WO2022198540A1 - 一种分层多晶硒化铅光电薄膜及其制备方法 - Google Patents

一种分层多晶硒化铅光电薄膜及其制备方法 Download PDF

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WO2022198540A1
WO2022198540A1 PCT/CN2021/082884 CN2021082884W WO2022198540A1 WO 2022198540 A1 WO2022198540 A1 WO 2022198540A1 CN 2021082884 W CN2021082884 W CN 2021082884W WO 2022198540 A1 WO2022198540 A1 WO 2022198540A1
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lead selenide
layer
lead
solution
dense
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刘桂武
刘军林
祝园
乔冠军
张相召
吕全江
侯海港
杨建�
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Jiangsu University
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Definitions

  • the invention relates to a photoelectric film and a preparation method thereof, in particular to a layered polycrystalline lead selenide photoelectric film with high light absorption and low forbidden band width and a preparation method thereof.
  • the photoelectric film can be used for manufacturing infrared sensors, solar cells, Components in the field of photoelectric conversion or thermoelectric conversion such as laser emission and thermoelectric converters.
  • the photoconductive detector is essentially a resistor sensitive to infrared radiation, and is divided into a cooled photoconductive detector and an uncooled photoconductive detector according to whether refrigeration is required. Uncooled photoconductive detectors have been widely studied and applied due to their simpler structure, low manufacturing cost, long life, stable performance, and high degree of integration, and have become the mainstay of civilian infrared sensors.
  • One of the key components in photoconductive detection is the photoelectric thin film.
  • the main materials of the photoelectric thin film include lead sulfide, lead selenide, lead telluride, cadmium telluride, and indium arsenide telluride.
  • lead selenide photoelectric thin films have higher reliability and sensitivity in the mid-infrared range. Therefore, lead selenide photoelectric film is more widely used in industrial temperature measurement, military guidance, agricultural detection, astronomical observation and other fields.
  • the methods for preparing lead selenide photoconductive detector films mainly include: electrochemical deposition, magnetron sputtering, molecular beam epitaxy, thermal evaporation, microwave, photochemical and chemical bath methods, among which chemical bath method
  • the method has the advantages of simple production equipment, high production efficiency, adaptability to different types and shapes of substrates, low deposition temperature, and simple doping.
  • the document "Hone FG, et al., The effect of deposition temperature on the structural, morphological and optical band gap of lead selenide thin films synthesized by chemical bath deposition method. Materials Chemistry and Physics, 2016, 1-6.” is in On silica glass, polycrystalline lead selenide films were prepared by chemical bath method at temperatures of 60°C, 75°C, and 90°C, respectively. Compared with the present application, it does not have a layered structure, and the grains are uneven and irregular in size.
  • the optical band gap of the sample prepared at 90°C is 1.13 eV, which is much larger than that of the present application, and the preparation method does not contain ion exchange. process.
  • the document “Kale RB, et al., Room temperature chemical synthesis of lead selenide thin films with preferred orientation. Applied Surface Science, 2006, 253: 930-936.” uses lead acetate, ammonia water, and sodium selenosulfate as raw materials, through chemical The polycrystalline lead selenide films were obtained by bath deposition at room temperature for 28 hours. Compared with the present application, it does not have a layered structure, the reaction time is longer, but the cubic grain size is about 350 nm, which is smaller than the grain size of the dense layer of the present application, and the preparation method does not contain an ion exchange process.
  • the document "Zhu Y, et al., P-type PbSe nanocrystalline films fabricated using high concentration of ammonia as complexing agent, Materials letters, 2020, 281:128621” uses high concentration ammonia water, lead acetate and sodium selenosulfate as raw materials.
  • the chemical bath method deposits P-type polycrystalline lead selenide films at room temperature.
  • the grain size is 70-160 nm, which is much smaller than the grain size of the dense layer of the present application
  • the optical forbidden band width is 1.36 eV, which is much larger than that of the present application, and its preparation method is not Contains ion exchange process.
  • the oxygen-containing basic lead carbonate layer is used as the precursor layer for preparing the lead selenide loose layer, and its preparation process and structure determine the structure and performance of the loose layer.
  • most of the processes for preparing oxygen-containing basic lead carbonate are ultraviolet light irradiation chemical bath method and chemical method, the prepared films are mostly dense films, and the crystal shape is mostly hexagonal.
  • the document "Urbiola IRC, et al., Lead Telluride through transformation of plumbonacrite in tellurium atmosphere and its behavior as part of PbTe-Si photodiode. IEEE Sensors Journal, 2016, 16(15): 1-1.” is to add lead acetate in turn , sodium citrate, potassium hydroxide, and deionized water, followed by chemical bath deposition of oxygen-containing basic lead carbonate films that can be used in chemical vapor deposition reactions under UV light.
  • the process is cumbersome, and the oxygen-containing basic lead carbonate film is formed by the close packing of flaky crystals without a large number of pores, so the ion exchange technology cannot be used to prepare loose films in the future.
  • the lead selenide film can be prepared by ion exchange technology.
  • the grain shape and distribution of the lead selenide film are determined by the structure and performance of the precursor layer, the immersion time, and the concentration of the ion exchange solution.
  • the oxygen-containing basic lead carbonate thin film was prepared by a chemical bath method under ultraviolet light irradiation, and the thin film was annealed at 700 °C for 1 hour in a nitrogen atmosphere, and then placed in a selenium ion solution to prepare PbSe.
  • the process for preparing oxygen-containing basic lead carbonate and lead selenide is more complicated, and the crystal shape of oxygen-containing basic lead carbonate is not "round cake", and the cubic lead selenide crystal grains will be mixed with lead crystals.
  • the particles are agglomerated into spherical shape and contain a large amount of impurity lead.
  • the used sodium formaldehyde sulfoxylate has serious toxic and side effects on the human body, and a large number of impurity phases appear in the film, and no obvious cubic PbSe crystal grains can be seen.
  • PbSe films by ion exchange of synthetic plumbonacrite layers immersed in a selenium ionic solution.
  • Ethanolamine, sodium formaldehyde sulfoxylate-ammonia were used as raw materials, and oxygen-containing basic lead carbonate films with hexagonal structure and cross-vertical arrangement were prepared by chemical bath method, and PbSe was prepared by ion exchange method immersed in sodium selenosulfate solution film.
  • the used sodium formaldehyde sulfoxylate has serious toxic and side effects on the human body, and clear cubic PbSe crystal grains cannot be seen.
  • the above documents and patents do not have a layered film structure except for the difference in the preparation materials and process parameters of the dense lead selenide layer, the oxygen-containing basic lead carbonate layer and the loose lead selenide layer. , that is, a loose smaller-grain cubic lead selenide layer is formed on the dense large-grain cubic lead selenide layer.
  • This layered film structure can greatly reduce the strong reflection at the interface when light is incident on the lead selenide film from the air, and at the same time, the film has a low forbidden band due to fewer defects and large grains. Therefore, the film can have better application in a wide range of light wavelengths.
