Application of an organic-inorganic hybrid photodetecting material in preparation of a photovoltaic thin film device

Abstract

The application relates to the field of photoelectric technology, in particular to application of an organic-inorganic hybrid light detection material in preparation of a photoelectric thin film device. First, the organic-inorganic hybrid light detection material, dimethyl sulfoxide and N,N-dimethylformamide are uniformly mixed to obtain a mixed solution; then the solution is spin-coated on a conductive substrate, and a photoelectric thin film is obtained after vacuum annealing treatment; finally, a photoelectric thin film device is prepared by screen printing silver paste on the photoelectric thin film; wherein the chemical structural formula of the organic-inorganic hybrid light detection material is [C4N2H 14 ][SbBr5], and the following cell parameters are possessed: angles are alpha=90°, beta=118.763(2)° and gamma=90°.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of optoelectronic technology, and in particular to an application of an organic-inorganic hybrid light detection material in preparation of an optoelectronic thin film device. BACKGROUND

[0002] With the rapid development of optoelectronic device technology, organic-inorganic hybrid materials have become an important research direction in the field of optoelectronic devices due to their unique structure, excellent optoelectronic properties, and good adjustability. In particular, in the preparation of optoelectronic devices, these materials have become ideal candidate materials for realizing efficient light energy conversion and storage due to their low cost, easy synthesis, adjustable band gap, and nonlinear optical response. Research in the fields of photovoltaic cells, photoelectrocatalysis, sensors, and energy storage devices shows that reasonable design of organic-inorganic hybrid materials can significantly improve the photoelectric conversion efficiency, reduce energy loss, and enhance the stability and environmental adaptability of the device. However, the existing technology still faces many challenges, including poor environmental stability of the material, complex synthesis process, limited performance adjustability, interface effect problems, and limitations in material design. The existing organic-inorganic hybrid materials are prone to degradation under harsh conditions such as high humidity, high temperature, and ultraviolet light, and the high cost and low yield in the synthesis process also limit their widespread application. In addition, there are still certain bottlenecks in the performance adjustment of the material, which is difficult to meet the special needs of improving the photoelectric conversion efficiency or enhancing the carrier mobility. SUMMARY

[0003] To solve the above problems, the purpose of the present application is to provide an application of an organic-inorganic hybrid light detection material in preparation of an optoelectronic thin film device.

[0004] The present application aims to solve the technical problems of environmental stability, synthesis process, performance adjustability, and poor light absorption of organic-inorganic hybrid materials in the preparation of optoelectronic devices, thereby further improving the overall performance and application potential of optoelectronic devices. 14 As an organic-inorganic hybrid material, [C4N2H 14 ][SbBr5] has good optoelectronic properties and adjustability, which can provide new ideas for the research of optoelectronic devices.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] The first purpose of the present application is to provide an application of an organic-inorganic hybrid light detection material in preparation of an optoelectronic thin film device, wherein the chemical structural formula of the organic-inorganic hybrid light detection material is [C4N2H 14 ][SbBr5], and has the following unit cell parameters: The angle is α = 90°, β = 118.763(2)°, and γ = 90°.

[0007] In one embodiment of the present application, the organic-inorganic hybrid light detection material is prepared by the following method:

[0008] (S1) mixing Sb2O3 and HBr sufficiently to obtain a SbBr3 solution;

[0009] (S2) adding 1,4-diaminobutane to the SbBr3 solution obtained in step (S1) and carrying out hydrothermal reaction and post-treatment to obtain the organic-inorganic hybrid light detection material.

[0010] Further, in step (S1), the amount ratio of Sb2O3 to HBr is 1 mmol: 3-8 mL;

[0011] In step (S2), the amount ratio of 1,4-diaminobutane to the SbBr3 solution is 1 mmol: 3-8 mL;

[0012] In the hydrothermal reaction process, the temperature is 100-150℃ and the time is 10-14 h;

[0013] The post-treatment is carried out by centrifugation, washing and drying in sequence.

[0014] Further, in the centrifugation process, the rotation speed is 3000 r / min and the time is 20 s;

[0015] In the washing process, the washing agent is ethyl acetate;

[0016] In the drying process, the temperature is 60℃ and the time is 6 h.

