semiconductor physics and drive the development of related new technologies.
Disclosure of Invention
The invention aims to provide a single cell PN junction and a precise construction method thereof in order to overcome the defects of the prior art. The single-cell PN junction is uniform and neat, has transparent feeling and has the size of micron level; the thickness of the single-cell PN junction of the invention is completely consistent with the thickness and the number of atomic layers of a single-cell semiconductor material; the construction method of the invention has accurate controllability and is widely applicable to various semiconductor materials.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a single-cell PN junction, which is constructed in a single cell by using a semiconductor material.
Preferably, the semiconductor material is ZnIn 2 S 4 Or a bi-element semiconductor material.
Preferably, the double-element semiconductor material is TiO 2 、In 2 O 3 、ZnO、Fe 2 O 3 、MoS 2 ZnS, cdS or SnS 2 。
The invention also provides a precise construction method of the single-cell PN junction, which comprises the following steps:
1) Mixing zinc salt, indium salt, sulfur source and water to obtain reaction liquid;
2) Reacting the reaction solution with SnO doped with fluorine 2 Mixing the conductive glass and reacting to obtain a unit cell indium zinc tetrasulfide nanosheet array;
3) And reacting the substance containing the fifth main group element with the unit cell indium zinc tetrasulfide nanosheet array in an inert atmosphere to obtain the unit cell PN junction.
Preferably, the zinc salt in the step 1) is zinc chloride, zinc nitrate or zinc sulfate, the indium salt is indium chloride or indium sulfate, and the sulfur source is thiourea, thioacetamide or sodium thiosulfate.
Preferably, the reaction temperature of the step 2) is 100-200 ℃, and the reaction time is 1-24 h.
Preferably, the SnO doped with fluorine before mixing in the step 2) 2 Conducting ultrasonic cleaning on the conductive glass, wherein the fluorine-doped SnO 2 The volume ratio of the conductive glass to the reaction liquid is 1-10, and the conductive glass is dried under the vacuum condition after the reaction is finished, wherein the drying temperature is 50-70 ℃, and the vacuum degree is 0.03-0.07 MPa.
Preferably, the reaction temperature in the step 3) is 200-600 ℃, the time is 1-240 min, the flow rate of the inert gas is 30-100 sccm, and the inert gas is argon.
Preferably, the substance containing the fifth main group element in the step 3) is red phosphorus, sodium hypophosphite, phosphine gas, ammonia gas, ammonium bicarbonate, ammonium chloride or ammonium nitrate.
Preferably, the rate of raising the temperature to the reaction temperature in step 3) is 2 to 10 ℃/min, and when the substance containing a fifth main group element is a gas, the flow rate of the gas is 1 to 30% of the total flow rate.
The beneficial effects of the invention include the following:
1) The single cell PN junction of the invention is uniform and regular, has transparent sense and has the size of micron level.
2) The single-cell PN junction has accurate controllability, and has great significance for exerting the properties of the material and further improving the photoelectrochemical performance.
Drawings
FIG. 1 is an XRD pattern of the unit cell PN junction of example 3;
FIG. 2 is an SEM image of the unit cell PN junction of example 3, wherein (b) is a top view and (c) is a front view;
FIG. 3 is a HRTEM image of the unit cell PN junction of example 3 in the 001 direction;
FIG. 4 is an atomic model diagram of the unit cell PN junction of example 3 along the 001 direction;
FIG. 5 is a front HRTEM image of the unit cell PN junction of example 3;
FIG. 6 is an AFM plot of the single cell PN junction of example 3;
FIG. 7 is a diagram of EDSmapping of the unit cell PN junction of example 3;
FIG. 8 is the Mott Schottky curve for the unit cell PN junction of example 3;
FIG. 9 is a schematic diagram of a unit cell PN junction;
FIG. 10 is the XRD pattern of the unit cell PN junction of example 4;
FIG. 11 is an XRD pattern of the unit cell PN junction of example 5;
FIG. 12 is the XRD pattern of the unit cell PN junction of example 6;
FIG. 13 is the XRD pattern of the unit cell PN junction of example 7;
FIG. 14 is the XRD pattern of the unit cell PN junction of example 8;
FIG. 15 is the XRD pattern of the unit cell PN junction of example 9;
FIG. 16 is the XRD pattern of the unit cell PN junction of example 10;
figure 17 is an XRD pattern of the unit cell PN junction of example 11.