  • the present invention provides a layered polycrystalline lead selenide photoelectric film and a preparation method thereof, which form a layer of loose lead selenide on the basis of the dense lead selenide film
  • the layer can greatly alleviate the light reflection at the interface between the air and the lead selenide film, improve the light absorption of the lead selenide film, enhance the photoconductive effect of the lead selenide film, and also significantly reduce the forbidden band width of the lead selenide film.
  • a layered polycrystalline lead selenide photoelectric thin film comprising a substrate and a lead selenide thin film layer, characterized in that: the lead selenide thin film layer is composed of a dense lead selenide layer located on the substrate and a dense lead selenide layer located on the dense lead selenide layer.
  • the dense lead selenide layer is formed by the close arrangement and accumulation of cubic crystal grains with a particle size of 0.7-1.5 ⁇ m, with a thickness of 1.5-5 ⁇ m; the loose lead selenide layer is composed of cubic crystals with a particle size of 0.2-0.5 ⁇ m
  • the grains are randomly arranged and stacked, and there are a large number of micron or submicron voids between the grain piles and between the grains, with a thickness of 5-15 ⁇ m.
  • the substrate is one of glass, silicon, silicon oxide, gallium nitride, steel and quartz.
  • the substrate was sequentially cleaned in deionized water, sulfuric acid hydrogen peroxide solution, deionized water, and absolute ethanol for 5 min, 10 min, 5 min and 5 min, and then stored after drying with nitrogen;
  • the prepared above-mentioned yellow-brown suspension is placed in a water bath at 60 to 85° C., and the substrate obtained in step (1) is exposed to one side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath to deposit 3 ⁇ 5h to deposit a dense lead selenide layer on the substrate;
  • the prepared clear solution is placed in a water bath at 20-50°C, and the substrate on which the dense lead selenide layer is deposited is vertically inserted into the heat-stabilized clear solution of the water bath through single-sided exposure of the mold, and the deposition time is 8-24 hours. forming an oxygen-containing basic lead carbonate layer by depositing on the dense lead selenide layer;
  • the substrate containing the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) is immersed in a solution containing selenium ions to generate an ion exchange reaction, wherein the ion exchange reaction temperature is 20 to 40 ° C, and the immersion time for 0.5 to 5h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer.
  • the solution containing selenium ions is 0.01-0.1 mol/L of sodium selenosulfate and selenourea or a combination of the two.
  • the beneficial effects of the present invention compared with the existing polycrystalline lead selenide photoelectric thin film are: (1) the layered polycrystalline lead selenide thin film structure composed of the dense lead selenide layer and the loose lead selenide layer can greatly reduce the When ultraviolet to mid-near-infrared light is incident on the lead selenide film from the air, strong reflection occurs at the interface, which helps to improve the absorbance of the film in a wide range of light wavelengths; (2) it has fewer cubic crystal defects and large (3)
  • the oxygen-containing basic lead carbonate precursor layer has a special "cake-like" loosely arranged structure, which is helpful for the subsequent ion exchange process.
  • a loose lead selenide layer is formed; (4) the preparation method of the lead selenide film is simple in process, low in cost, high in controllability, and the raw materials are relatively environmentally friendly, suitable for large-scale production, and can be widely used in the manufacture of infrared sensors, solar energy Components in the field of photoelectric conversion or thermoelectric conversion such as batteries, laser emission, and thermoelectric converters.
  • FIG. 1 is a schematic diagram of a chemical bath device for preparing a layered polycrystalline lead selenide photoelectric thin film according to the present invention.
  • FIG. 2 is a flow chart of a layered polycrystalline lead selenide photoelectric thin film prepared according to the present invention, wherein FIG. 2d is a schematic structural diagram of the layered polycrystalline lead selenide photoelectric thin film.
  • FIG. 3 is a scanning electron microscope photograph of a typical sample of a layered polycrystalline lead selenide film prepared according to the present invention: (a) the surface of the dense lead selenide layer, (b) the surface of the oxygen-containing basic lead carbonate layer Surface, (c) surface of loose lead selenide layer, (d) cross section of layered polycrystalline lead selenide film.
  • Fig. 4 is a reflection and absorption spectrum of a typical sample of a layered polycrystalline lead selenide film prepared by the present invention: (a) a reflection spectrum at a wavelength of 450-2500 nm, (b) a reflection spectrum at a wavelength of 2500-5000 nm, (c) 450-2500nm band absorption spectrum, (d) 2500-5000nm band absorption spectrum; the layered polycrystalline lead selenide film has an average absorbance of 0.89-1.31 in the wavelength range of 450-5000nm, and an average optical reflection It is 8.58% ⁇ 13.63%.
  • FIG. 5 is a graph of the optical band gap of a typical sample of a layered polycrystalline lead selenide film prepared according to the present invention: (a) dense lead selenide layer, (b) sample one, (c) sample two , (d) Sample three; the forbidden band width of the layered polycrystalline lead selenide film is 0.30-0.32 eV.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the two-inch glass wafer substrate was sequentially cleaned in deionized water, sulfuric acid hydrogen peroxide solution, deionized water, and absolute ethanol for 5min, 10min, 5min, and 5min, and stored after drying with nitrogen;
  • the prepared yellow-brown suspension was placed in a water bath at 75°C, and the substrate obtained in step (1) was exposed to one side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath, and deposited for 4 hours, so that A dense lead selenide layer is formed by deposition on the substrate;
  • the grain size of the dense lead selenide layer film prepared by this process is 0.98 ⁇ m and the thickness is 2.4 ⁇ m.
  • the sample is named as "dense lead selenide layer", its surface morphology is shown in Figure 3a, and the optical reflection, absorption and forbidden band width of the "dense lead selenide layer” are shown in Figures 4 and 5, respectively , its optical reflection is about 24.37% in the range of 450-2500nm, about 28.26% in the range of 2500-5000nm, the optical absorption is about 0.61 in the range of 450-2500nm, about 0.55 in the range of 2500-5000nm, and the band gap is about 0.55.
  • the width is about 0.5eV.
  • the prepared clear solution was placed in a water bath at 25°C, and the substrate on which the dense lead selenide layer was deposited was vertically inserted into the heat-stabilized clear solution in the water bath through single-sided exposure of the mold. Deposition on the lead selenide layer to form an oxygen-containing basic lead carbonate layer;
  • the surface morphology of the prepared oxygen-containing basic lead carbonate layer on the dense lead selenide layer is shown in Fig. 3b.
  • step (3) the substrate with the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) is placed in a solution with a concentration of 0.026mol/L sodium selenosulfate and an ion exchange reaction occurs, wherein The ion exchange reaction temperature is 25°C and the time is 2h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer;
  • the layered polycrystalline lead selenide film with high light absorption and low band gap prepared by this process is named "Sample 1" in this application.
  • the grain size of the loose lead selenide layer is about 0.42 ⁇ m, and the layer thickness is about 5.2 ⁇ m, and their surface morphologies are shown in Figure 3c, respectively.
  • the optical reflection, absorption and band gap of "Sample 1" are shown in Figure 4 and Figure 5, respectively.
