WO2021258728A1 - Preparation method for pure phase cuprous oxide thin film having high crystalline quality - Google Patents

Preparation method for pure phase cuprous oxide thin film having high crystalline quality Download PDF

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WO2021258728A1
WO2021258728A1 PCT/CN2021/073525 CN2021073525W WO2021258728A1 WO 2021258728 A1 WO2021258728 A1 WO 2021258728A1 CN 2021073525 W CN2021073525 W CN 2021073525W WO 2021258728 A1 WO2021258728 A1 WO 2021258728A1
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ceramic sheet
copper foil
cuprous oxide
pure copper
reaction space
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方国家
肖蒙
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武汉大学
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

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  • the invention belongs to the technical field of semiconductor material preparation, and specifically relates to a method for preparing a pure phase cuprous oxide film with high crystalline quality.
  • Cuprous oxide (Cu 2 O) is an excellent P-type semiconductor material with a cubic crystal structure and a direct band gap between 1.9-2.5 eV. It has good hole mobility at room temperature, Cu 2 O has a large light absorption coefficient, a long carrier diffusion length, and has a rich reserve of constituent elements and is non-toxic. Therefore, it is a promising photovoltaic material. Theoretically, a cell with Cu 2 O as the light-absorbing layer can achieve a photoelectric conversion efficiency of 20%. According to estimates, if a cell with a photoelectric conversion efficiency of 5% can be prepared, Cu 2 O will have a very high application in the photovoltaic field. Economic Value.
  • the solar cells using Cu 2 O as the light-absorbing material in the laboratory generally have low photoelectric conversion efficiency.
  • the most important factor is the poor crystalline quality of the prepared cuprous oxide film. Causes serious non-radiation recombination of the interface and the body.
  • the most researched preparation techniques of cuprous oxide films mainly include: electrochemical deposition, thermal oxidation, magnetron sputtering, pulsed laser deposition, etc.
  • some physical methods are difficult to produce thin films with high crystalline quality and pure phases, and it is difficult to apply electrochemical deposition on a large scale.
  • Professor Minami from Japan can obtain large-grained Cu 2 O by thermal oxidation.
  • the purpose of the present invention is to provide a method for preparing a pure phase cuprous oxide film with high crystalline quality.
  • This method restricts the reaction, crystallization, and growth of cuprous oxide in a small space by constructing a small reaction space structure, so that the cuprous oxide has a more stable environment during the oxidation and crystallization process, and the growth process is more orderly.
  • the obtained cuprous oxide has large crystal grains, excellent electrical properties, small band gap, simple preparation process and good repeatability.
  • the present invention adopts the following technical solutions as follows:
  • a method for preparing high-quality cuprous oxide thin film A small reaction space is constructed by ceramic sheets, pure copper foil is used as the copper source, and oxygen or air is used as the reactive gas source to prepare high-quality cuprous oxide thin film by thermal oxidation; wherein:
  • the method for constructing the small reaction space is: take the upper ceramic sheet and the lower ceramic sheet, and place the two supporting ceramic sheets between the upper ceramic sheet and the lower ceramic sheet, respectively, between the upper ceramic sheet and the lower ceramic sheet.
  • the small space between the ceramic pieces is the small reaction space constructed;
  • the pure copper foil is placed on the surface of the lower ceramic sheet in the small reaction space obtained by the structure;
  • the thickness of the supporting ceramic sheet is 0.1-1 mm, the thickness of the pure copper foil is 0.05-0.2 mm, and the thickness of the supporting ceramic sheet is at least 1.5 times the thickness of the pure copper foil.
  • the method for preparing the high-quality cuprous oxide film includes the following steps:
  • step 2 Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1).
  • an inert gas atmosphere raise it to 800-850°C, reduce the heating rate and continue to rise to 1010- 1050°C, then replace the inert gas atmosphere with oxygen or air atmosphere, keep it for 60-180min for thermal oxidation reaction, Cu generates Cu 2 O;
  • step 2) After the step 2) the thermal oxidation reaction is completed, the oxygen or air atmosphere is replaced with an argon atmosphere, the temperature is kept for a period of time and then cooled to 500-600°C, and naturally cooled to room temperature, to obtain a cuprous oxide film with high crystalline quality.
  • the heating rate should be controlled within 6-10°C/min before 800-850°C, and within 6°C/min after 800-850°C.
  • the oxygen or air atmosphere is replaced with an argon atmosphere and the temperature is kept for 60-180 minutes, and then the temperature is reduced to 500-600°C at a rate of 3-5°C/min.
  • the temperature of the thermal oxidation reaction is continued to rise by 5-10°C, and the oxygen or air atmosphere is replaced with an argon atmosphere during the heating process.
  • the volume flow rate of the inert gas is 50 sccm-100 sccm.
  • the inert gas is argon or nitrogen.
  • the volume flow rate of oxygen is 100-200 sccm.
  • the ceramic sheet is corundum, zirconia or aluminum nitride, wherein the material of the upper ceramic sheet and the lower ceramic sheet are the same, and the materials of the upper ceramic sheet, the lower ceramic sheet and the supporting ceramic sheet may be the same or different.
  • a small reaction space is constructed by ceramic sheets to support the thickness of the ceramic sheet to adjust the distance between the upper ceramic sheet and the lower ceramic sheet to adjust the size of the small reaction space.
  • the flat upper ceramic sheet and the lower ceramic sheet are used as pure.
  • the upper and lower surface coverings of the copper foil restrict the reaction, crystallization and growth of cuprous oxide in a small space, so that the cuprous oxide has a more stable environment during the oxidation and crystallization process, so that larger crystals can be grown in a certain orientation.
  • the size of the cuprous oxide obtained by this method is large, up to 1.5mm, and the electrochemical performance is excellent.
  • the carrier mobility can reach 72cm 2 /V ⁇ s, which is about twice as high as the general method.
  • the band gap is 1.91eV, which can be used as a light-absorbing layer material in the field of solar cells.
  • the invention uses ordinary ceramic materials as an auxiliary to construct a small reaction space, which is cheap, reusable, simple in process, good in repeatability, simple in equipment requirements, and does not require expensive large-scale vacuum equipment, and does not require expensive raw materials , No complicated etching process, low cost, and potential for large-scale industrial production.
  • Fig. 1 is a schematic diagram of a small reaction space constructed in an embodiment of the present invention, in which 1-upper ceramic sheet, 2-supporting ceramic sheet, 3-pure copper foil, 4-lower ceramic sheet.
  • Figure 2 is a scanning electron micrograph of cuprous oxide prepared in different processes in Examples 1-2 and 6 and Comparative Example 1-2, in which (a) and (b) Example 1, (c) Example 2 , (D) Example 6, (e) Comparative Example 2, (f) Comparative Example 1.
  • Figure 3 is an X-ray diffraction pattern of cuprous oxide prepared when using different ceramic sheets as substrates in Example 1-2, in which (a) Example 1 corundum substrate, (b) Example 2 zirconia lining end.
  • Figure 4 is an optical microscope photograph of cuprous oxide prepared with pure copper foil sources of different thicknesses in Examples 1 and 3, where (a) and (b) are the front and cross sections of 100 ⁇ m thick pure copper foil in Example 3, respectively. (c) and (d) are the front and cross section of the 200 ⁇ m thick pure copper foil in Example 1, respectively.
  • Fig. 5 is (a) the ultraviolet-visible absorption spectrum and (b) the Taut-Plot diagram of the cuprous oxide prepared by the space structuring method in Example 1.
  • the present invention provides a method for preparing a thin film of pure phase cuprous oxide with high crystalline quality.
  • the present invention will be further described in detail below in conjunction with specific implementation examples and with reference to the accompanying drawings. .
  • a method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
  • step 2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, maintain the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
  • a method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
  • step 2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, maintain the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
  • a method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
  • step 2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, maintain the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
  • a method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
  • step 2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 100sccm, keep the argon atmosphere in the tube furnace, set 90min to 800°C, and then 60min to 1010°C; after the temperature reaches 1010°C, close and open the oxygen valve, set the oxygen volume flow to 100sccm, keep the temperature for 120min .
  • a method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
  • step 2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, keep the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1050°C for 60 minutes; after the temperature reaches 1050°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
  • a method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
  • step 2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set it to 50sccm, keep the argon atmosphere in the tube furnace, set it to rise to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the vent valve, and breathe in air. Keep for 120min.
  • a method for preparing a cuprous oxide film is provided, and the specific steps are as follows:
  • a method for preparing a cuprous oxide film is provided, and the specific steps are as follows:
  • test results of analysis examples 1-6 and comparative examples 1-2 are as follows:
  • Figure 2 is a scanning electron micrograph of cuprous oxide prepared in different processes in Examples 1-2 and 6 and Comparative Example 1-2, in which (a) and (b) Example 1, (c) Example 2 , (D) Example 6, (e) Comparative Example 2, (f) Comparative Example 1.
  • the cuprous oxide film prepared by using a corundum ceramic substrate to build a space has large crystal grains and a very flat surface, as can be seen in Figure 2b By the time the grain size has reached 1.5mm, the size of the cuprous oxide can reach the millimeter level.
  • Figure c (Example 2) and Figure d (Example 6) respectively show the use of zirconia ceramics to construct the space and the use of air as an oxygen source to prepare cuprous oxide.
  • the crystal quality is also relatively high. But when we do not use the space construction method, as shown in Figure e (Comparative Example 2) and Figure f (Comparative Example 1), no matter whether the substrate is a quartz plate or a corundum crucible, the crystal quality is not as good as the previous results.
  • Figure 3 is an X-ray diffraction pattern of cuprous oxide prepared when different ceramic sheets are used as substrates in Example 1-2, in which (a) Example 1 corundum substrate, (b) Example 2 zirconia substrate .
  • the figure shows that both Example 1 and Example 2 can prepare pure phase cuprous oxide, and it mainly grows along the (110) and (220) crystal plane orientations.
  • Figure 4 is an optical micrograph of the cuprous oxide prepared by the space construction method when the thickness of the pure copper foil source is 100 ⁇ m (Example 3) and 200 ⁇ m (Example 1), the magnification is both 10 times, of which (a) 100 ⁇ m front , (B) 100 ⁇ m cross-section, (c) 200 ⁇ m front side, (d) 200 ⁇ m cross-section.
  • the figure shows that when the thickness of the pure copper foil is 100 ⁇ m, the prepared cuprous oxide crystal grains are smaller than the thickness of 200 ⁇ m. However, it can be seen from the cross-sectional view that the entire cuprous oxide crystal penetrates the entire thickness. Application is an advantage.
  • Fig. 5 shows (a) the ultraviolet-visible absorption spectrum and (b) the Taut-Plot diagram of the cuprous oxide prepared by the space structuring method in Example 1.
  • the figure shows that the Cu 2 O prepared in Example 1 has a relatively small band gap of 1.91 eV, and is more suitable for use as a light-absorbing layer material in the field of solar cells.
  • Table 1 shows the results of the Hall test of the cuprous oxide prepared in Examples 1 and 3 and Comparative Example 1.
  • the table shows that the carrier mobility of the cuprous oxide obtained in Example 1 can reach 72 cm 2 /V ⁇ s. Compared with the cuprous oxide obtained by the general method in Comparative Example 1, it is doubled, and the electrical properties are very excellent.
  • the present invention uses flat ceramic sheets as the upper and lower surface coverings of pure copper foil to limit the reaction, crystallization, and growth of cuprous oxide in a small space, so that the cuprous oxide has a better effect in the process of oxidation and crystallization.
  • larger crystal grains are grown in a certain orientation.
  • the preparation method is simple and controllable, has strong repeatability, and the prepared material has good structural properties and electrical properties, and is suitable for preparing solar cells.

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Abstract

Disclosed is a preparation method for a high-quality cuprous oxide thin film. The steps are as follows: constructing a tiny reaction space by means of ceramic pieces, and preparing a cuprous oxide thin film by using a pure copper foil as a copper source and using oxygen or air as a reaction gas source and using a thermal oxidation method, in which a method for constructing the tiny reaction space comprises: taking an upper ceramic piece and a lower ceramic piece, and respectively placing two supporting ceramic pieces between the upper ceramic piece and the lower ceramic piece to support a tiny space, i.e. the constructed tiny reaction space; and placing a pure copper foil on the surface of the lower ceramic piece in the tiny reaction space. The thickness of the supporting ceramic pieces is 0.1-1 mm, the thickness of the pure copper foil is 0.05-0.2 mm, and the thickness of the supporting ceramic pieces is at least 1.5 times the thickness of the pure copper foil. The copper oxide crystal obtained by the method has a high quality, a large grain size which can reach 1.5 mm, excellent electrochemical properties, and a small band gap. The method is simple to operate and stable in result, and has a good application prospect in terms of photovoltaic, photocatalysis, etc.

Description

一种高结晶质量纯相氧化亚铜薄膜的制备方法Preparation method of pure phase cuprous oxide film with high crystalline quality 技术领域Technical field
本发明属于半导体材料制备技术领域，具体涉及一种高结晶质量纯相氧化亚铜薄膜的制备方法。The invention belongs to the technical field of semiconductor material preparation, and specifically relates to a method for preparing a pure phase cuprous oxide film with high crystalline quality.
背景技术Background technique
氧化亚铜(Cu 2O)是一种优良的P型半导体材料，其具有立方相晶体结构，直接带隙在1.9-2.5eV之间。在室温下其具有良好的空穴迁移率，且Cu 2O光吸收系数大，载流子扩散长度长，组成元素储量丰富、无毒，因此是一种很有发展前途的光伏材料。理论上，以Cu 2O作为吸光层的电池可以达到20％的光电转换效率，据估算，如果能制备出达到5％光电转换效率的电池，Cu 2O在光伏领域的应用便具有很高的经济价值。 Cuprous oxide (Cu 2 O) is an excellent P-type semiconductor material with a cubic crystal structure and a direct band gap between 1.9-2.5 eV. It has good hole mobility at room temperature, Cu 2 O has a large light absorption coefficient, a long carrier diffusion length, and has a rich reserve of constituent elements and is non-toxic. Therefore, it is a promising photovoltaic material. Theoretically, a cell with Cu 2 O as the light-absorbing layer can achieve a photoelectric conversion efficiency of 20%. According to estimates, if a cell with a photoelectric conversion efficiency of 5% can be prepared, Cu 2 O will have a very high application in the photovoltaic field. Economic Value.
然而，目前实验室以Cu 2O作为吸光材料的太阳能电池普遍光电转换效率较低，除了难以找到与之匹配的n型半导体材料，最重要的因素是制备的氧化亚铜薄膜结晶质量较差，导致界面以及体内非辐射复合严重。目前研究较多的氧化亚铜薄膜制备技术主要有：电化学沉积法，热氧化法，磁控溅射法，脉冲激光沉积法等。但一些物理方法很难做出厚度达到要求，结晶质量高且纯相的薄膜，电化学沉积又很难大规模应用。日本的minami教授采用热氧化法可以得到大晶粒的Cu 2O，但由于制备温度很高，在制备的过程中表面产生大量的缺陷，通常还需要在高温下进行淬火处理和酸刻蚀才能得到较好的结晶，但这又会增加工艺的成本和复杂性，且会有部分氧化铜产生。因此，现有的技术还有待改进，问题是在于如何在制备工艺更简便的条件下得到结晶质量高且单一相的氧化亚铜。 However, the solar cells using Cu 2 O as the light-absorbing material in the laboratory generally have low photoelectric conversion efficiency. In addition to the difficulty in finding a matching n-type semiconductor material, the most important factor is the poor crystalline quality of the prepared cuprous oxide film. Causes serious non-radiation recombination of the interface and the body. At present, the most researched preparation techniques of cuprous oxide films mainly include: electrochemical deposition, thermal oxidation, magnetron sputtering, pulsed laser deposition, etc. However, some physical methods are difficult to produce thin films with high crystalline quality and pure phases, and it is difficult to apply electrochemical deposition on a large scale. Professor Minami from Japan can obtain large-grained Cu 2 O by thermal oxidation. However, due to the high preparation temperature, a large number of defects are generated on the surface during the preparation process, and it is usually necessary to perform quenching treatment and acid etching at high temperature. Better crystallization is obtained, but this will increase the cost and complexity of the process, and some copper oxide will be produced. Therefore, the existing technology still needs to be improved, and the problem is how to obtain cuprous oxide with high crystal quality and single phase under the conditions of a simpler preparation process.
发明内容Summary of the invention
本发明的目的在于提供一种高结晶质量纯相氧化亚铜薄膜的制备方法。该方法通过构筑微小反应空间结构，限制氧化亚铜在狭小的空间反应、结晶、生长，从而使得氧化亚铜在氧化结晶的过程中有更为稳定的环境，在生长的过程中更加有序，所得氧化亚铜晶粒大，电学性能优异，带隙小，制备工艺简单，重复性好。The purpose of the present invention is to provide a method for preparing a pure phase cuprous oxide film with high crystalline quality. This method restricts the reaction, crystallization, and growth of cuprous oxide in a small space by constructing a small reaction space structure, so that the cuprous oxide has a more stable environment during the oxidation and crystallization process, and the growth process is more orderly. The obtained cuprous oxide has large crystal grains, excellent electrical properties, small band gap, simple preparation process and good repeatability.
为了解决上述技术问题，本发明采用以下技术方案如下：In order to solve the above technical problems, the present invention adopts the following technical solutions as follows:
一种高质量氧化亚铜薄膜的制备方法，通过陶瓷片构筑微小反应空间，以纯铜箔为铜源，氧气或者空气作为反应气源采用热氧化法制备得到高质量氧化亚铜薄膜；其中：A method for preparing high-quality cuprous oxide thin film. A small reaction space is constructed by ceramic sheets, pure copper foil is used as the copper source, and oxygen or air is used as the reactive gas source to prepare high-quality cuprous oxide thin film by thermal oxidation; wherein:
微小反应空间的构筑方法为：取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于所述 上陶瓷片和所述下陶瓷片之间，在所述上陶瓷片和所述下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；The method for constructing the small reaction space is: take the upper ceramic sheet and the lower ceramic sheet, and place the two supporting ceramic sheets between the upper ceramic sheet and the lower ceramic sheet, respectively, between the upper ceramic sheet and the lower ceramic sheet. The small space between the ceramic pieces is the small reaction space constructed;
所述纯铜箔置于构筑得到的所述微小反应空间内的所述下陶瓷片表面；The pure copper foil is placed on the surface of the lower ceramic sheet in the small reaction space obtained by the structure;
所述支撑陶瓷片厚度为0.1-1mm，所述纯铜箔厚度为0.05-0.2mm，所述支撑陶瓷片厚度至少是所述纯铜箔厚度的1.5倍。The thickness of the supporting ceramic sheet is 0.1-1 mm, the thickness of the pure copper foil is 0.05-0.2 mm, and the thickness of the supporting ceramic sheet is at least 1.5 times the thickness of the pure copper foil.
