阅读说明：本技术 一种层状氧硫族光电材料FeOCuQ及其制备方法和应用 (Layered oxygen sulfur group photoelectric material FeOOCuQ and preparation method and application thereof ) 是由 张刚华 王静 房永征 侯京山 于 2021-09-15 设计创作，主要内容包括：本发明公开了一种层状氧硫族光电材料FeOCuQ及其制备方法。本发明的层状氧硫族光电材料FeOCuQ中,Q为S、Se或S与Se的混合,该体系晶体结构由FeO层和CuQ层间隔排列堆积成反PbO型层状结构,其中FeO层是以Fe为中心原子的FeO4四面体共边连接构成,CuQ由以Cu为中心原子的CuQ4四面体共边连接构成。本发明采用水热法合成了光电材料FeOCuQ,具有高效、低耗、原料来源丰富且工艺简单的特点。本发明制得的FeOCuQ光电材料在模拟太阳光照下表现出明显的光电效应和快速的响应时间,在光电探测以及太阳能电池等领域有广阔的应用前景。(The invention discloses a layered chalcogen oxide photoelectric material FeOOCuQ and a preparation method thereof. In the layered chalcogeno photoelectric material FeOOCuQ, Q is S, Se or the mixture of S and Se, the crystal structure of the system is a layered structure of an inverted PbO layer formed by alternately arranging and stacking FeO layers and CuQ layers, wherein the FeO layers are formed by connecting FeO4 tetrahedrons with Fe as a central atom in a shared-edge mode, and CuQ is formed by connecting CuQ4 tetrahedrons with Cu as a central atom in a shared-edge mode. The invention synthesizes the photoelectric material FeOOCuQ by a hydrothermal method, and has the characteristics of high efficiency, low consumption, rich raw material sources and simple process. The FeOOCuQ photoelectric material prepared by the invention shows obvious photoelectric effect and quick response time under simulated solar illumination, and has wide application prospect in the fields of photoelectric detection, solar cells and the like.)

1. The layered chalcogen oxide photoelectric material is characterized in that the chemical composition of the layered chalcogen oxide photoelectric material is FeOOCuQ, wherein Q is S, Se or the mixture of the two.

2. The layered chalcogenox photoelectric material of claim 1, wherein the layered chalcogenox photoelectric material has a layered structure of an inverted PbO layer having an FeO layer and CuQ layers arranged at intervals, the FeO layer being FeO having Fe as a central atom and O as a coordinating atom₄The tetrahedrons are connected in a shared edge manner to form a two-dimensional network structure; the CuQ layer is CuQ taking Cu as a central atom and Q as a coordination atom₄The tetrahedrons are connected in a shared edge manner to form a two-dimensional network structure.

3. The method for preparing the layered oxysulfide group photoelectric material according to claim 1 or 2, characterized by comprising the steps of:

step 1: adding a Fe source and a Cu source into deionized water, mixing and uniformly stirring to obtain a solution A;

step 2: adding a Q source into the solution A, adding solid base AOH, and uniformly stirring and mixing to obtain a mixed solution;

and step 3: after the mixed solution obtained in the step 2 is cooled to room temperature, transferring the mixed solution into a reaction kettle for reaction;

and 4, step 4: after the reaction is finished, washing, centrifuging and drying a product to obtain a sample;

and 5: and (4) tabletting and calcining the sample obtained in the step (4) to obtain the layered oxysulfide photoelectric material FeOOCuQ.

4. The method for preparing a layered chalcogenox photoelectric material of claim 3, wherein the Fe source in step 1 is a soluble Fe salt, the Cu source is a soluble Cu salt, and the molar ratio of the Fe source to the Cu source is 1: 1; the concentration of the Fe source and the Cu source in the solution A is 0.02 mol/L.

5. The method of preparing a layered chalcogenone photovoltaic material of claim 4, wherein said soluble Fe salt is ferric nitrate and said soluble Cu salt is cupric acetate.