  • Example 1 has an average absorbance of 0.95 in the wavelength range of 450 to 5000 nm, an average optical reflection of about 11.41%, and the forbidden band width is reduced from about 0.5 eV to 0.307 eV.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the two-inch glass wafer substrate was sequentially cleaned in deionized water, sulfuric acid hydrogen peroxide solution, deionized water, and absolute ethanol for 5min, 10min, 5min, and 5min, and stored after drying with nitrogen;
  • the prepared yellow-brown suspension was placed in a water bath at 75°C, and the substrate obtained in step (1) was exposed to one side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath, and deposited for 4 hours, so that A dense lead selenide layer is formed by deposition on the substrate;
  • the prepared clear solution was placed in a water bath at 25°C, and the substrate on which the dense lead selenide layer was deposited was vertically inserted into the heat-stabilized clear solution in the water bath through single-sided exposure of the mold. Deposition on the lead oxide layer to form an oxygen-containing basic lead carbonate layer;
  • step (3) the substrate with the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) is placed in a solution with a concentration of 0.026mol/L sodium selenosulfate and an ion exchange reaction occurs, wherein The ion exchange reaction temperature is 25°C and the time is 1h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer;
  • the layered polycrystalline lead selenide film with high light absorption and low band gap prepared by this process is named "Sample 2" in this application, and the grain size of the loose lead selenide layer is about 0.2 ⁇ m and the thickness is about 6.1 ⁇ m. ⁇ m.
  • the optical reflection, absorption and band gap of “Sample 2" are shown in Figures 4 and 5, respectively. The results show that the optical reflection of "Sample 2" is 54.74% lower than that of "Dense lead selenide layer” in the range of 450-2500 nm. It decreased by 44.09% in the range of 2500-5000nm, the optical absorption increased by 57.07% in the range of 450-2500nm, and increased by 46.2% in the range of 2500-5000nm.
  • Sample 2 has an average absorbance of 0.89 in the wavelength range of 450 to 5000 nm, an average optical reflection of about 13.63%, and the forbidden band width is reduced from about 0.5 eV to 0.309 eV.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the two-inch glass wafer substrate was sequentially cleaned in deionized water, sulfuric acid hydrogen peroxide solution, deionized water, and absolute ethanol for 5min, 10min, 5min, and 5min, and stored after drying with nitrogen;
  • the prepared yellow-brown suspension was placed in a water bath at 75°C, and the substrate obtained in step (1) was exposed to one side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath, and deposited for 4 hours, so that A dense lead selenide layer is formed by deposition on the substrate;
  • the prepared clear solution was placed in a water bath at 25°C, and the substrate on which the dense lead selenide layer was deposited was vertically inserted into the heat-stabilized clear solution in the water bath through single-sided exposure of the mold. Deposition on the lead oxide layer to form an oxygen-containing basic lead carbonate layer;
  • step (3) the substrate with the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) is placed in a solution with a concentration of 0.026mol/L sodium selenosulfate and an ion exchange reaction occurs, wherein The ion exchange reaction temperature is 25°C and the time is 2h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer;
  • the layered polycrystalline lead selenide film with high light absorption and low band gap prepared by this process is named "Sample 3" in this application.
  • the grain size of the loose lead selenide layer is about 0.38 ⁇ m and the thickness is about 6.4 ⁇ m.
  • the optical reflection, absorption and band gap of “Sample 3" are shown in Figures 4 and 5, respectively.
  • the results show that the optical reflection of "Sample 3" is lower than that of "Dense PbSe layer” by about 63.3% in the range of 450-2500 nm. , decreased by 55.64% in the range of 2500-5000nm, the optical absorption increased by 72.46% in the range of 450-2500nm, and increased by 64.42% in the range of 2500-5000nm.
  • Sample three has an average absorbance of 0.97 in the wavelength range of 450 to 5000 nm, and an average optical reflection of about 10.91%.
  • the forbidden band width is reduced from about 0.5eV to 0.313eV.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the two-inch polycrystalline silicon substrate was sequentially cleaned in deionized water, sulfuric acid hydrogen peroxide solution, deionized water, and absolute ethanol for 5min, 10min, 5min and 5min, and stored after nitrogen drying;
  • the prepared yellow-brown suspension was placed in a 60°C water bath, and the substrate obtained in step (1) was exposed to one side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath, and deposited for 3 hours to make depositing a dense lead selenide layer on the substrate;
  • the grain size of the dense lead selenide layer is about 0.7 ⁇ m and the thickness is about 1.5 ⁇ m.
  • the prepared clear solution was placed in a 20°C water bath, and the substrate on which the dense lead selenide layer was deposited was vertically inserted into the heat-stabilized clear solution in the water bath through single-sided exposure of the mold. Deposition on the lead selenide layer to form an oxygen-containing basic lead carbonate layer;
  • the substrate with the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) is placed in a solution with a concentration of 0.01 mol/L sodium selenosulfate and an ion exchange reaction occurs, wherein
  • the ion exchange reaction temperature is 20°C and the time is 5h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer;
  • the grain size of the loose lead selenide layer in the layered polycrystalline lead selenide film is about 0.2 ⁇ m, and the thickness of the loose lead selenide layer is about 5 ⁇ m.
  • the sample has an average absorbance of 0.87 and an average optical reflection of about 14.43% in the wavelength range of 450 to 5000 nm.
  • the forbidden band width is about 0.32eV.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the prepared yellow-brown suspension was placed in a water bath at 85° C., and the substrate obtained in step (1) was exposed to one side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath, and deposited for 5 hours, so as to be deposited in the water bath for 5 hours.
  • a dense lead selenide layer is formed by deposition on the substrate;
  • the grain size of the dense lead selenide layer is about 1.5 ⁇ m and the thickness is about 5 ⁇ m.
  • the prepared clear solution was placed in a 50°C water bath, and the substrate on which the dense lead selenide layer was deposited was vertically inserted into the heat-stabilized clear solution in the water bath through single-sided exposure of the mold. Deposition on the lead oxide layer to form an oxygen-containing basic lead carbonate layer;
  • step (3) placing the substrate with the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) on a mixed selenium containing 0.05mol/L sodium selenosulfate and 0.05mol/L selenourea
  • An ion exchange reaction occurs in the ion solution, wherein the ion exchange reaction temperature is 40 ° C and the time is 0.5 h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer;
  • the grain size of the loose lead selenide layer is about 0.5 ⁇ m and the thickness is about 15 ⁇ m.
  • the sample has an average absorbance of 1.31 and an average optical reflection of about 8.58% in the wavelength range of 450 to 5000 nm.
  • the forbidden band width is about 0.30eV.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the gallium nitride substrate was sequentially cleaned in deionized water, sulfuric acid hydrogen peroxide solution, deionized water, and absolute ethanol for 5 min, 10 min, 5 min, and 5 min, and then stored after drying with nitrogen;
  • the prepared yellow-brown suspension was placed in a water bath at 80°C, and the substrate obtained in step (1) was exposed to one side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath, and was deposited for 4 hours to form a heat-stabilized yellow-brown suspension.