[0017] A second object of the present application is to provide a preparation method of a photoelectric thin film device, which specifically comprises the following steps:

[0018] (A1) mixing the organic-inorganic hybrid light detection material, dimethyl sulfoxide and N,N-dimethylformamide uniformly to obtain a mixed solution;

[0019] (A2) spin-coating the solution prepared in step (A1) on a conductive substrate and carrying out vacuum annealing treatment to obtain a photoelectric thin film;

[0020] (A3) preparing a photoelectric thin film device by screen printing silver paste on the photoelectric thin film prepared in step (A2);

[0021] The chemical structural formula of the organic-inorganic hybrid light detection material is [C4N2H 14 ][SbBr5] and has the following cell parameters: The angles are α=90°, β=118.763(2)° and γ=90°.

[0022] In one embodiment of the present application, in step (A1), the ratio of the amounts of the organic-inorganic hybrid light detection material, dimethyl sulfoxide and N,N-dimethylformamide is 1 g: 0.3-0.8 mL: 0.3-0.8 mL.

[0023] In one embodiment of the present application, the ratio of the amounts of the organic-inorganic hybrid light detection material, dimethyl sulfoxide and N,N-dimethylformamide is 1 g: 0.5 mL: 0.5 mL.

[0024] In one embodiment of the present application, in step (A2), the temperature during the vacuum annealing process is 120-150°C, and the time is 0.5-1 h.

[0025] In one embodiment of the present application, in step (A2), the thickness of the photoelectric thin film is 3.21-3.68 μm.

[0026] Preferably, the thickness of the photoelectric thin film is 3.68 μm.

[0027] A third object of the present application is to provide a photoelectric thin film device prepared by the above method.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] (1) The photoelectric thin film prepared has uniform thickness, high compactness and good photoelectric response characteristics. The vacuum annealing process ensures that the lattice structure of the thin film is optimized, thereby enhancing the electron transport capacity and overall performance of the thin film.

[0030] (2) The preparation method of the photoelectric thin film device provided by the present application prepares the organic-inorganic hybrid light detection material by a simple hydrothermal reaction method, and then prepares the photoelectric thin film device by spin coating, vacuum annealing and screen printing processes. The process flow is simple, the operability is strong, and the industrial production is easy. The optimization of the temperature, time and other conditions in the steps ensures the quality of the material and the device.

[0031] (3) The organic-inorganic hybrid light detection material [C4N2H 14 ][SbBr5] provided by the present application has a specific crystal structure and good photoelectric performance, and can effectively improve the light response speed and detection sensitivity of the photoelectric thin film device. Its excellent photoelectric performance makes its application in the photoelectric thin film device have higher efficiency and stability. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The XRD pattern of the organic-inorganic hybrid light detection material [C4N2H 14 ][SbBr5] prepared for Example 1;

[0033] Figure 2 Structure diagram of the organic-inorganic hybrid photodetecting material [C4N2H 14 ][SbBr5] prepared in Example 1 (I);

[0034] Figure 3 Structure diagram of the organic-inorganic hybrid photodetecting material [C4N2H 14 ][SbBr5] prepared in Example 1 (II);

[0035] Figure 4 Optical photograph of the organic-inorganic hybrid photodetecting material [C4N2H 14 ][SbBr5] prepared in Example 1;

[0036] Figure 5 Absorption-band diagram of the organic-inorganic hybrid photodetecting material [C4N2H 14 ][SbBr5] prepared in Example 1;

[0037] Figure 6 SEM cross-sectional diagram of the photoelectric thin film of different thicknesses in Example 2;

[0038] Figure 7 I-T curve diagram of the photoelectric thin film of different thicknesses in Example 2;

[0039] Figure 8 I-T curve diagram of the [C4N2H 14 ][SbBr5] photoelectric material under different polarization voltages in Example 4. DETAILED DESCRIPTION

[0040] The present application will be described in detail below with reference to the accompanying drawings and specific examples.

[0041] In the following examples, the reagents used are all commercially available reagents, and the detection means and methods used are all conventional detection means and methods in the art, unless otherwise specified.