6. The method for preparing a layered chalcogenox photoelectric material of claim 3, wherein the source Q in step 2 is at least one of sulfur powder, thiourea, selenium powder and selenourea, and the solid base AOH is at least one of NaOH, KOH, RbOH and CsOH; the concentration of AOH in the mixed solution is more than 2mo 1/L.

7. The method for preparing a layered chalcogenone photoelectric material according to claim 3, wherein the reaction temperature in step 3 is 120-200 ℃ for 1-7 days.

8. The method for preparing a layered chalcogenox photoelectric material of claim 3, wherein the calcination in step 5 is performed under the following conditions: the temperature is 400-500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 8-12 h.

9. Use of the layered oxysulfide group photovoltaic material according to claim 1 or 2.

10. The use of claim 9, including use in the manufacture of photodetectors and solar cells.

Technical Field

The invention relates to a layered chalcogen oxygen photoelectric material FeOOCuQ and a preparation method and application thereof, belonging to the technical field of photoelectricity.

Background

Among the solar cell materials, chalcogenide has a wide variety of structures, high current-carrying concentration, and band gap junctionHas a plurality of advantages such as outstanding adaptability and photoelectric performance, and is favored in the field of thin film batteries. However, the chalcogen compounds with excellent photoelectric properties are mostly limited in chalcopyrite and chalcogen compounds with derivative structures thereof (such as CdTe, CIS, CIGS, CZTS and the like), and the chalcogen photoelectric materials with the structures are limited in application due to the disadvantages of high manufacturing cost, low material utilization rate, environmental incompatibility and the like, and are not ideal substitute materials for silicon. Compared with the prior art, the layered oxygen-sulfur compound has the advantages of tunable band gap, ultrahigh carrier mobility in the layer, reliable environmental stability and the like, and becomes a research hotspot in the fields of high-speed low-power devices, quantum transport devices, ultrafast high-sensitivity infrared detection, photoelectric devices and the like. Although theoretical calculation research shows that the ideal conversion efficiency of the layered bismuth oxygen sulfur compound BiOCuS In photoelectric application is as high as 18.8%, the photocurrent of the material is still far lower than that of the traditional sulfur group photoelectric material Cu (In)_xGa_1～x)Se₂(CIGS) and CdTe, greatly limiting their further applications in the field of photovoltaics. How to further improve the photoelectric conversion efficiency and reduce the cost is one of the decisive factors for the practical application of the layered chalcogen oxide photoelectric material. From the technical point of view, the abundant, nontoxic and pollution-free raw material reserves are important factors for practical application of photoelectric materials. Therefore, the search for a novel oxygen-sulfur group photoelectric material with high efficiency and low consumption is very meaningful for the practical application and theoretical research of the oxygen-sulfur group photoelectric material. On the other hand, the conventional solid phase method usually requires extreme reaction conditions and high cost, the solvothermal method usually requires the use of unique precursors, and the synthesis process is usually complicated. Therefore, a simpler and faster hydrothermal synthesis path without any auxiliary organic solvent or harmful reagent is searched, a novel multi-element layered oxygen sulfur group semiconductor material with high crystallinity, high purity and excellent performance is prepared, the photoelectric performance of the material is researched, and the material has very important significance from the aspects of basic research, performance and application.

Disclosure of Invention

The technical problem solved by the invention is as follows: the technical problem of how to obtain a novel multi-element layered oxygen sulfur group semiconductor material with high crystallinity, high purity and excellent performance.

In order to solve the technical problem, the invention provides a layered chalcogen oxide photoelectric material, the chemical composition of which is FeOOCuQ, wherein Q is S, Se or the mixture of the two.

Preferably, the layered chalcogeno photoelectric material has a layered structure of reverse PbO layers arranged at intervals between an FeO layer and CuQ layers, wherein the FeO layer is FeO with Fe as a central atom and O as a coordination atom₄The tetrahedrons are connected in a shared edge manner to form a two-dimensional network structure; the CuQ layer is CuQ taking Cu as a central atom and Q as a coordination atom₄The tetrahedrons are connected in a shared edge manner to form a two-dimensional network structure.

The invention also provides a preparation method of the layered oxygen-sulfur group photoelectric material, which comprises the following steps:

step 1: adding a Fe source and a Cu source into deionized water, mixing and uniformly stirring to obtain a solution A;

step 2: adding a Q source into the solution A, adding solid base AOH, and uniformly stirring and mixing to obtain a mixed solution;

and step 3: after the mixed solution obtained in the step 2 is cooled to room temperature, transferring the mixed solution into a reaction kettle for reaction;

and 4, step 4: after the reaction is finished, washing, centrifuging and drying a product to obtain a sample;

and 5: and (4) tabletting and calcining the sample obtained in the step (4) to obtain the layered oxysulfide photoelectric material FeOOCuQ.

Preferably, the Fe source in the step 1 is soluble Fe salt, the Cu source is soluble Cu salt, and the molar ratio of the Fe source to the Cu source is 1: 1; the concentration of the Fe source and the Cu source in the solution A is 0.02 mol/L.

More preferably, the soluble Fe salt is ferric nitrate and the soluble Cu salt is cupric acetate.

Preferably, the source of Q in step 2 is at least one of sulfur powder, thiourea, selenium powder and selenourea, and the solid base AOH is at least one of NaOH, KOH, RbOH and CsOH; the concentration of AOH in the mixed solution is more than 2mo 1/L.

Preferably, the reaction temperature in the step 3 is 120-200 ℃ and the reaction time is 1-7 days.

Preferably, the calcining conditions in step 5 are: the temperature is 400-500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 8-12 h.

The invention also provides application of the layered oxygen-sulfur group photoelectric material.

Preferably, the applications include applications in the preparation of photodetectors and solar cells.

Compared with the prior art, the invention has the following beneficial effects:

the FeOOCuQ type layered oxysulfide group photoelectric material is prepared by a mild and simple hydrothermal method, the sample prepared by the hydrothermal method has good quality and regular appearance, the FeOOCuQ sample in the system shows obvious photoproduction current and quick photoelectric response under the sunlight, and the photoproduction current density is respectively as follows when the voltage is applied at 0.05V: FeOOCuS sample 5.95mA/cm²FeOOCuSe sample 0.19mA/cm²(ii) a The photoelectric response time is respectively as follows: the FeOOCuS sample is about 0.94s, the FeOOCuSe sample is about 4.9s, and the synthesis of the photoelectric material provided by the invention provides a good reference for finding more new systems of the chalcogen photoelectric material.

Drawings

Fig. 1 is a schematic structural diagram of a FeOCuQ (Q ═ S or Se) material of the present invention;

FIG. 2 is a powder XRD pattern of FeOOQ (Q ═ S or Se) material prepared in the examples of the present invention;

FIG. 3 is SEM and EDS graphs of the crystal morphology of FeOOQ (Q ═ S or Se) material prepared in the examples of the present invention;

FIG. 4 is the I-T curve of the FeOOS material prepared in example 1 under visible light irradiation and 0.05V bias voltage;

FIG. 5 is the I-T curve of FeOOCuSe material prepared in example 2 under visible light irradiation and 0.05V bias.

Detailed Description

In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.

Example 1

A preparation method of a layered chalcogeno photoelectric material FeOOS specifically comprises the following steps:

1) reacting raw material Fe (NO)₃)₃And Cu (CH)₃COO)₂Preparing a 0.02mo1/L clear solution, taking the clear solution according to the mass ratio of 1:1, mixing and uniformly stirring to obtain a mixed solution;

2) adding 2.2g of thiourea into the mixed solution, and uniformly stirring on a magnetic stirrer;

3) adding KOH solid into the mixed solution to ensure that the alkalinity of the solution reaches more than 2mo1/L, and stirring to uniformly mix the mixture;

4) after the mixture is cooled to room temperature, transferring the mixture into a reaction kettle, wherein the filling degree is lower than 80% of the volume of the kettle, reacting in an oven at 150 ℃ for 2 days, cooling the reaction kettle to room temperature, and releasing the pressure;

5) washing and centrifuging the reaction product, wherein the centrifugation is carried out for 5 times at the rotating speed of 8000 revolutions per minute, and then the reaction product is dried in a 50 ℃ oven;

6) grinding the prepared FeOOCuS sample uniformly, and pressing the sample into a sheet with the diameter of 12mm under 8 MPa;

7) and sealing the slice in a quartz tube in a vacuum state, preserving the heat for 10h at 400 ℃ in a muffle furnace, and setting the heating rate to be 5 ℃/min to obtain the layered chalcogen oxide photoelectric material FeOCuS.

The prepared layered chalcogeno photoelectric material FeOO CuS has a layered structure of a reverse PbO layer with an FeO layer and a CuS layer arranged at intervals, wherein the FeO layer is FeO with Fe as a central atom and O as a coordination atom₄The tetrahedrons are connected in a shared edge manner to form a two-dimensional network structure; the CuS layer is a CuS layer with Cu as a central atom and S as a coordination atom₄The two-dimensional network structure formed by connecting tetrahedrons in a shared edge mode is shown in figure 1.

Example 2

A preparation method of a layered chalcogeno photoelectric material FeOOCuSe specifically comprises the following steps:

1) reacting raw material Fe (NO)₃)₃And Cu (CH)₃COO)₂Preparing a 0.02mo1/L clear solution, taking the clear solution according to the mass ratio of 1:1, mixing and uniformly stirring to obtain a mixed solution;

2) adding 0.8g of selenium powder into the mixed solution, and uniformly stirring on a magnetic stirrer;

3) adding KOH solid into the mixed solution to ensure that the alkalinity of the solution reaches more than 2mo1/L, and stirring to uniformly mix the mixture;

4) after the mixture is cooled to room temperature, transferring the mixture into a reaction kettle, wherein the filling degree is lower than 80% of the volume of the kettle, reacting in a 160 ℃ oven for 2 days, cooling the reaction kettle to room temperature, and releasing the pressure;

5) washing and centrifuging the reaction product, wherein the centrifugation is carried out for 5 times at the rotating speed of 8000 revolutions per minute, and then the reaction product is dried in a 50 ℃ oven;

6) uniformly grinding the prepared FeOOCuSe sample, and pressing the sample into a sheet with the diameter of 12mm under 8 MPa;

7) and sealing the slice in a quartz tube in a vacuum state, preserving the heat for 10h at 500 ℃ in a muffle furnace, and setting the heating rate to be 5 ℃/min to obtain the layered chalcogen oxide photoelectric material FeOOCuSe.

The prepared layered chalcogeno photoelectric material FeOOCuSe has a layered structure of a reverse PbO layer with an FeO layer and a CuSe layer arranged at intervals, wherein the FeO layer is FeO with Fe as a central atom and O as a coordination atom₄The tetrahedrons are connected in a shared edge manner to form a two-dimensional network structure; the CuSe layer is CuSe with Cu as central atom and Se as coordination atom₄The two-dimensional network structure formed by connecting tetrahedrons in a shared edge mode is shown in figure 1.

FIG. 2 is a powder XRD pattern of FeOOCuQ materials prepared in examples 1 and 2. from FIG. 2, it can be seen that the FeOOCuQ sample prepared by the hydrothermal method is pure phase and has high crystallinity; FIG. 3 is SEM and EDS graphs of crystal morphology of FeOOCuQ materials prepared in examples 1 and 2, wherein the sample has micron sheet morphology and chemical composition element ratio of 1:1:1: 1. FIGS. 4 and 5 are graphs of photo-generated currents of FeOOS and FeOOSe prepared in examples 1 and 2 under irradiation of visible light, from which photoelectric test results of the samples can be obtained in FIGS. 4 and 5: the photoproduction current density of the FeOOCuS sample is 5.95mA/cm²PhotoelectricThe response time was about 0.94 s; the photoproduction current density of the FeOOCuSe sample is 0.19mA/cm²The photoelectric response time is about 4.9 s; all show remarkable photoelectric response performance.

While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.