  • a dense lead selenide layer is formed by deposition on the substrate;
  • the grain size of the dense lead selenide layer is about 1 ⁇ m and the thickness is about 4.45 ⁇ m, as shown in Fig. 3d.
  • the prepared clear solution was placed in a water bath at 40°C, and the substrate with the dense lead selenide layer deposited was vertically inserted into the clear solution after being thermally stabilized in the water bath by exposing one side of the mold. Deposition on the lead oxide layer to form an oxygen-containing basic lead carbonate layer;
  • the substrate with the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) is placed in a solution containing 0.05mol/L sodium selenosulfate, and an ion exchange reaction occurs, wherein the ion exchange reaction occurs.
  • the exchange reaction temperature is 35°C, and the time is 2.5h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer; the layered polycrystalline lead selenide film with high light absorption and low band gap is loose selenide in the layered polycrystalline lead selenide film.
  • the grain size of the lead layer is about 0.42 ⁇ m and the thickness is about 15 ⁇ m.
  • the sample has an average absorbance of 0.95 and an average optical reflection of about 10.65% in the wavelength range of 450 to 5000 nm.
  • the forbidden band width is about 0.30eV.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • quartz substrate was sequentially cleaned in deionized water, sulfuric acid hydrogen peroxide solution, deionized water, and absolute ethanol for 5 min, 10 min, 5 min and 5 min, and then stored after drying with nitrogen;
  • the prepared yellow-brown suspension was placed in a water bath at 70°C, and the substrate obtained in step (1) was exposed to a single side of the mold and inserted vertically into the heat-stabilized yellow-brown suspension in the water bath, and deposited for 3 hours to form a thermally stabilized yellow-brown suspension.
  • a dense lead selenide layer is formed by deposition on the substrate;
  • the grain size of the dense lead selenide layer is about 0.9 ⁇ m and the thickness is about 3.1 ⁇ m.
  • the prepared clear solution was placed in a water bath at 45°C, and the substrate on which the dense lead selenide layer was deposited was vertically inserted into the heat-stabilized clear solution in the water bath through single-sided exposure of the mold. Deposition on the lead oxide layer to form an oxygen-containing basic lead carbonate layer;
  • step (3) placing the substrate with the dense lead selenide layer and the oxygen-containing basic lead carbonate layer obtained in step (3) in a solution containing 0.05mol/L selenourea to undergo an ion exchange reaction, wherein the ion exchange reaction temperature
  • the temperature is 40 °C and the time is 2.5h, so that the oxygen-containing basic lead carbonate layer is transformed into a loose lead selenide layer; the grain size of the loose lead selenide layer in the layered polycrystalline lead selenide film is about 0.45 ⁇ m, The thickness is about 14.6 ⁇ m.
  • the sample has an average absorbance of 0.96 and an average optical reflection of about 10.92% in the wavelength range of 450 to 5000 nm.
  • the forbidden band width is about 0.30eV.

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Abstract

一种光电薄膜及其制备方法，特别是一种分层多晶硒化铅薄膜及其制备方法。制备方法主要包括：(1)在衬底(2)上用化学浴法制备致密硒化铅层；(2)在致密硒化铅层上用化学浴法制备疏松含氧碱式碳酸铅层；(3)将附有致密硒化铅层和含氧碱式碳酸铅层的样品置于含硒离子溶液中通过离子交换反应，最终形成分层多晶硒化铅薄膜。制备方法工艺简便、成本低，可控性好，制备的硒化铅薄膜由下层致密的多晶立方硒化铅层和上层疏松的多晶立方硒化铅层构成，可广泛应用于制造红外传感器、太阳能电池、激光发射、热电转化器等光电转换或者热电转换领域的元器件。

Description

一种分层多晶硒化铅光电薄膜及其制备方法 技术领域
本发明涉及一种光电薄膜及其制备方法，特别是一种高光吸收、低禁带宽度的分层多晶硒化铅光电薄膜及其制备方法，该光电薄膜可用于制造红外传感器、太阳能电池、激光发射、热电转化器等光电转换或者热电转换领域的元器件。
背景技术