[0042] Example 1

[0043] The present example provides a hydrothermal synthesis method of an organic-inorganic hybrid photodetecting material, which specifically comprises the following steps:

[0044] (S1) uniformly mixing Sb2O3 and HBr solvent to obtain a SbBr3 solution.

[0045] wherein the ratio of the amount of Sb2O3 to HBr is 5 mmol: 25 mL;

[0046] (S2) adding 5 mmol of 1,4-diaminobutane into the SbBr3 solution obtained in step (S1), stirring and mixing to obtain a mixture;

[0047] (S3) The mixture prepared in step (S2) was transferred to a reaction kettle and reacted under hydrothermal reaction (temperature 120℃, time 12h).

[0048] (S4) The product obtained after hydrothermal reaction in step (S3) was centrifuged (speed 3000r / min, time 20s), and the precipitate was collected and washed with ethyl acetate, and then the washed product was placed in an oven at 60℃ for drying for 6h to obtain an organic-inorganic hybrid light detection material: [C4N2H 14 ][SbBr5] (rod, purity 98%).

[0049] Performance test and result analysis:

[0050] In this embodiment, the organic-inorganic hybrid light detection material [C4N2H 14 ][SbBr5] prepared was detected by an X-ray diffraction (XRD) instrument, and the results are shown in Figure 1 , indicating that the obtained sample is a single phase. In the test, graphite monochromatized Mo Kα radiation (wavelength ) was used, and the single crystal X-ray diffraction data were collected by ω-2θ scanning method. According to the room temperature single crystal XRD data analysis, the material exhibits a polar monoclinic structure of P21 space group, and the crystal structure is composed of one-dimensional angle-shared SbBr6 octahedral chains along the b-axis direction and independent 1.4-diaminobutane molecules, and the structural schematic diagram is shown in Figure 2 and Figure 3 .

[0051] Table 1 [C4N2H 14 Cell parameters of [SbBr5] organic-inorganic hybrid photodetecting material crystal

[0052]

[0053] In addition, the morphology of the [C4N2H 14 ][SbBr5] single crystal was observed by optical microscope (see Figure 4 ), and it was found that the material presented yellow rod, smooth surface and no obvious defects. The optical absorption characteristics and band gap of the single crystal material were determined by ultraviolet-visible-near infrared spectrophotometer (see Figure 5 ), and the results showed that the absorption edge of the material was at 506nm, and the optical band gap was 2.58eV.

[0054] Example 2

[0055] The embodiment provides a preparation method of an organic-inorganic hybrid light detection material photoelectric film, and specifically includes the following steps:

[0056] (1) 0.3g [C4N2H14 ][SbBr5] single crystal powder was dissolved in 0.3 mL of DMSO and DMF solution (volume ratio of DMSO and DMF was 1:1), and the mixture was stirred well to make [C4N2H 14 ][SbBr5] single crystal powder was completely dissolved to obtain a mixed solution;

[0057] (2) The mixed solution prepared in step (1) was spin-coated on an ITO conductive substrate, the spin-coating amount was 50 μL / time, the rotation speed of the spin-coater was set to 3000 rpm, and the spin-coating time was 30 s, and the spin-coating sample was obtained by spin-coating 1 time, 3 times, 5 times, 8 times and 10 times, respectively;

[0058] The obtained spin-coating sample was placed in a tube furnace, heated to 120℃ at a rate of 1℃ / min, vacuum calcined for 0.5 h, and then vacuum cooled to room temperature to obtain [C4N2H 14 ][SbBr5] photoelectric thin film (photoelectric thin films with thicknesses of 2.73 μm, 3.21 μm, 3.68 μm, 4.48 μm, and 5.76 μm were obtained, respectively);

[0059] (3) The [C4N2H 14 ][SbBr5] photoelectric thin film prepared in step (2) was coated with silver paste (as a back electrode) by screen printing to obtain a [C4N2H 14 ][SbBr5] photoelectric thin film device: from bottom to top, it includes an ITO conductive substrate, a [C4N2H 14 ][SbBr5] thin film, and an Ag electrode.

