CN111822013A - Single-cell PN junction and accurate construction method thereof - Google Patents

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

Info

Publication number
CN111822013A
CN111822013A CN202010640549.2A CN202010640549A CN111822013A CN 111822013 A CN111822013 A CN 111822013A CN 202010640549 A CN202010640549 A CN 202010640549A CN 111822013 A CN111822013 A CN 111822013A
Authority
CN
China
Prior art keywords
junction
unit cell
cell
construction method
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010640549.2A
Other languages
Chinese (zh)
Other versions
CN111822013B (en
Inventor
王煜
张慧娟
吴俣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing University
Original Assignee
Chongqing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chongqing University filed Critical Chongqing University
Priority to CN202010640549.2A priority Critical patent/CN111822013B/en
Publication of CN111822013A publication Critical patent/CN111822013A/en
Application granted granted Critical
Publication of CN111822013B publication Critical patent/CN111822013B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J35/39—
    • B01J35/40—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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 order; 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 alleviated. 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 cells will deepen understanding of semiconductor physics and drive the development of new related technologies.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a single cell PN junction and a precise construction method thereof. The single-cell PN junction is uniform and neat, has transparent feeling and has the size of micron order; 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, theThe semiconductor material is ZnIn2S4Or a bi-element semiconductor material.
Preferably, the double-element semiconductor material is TiO2、In2O3、ZnO、Fe2O3、MoS2ZnS, CdS or SnS2。
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 fluorine2Mixing 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 in 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)2Conducting ultrasonic cleaning on the conductive glass, wherein the fluorine-doped SnO2The volume ratio of the conductive glass to the reaction liquid is 1: 1-10, and after the reaction is finished, drying is carried out under a vacuum condition, 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 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 heating to the reaction temperature in the step 3) is 2-10 ℃/min, and when the substance containing the fifth main group element is a gas, the flow rate of the gas is 1-30% 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 neat, has transparent sense and has the size of micron order.
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 the 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 an 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 an EDSmapping diagram 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 the 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 ZnIn2S4Or a bi-element semiconductor material, preferably TiO2、In2O3、ZnO、Fe2O3、MoS2ZnS, CdS or SnS2。
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 fluorine2Mixing 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 invention2The 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 H2SO4、H2O2And hydrofluoric acid, preferably mixed solvent of acetone, ethanol and deionized water, and concentrated H2SO4And H2O2The 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 doping with fluorineSnO2The 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 invention2The volume ratio of the conductive glass to the reaction solution is preferably 1:1 to 10, and more preferably 1:3 to 7.
According to the mixing method in the step 2), preferably, the dried conductive glass is placed in a polytetrafluoroethylene inner container, then, the reaction liquid is slowly dropped into the inner container, and preferably, the reaction liquid is 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 1-24 h, more preferably 5-20 h, and even more preferably 10-15 h.
The fluorine-doped SnO of the invention2The 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 liquid2S4Film, ZnIn2S4The film is relatively uniformly thick and will fully 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 SnO2The conductive glass is preferably dried under a vacuum condition, the drying temperature is preferably 50-70 ℃, more preferably 60-65 ℃, and the vacuum degree is preferably 0.03-0.07 MPa, more preferably 0.04-0.06 MPa.
Step 2) of the invention is to mix SnO doped with fluorine2The 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 1-240 min, more preferably 10-200 min, and even more preferably 100-150 min; the flow rate of the inert gas is preferably 30-100 sccm, more preferably 50-90 sccm, and even more preferably 60-80 sccm; 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 starting 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) is a gas, the flow rate of the gas is preferably 1 to 30% of the total flow rate, more preferably 5 to 20%, and even more preferably 10 to 15%; 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 inventive zinc indium tetrasulfide (ZnIn)2S4) 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 ZnIn2S4The 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 fluorine2Conducting glass (conducting glass FTO) is respectively and continuously subjected to ultrasonic treatment in acetone, ethanol and deionized water for 30min, and is dried for standby. Putting zinc chloride, indium chloride and thiourea into a beaker according to the atomic ratio of Zn to In to S to be 1 to 2 to 4, adding a proper amount of deionized water, and fully stirring to obtain a reaction solution. And 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 1:2, and the reaction liquid is not completely immersed in the conductive glass. And (3) putting the polytetrafluoroethylene liner into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, and reacting 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 doped with fluorine2Conductive glass (conductive glass FTO) concentrated H with volume ratio of 3:12SO4And H2O2Cleaning 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 the atomic ratio of Zn to In to S to be 1 to 2 to 4, adding a proper amount of deionized water, and fully stirring to obtain a reaction solution. And 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 1:10, and the reaction liquid is not completely immersed in the conductive glass. 