红外辐射与光子相互作用会产生一些光电效应，例如光导、光伏、光电磁、Dember和光子索引效应。光电导探测器实质上就是一个对红外辐射敏感的电阻，根据是否需要制冷分为制冷型光电导探测器和非制冷型光电导探测器。非制冷型光电导探测器由于其结构更加简单、制造成本低廉、寿命长、性能稳定、可集成化程度高等优点而更加的被广泛研究和应用，已然成为民用红外传感器的中流砥柱。光电导探测中关键部件之一就是光电薄膜，目前光电薄膜主要材质包括硫化铅、硒化铅、碲化铅、碲化镉、碲砷铟等。然而，硒化铅光电薄膜在中红外范围内有更高的可靠性和灵敏度。因此，硒化铅光电薄膜更为广泛应用于工业测温、军事制导、农业检测、天文观测等领域。
目前，制备硒化铅光电导探测器薄膜的方法主要有：电化学沉积法、磁控溅射法、分子束外延法、热蒸发法、微波法、光化学法和化学浴法等，其中化学浴法生产设备简单、生产效率高，可以适应不同种类、形状衬底，沉积温度低，掺杂简单等优点，成为备受关注的重要技术之一。如文献“姚官生等，短波红外纳米PbSe薄膜的制备及光电性能研究，航空兵器，20011，3:17-27.”以石英为衬底，以硒脲、醋酸铅和联胺为原料，常温下通过化学浴法沉积90min得到多晶硒化铅薄膜。与本申请相比，不具有分层结构，其硒化铅晶粒尺寸仅为10nm，与本申请的致密层和疏松层硒化铅晶粒相差1～2个数量级，由于量子尺寸效应发生严重蓝移导致其禁带宽度增大，且其制备方法不含离子交换过程。如中国专利201510199477.1“一种中红外探测器及其制备方法”采用的是氢氧化钾、硒代硫酸钠和醋酸铅为原料，化学浴生长硒化铅薄膜，经过退火处理、钝化保护以及封装工艺制备成硒化铅红外探测器。与本申请相比，该薄膜不含疏松层，即不具有分层结构，且其制备方法不含离子交换过程。如文献“Hone FG,et al.,The effect of deposition time on the structural,morphological and optical band gap of lead  selenide thin films synthesized by chemical bath deposition method.Materials Letters,2015,155:58-61.”是通过化学浴法，以醋酸铅、硒代硫酸钠、氢氧化钠、氨水为原料在温度90℃、pH为12的条件下，在石英玻璃衬底上制备纳米晶硒化铅薄膜。与本申请相比，不具有分层结构，其硒化铅晶粒尺寸远小于本申请的致密层和疏松层的晶粒，其立方晶粒发育不完善，存在大量不规则晶粒，其光学禁带宽度为1.11eV，远大于本申请，且其制备方法不含离子交换过程。如文献“Ghobadi N,et al.,Nanoparticle shape and optical band gap alteration in PbSe nanostructure thin films with deposition temperature controlling.Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry,2015,45:1407-1411.”是以化学浴法在普通玻璃上沉积硒化铅薄膜，通过改变沉积温度来改变薄膜的形状和光学禁带宽度。与本申请相比，不具有分层结构，其制备的薄膜出现大量的裂缝、平整度较差，硒化铅的结晶度差，薄膜在波长400nm会出现吸光度快速下降，光学禁带宽度最小为1.2eV，远大于本申请，且其制备方法不含离子交换过程。如文献“Hone FG,et al.,The effect of deposition temperature on the structural,morphological and optical band gap of lead selenide thin films synthesized by chemical bath deposition method.Materials Chemistry and Physics,2016,1-6.”是在二氧化硅玻璃上，分别在60℃、75℃、90℃温度下化学浴法制备多晶硒化铅薄膜。与本申请相比，不具有分层结构，晶粒为大小不均、不规则，90℃时制备的样品的光学禁带宽度为1.13eV，远大于本申请，且其制备方法不含离子交换过程。如文献“Kale RB,et al.,Room temperature chemical synthesis of lead selenide thin films with preferred orientation.Applied Surface Science,2006,253:930-936.”以醋酸铅、氨水、硒代硫酸钠为原料，通过化学浴法在室温下沉积28小时获得多晶硒化铅薄膜。与本申请相比，不具有分层结构，其反应时间较长，但立方晶粒大小约为350nm，小于本申请的致密层晶粒大小，且其制备方法不含离子交换过程。如文献“Karper A,Amorphous PbSe thin film produced by chemical bath deposition at pH of 5-8.Surface Review and Letters,2019,1950128:1-5.”在弱碱性、中性和弱酸性条件下，化学浴法在室温下沉积12小时制备硒化铅薄膜。与本申请相比，不具有分层结构，其薄膜由非晶态片状硒化铅构成，在400-1000nm波长内反射率低于20％、吸光度低于0.4，光学禁带宽度最低为1.46eV，远大于本申请，且其制备方法不含离子交换过程。如文献“Zhu Y,et al., P-type PbSe nanocrystalline films fabricated using high concentration of ammonia as complexing agent,Materials letters,2020,281:128621”以高浓度氨水、醋酸铅、硒代硫酸钠为原料，通过化学浴法在室温下沉积P型多晶硒化铅薄膜。与本申请相比，不具有分层结构，其晶粒大小为70～160nm，远小于本申请的致密层晶粒大小，光学禁带宽度为1.36eV，远大于本申请，且其制备方法不含离子交换过程。
含氧碱式碳酸铅层作为制备硒化铅疏松层的前驱层，其制备工艺和结构决定了疏松层的结构和性能。目前，制备含氧碱式碳酸铅的工艺多为紫外光照射化学浴法和化学法，制备的薄膜多为致密薄膜，晶体形状多为六边形。如文献“Mendivil-Reynoso T,et al.,Synthetic plumbonacrite thin films grown by chemical bath deposition technique.Chalcogenide Letters,2013,10:11-17.”以醋酸铅、氢氧化钠、三乙醇胺、甲醛次硫酸氢钠-氢氧化钠以及氨水/氯化铵为原料，通过化学浴法制备了具有六边形结构、光学禁带宽度为1.8eV的含氧碱式碳酸铅薄膜。与本申请相比，制备原料中的甲醛次硫酸氢钠对人体有严重的毒副作用，薄膜也不是由“圆饼状”晶体的堆积构成。如文献“Urbiola IRC,et al.,Lead Telluride through transformation of plumbonacrite in tellurium atmosphere and its behavior as part of PbTe-Si photodiode.IEEE Sensors Journal,2016,16(15):1-1.”是依次添加醋酸铅、柠檬酸钠、氢氧化钾和去离子水，然后在紫外灯照射下化学浴沉积可以用于化学气相沉积反应的含氧碱式碳酸铅薄膜。与本申请相比，该工艺较为繁琐，且含氧碱式碳酸铅薄膜为片状晶体紧密堆积形成，不存在着大量的孔隙，因此后续无法采用离子交换技术制备疏松薄膜。