[0060] In this embodiment, five [C4N2H 14 ][SbBr5] photoelectric thin films with different thicknesses were prepared by spin coating method, and the thickness of the [C4N2H 14 ][SbBr5] thin film can be estimated from the SEM cross-sectional image (see Figure 6 ) The current-time (I-t) curve related to the thickness is shown in Figure 7 .

[0061] It can be found from Figure 6 and Figure 7 that with the increase of the thickness of the photoelectric thin film, the photocurrent density first increases, reaches a maximum value of 63 pA at 3.68 μm, and then decreases with the further increase of the thickness of the photoelectric thin film. Since the recombination rate of photo-generated carriers is significantly increased in a thicker photoelectric thin film, especially when the thickness of the photoelectric thin film exceeds a certain critical value, the diffusion time of the photo-generated carriers in the film increases, which may be recombined with defects or impurities before reaching the electrode, resulting in a decrease in the effective carrier concentration. Therefore, the [C4N2H 14The optimal thickness of the [SbBr5] photoelectric film is fixed at 3.68 μm for further photoelectric measurement.

[0062] Example 3

[0063] The present example provides a preparation method of an organic-inorganic hybrid photo-detection material photoelectric film, which specifically comprises the following steps:

[0064] (1) 0.3 g of [C4N2H 14 ] prepared in Example 1 is dissolved into 0.3 mL of DMSO and DMF solution (the volume ratio of DMSO and DMF is 1:1), and the mixture is fully stirred and uniformly mixed to completely dissolve the [C4N2H 14 ] single crystal powder, to obtain a mixed solution;

[0065] (2) The mixed solution prepared in step (1) is spin-coated on an ITO conductive substrate, the spin-coating amount is 50 μL / time, the rotation speed of the glue homogenizer is set to 3000 rpm, the spin-coating time is 30 s, and the spin-coating is performed 5 times to obtain a spin-coated sample;

[0066] The obtained spin-coated sample is placed in a tube furnace, heated to 150℃ at a rate of 1℃ / min, vacuum calcined for 1 h, and then vacuum cooled to room temperature to obtain a [C4N2H 14 ][SbBr5] photoelectric film (thickness of 3.68 μm);

[0067] (3) A silver paste (as a back electrode) is screen-printed on the [C4N2H 14 ][SbBr5] photoelectric film prepared in step (2), to obtain a [C4N2H 14 ][SbBr5] photoelectric film device: from bottom to top, it comprises an ITO conductive substrate, a [C4N2H 14 ][SbBr5] film and an Ag electrode.

[0068] In the present example, the prepared photoelectric film device is tested under the irradiation of a 500 W (AM 1.5G) xenon lamp using a 4200A-SCS digital source table, and the current of the photoelectric film device shows a change trend with the change of the applied voltage under the condition of zero bias voltage. Specifically, the photocurrent size shows a trend of first increasing and then decreasing with the increase of the polarization voltage. In the negative polarization state, when a voltage of-8 V is applied, the measured photocurrent peak value is 223.6 pA; while in the positive polarization state, when a voltage of 8 V is applied, the photocurrent peak value is-158.4 pA. Therefore, the optimal photocurrent response is obtained under the condition of-8 V voltage (as shown in Figure 8 ).

[0069] Comparative Example 1

[0070] The present comparative example provides a preparation method of an organic-inorganic hybrid photodetecting material photoelectric film, specifically comprising the following steps:

[0071] (1) 0.3 g of [C4N2H 14 ][SbBr5] single crystal powder prepared in Example 1 was dissolved into 0.3 mL of DMSO solution, and the mixture was fully stirred and mixed until the [C4N2H 14 ][SbBr5] single crystal powder was completely dissolved, to obtain a mixed solution;

[0072] (2) The mixed solution prepared in step (1) was spin-coated on an ITO conductive substrate, the spin-coating amount was 50 μL / time, the rotation speed of the film uniformizer was set to 3000 rpm, the spin-coating time was 30 s, and the spin-coating was performed 5 times to obtain a spin-coated sample;

[0073] The obtained spin-coated sample was placed in a tube furnace, heated to 120°C at a rate of 1°C / min, vacuum calcined for 0.5 h, and then vacuum cooled to room temperature to obtain a [C4N2H 14 ][SbBr5] photoelectric film (the thickness thereof was controlled to be 3.68 μm, but the photoelectric film was non-uniform, had very poor crystallinity, and was uneven);

[0074] (3) Silver paste was screen-printed on the [C4N2H 14 ][SbBr5] photoelectric film prepared in step (2) (as a back electrode), to obtain a [C4N2H 14 ][SbBr5] photoelectric film device: from bottom to top, comprising an ITO conductive substrate, a [C4N2H 14 ][SbBr5] film, and an Ag electrode.