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 a programmable temperature control function, wherein sodium hypophosphite 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 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 doped with fluorine2Cleaning conductive glass (conductive glass FTO) in hydrofluoric acid and deionized water at a volume ratio of 1:10 for 15min, ultrasonically cleaning in the solution for 5min, and drying for later use. Putting zinc sulfate, indium sulfate and sodium thiosulfate into a beaker according to the atomic ratio Zn to In to S to be 1 to 2 to 4, and adding a proper amount of deionized water for carrying outAnd fully stirring to obtain a reaction solution. And 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 1:6, and the reaction liquid is not completely immersed in the conductive glass. And (3) putting the polytetrafluoroethylene liner 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 nano sheet 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 exhaust air, heating to 400 ℃ at the initial temperature of 20 ℃ at the heating rate of 7 ℃/min, immediately introducing a hydrogen phosphide gas when the temperature of the tubular furnace reaches 400 ℃, wherein the molar ratio of the hydrogen phosphide gas to the unit cell zinc indium tetrasulfide nano sheet 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 32S4Substituted by TiO2Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
Example 5
ZnIn of example 32S4Substitution with In2O3Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
Example 6
ZnIn of example 32S4ZnO 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 32S4Replacement by Fe2O3Other steps and embodiments3, the same, successfully preparing the single cell PN junction.
Example 8
ZnIn of example 32S4Replacement to MoS2Other steps are the same as the example 3, and the unit cell PN junction is successfully prepared.
Example 9
ZnIn of example 32S4The ZnS was replaced and the other steps were the same as in example 3 to successfully produce the single cell PN junction.
Example 10
ZnIn of example 32S4The substitution is made to CdS, and other steps are the same as those in example 3, so that the single cell PN junction is successfully prepared.
Example 11
ZnIn of example 32S4Substituted by SnS2Other 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 found2S4The 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 has a micron-sized size and a transparent feeling, which indicates that the material is 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 ZnIn2S4The 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 1.234 nm; 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 in this patent is 0.33nm, corresponding to the (100) plane and the (010) plane, and the included angle is 60 °, which indicates that the cell PN junction mainly has the exposed crystal plane of (001).
From the AFM plot of FIG. 6, the thickness of the unit cell PN junction is 1.25nm, which is related to ZnIn2S4The 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 decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The unit cell PN junction is characterized in that the unit cell PN junction is constructed in a unit cell by utilizing a semiconductor material.
2. The unit cell PN junction of claim 1, wherein the semiconductor material is ZnIn2S4Or a bi-element semiconductor material.
3. The unit cell PN junction of claim 1 or 2, wherein the bi-element semiconductor material is TiO2、In2O3、ZnO、Fe2O3、MoS2ZnS, CdS or SnS2。
4. The precise construction method of a single-cell PN junction according to any one of claims 1 to 3, characterized by comprising 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 fluorine2Mixing 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.
5. The construction method according to claim 4, 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.
6. The construction method according to claim 5, wherein the reaction temperature in step 2) is 100 to 200 ℃ and the reaction time is 1 to 24 hours.
7. The construction method according to claim 6, wherein said SnO doped with fluorine before mixing in step 2)2Conducting ultrasonic cleaning on the conductive glass, wherein the fluorine-doped SnO2The volume ratio of the conductive glass to the reaction liquid is 1: 1-10, and after the reaction is finished, drying is carried out under a vacuum condition, wherein the drying temperature is 50-70 ℃, and the vacuum degree is 0.03-0.07 MPa.
8. The construction method according to claim 5 or 7, wherein the reaction in step 3) is carried out at a temperature of 200 to 600 ℃ for 1 to 240min, and the inert gas is supplied at a flow rate of 30 to 100sccm and is argon gas.
9. The method of constructing according to claim 8, wherein the group V element-containing substance of step 3) is red phosphorus, sodium hypophosphite, phosphine gas, ammonia gas, ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
10. The construction method according to claim 9, wherein the rate of raising the temperature to the reaction temperature in step 3) is 2 to 10 ℃/min, and when the substance containing a group V element is a gas, the flow rate of the gas is 1 to 30% of the total flow rate.
CN202010640549.2A 2020-07-06 2020-07-06 Single-cell PN junction and accurate construction method thereof Active CN111822013B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010640549.2A CN111822013B (en) 2020-07-06 2020-07-06 Single-cell PN junction and accurate construction method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010640549.2A CN111822013B (en) 2020-07-06 2020-07-06 Single-cell PN junction and accurate construction method thereof