采用离子交换技术可制备硒化铅薄膜，一般硒化铅薄膜的晶粒形状和分布由前驱层的结构和性能、浸没时间、离子交换溶液浓度等决定。如文献“Samaniego-Benitez JE,et al.,Thermal transformation of plumbonacrite/Si films into microstructured Pb/Si ones.Materials Letters,2017,198:38-41.”以醋酸铅、柠檬酸钠、氢氧化钾为原料，通过在紫外光照射下的化学浴法制备含氧碱式碳酸铅薄膜，将该薄膜在氮气氛中700℃退火1小时后置于硒离子溶液中制备PbSe。与本申请相比，制备含氧碱式碳酸铅、硒化铅的工艺更为复杂，含氧碱式碳酸铅的晶体形状不是“圆饼状”，立方状硒化铅晶粒会与铅晶粒团聚成球状，且含有大量的杂质铅。如文献“Heredia-Cancino JA,et al.,Optical and structural properties  of PbSe films obtained by ionic exchange of lead oxyhydroxicarbonate in a selenium-rongalite solution.Materials Science in Semiconductor Processing,2016,56:90-93.”以醋酸铅、氢氧化钠、三乙醇胺为原料，化学浴法制备六边形晶体交叉垂直排列的致密含氧碱式碳酸铅薄膜，将该薄膜浸没在由硒粉、柠檬酸钠和甲醛次硫酸氢钠制备的硒离子溶液中通过离子交换反应制备硒化铅薄膜。与本申请相比，采用的甲醛次硫酸氢钠对人体有严重的毒副作用，且薄膜会出现了大量杂相，也看不到明显的立方PbSe晶粒。如文献“Mendivil-Reynoso T,et al.,PbSe films by ion exchange of synthetic plumbonacrite layers immersed in a selenium ionic solution.Journal of Crystal Growth,2016,443:20-24.”以醋酸铅、氢氧化钠、三乙醇胺、甲醛次硫酸氢钠-氨水为原料，通过化学浴法制备了具有六边形结构且交叉垂直排列的含氧碱式碳酸铅薄膜，浸没在硒代硫酸钠溶液中通过离子交换法制备PbSe薄膜。与本申请相比，采用的甲醛次硫酸氢钠对人体有严重的毒副作用，也看不到清晰的立方PbSe晶粒。
总之，上述文献和专利与本申请相比，除了致密硒化铅层、含氧碱式碳酸铅层和疏松硒化铅层的制备原料和工艺参数上的不同外，均不具有分层薄膜结构，即在致密的大晶粒立方硒化铅层上形成疏松的较小晶粒立方硒化铅层。这种分层薄膜结构可以大幅度降低光从空气中入射到硒化铅薄膜时在界面处发生很强的反射，同时由于具有较少的缺陷和大的晶粒可以使薄膜拥有低的禁带宽度，因此该薄膜可以在宽光波波长范围内有更好的应用。
发明内容
本发明的目的是针对现有技术中的上述问题，本发明提供了一种分层多晶硒化铅光电薄膜及其制备方法，在致密硒化铅薄膜的基础上形成一层疏松硒化铅层，可以大幅缓解了空气和硒化铅薄膜界面的光反射，提高硒化铅薄膜的光吸收，增强硒化铅薄膜的光电导效应，同时还可显著降低硒化铅薄膜的禁带宽度。
为了实现上述目的，本发明是采取如下具体技术方案予以实现:
一种分层多晶硒化铅光电薄膜，包括衬底、硒化铅薄膜层，其特征在于：硒化铅薄膜层由位于衬底上的致密硒化铅层和位于致密硒化铅层上的疏松硒化铅层构成，致密硒化铅层由粒径为0.7～1.5μm立方晶粒紧密排列堆积形成，厚度1.5～5μm；疏松硒化铅层是由粒径为0.2～0.5μm立方晶粒随机排列堆积形成，晶粒堆之间和晶粒之间存在着大量微米或亚微米级空隙，厚度5～15μm。
更进一步，所述衬底为玻璃、硅、氧化硅、氮化镓、钢和石英中的一种。
上述的一种分层多晶硒化铅光电薄膜的制备方法，其特征在于，主要包括如下步骤：
(1)衬底清洗：
将衬底依次在去离子水、硫酸双氧水溶液、去离子水、无水乙醇中清洗5min、10min、5min和5min，氮气吹干后储存；
(2)化学浴法制备致密硒化铅层：
在浓度为0.45～1.1mol/L氢氧化钾溶液中滴加浓度为0.3～0.6mol/L醋酸铅溶液，在600转/分钟转速下完全反应再逐滴滴加0.2～0.6mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为2～4:1:1；
将配制好的上述黄褐色悬浊液置于60～85℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入在水浴热稳定后的黄褐色悬浊液中，沉积3～5h，以在衬底上沉积形成致密硒化铅层；
(3)化学浴法制备含氧碱式碳酸铅层：
在浓度为0.0164～0.0306mol/L的醋酸铅溶液中倒入浓度为0.2～0.3mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，倒入28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为9.8～12.2:2.8～3.2:0.8～1.2；
将配制好的上述澄清溶液放置于20～50℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为8～24h，以在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
(4)离子交换法制备疏松硒化铅层：
将步骤(3)得到的含有致密硒化铅层和含氧碱式碳酸铅层的衬底浸没在含有硒离子的溶液中发生离子交换反应，其中离子交换反应温度为20～40℃，浸没时间为0.5～5h，以使含氧碱式碳酸铅层转变为疏松硒化铅层。
更进一步，所述含有硒离子的溶液为0.01～0.1mol/L硒代硫酸钠和硒脲中的一种或二者的组合。
本发明与现有的多晶硒化铅光电薄膜对比的有益效果是:(1)由致密硒化铅层和疏松硒化铅层构成的分层多晶硒化铅薄膜结构，可以大幅度降低紫外至中近 红外光从空气中入射到硒化铅薄膜时在界面处发生很强的反射，有助于提高薄膜在宽光波波长范围内的吸光度；(2)具有少的立方晶体缺陷和大的晶粒尺寸，有助于降低硒化铅薄膜的禁带宽度；(3)含氧碱式碳酸铅前驱层具有特殊的“圆饼状”疏松排列的结构，有助于后续通过离子交换工艺形成疏松的硒化铅层；(4)硒化铅薄膜的制备方法工艺简单、成本低、可控性高，且原料相对更为环保，适合大规模生产，可广泛应用于制造红外传感器、太阳能电池、激光发射、热电转化器等光电转换或者热电转换领域的元器件。
附图说明
构成本申请的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为本发明所述制备一种分层多晶硒化铅光电薄膜的化学浴装置示意图。
1.模具；2.衬底；3.磁力搅拌子；4.反应液；5.硅油；6.温度调节及显示；7.转速调节。
图2为本发明所述制备的一种分层多晶硒化铅光电薄膜的流程图，其中图2d为所述分层多晶硒化铅光电薄膜的结构示意图。
图3为本发明所述制备的一种分层多晶硒化铅薄膜的典型试样的扫描电镜照片：(a)致密硒化铅层的表面，(b)含氧碱式碳酸铅层的表面，(c)疏松硒化铅层的表面，(d)分层多晶硒化铅薄膜的剖面。
图4为本发明制备的一种分层多晶硒化铅薄膜的典型试样的反射、吸收谱图：(a)450～2500nm波段反射谱图，(b)2500～5000nm波段反射谱图，(c)450～2500nm波段吸收谱图，(d)2500～5000nm波段吸收谱图；所述分层多晶硒化铅薄膜在波长450至5000nm范围内，平均吸光度达0.89～1.31，平均光学反射为8.58％～13.63％。
图5为本发明所述制备的一种分层多晶硒化铅薄膜的典型试样的光学禁带宽度图：(a)致密硒化铅层，(b)样品一，(c)样品二，(d)样品三；所述分层多晶硒化铅薄膜的禁带宽度为0.30～0.32eV。
具体实施方式
为更进一步阐述本发明的技术方案及其特点，以下结合附图1、图2、图3、图4、图5及典型实施案例，对依据本发明提出的一种分层多晶硒化铅光电薄膜及其制备方法做出进一步说明，其制备步骤包括:(1)衬底清洗；(2)化学浴法 制备致密硒化铅层；(3)化学浴法制备含氧碱式碳酸铅层；(4)离子交换法制备疏松硒化铅层。值得注意的是，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
详细案例说明如下:
实施例1:
(1)将两寸玻璃圆片衬底依次在去离子水、硫酸双氧水溶液、去离子水、无水乙醇中清洗5min、10min、5min和5min，氮气吹干后储存；
(2)在浓度为0.667mol/L氢氧化钾溶液中滴加浓度为0.45mol/L醋酸铅溶液，在600转/分钟转速下完全反应后逐滴滴加浓度为0.56mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为3:1:1。
称量4.62g的硒粉和14.749g无水亚硫酸钠(硒粉与无水亚硫酸钠的摩尔比为1:2)加入到105ml的去离子水中，在85℃的温度下回流3h，过滤掉不溶杂质后获得澄清透明浓度为0.56mol/L硒代硫酸钠溶液；
将配制好的上述黄褐色悬浊液放置于75℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积4h，以在衬底上沉积形成致密硒化铅层；
该工艺制备的致密硒化铅层薄膜的晶粒大小为0.98μm，厚度为2.4μm。本发明中把该样品命名为“致密硒化铅层”，其表面形貌如图3a所示，“致密硒化铅层”的光学反射、吸收以及禁带宽度分别如图4和5所示，其光学反射在450～2500nm范围内约为24.37％，在2500～5000nm范围内约为28.26％，光学吸收在450～2500nm范围内约为0.61，在2500～5000nm范围内约为0.55，禁带宽度约0.5eV。
(3)在浓度为0.1812mol/L的醋酸铅溶液中倒入浓度为0.2mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为11:3:1；
将配制好的上述澄清溶液放置于25℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为9h，以使得在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
在致密硒化铅层上制备好的含氧碱式碳酸铅层的表面形貌如图3b所示。
(4)将步骤(3)得到的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于在浓度为0.026mol/L硒代硫酸钠的溶液中发生离子交换反应，其中离子交换反应温度为25℃，时间为2h，以使含氧碱式碳酸铅层转变为疏松硒化铅层；
本申请中将此工艺制备的高光吸收、低禁带宽度的分层多晶硒化铅薄膜命名为“样品一”，其疏松硒化铅层的晶粒大小约为0.42μm，层厚度约为5.2μm，其表面形貌分别如图3c所示。“样品一”的光学反射、吸收以及禁带宽度分别如图4和图5所示，结果表明“样品一”比“致密硒化铅层”的光学反射在450～2500nm范围内降低了59.62％，在2500～5000nm范围内降低了55.01％，光学吸收在450～2500nm范围内提高了65.34％，在2500～5000nm范围内提高了63.24％。“样品一”在波长450至5000nm范围内，平均吸光度达0.95，平均光学反射约为11.41％，禁带宽度由约0.5eV降低到0.307eV。
实施例2:
(1)将两寸玻璃圆片衬底依次在去离子水、硫酸双氧水溶液、去离子水、无水乙醇中清洗5min、10min、5min和5min，氮气吹干后储存；
(2)在浓度为0.667mol/L氢氧化钾溶液中滴加浓度为0.45mol/L醋酸铅溶液，在600转/分钟转速下完全反应后逐滴滴加浓度为0.56mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为3:1:1。
将配制好的上述黄褐色悬浊液放置于75℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积4h，以在衬底上沉积形成致密硒化铅层；
(3)在浓度为0.1812mol/L的醋酸铅溶液中倒入浓度为0.2mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为11:3:1；
将配制好的上述澄清溶液放置于25℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为8h，以在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
(4)将步骤(3)得到的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于在浓度为0.026mol/L硒代硫酸钠的溶液中发生离子交换反应，其中离子交换反应温度为25℃，时间为1h，以使含氧碱式碳酸铅层转变为疏松硒化铅层；
本申请中将此工艺制备的高光吸收、低禁带宽度的分层多晶硒化铅薄膜命名为“样品二”，其疏松硒化铅层的晶粒大小约为0.2μm，厚度约为6.1μm。“样品二”的光学反射、吸收以及禁带宽度分别如图4和5所示，结果表明“样品二”比“致密硒化铅层”的光学反射在450～2500nm范围内降低了54.74％，在2500～5000nm范围内降低了44.09％，光学吸收在450～2500nm范围内提高了57.07％，在2500～5000nm范围内提高了46.2％。“样品二”在波长450至5000nm范围内，平均吸光度达0.89，平均光学反射约为13.63％，禁带宽度由约0.5eV降低到0.309eV。
实施例3:
(1)将两寸玻璃圆片衬底依次在去离子水、硫酸双氧水溶液、去离子水、无水乙醇中清洗5min、10min、5min和5min，氮气吹干后储存；
(2)在浓度为0.667mol/L氢氧化钾溶液中滴加浓度为0.45mol/L醋酸铅溶液，在600转/分钟转速下完全反应后逐滴滴加浓度为0.56mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为3:1:1。
将配制好的上述黄褐色悬浊液放置于75℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积4h，以在衬底上沉积形成致密硒化铅层；
(3)在浓度为0.1812mol/L的醋酸铅溶液中倒入浓度为0.2mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为11:3:1；
将配制好的上述澄清溶液放置于25℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为8h，以在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
(4)将步骤(3)得到的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于在浓度为0.026mol/L硒代硫酸钠的溶液中发生离子交换反应，其中离子交换反应温度为25℃，时间为2h，以使含氧碱式碳酸铅层转变为疏松硒化铅层；
本申请中将此工艺制备的高光吸收、低禁带宽度的分层多晶硒化铅薄膜命名为为“样品三”，其疏松硒化铅层的晶粒大小约为0.38μm，厚度约为6.4μm。“样品三”的光学反射、吸收以及禁带宽度分别如图4和5所示，结果表明“样品三” 比“致密硒化铅层”的光学反射在450～2500nm范围内降低了约63.3％，在2500～5000nm范围内降低了55.64％，光学吸收在450～2500nm范围内提高了72.46％，在2500～5000nm范围内提高了64.42％。“样品三”在波长450至5000nm范围内，平均吸光度达0.97，平均光学反射约为10.91％。禁带宽度由约0.5eV降低到0.313eV。
实施例4:
(1)将两寸多晶硅衬底依次在去离子水、硫酸双氧水溶液、去离子水、无水乙醇中清洗5min、10min、5min和5min，氮气吹干后储存；
(2)在浓度为0.45mol/L氢氧化钾溶液中滴加浓度为0.3mol/L醋酸铅溶液，在600转/分钟转速下完全反应后逐滴滴加浓度为0.2mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中去离子水、氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为4:1:1；
将配制好的上述黄褐色悬浊液放置于60℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积3h，以使得在衬底上沉积形成致密硒化铅层；
致密硒化铅层的晶粒大小约为0.7μm，厚度约为1.5μm。
(3)在浓度为0.0164mol/L的醋酸铅溶液中倒入浓度为0.2mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为12.2:2.8:0.8；
将配制好的上述澄清溶液放置于20℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为10h，以使得在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
(4)将步骤(3)得到的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于在浓度为0.01mol/L硒代硫酸钠的溶液中发生离子交换反应，其中离子交换反应温度为20℃，时间为5h，以使含氧碱式碳酸铅层转变为疏松硒化铅层；该分层多晶硒化铅薄膜中疏松硒化铅层晶粒大小约为0.2μm，疏松硒化铅层厚度约为5μm。该样品在波长450至5000nm范围内，平均吸光度达0.87，平均光学反射约为14.43％。禁带宽度约为0.32eV。
实施例5:
(1)将两寸氧化硅衬底依次在去离子水、硫酸双氧水溶液、去离子水、无 水乙醇中清洗5min、10min、5min和5min，氮气吹干后储存；
(2)在浓度为1.1mol/L氢氧化钾溶液中滴加浓度为0.6mol/L醋酸铅溶液，在600转/分钟转速下完全反应后逐滴滴加浓度为0.6mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为2:1:1；
将配制好的上述黄褐色悬浊液放置于85℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积5h，以在衬底上沉积形成致密硒化铅层；
致密硒化铅层的晶粒大小约为1.5μm，厚度约为5μm。
(3)在浓度为0.0306mol/L的醋酸铅溶液中倒入浓度为0.3mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为9.8:3.2:1.2；
将配制好的上述澄清溶液放置于50℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为24h，以在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
(4)将步骤(3)得到的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于在含有0.05mol/L硒代硫酸钠与0.05mol/L硒脲的混合硒离子的溶液中发生离子交换反应，其中离子交换反应温度为40℃，时间为0.5h，以使含氧碱式碳酸铅层转变为疏松硒化铅层；该分层多晶硒化铅薄膜中疏松硒化铅层的晶粒大小约为0.5μm，厚度约为15μm。该样品在波长450至5000nm范围内，平均吸光度达1.31，平均光学反射约为8.58％。禁带宽度约为0.30eV。
实施例6:
(1)将氮化镓衬底依次在去离子水、硫酸双氧水溶液、去离子水、无水乙醇中清洗5min、10min、5min、5min，氮气吹干后储存；
(2)在浓度为1mol/L氢氧化钾溶液中缓慢滴加浓度为0.4mol/L醋酸铅溶液，在600转/分钟转速下完全反应后逐滴滴加浓度为0.5mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为2:1:1；
将配制好的上述黄褐色悬浊液放置于80℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积4h，以在衬 底上沉积形成致密硒化铅层；
致密硒化铅层的晶粒大小约为1μm，厚度约为4.45μm，如图3d所示。
(3)在浓度为0.0229mol/L的醋酸铅溶液中倒入浓度为0.25mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为10.9:3:1；
将配制好的上述澄清溶液放置于40℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为24h，以在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
(4)将步骤(3)得到的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于在含有0.05mol/L硒代硫酸钠的溶液中发生离子交换反应，其中离子交换反应温度为35℃，时间为2.5h，以使含氧碱式碳酸铅层转变为疏松硒化铅层；该高光吸收、低禁带宽度的分层多晶硒化铅薄膜中疏松硒化铅层的晶粒大小约为0.42μm，厚度约为15μm。该样品在波长450至5000nm范围内，平均吸光度达0.95，平均光学反射约为10.65％。禁带宽度约为0.30eV。
实施例7:
(1)将石英衬底依次在去离子水、硫酸双氧水溶液、去离子水、无水乙醇中清洗5min、10min、5min和5min，氮气吹干后储存；
(2)在浓度为0.76mol/L氢氧化钾溶液中滴加浓度为0.6mol/L醋酸铅溶液，在600转/分钟转速下完全反应后逐滴滴加浓度为0.4mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为2.5:1:1；
将配制好的上述黄褐色悬浊液放置于70℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积3h，以在衬底上沉积形成致密硒化铅层；
致密硒化铅层的晶粒大小约为0.9μm，厚度约为3.1μm。
(3)在浓度为0.0283mol/L的醋酸铅溶液中倒入浓度为0.25mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加28wt％氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、28wt％氨水的体积比为9.9:3:0.9；
将配制好的上述澄清溶液放置于45℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为15h，以 在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
(4)将步骤(3)得到的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于在含0.05mol/L硒脲溶液中发生离子交换反应，其中离子交换反应温度为40℃，时间为2.5h，以使含氧碱式碳酸铅层转变为疏松硒化铅层；该分层多晶硒化铅薄膜中疏松硒化铅层的晶粒大小约为0.45μm，厚度约为14.6μm。该样品在波长450至5000nm范围内，平均吸光度达0.96，平均光学反射约为10.92％。禁带宽度约为0.30eV。
以上所述，仅是本发明的部分典型案例，并不以此对本发明限制，凡是根据本发明工艺实质对以上实施例所作的任何修改、变更以及等效元素的变换，均仍属于本发明技术方案的保护范围内。

Claims (9)

  1. 一种分层多晶硒化铅薄膜，包括衬底、硒化铅薄膜层，其特征在于，所述的硒化铅薄膜层由位于衬底上的致密硒化铅层和位于致密硒化铅层上的疏松硒化铅层构成，致密硒化铅层由粒径为0.7～1.5μm立方晶粒紧密排列堆积形成，厚度1.5～5μm；疏松硒化铅层是由粒径为0.2～0.5μm立方晶粒随机排列堆积形成，晶粒堆之间和晶粒之间存在着大量微米或亚微米级空隙，厚度5～15μm。
  2. 如权利要求1所述的一种分层多晶硒化铅薄膜，其特征在于，所述分层多晶硒化铅薄膜在波长450至5000nm范围内，平均吸光度达0.89～1.31，平均光学反射为8.58％～13.63％。
  3. 如权利要求1所述的一种分层多晶硒化铅薄膜，其特征在于，所述分层多晶硒化铅薄膜的禁带宽度为0.30～0.32eV。
  4. 如权利要求1所述的一种分层多晶硒化铅薄膜，其特征在于，所述衬底为玻璃、硅、氧化硅、氮化镓和石英中的一种。
  5. 如权利要求1所述的一种分层多晶硒化铅薄膜的制备方法，其特征在于，具体步骤如下：
    (1)衬底清洗：
    (2)化学浴法制备致密硒化铅层：
    在浓度为0.45～1.1mol/L氢氧化钾溶液中滴加浓度为0.3～0.6mol/L醋酸铅溶液，搅拌条件下完全反应后再逐滴滴加浓度为0.2～0.6mol/L硒代硫酸钠溶液，搅拌均匀后获得黄褐色悬浊液，其中氢氧化钾溶液、醋酸铅溶液、硒代硫酸钠溶液的体积比为2～4:1:1；
    将配制好的上述黄褐色悬浊液放置于60～85℃水浴中，将步骤(1)获得的衬底通过模具单面暴露垂直插入水浴热稳定后的黄褐色悬浊液中，沉积3～5h，以在衬底上沉积形成致密硒化铅层；
    (3)化学浴法制备含氧碱式碳酸铅层：
    在浓度为0.0164～0.0306mol/L的醋酸铅溶液中倒入浓度为0.2～0.3mol/L柠檬酸三钠溶液，玻璃棒搅拌后获得乳白色胶体，再添加氨水搅拌后变为澄清溶液，其中醋酸铅溶液、柠檬酸三钠溶液、氨水的体积比为9.8～12.2:2.8～3.2:0.8～1.2；
    将配制好的上述澄清溶液放置于20～50℃水浴中，将沉积有致密硒化铅层的衬底通过模具单面暴露垂直插入水浴热稳定后的澄清溶液中，沉积时间为8～24h，以在致密硒化铅层上沉积形成含氧碱式碳酸铅层；
    (4)离子交换法制备疏松硒化铅层：将步骤(3)获得的附有致密硒化铅层和含氧碱式碳酸铅层的衬底置于含有硒离子的溶液中发生离子交换反应，其中离子交换反应温度为20～40℃，时间为0.5～5h，以使含氧碱式碳酸铅层转变为疏松硒化铅层。
  6. 如权利要求5所述的一种分层多晶硒化铅薄膜的制备方法，其特征在于，步骤(1)中，所述衬底清洗的步骤如下：将衬底分别置于去离子水、硫酸双氧水溶液、去离子水、无水乙醇中依次清洗5min、10min、5min和5min，取出后用氮气枪吹干后储存。
  7. 如权利要求5所述的一种分层多晶硒化铅薄膜的制备方法，其特征在于，步骤(2)中，搅拌转速为600转/分钟。
  8. 如权利要求5所述的一种分层多晶硒化铅薄膜的制备方法，其特征在于，步骤(3)中，氨水浓度为28wt％。
  9. 如权利要求5所述的一种分层多晶硒化铅薄膜的制备方法，其特征在于：步骤(4)中，所述含有硒离子的溶液为0.01～0.1mol/L硒代硫酸钠和硒脲中的一种或二者的组合。
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