[0075] The results show that the [C4N2H 14 ][SbBr5] single crystal powder cannot be well dissolved in the DMSO solution, the prepared film is non-uniform, has very poor crystallinity, and is uneven, which affects the optical performance of the film.

[0076] Comparative Example 2

[0077] The present comparative example provides a preparation method of an organic-inorganic hybrid photodetecting material photoelectric film, specifically comprising the following steps:

[0078] (1) 0.3 g of [C4N2H 14 ][SbBr5] single crystal powder prepared in Example 1 was dissolved into 0.3 mL of DMF solution, and the mixture was fully stirred and mixed until the [C4N2H 14 ][SbBr5] single crystal powder was completely dissolved, to obtain a mixed solution;

[0079] (2) The mixed solution prepared in step (1) is spin-coated on an ITO conductive substrate, the spin-coating amount is 50 μL / time, the rotation speed of the film applicator is set to 3000 rpm, the spin-coating time is 30 s, and the spin-coating is performed 5 times to obtain a spin-coated sample;

[0080] The obtained spin-coated sample is placed in a tube furnace, heated to 120°C at a rate of 1°C / min, vacuum calcined for 0.5 h, and then vacuum cooled to room temperature to obtain a [C4N2H 14 ][SbBr5] photoelectric thin film (the thickness thereof is controlled to be 3.68 μm, but the photoelectric thin film is non-uniform, has poor crystallinity, and is uneven);

[0081] (3) A silver paste (as a back electrode) is screen-printed on the [C4N2H 14 ][SbBr5] photoelectric thin film prepared in step (2) to obtain a [C4N2H 14 ][SbBr5] photoelectric thin film device: from bottom to top, it includes an ITO conductive substrate, a [C4N2H 14 ][SbBr5] thin film, and an Ag electrode.

[0082] The results show that the [C4N2H 14 ][SbBr5] single crystal powder cannot be well dissolved in a DMF solution, the thin film appears granular powder, the thin film has poor compactness, and the optical performance of the thin film is affected.

[0083] By comparing the comparative example 1, the comparative example 2, and the embodiment 2, it is found that only the mixed solution of DMF and DMSO (the volume ratio of DMF and DMSO is 1:1) can dissolve the [C4N2H 14 ][SbBr5] single crystal powder, this measure breaks the conventional cognition of the person skilled in the art, which may be because DMF has strong hydrogen bond accepting ability, and DMSO has strong hydrogen bond donor ability, and after mixing, a more diversified hydrogen bond network can be formed, and the solubility of the [C4N2H 14 ][SbBr5] single crystal powder is enhanced.

[0084] Comparative example 3

[0085] The present comparative example provides a preparation method of an organic-inorganic hybrid light detection material photoelectric thin film, specifically including the following steps:

[0086] (1) 0.3 g of [C4N2H 14 ][SbBr5] single crystal powder prepared in the embodiment 1 is dissolved in 0.3 mL of DMSO and DMF solution (the volume ratio of DMSO and DMF is 1:1), and the [C4N2H 14The [SbBr5] monocrystal powder is completely dissolved to obtain a mixed solution;

[0087] (2) The mixed solution prepared in step (1) is spin-coated on an ITO conductive substrate, 10 μL of the mixed solution is dropped on the ITO conductive substrate by means of doctor blading, and a photoelectric film is obtained;

[0088] The obtained photoelectric film is placed in a tube furnace, heated to 120℃ at a rate of 1℃ / min, vacuum calcined for 0.5 h, and then vacuum cooled to room temperature to obtain a [C4N2H 14 ] [SbBr5] photoelectric film;

[0089] (3) A silver paste (as a back electrode) is screen-printed on the [C4N2H 14 ] [SbBr5] photoelectric film prepared in step (2), and a [C4N2H 14 ] [SbBr5] photoelectric film device is obtained: from bottom to top, it comprises an ITO conductive substrate, a [C4N2H 14 ] [SbBr5] film and an Ag electrode.