Publications (2)

Publication Number Publication Date
CN111822013A true CN111822013A (en) 2020-10-27
CN111822013B CN111822013B (en) 2022-11-18

Family

ID=72901182

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010640549.2A Active CN111822013B (en) 2020-07-06 2020-07-06 Single-cell PN junction and accurate construction method thereof

Country Status (1)

Country Link
CN (1) CN111822013B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705139A (en) * 2004-05-25 2005-12-07 中国科学院福建物质结构研究所 A series of semiconductor material
CN101792931A (en) * 2010-03-24 2010-08-04 南开大学 Metal sulfide single crystal material and preparation method
CN101805136A (en) * 2010-03-11 2010-08-18 许昌学院 Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ
CN102068979A (en) * 2011-01-07 2011-05-25 大连海事大学 Method for degrading methyl orange dye wastewater with ZnIn2S4 visible light catalyst
US20150333212A1 (en) * 2013-01-29 2015-11-19 Imra Europe Sas Method for preparing a thin layer of an absorber made of copper, zinc and tin sulfide(s), annealed thin layer and photovoltaic device thus obtained
CN106025302A (en) * 2016-07-18 2016-10-12 天津理工大学 Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material
CN109052988A (en) * 2018-10-19 2018-12-21 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of zinc indium sulphur nano-chip arrays film
CN109621979A (en) * 2018-12-13 2019-04-16 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of ZnO/ zinc indium sulphur nano heterojunction
CN109821562A (en) * 2019-04-09 2019-05-31 淮北师范大学 A kind of MoP-Zn3In2S6The preparation method of composite nano materials
CN110560105A (en) * 2019-09-03 2019-12-13 西北师范大学 Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production
CN111863625A (en) * 2020-07-28 2020-10-30 哈尔滨工业大学 Single-material PN heterojunction and design method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705139A (en) * 2004-05-25 2005-12-07 中国科学院福建物质结构研究所 A series of semiconductor material
CN101805136A (en) * 2010-03-11 2010-08-18 许昌学院 Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ
CN101792931A (en) * 2010-03-24 2010-08-04 南开大学 Metal sulfide single crystal material and preparation method
CN102068979A (en) * 2011-01-07 2011-05-25 大连海事大学 Method for degrading methyl orange dye wastewater with ZnIn2S4 visible light catalyst
US20150333212A1 (en) * 2013-01-29 2015-11-19 Imra Europe Sas Method for preparing a thin layer of an absorber made of copper, zinc and tin sulfide(s), annealed thin layer and photovoltaic device thus obtained
CN106025302A (en) * 2016-07-18 2016-10-12 天津理工大学 Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material
CN109052988A (en) * 2018-10-19 2018-12-21 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of zinc indium sulphur nano-chip arrays film
CN109621979A (en) * 2018-12-13 2019-04-16 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of ZnO/ zinc indium sulphur nano heterojunction
CN109821562A (en) * 2019-04-09 2019-05-31 淮北师范大学 A kind of MoP-Zn3In2S6The preparation method of composite nano materials
CN110560105A (en) * 2019-09-03 2019-12-13 西北师范大学 Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production
CN111863625A (en) * 2020-07-28 2020-10-30 哈尔滨工业大学 Single-material PN heterojunction and design method thereof