Detailed Description
The invention provides a single-cell PN junction, which is constructed in a single cell by using a semiconductor material.
The semiconductor material is preferably ZnIn 2 S 4 Or a bi-element semiconductor material, preferably TiO 2 、In 2 O 3 、ZnO、Fe 2 O 3 、MoS 2 ZnS, cdS or SnS 2 。
The invention also provides a precise construction method of the single-cell PN junction, which comprises the following steps:
1) Mixing zinc salt, indium salt, sulfur source and water to obtain reaction liquid;
2) Reacting the reaction liquid with SnO doped with fluorine 2 Mixing the conductive glass and reacting to obtain a unit cell indium zinc tetrasulfide nanosheet array;
3) And reacting the substance containing the fifth main group element with the unit cell indium zinc tetrasulfide nanosheet array in an inert atmosphere to obtain the unit cell PN junction.
The zinc salt in step 1) of the present invention is preferably zinc chloride, zinc nitrate or zinc sulfate, the indium salt is preferably indium chloride or indium sulfate, and the sulfur source is preferably thiourea, thioacetamide or sodium thiosulfate.
The water in the step 1) of the invention is preferably deionized water, and the amount of the deionized water is preferably enough to dissolve zinc salt, indium salt and sulfur source.
SnO doped with fluorine before mixing in step 2) of the invention 2 The conductive glass is preferably cleaned, and further preferably ultrasonically cleaned, and the solvent for ultrasonically cleaning is preferably acetone, ethanol, deionized water, isopropyl ketone, liquid detergent, professional conductive glass cleaning solution and concentrated H 2 SO 4 、H 2 O 2 And hydrofluoric acid, preferably mixed solvent of acetone, ethanol and deionized water, and concentrated H 2 SO 4 And H 2 O 2 The mixed solvent of hydrofluoric acid and deionized water; the ultrasonic cleaning time is preferably 5-40 min, and more preferably 10-30 min; the conductive glass is preferably dried after being washed.
The invention is based on fluorine-doped SnO 2 The amount of dirt on the conductive glass is selected to be proper in cleaning mode and ultrasonic time, and the ultrasonic time can be properly prolonged in order to ensure the cleanliness of cleaning.
The fluorine-doped SnO in step 2) of the invention 2 The volume ratio of the conductive glass to the reaction solution is preferably 1.
In the mixing step 2), preferably, the dried conductive glass is placed in a polytetrafluoroethylene inner container, and then the reaction solution is slowly dripped into the inner container, wherein the reaction solution is preferably not completely immersed in the conductive glass.
The reaction temperature in the step 2) of the invention is preferably 100-200 ℃, more preferably 120-180 ℃, and more preferably 140-160 ℃; the reaction time is preferably 1 to 24 hours, more preferably 5 to 20 hours, and still more preferably 10 to 15 hours.
The fluorine-doped SnO of the invention 2 The conductive glass is smooth and transparent before reaction, and a layer of yellow ZnIn is arranged on the conductive glass after the reaction with the reaction liquid 2 S 4 Film, znIn 2 S 4 The film is relatively uniform and thick and will adequately contact and cover a portion of the conductive glass.
After the reaction in the step 2) of the invention is finished, preferably naturally cooling to room temperature; the fluorine-doped SnO 2 The conductive glass is preferably dried under vacuum conditions, the drying temperature is preferably 50 to 70 ℃, more preferably 60 to 65 ℃, and the vacuum degree is preferably 0.03 to 0.07MPa, more preferably 0.04 to 0.06MPa.
Step 2) of the invention is to mix SnO doped with fluorine 2 The purpose of drying the conductive glass under vacuum is to reduce the oxygen content and prevent oxidation.
The reaction temperature in the step 3) of the invention is preferably 200-600 ℃, more preferably 300-500 ℃, and more preferably 400 ℃; the reaction time is preferably 1 to 240min, more preferably 10 to 200min, and even more preferably 100 to 150min; the flow rate of the inert gas is preferably 30 to 100sccm, more preferably 50 to 90sccm, and even more preferably 60 to 80sccm; the inert gas is preferably argon.
The substance containing the fifth main group element in the step 3) of the invention is preferably red phosphorus, sodium hypophosphite, phosphine gas, ammonia gas, ammonium bicarbonate, ammonium chloride or ammonium nitrate, and is further preferably red phosphorus, sodium hypophosphite or phosphine gas.
The molar ratio of the substance containing the fifth main group element in the step 3) to the unit cell indium zinc tetrasulfide nanosheet array is preferably 5-200: 1, more preferably 20 to 150:1, more preferably 50 to 100:1.
the rate of heating to the reaction temperature in the step 3) is preferably 2-10 ℃/min, more preferably 4-8 ℃/min, and even more preferably 5-7 ℃/min; the initial temperature of the temperature rise is preferably 20 ℃; the reaction is preferably carried out in a sealed environment, and an inert gas is preferably introduced to evacuate air before the reaction.
When the substance containing the fifth main group element in step 3) of the present invention is a gas, the flow rate of the gas is preferably 1 to 30%, more preferably 5 to 20%, and still more preferably 10 to 15% of the total flow rate; the gas is preferably passed for the same time as the reaction.
The total flow rate of the gas containing the fifth main group element and the inert gas is the total flow rate of the inert gas, and the inert gas plays a role of a carrier gas so as to control the proportion of the gas containing the fifth main group element.
The principle of the reaction of the substance containing the fifth main group element and the unit cell indium zinc tetrasulfide nanosheet array is that the substance containing the fifth main group element is gasified or decomposed into gas containing the fifth main group element, the gas generates the fifth main group element after chemical bonds are broken under a high-temperature environment, and the fifth main group element is combined with the unit cell indium zinc tetrasulfide nanosheet to occupy crystal lattices.
The zinc indium tetrasulfide (ZnIn) of the invention 2 S 4 ) The material is a semiconductor material with visible light response, stable structure and good activity, and the material presents N-type conductivity due to a small amount of inherent sulfur vacancies, and can be used as a good model for researching a single-cell PN junction. The single-cell PN junction obtained by the construction method is uniform and neat, has transparent feeling and has micron-sized size; the unit cell PN junction has a thickness of 1.25nm and has 7 layers of atoms, and one unit cell ZnIn 2 S 4 The thickness and the number of atomic layers are completely consistent. The phosphorus element obtained by the construction method of the single-cell PN junction is fully doped on one surface of the single-cell PN junction, so that the construction method has accurate controllability.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
SnO doped with fluorine 2 And (3) continuously performing ultrasonic treatment on the conductive glass (conductive glass FTO) in acetone, ethanol and deionized water for 30min respectively, and drying for later use. Putting zinc chloride, indium chloride and thiourea into a beaker according to an atomic ratio of Zn to In to S =1 to 4, and adding a proper amount of deionized water to fully stir to obtain a reaction solution. Then, putting the dried conductive glass FTO into a polytetrafluoroethylene inner container, slowly dropping the reaction liquid into the inner container, wherein the volume ratio of the conductive glass FTO to the reaction liquid is 1. Putting the inner liner of the polytetrafluoroethylene into a high pressure reactorThe autoclave is put into an oven and reacts for 24 hours at 100 ℃. And after the reaction is finished, naturally cooling to room temperature. And opening the reaction kettle, forming a film on the conductive glass FTO, taking out the conductive glass FTO, repeatedly cleaning the conductive glass FTO by using deionized water and ethanol, and drying the conductive glass FTO in a vacuum drying oven with the vacuum degree of 0.03MPa and the temperature of 60 ℃ to obtain the unit cell indium zinc tetrasulfide nanosheet array.
50g of red phosphorus solid and unit cell indium zinc tetrasulfide nanosheet arrays are respectively placed at the head end and the tail end of the graphite boat, and the molar ratio of the red phosphorus solid to the unit cell indium zinc tetrasulfide nanosheet arrays is 10: and 1, placing the graphite boat in a tubular furnace with programmable temperature control, wherein the red phosphorus solid is placed at the upstream of the airflow, and the unit cell indium zinc tetrasulfide nanosheet array is placed in a central temperature area. Sealing the tube furnace, introducing argon with the flow of 30sccm to exhaust air, heating to 300 ℃ at the initial temperature of 20 ℃ at the heating rate of 2 ℃/min, reacting for 240min, and naturally cooling to room temperature to obtain the single-cell PN junction.
Example 2
SnO to be doped with fluorine 2 Conductive glass (conductive glass FTO) in a concentrated H at a volume ratio of 3 2 SO 4 And H 2 O 2 Cleaning in the solution for 15min, ultrasonic cleaning in the solution for 5min, and drying. Putting zinc nitrate, indium sulfate and thioacetamide into a beaker according to an atomic ratio of Zn to In to S = 1. Then, putting the dried conductive glass FTO into a polytetrafluoroethylene inner container, slowly dropping the reaction liquid into the inner container, wherein the volume ratio of the conductive glass FTO to the reaction liquid is 1. And (3) putting the polytetrafluoroethylene liner into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, and reacting for 2 hours at 200 ℃. And after the reaction is finished, naturally cooling to room temperature. And opening the reaction kettle, forming a film on the conductive glass FTO, taking out the conductive glass FTO, repeatedly cleaning the conductive glass FTO by using deionized water and ethanol, and drying the conductive glass FTO in a vacuum drying oven with the vacuum degree of 0.07MPa and the temperature of 50 ℃ to obtain the unit cell indium zinc tetrasulfide nanosheet array.
Respectively placing 200g of sodium hypophosphite solid and unit cell indium zinc tetrasulfide nanosheet arrays at the head and tail ends of a graphite boat, wherein the molar ratio of the sodium hypophosphite solid to the unit cell indium zinc tetrasulfide nanosheet arrays is 100: and 1, placing the graphite boat in a tubular furnace with programmable temperature control, wherein the sodium hypophosphite solid is placed at the upstream of the airflow, and the unit cell indium zinc tetrasulfide array is placed in a central temperature area. Sealing the tubular furnace, introducing argon with the flow of 100sccm to exhaust air, heating to 600 ℃ at the initial temperature of 20 ℃ at the heating rate of 10 ℃/min, reacting for 10min, and naturally cooling to room temperature to obtain the single-cell PN junction.
Example 3
SnO to be doped with fluorine 2 And cleaning conductive glass (conductive glass FTO) in hydrofluoric acid and deionized water at a volume ratio of 1. The preparation method comprises the following steps of putting zinc sulfate, indium sulfate and sodium thiosulfate into a beaker according to an atomic ratio of Zn to In to S = 1. Then, putting the dried conductive glass FTO into a polytetrafluoroethylene inner container, slowly dropping the reaction liquid into the inner container, wherein the volume ratio of the conductive glass FTO to the reaction liquid is 1. And (3) putting the polytetrafluoroethylene inner container into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, and reacting for 15 hours at 150 ℃. And after the reaction is finished, naturally cooling to room temperature. And opening the reaction kettle, forming a film on the conductive glass FTO, taking out the conductive glass FTO, repeatedly cleaning the conductive glass FTO by using deionized water and ethanol, and drying the conductive glass FTO in a vacuum drying oven with the vacuum degree of 0.05MPa and the temperature of 70 ℃ to obtain the unit cell indium zinc tetrasulfide nanosheet array.
Placing the unit cell zinc indium tetrasulfide nanosheet array in a graphite boat, placing the graphite boat at a central temperature area of a tubular furnace with programmable temperature control, sealing the tubular furnace, introducing argon with the flow of 70sccm to evacuate air, heating to 400 ℃ at the initial temperature of 20 ℃ at the heating rate of 7 ℃/min, immediately introducing phosphine gas when the temperature of the tubular furnace reaches 400 ℃, wherein the molar ratio of the phosphine gas to the unit cell zinc indium tetrasulfide nanosheet array is 50: and 1, reacting for 100min to ensure that the introduction time of phosphine gas is consistent with the reaction time, and naturally cooling to room temperature after the reaction is finished to obtain the single-cell PN junction.
Example 4
ZnIn of example 3 2 S 4 Substituted by TiO 2 Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
Example 5
ZnIn of example 3 2 S 4 Substitution with In 2 O 3 Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
Example 6
ZnIn of example 3 2 S 4 ZnO was replaced with ZnO, and the other steps were the same as in example 3, to successfully produce a single-cell PN junction.
Example 7
ZnIn of example 3 2 S 4 Substitution to Fe 2 O 3 Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
Example 8
ZnIn of example 3 2 S 4 Replacement to MoS 2 Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
Example 9
ZnIn of example 3 2 S 4 Substituting ZnS, the other steps are the same as the example 3, and the single cell PN junction is successfully prepared.
Example 10
ZnIn of example 3 2 S 4 And replacing CdS with CdS, and performing the same steps as those in the embodiment 3 to successfully prepare the single-cell PN junction.
Example 11
ZnIn of example 3 2 S 4 Replaced by SnS 2 Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
The unit cell PN junction of example 3 was tested, and from the XRD pattern of FIG. 1, znIn was found 2 S 4 The crystal is a pure phase hexagonal crystal form, and no impurity is generated; as can be seen from the SEM image of FIG. 2, the single-cell PN junction grows uniformly and neatly,and the size is in micron order, has transparent sense, explains that the material is very thin.
From the HRTEM image of FIG. 3, it can be seen that the unit cell PN junction grows in the 001 direction with a thickness of about 1.24nm and with 7 layers of atoms, and one unit cell ZnIn 2 S 4 The thickness and the number of atomic layers are completely consistent; as can be seen from the atomic model diagram of FIG. 4, the thickness of the atomic model and the corresponding unit cell material along the 001 direction is 1.234nm; as can be seen from the front HRTEM of fig. 5, the atomic structure of the unit cell PN junction is still intact after P doping, which shows that the control of the P doping amount is very precise and has little influence on the structural properties of the material. If the doping is excessive, a plurality of defects are necessarily introduced, so that the electron-hole recombination degree is increased, and the material performance is damaged. Next, the cell PN crystal lattice distance d =0.33nm, the included angle is 60 ° with respect to the (100) plane and the (010) plane, which indicates that the main exposed crystal plane of the cell PN junction is (001).
From the AFM plot of FIG. 6, the thickness of the unit cell PN junction is 1.25nm, which is related to ZnIn 2 S 4 The unit cell thickness is consistent; as can be seen from the EDSmapping data in FIG. 7, phosphorus is successfully doped into the material and is controllably doped on one surface, which proves the accurate controllability of the construction method in the patent; as can be seen from the mott schottky graph of fig. 8, P-type and N-type of the unit cell PN junction coexist, and the method of the present patent successfully constructs a PN junction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (8)

1. The single-cell PN junction is characterized in that the single-cell PN junction is constructed in a single cell by utilizing a semiconductor material;
the semiconductor material is ZnIn 2 S 4 ；
The accurate construction method of the single-cell PN junction comprises the following steps:
1) Mixing zinc salt, indium salt, sulfur source and water to obtain reaction liquid;
2) Reacting the reaction liquid with SnO doped with fluorine 2 Mixing the conductive glass and reacting to obtain a unit cell indium zinc tetrasulfide nanosheet array;
3) And reacting the substance containing the fifth main group element with the unit cell indium zinc tetrasulfide nanosheet array in an inert atmosphere to obtain the unit cell PN junction.
2. The precise construction method of a single cell PN junction of claim 1, comprising the steps of:
1) Mixing zinc salt, indium salt, sulfur source and water to obtain reaction liquid;
2) Reacting the reaction liquid with SnO doped with fluorine 2 Mixing the conductive glass and reacting to obtain a unit cell indium zinc tetrasulfide nanosheet array;
3) And reacting the substance containing the fifth main group element with the unit cell indium zinc tetrasulfide nanosheet array in an inert atmosphere to obtain the unit cell PN junction.
3. The construction method according to claim 2, wherein the zinc salt in step 1) is zinc chloride, zinc nitrate or zinc sulfate, the indium salt is indium chloride or indium sulfate, and the sulfur source is thiourea, thioacetamide or sodium thiosulfate.
4. The construction method according to claim 3, wherein the reaction in step 2) is carried out at a temperature of 100 to 200 ℃ for 1 to 24h.
5. The construction method according to claim 4, wherein said SnO doped with fluorine before mixing in step 2) 2 Conducting ultrasonic cleaning on the conductive glass, wherein the fluorine-doped SnO 2 The volume ratio of the conductive glass to the reaction liquid is 1-10, and after the reaction is finished, drying is carried out under the vacuum condition, wherein the drying temperature is 50-70 ℃, and the vacuum degree is 0.03-0.07MPa.
6. The construction method according to claim 3 or 5, wherein the reaction temperature in step 3) is 200 to 600 ℃, the reaction time is 1 to 240min, the flow rate of the inert gas is 30 to 100sccm, and the inert gas is argon.
7. The construction method according to claim 6, wherein the group V element-containing substance in step 3) is red phosphorus, sodium hypophosphite, phosphine gas, ammonia gas, ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
8. The construction method according to claim 7, wherein the rate of heating to the reaction temperature in step 3) is 2 to 10 ℃/min, and when the substance containing the fifth main group element is a gas, the flow rate of the gas is 1 to 30% of the total flow rate.
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