[0090] The results show that the photoelectric film prepared in the comparative example has uneven thickness, poor photoelectric performance, poor stability, and the minimum thickness of the photoelectric film prepared by means of doctor blading is 7 μm. The defects in the film cannot be effectively repaired by means of annealing for 0.5 h, which leads to a decrease in electron mobility, and thus affects the overall photoelectric conversion efficiency.

[0091] The above description of the examples is for the purpose of facilitating the understanding and use of the invention by those skilled in the art. Those skilled in the art can easily make various modifications to the examples, and apply the general principles described herein to other examples without creative labor. Therefore, the present application is not limited to the above examples, and the improvements and modifications made by those skilled in the art without departing from the scope of the present application should be within the protection scope of the present application.

Claims

1. Use of an organic-inorganic hybrid photodetecting material in the preparation of a photovoltaic thin film device, characterized in that, The chemical structural formula of the organic-inorganic hybrid light detection material is [C4N2H 14 ][SbBr5], and has the following cell parameters: The angle is α=90°, β=118.763(2)°, and γ=90°.

2. Use according to claim 1, characterized in that, The organic-inorganic hybrid light detecting material is prepared by the following method: (S1) mixing Sb2O3 and HBr to obtain a SbBr3 solution; (S2) adding 1,4-diaminobutane to the SbBr3 solution obtained in step (S1) and performing hydrothermal reaction and post-treatment to obtain the organic-inorganic hybrid light detecting material.

3. Use according to claim 2, characterized in that, In step (S1), the amount ratio of Sb2O3 to HBr is 1 mmol: 3-8 mL; In step (S2), the amount ratio of 1,4-diaminobutane to the SbBr3 solution is 1 mmol: 3-8 mL; In the hydrothermal reaction process, the temperature is 100-150°C and the time is 10-14 h; The post-treatment is centrifugation, washing and drying in sequence.

4. A method for fabricating a photoelectric thin-film device, characterized in that, Specifically comprising the following steps: (A1) mixing the organic-inorganic hybrid light detecting material, dimethyl sulfoxide and N,N-dimethylformamide to obtain a mixed solution; (A2) spin-coating the solution prepared in step (A1) on a conductive substrate and performing vacuum annealing treatment to obtain a photoelectric thin film; (A3) preparing a photoelectric thin film device by screen printing silver paste on the photoelectric thin film prepared in step (A2); The chemical structural formula of the organic-inorganic hybrid light detection material is [C4N2H 14 ][SbBr5], and has the following cell parameters: The angle is α = 90°, β = 118.763(2)°, and γ = 90°.

5. The method for fabricating a photoelectric thin-film device according to claim 4, characterized in that, In step (A1), the amount ratio of the organic-inorganic hybrid light detecting material, dimethyl sulfoxide and N,N-dimethylformamide is 1 g: 0.3-0.8 mL: 0.3-0.8 mL.

6. The method of claim 5, wherein the photoelectric thin film device is prepared by a process comprising: The amount ratio of the organic-inorganic hybrid light detecting material, dimethyl sulfoxide and N,N-dimethylformamide is 1 g: 0.5 mL: 0.5 mL.

7. The method for fabricating a photoelectric thin-film device according to claim 4, characterized in that, In step (A2), the temperature in the vacuum annealing treatment process is 120-150°C and the time is 0.5-1 h.

8. The method for fabricating a photoelectric thin-film device according to claim 4, characterized in that, In step (A2), the thickness of the photoelectric thin film is 3.21-3.68 μm.

9. The method for fabricating a photoelectric thin-film device according to claim 8, characterized in that, The thickness of the photoelectric thin film is 3.68 μm.

10. An optoelectronic thin film device, characterized in that Prepared by the method of any one of claims 4-9.

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