Also Published As

Publication number Publication date
CN111822013B (en) 2022-11-18

Similar Documents

Publication Publication Date Title
CN109621979B (en) Preparation method of ZnO/zinc indium sulfide nano heterojunction
Guo et al. Fabrication of TiO2 nano-branched arrays/Cu2S composite structure and its photoelectric performance
CN104393103B (en) A kind of Cu2ZnSnS4The preparation method of semiconductive thin film and application thereof
CN111261413B (en) Ti-doped alpha-Fe2O3Nanorod composite MOFs heterojunction photo-anode and preparation method and application thereof
CN104659157B (en) Based on the preparation method of BiOBr/CdS heterojunction photovoltaic thin-film material
CN102637755B (en) Nanometer structure copper zinc tin sulfide (CZTS) film photovoltaic cell and preparation method of nanometer structure CZTS film photovoltaic cell
CN108922927B (en) Stable compound semiconductor sunlight decomposition water hydrogen production electronic device, electrode system and preparation method thereof
CN112195483B (en) Method for constructing Z-type heterojunction photo-anode and Z-type heterojunction photo-anode
CN110252352A (en) A kind of carbon quantum dot modification bismuth tungstate/ordered big hole fluorine-doped tin oxide composite photo-catalyst and its preparation method and application
CN105261483B (en) Cu2ZnSnS4It is sensitized TiO2Light anode and its in-situ preparation method and application
CN107680816B (en) Preparation method of the porous Ti load hollow needle NiCo2S4 to electrode
Sheela et al. Progress in transition metal chalcogenides-based counter electrode materials for dye-sensitized solar cells
CN112310287A (en) Preparation method of high-stability inorganic hole transport film capable of being produced in large scale
CN106328381B (en) All solid state quantum dot sensitized solar cell of one kind and preparation method thereof
CN107994122A (en) Zinc doping nickel oxide nanoparticle hole transmission layer is just putting perovskite solar cell and preparation method
Chen et al. Morphology selective electrodeposition of Cu2O microcrystals on ZnO nanotube arrays as efficient visible-light-driven photo-electrode
CN106835183B (en) A kind of WSe2The preparation method of base composite nano piece optoelectronic pole
CN103545112A (en) Solar cell photo-anode using semiconductor thin film as sensitizing agent and preparation method of solar cell photo-anode
Mendhe et al. Sequential growth-controlled silver selenide nanoparticles embedded 1D-CdS nanowires: Heterostructure design to enhance power conversion efficiency
Liu et al. Sequential synthesis and improved photoelectrochemical properties of ZnO/CdTe/CdS nanocable arrays photoanode
CN112234110B (en) Sandwich-shaped PN junction and accurate construction method thereof
CN111962090B (en) Ti3C2-MXene modified alpha-iron oxide photoelectrode and preparation method thereof
Luo et al. 3D hierarchically branched Cu2S/ZnO heterojunction nanowire arrays for enhanced solar water splitting
CN104037267B (en) A kind of method that copper-zinc-tin-selefilm film solar battery obsorbing layer is modified
CN105568309A (en) Preparation method for photoelectrode of photoelectrochemical cell

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant