WO2021128646A1

WO2021128646A1 - Spectrally-resolved detection assembly and manufacturing method

Info

Publication number: WO2021128646A1
Application number: PCT/CN2020/083103
Authority: WO
Inventors: 钟海政; 施立甫; 朱晓秀; 柏泽龙
Original assignee: 北京理工大学; 致晶科技（北京）有限公司
Priority date: 2019-12-24
Filing date: 2020-04-03
Publication date: 2021-07-01
Also published as: CN113029338A; CN113029338B

Abstract

The present application discloses a spectrally-resolved detection assembly and a manufacturing method, belonging to the technical field of spectrum resolution, and being able to solve the problems of the existing spectrum detector that the detection cost is high, the process is more complicated, and the discriminative detection of any wavelength cannot be realized. The spectrally-resolved detection assembly comprises: a substrate and a plurality of detection structures provided on the substrate; the plurality of detection structures are regularly arranged; different detection structures are made of perovskite precursor solutions of different components; and the absorption edge wavelengths of different detection structures are different. The present application is used for making a spectrometer device and a multi-spectral imaging device.

Description

Spectral resolution detection component and preparation method

Technical field

The application relates to a spectrum-resolved detection component and a preparation method, belonging to the technical field of spectrum-resolved detection and imaging.

Background technique

As a photoelectric conversion material with excellent performance, perovskite has been widely used in solar cells and detectors. The composition of perovskite mainly depends on the type and proportion of halogen elements, and its composition will affect the perovskite Therefore, the perovskite band gap can be adjusted by adjusting the composition of the perovskite material, and then the absorption spectrum and transmission spectrum of the perovskite can be adjusted to realize the preparation of a multi-wavelength detector.

At present, the existing perovskite detectors are almost all based on the monochromatic imaging detection of the same material, and cannot distinguish the detected spectra. To achieve spectrally resolved detection, it is necessary to add filtering as existing silicon-based devices. The cost of the optical film is relatively high, the preparation process is relatively complicated, and the optional wavelength of the optical filter is small, and it is impossible to realize the discrimination detection of any wavelength.

Summary of the invention

The present application provides a spectrum-resolved detection component and a preparation method, which can solve the problems of high detection cost of the existing spectrum detector, complicated preparation process, and inability to realize arbitrary wavelength discrimination detection.

The present application provides a spectrally resolved detection assembly, including: a substrate and a plurality of detection structures arranged on the substrate; the plurality of detection structures are arranged regularly; and the different detection structures are composed of perovskites with different compositions. The precursor solution is made; the absorption edge wavelengths of different detection structures are different.

Optionally, the perovskite precursor solution includes a first solute, a second solute, and a solvent; the chemical formula of the first solute is AX; where A is CH ₃ NH ₂ , CH(NH)NH ₂ , At least one of Cs; X is selected from at least one of halogen elements; the general chemical formula of the second solute is BX ₂ ; B is Pb, Sn, Cu, Mn, Ag, Sb, Bi, In , At least one of Al; the solvent is N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethyl acetate, N-methylpyrrolidone, tetrahydrofuran, toluene, chloroform, At least one of acetone.

Optionally, each detection structure is provided with an packaging structure surrounding the detection structure, and the packaging structure is made of a polymer material or a composite material composed of a polymer material and a semiconductor nano material.

Optionally, the packaging structure is in the shape of a convex lens.

Optionally, the polymer material is selected from polyvinylidene fluoride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, polysulfone, polyamide, polyimide, polycarbonate, and polystyrene , At least one of polyvinyl chloride, polyvinyl alcohol, transparent ABS plastic, polyacrylonitrile, polyolefin elastomer, thermoplastic polyurethane, polyvinyl carbazole; the general chemical formula of the semiconductor nanomaterial is A ₃ B ₂ X _9. At least one of ABX ₃ and A ₂ BX ₆ ; wherein, A is selected from at least one of CH ₃ NH ₂ , CH(NH)NH ₂ and Cs; B is selected from Pb, Sn, Cu, Mn, At least one of Ag, Sb, Bi, In, and Al; X is selected from at least one of halogen elements.

Optionally, the solid content of the semiconductor nanomaterial is 2wt.%-99wt.%.

Optionally, the detection component is applied to a spectroscopic instrument or a multispectral imaging device.

The present application also provides a method for preparing a spectrally resolved detection component, the preparation method comprising: configuring a plurality of perovskite precursor solutions of different components; transferring a plurality of the perovskite precursor solutions to a substrate , Forming a plurality of regularly arranged detection structures; different detection structures have different absorption edge wavelengths.

Optionally, a variety of the perovskite precursor solutions can be printed by inkjet printing, spraying, screen printing, air jet printing, transfer printing, roll-to-roll patterning, micro-nano imprinting, brush coating, spin coating Any one of the processes is transferred to the substrate.

Optionally, the preparation method further includes: arranging an encapsulation structure surrounding the detection structure on each detection structure, and the encapsulation structure is made of a polymer material or a combination of a polymer material and a semiconductor nano material Composite materials.

The beneficial effects that this application can produce include:

The spectrum-resolved detection component provided by the present application is provided by arranging multiple detection structures regularly arranged on the substrate; since different detection structures are made of different compositions of perovskite precursor solutions, the absorption edge wavelengths of different detection structures are different, Therefore, different detection structures can distinguish different spectra. Compared with the prior art, the spectral detection component provided by the present application can realize detection of different spectra without additional filters, so the preparation cost is relatively low, the preparation process is simple, and it is suitable for large-area preparation and industrial production, and can Realize the discrimination and detection of any wavelength, which has great application prospects in military, scientific research, civil, space and other fields.

Description of the drawings

FIG. 1 is a schematic diagram of a detection structure arrangement of a spectrum-resolved detection component provided by an embodiment of the application;

FIG. 2 is a schematic diagram of solution transfer sites and pixel arrangement provided by an embodiment of the application;

FIG. 3 is a schematic diagram of a package structure provided by an embodiment of the application;

4 is a schematic diagram of the package structure of the detection structure provided by an embodiment of the application;

FIG. 5 is a flow chart of a method for manufacturing a spectrally resolved detection component provided by an embodiment of the application.

Detailed ways

The present application will be described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

The embodiment of the present application provides a spectrally resolved detection assembly. As shown in FIGS. 1 to 4, the detection assembly includes: a substrate 10 and a plurality of detection structures 20 arranged on the substrate 10; the plurality of detection structures 20 are arranged regularly; Different detection structures 20 are made of perovskite precursor solutions of different compositions; the absorption edge wavelengths of different detection structures 20 are different.

The embodiment of the present application does not limit the specific material of the substrate 10. For example, the substrate 10 may be any one of glass, quartz, silicon, silicon-on-insulator devices, complementary metal oxide semiconductor devices, and charge-coupled devices.

The morphology of the detection structure 20 can be controlled by heating, light, or air pressure to control the crystalline morphology of the perovskite, and the crystalline morphology can be any of perovskite single crystal, polycrystalline, amorphous, nanocrystalline, nanowire, and nanosheet.

The regular arrangement of the detection structures 20 means that a certain uniform interval is maintained between each detection structure 20, and the uniformly distributed shape can be any of rectangles, circles, and regular triangles.

The spectrally resolved detection component provided by the present application is provided by arranging a plurality of detection structures 20 regularly arranged on the substrate 10; since different detection structures 20 are made of different compositions of perovskite precursor solutions, the absorption of different detection structures 20 The edge wavelengths are different, so different detection structures 20 can distinguish different spectra. Compared with the prior art, the spectral detection component provided by the present application can realize detection of different spectra without additional filters, so the preparation cost is relatively low, the preparation process is simple, and it is suitable for large-area preparation and industrial production, and can Realize the discrimination and detection of any wavelength.

In practical applications, the perovskite precursor solution includes a first solute, a second solute and a solvent; the chemical formula of the first solute is AX; where A is CH ₃ NH ₂ , CH(NH)NH ₂ , and Cs X is selected from at least one of halogen elements; the general chemical formula of the second solute is BX ₂ ; B is at least one of Pb, Sn, Cu, Mn, Ag, Sb, Bi, In, and Al One; the solvent is at least one of N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethyl acetate, N-methylpyrrolidone, tetrahydrofuran, toluene, chloroform, and acetone.

Further, each detection structure 20 is provided with a packaging structure 30 surrounding the detection structure 20, and the packaging structure 30 is made of a polymer material or a composite material composed of a polymer material and a semiconductor nanomaterial. If the transmission wavelength λ>x nm of the composite material composed of polymer materials and semiconductor nanomaterials, and the absorption wavelength λ<y nm(y>x) of the perovskite precursor solution for preparing the detection structure 20, then the detection structure 20 In the end, the wavelength range of light that can be detected is x<λ<y, which can realize narrow-band detection of light and further improve the detection accuracy of the detection structure 20.

In the embodiment of the present application, the packaging structure 30 is in the shape of a convex lens, and the convex lens structure can achieve light convergence, so that a larger range of light can be concentrated on the effective detection position, and the light collection rate of the detection component can be improved.

Further, the packaging structure 30 can be realized by processes such as inkjet printing, air jet printing, transfer printing, and micro/nano imprinting.

The polymer material is selected from polyvinylidene fluoride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, polysulfone, polyamide, polyimide, polycarbonate, polystyrene, polyvinyl chloride, poly At least one of vinyl alcohol, transparent ABS plastic, polyacrylonitrile, polyolefin elastomer, thermoplastic polyurethane, polyvinyl carbazole; the general chemical formula of semiconductor nanomaterials is A ₃ B ₂ X ₉ , ABX ₃ , A ₂ BX at least one _6; wherein, a is selected from _{_{CH 3 NH 2, CH (NH}} ) NH 2, at least one of the Cs; B is selected from Ag, Sb, Bi, in, Al in the at least one; X is At least one selected from halogen elements; the solid content of the semiconductor nanomaterial is 2wt.%-99wt.%; the single particle size of the semiconductor nanomaterial is 2-100nm.

The embodiment of the present application provides a method for preparing a spectrally resolved detection component. As shown in FIG. 5, the method for preparing includes:

Step 501: Configure a plurality of perovskite precursor solutions of different components;

Step 502: Transfer a plurality of perovskite precursor solutions to the substrate 10 to form a plurality of regularly arranged detection structures 20; different detection structures 20 have different absorption edge wavelengths.

Further, a variety of perovskite precursor solutions can be used in any of inkjet printing, spraying, screen printing, air jet printing, transfer printing, roll-to-roll patterning, micro-nano imprinting, brush coating, and spin coating. A process is transferred to the substrate 10.

As shown in Fig. 5, the method for preparing the spectrally resolved detection component further includes:

Step 503: A packaging structure 30 surrounding the detection structure 20 is arranged on each detection structure 20. The packaging structure 30 is made of a polymer material or a composite material composed of a polymer material and a semiconductor nanomaterial.

Another embodiment of the present application provides a spectroscopic instrument, including any of the above-mentioned spectral resolution detection components, the absorption edge wavelength range of the spectroscopic instrument is between 250 nm and 3000 nm, and the minimum degree of spectral resolution is 0.001 nm.

1) As an example, the preparation process of the spectrometer is as follows:

Configure 61 kinds of perovskite precursor solutions of different components, respectively numbered 1 to 61, to adjust the type and proportion of halogen elements (X) in _{PbX 2} _{and CsX, so that the solute inside is CsPbCl x} Br _y I _z , the concentration of the above solution is 0.1mol/L, where x+y+z=3, in 1 to 31 bottles, z=0, x is 3,2.9,2.8...0.2,0.1,0,y=3 -x, in 32 to 61 bottles, x=0, z is 0.1, 0.2, 0.3...2.8, 2.9, 3, y=3-z, and the solvent used is dimethyl sulfoxide (DMSO).

When the glass substrate connected with the circuit was heated to 40° C., the 61 bottles of the perovskite precursor solution were printed on the glass substrate by inkjet printing. The array arrangement and corresponding numbers are shown in Figure 1. Each black circle represents a polycrystalline detector structure formed by printing a corresponding number of perovskite precursor solution, and each polycrystalline detection structure is electrically connected to the circuit unit. The band gaps of the polycrystalline detection structure printed by the perovskite precursor solutions of different components are different. The absorption edge wavelengths of the absorption spectra corresponding to the perovskite precursor solutions from No. 1 to No. 61 are also gradually shifted to the right, so you can According to whether there are photo-generated currents at different points, the spectral range of the irradiated light is judged, and the intensity of the irradiated light is calculated according to the intensity of the photo-generated current. The integration of the spectroscopic instrument with the relevant control system and the information processing output system can realize the detection function of the spectroscopic instrument.

Another embodiment of the present application provides a multi-spectral imaging device, including any one of the above-mentioned spectrally resolved detection components.

1) As an example, the preparation process of the multi-spectral imaging device is as follows:

Configure 4 kinds of perovskite precursor solutions of different components, respectively numbered as

solutions

1, 2, 3, and 4. The first solute in the first solution is 1mmol PbBr ₂ , and the second solute is 1mmol/L MACl, 2 The first solute in _{solution No. 3 is 1mmol/L PbBr 2} , the second solute is 1mmol/L MABr, the first solute in solution No. 3 is 1mmol PbBr ₂ , the second solute is 1mmol MAI, the first solute in solution No. 4 The solute is 1 mmol PbI ₂ , the second solute is 1 mmol MABr, the solvents used in

solutions

1, 2, 3, and 4 are all dimethyl sulfoxide (DMSO), and the solvent consumption is 10 mL.

When the glass substrate connected to the circuit is heated to 40°C, the 4 bottles of the perovskite precursor solution are printed on the glass substrate by inkjet printing. The printed array and the array layout are shown in Figure 2. As shown, each black circle represents a corresponding number of the polycrystalline detection structure printed by the perovskite precursor solution. The band gaps of the polycrystalline detection structure printed by the perovskite precursor solution of different compositions are different. The polycrystalline detection structures formed by

printing solutions

1, 2, 3, and 4 correspond to 21, 22, 23, and 24, respectively. The absorption edge wavelengths of the

polycrystalline detector structures

21, 22, 23, and 24 are 465nm and 525nm, respectively. , 570nm, 635nm, each detection structure can be absorbed before the corresponding absorption edge wavelength, the corresponding detectable wavelength of the

polycrystalline detection structure

21, 22, 23, 24 are λ<465, λ<525, λ< 570, λ<635, where the

polycrystalline detection structures

21, 22, 23, and 24 are circles with a diameter of 10μm, the distance between adjacent centers of each polycrystalline detection structure is 25μm, and the gaps between adjacent polycrystalline detection structures are all Electrically connected through circuit elements. The form and number of printing are shown in Figure 2.

The corresponding package structures of the

detection structures

21, 22, 23, and 24 are 31, 32, 33, and 34 in order. The

package structures

31, 32, 33, and 34 are all hemispherical convex lens structures with a diameter of 20 m. The specific package structure is shown in Figure 4.

The material of the packaging structure 31 is _{a composite material composed of PAN and MA 3} Bi ₂ Br ₉ , the material of the packaging structure 32 is a composite material composed of PAN and MA ₃ Bi ₂ Br ₆ I ₃ , and the material of the packaging structure 33 is PAN and The composite material composed of MA ₃ Bi ₂ Br ₃ I ₆ and the material of the packaging structure 34 are composite materials composed of PAN and MA ₃ Bi ₂ I _9. The transmission wavelengths of the

packaging structures

31, 32, 33, and 34 are respectively λ> 450, λ>510, λ>550, λ>610. After the packaging is completed, the wavelengths of light that can be detected by the

detection structures

21, 22, 23, 24 are 450<λ<465,510<λ<525,550<λ<570,610<λ<635.

The encapsulated

detection structure

21, 22, 23, 24 is used as a

pixel

40, and 1920 and 1080 pixels 40 are arranged horizontally and vertically. The imaging unit is electrically connected to each pixel 40 to realize the function of spectral resolution detection. Furthermore, a multi-spectral imaging device that can distinguish 4 spectra is made, and the multi-spectral imaging device can realize the multi-spectral imaging function by integrating with the control system, the information processing system and the output system.

The above are only a few embodiments of the application, and do not limit the application in any form. Although the application is disclosed as above with preferred embodiments, it is not intended to limit the application. Anyone familiar with the profession, Without departing from the scope of the technical solution of the present application, making some changes or modifications using the technical content disclosed above is equivalent to an equivalent implementation case and falls within the scope of the technical solution.

Claims

A spectrum-resolved detection component, which is characterized in that it comprises:

A substrate and a plurality of detection structures arranged on the substrate;

A plurality of the detection structures are arranged regularly; the different detection structures are made of perovskite precursor solutions of different compositions; and the absorption edge wavelengths of the different detection structures are different.
The detection assembly according to claim 1, wherein the perovskite precursor solution comprises a first solute, a second solute and a solvent;

The general chemical formula of the first solute is AX; wherein, A is at least one of CH 3 NH 2 , CH(NH)NH 2 , and Cs; X is selected from at least one of halogen elements;

The general chemical formula of the second solute is BX 2 ; B is at least one of Pb, Sn, Cu, Mn, Ag, Sb, Bi, In, and Al;

The solvent is at least one of N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethyl acetate, N-methylpyrrolidone, tetrahydrofuran, toluene, chloroform, and acetone.
The detection component according to claim 1, wherein each detection structure is provided with an packaging structure surrounding the detection structure, and the packaging structure is made of polymer materials or polymer materials and semiconductor nanometers. Composite materials composed of materials.
The detection assembly of claim 3, wherein the packaging structure is in the shape of a convex lens.
The detection component according to claim 3, wherein the polymer material is selected from the group consisting of polyvinylidene fluoride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, polysulfone, polyamide, and polyamide. At least one of imine, polycarbonate, polystyrene, polyvinyl chloride, polyvinyl alcohol, transparent ABS plastic, polyacrylonitrile, polyolefin elastomer, thermoplastic polyurethane, and polyvinyl carbazole;

The general chemical formula of the semiconductor nanomaterial is at least one of A 3 B 2 X 9 , ABX 3 , and A 2 BX 6;

Wherein, A is selected from at least one of CH 3 NH 2 , CH(NH)NH 2 , and Cs; B is selected from at least one of Pb, Sn, Cu, Mn, Ag, Sb, Bi, In, and Al; X is selected from at least one of halogen elements.
The detection assembly according to claim 5, wherein the solid content of the semiconductor nanomaterial is 2wt.%-99wt.%.
The detection assembly according to any one of claims 1 to 6, wherein the detection assembly is applied to a spectroscopic instrument or a multispectral imaging device.
A method for manufacturing a spectrally resolved detection component according to any one of claims 1 to 6, wherein the manufacturing method comprises:

Configure a variety of perovskite precursor solutions with different components;

A plurality of the perovskite precursor solutions are transferred to the substrate to form a plurality of regularly arranged detection structures; the absorption edge wavelengths of different detection structures are different.
The preparation method according to claim 8, wherein a plurality of the perovskite precursor solutions can be printed by inkjet printing, spraying, screen printing, air jet printing, transfer printing, roll-to-roll patterning, micro Any one of nano-imprinting, brush coating, and spin coating is transferred to the substrate.
The preparation method according to claim 8, wherein the preparation method further comprises:

An packaging structure surrounding the detection structure is arranged on each detection structure, and the packaging structure is made of a polymer material or a composite material composed of a polymer material and a semiconductor nano material.