按上述方案，所述高质量氧化亚铜薄膜的制备方法，包括如下步骤：According to the above scheme, the method for preparing the high-quality cuprous oxide film includes the following steps:
1)通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，然后将纯铜箔置于构筑得到的所述微小反应空间内的下陶瓷片表面；1) Construct a small reaction space by ceramic sheets, take the upper ceramic sheet and the lower ceramic sheet, and place the two supporting ceramic sheets between the upper ceramic sheet and the lower ceramic sheet, and prop up between the upper ceramic sheet and the lower ceramic sheet. A small space, and then pure copper foil is placed on the surface of the lower ceramic sheet in the constructed small reaction space;
2)将步骤1)通过陶瓷片构筑的微小反应空间结构及内部的纯铜箔一起置于管式炉中，在惰性气体氛围中，升至800-850℃，降低升温速率继续升至1010-1050℃，然后将惰性气体氛围置换成氧气或空气氛围，保温60-180min进行热氧化反应，Cu生成Cu 2O； 2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1). In an inert gas atmosphere, raise it to 800-850°C, reduce the heating rate and continue to rise to 1010- 1050°C, then replace the inert gas atmosphere with oxygen or air atmosphere, keep it for 60-180min for thermal oxidation reaction, Cu generates Cu 2 O;
3)在步骤2)热氧化反应结束后将氧气或空气氛围置换成氩气氛围，继续保温一段时间后降温至500-600℃，自然冷却至室温，即得高结晶质量的氧化亚铜薄膜。3) After the step 2) the thermal oxidation reaction is completed, the oxygen or air atmosphere is replaced with an argon atmosphere, the temperature is kept for a period of time and then cooled to 500-600°C, and naturally cooled to room temperature, to obtain a cuprous oxide film with high crystalline quality.
按上述方案，所述步骤2)中，800-850℃之前升温速率应控制在6-10℃/min，800-850℃之后控制在6℃/min之内。According to the above scheme, in the step 2), the heating rate should be controlled within 6-10°C/min before 800-850°C, and within 6°C/min after 800-850°C.
按上述方案，所述步骤3)中，将氧气或空气氛围置换成氩气氛围后继续保温60-180min，然后以3-5℃/min的速度降温至500-600℃。According to the above scheme, in the step 3), the oxygen or air atmosphere is replaced with an argon atmosphere and the temperature is kept for 60-180 minutes, and then the temperature is reduced to 500-600°C at a rate of 3-5°C/min.
按上述方案，所述步骤3)中，热氧化反应结束后，在热氧化反应温度基础上继续上升5-10℃，在升温过程中，将氧气或空气氛围置换成氩气氛围。According to the above scheme, in the step 3), after the thermal oxidation reaction is completed, the temperature of the thermal oxidation reaction is continued to rise by 5-10°C, and the oxygen or air atmosphere is replaced with an argon atmosphere during the heating process.
按上述方案，所述步骤3)中，惰性气体的体积流量为50sccm-100sccm。According to the above scheme, in the step 3), the volume flow rate of the inert gas is 50 sccm-100 sccm.
按上述方案，所述步骤3)中，惰性气体为氩气或氮气。According to the above scheme, in the step 3), the inert gas is argon or nitrogen.
按上述方案，所述步骤2)中，氧气的体积流量为100-200sccm。According to the above scheme, in the step 2), the volume flow rate of oxygen is 100-200 sccm.
按上述方案，所述陶瓷片为刚玉、氧化锆或氮化铝，其中上陶瓷片和下陶瓷片材质相同，上陶瓷片和下陶瓷片与支撑陶瓷片的材质可相同也可不同。According to the above solution, the ceramic sheet is corundum, zirconia or aluminum nitride, wherein the material of the upper ceramic sheet and the lower ceramic sheet are the same, and the materials of the upper ceramic sheet, the lower ceramic sheet and the supporting ceramic sheet may be the same or different.
本发明的有益效果为：The beneficial effects of the present invention are:
1.本发明通过陶瓷片构筑微小反应空间，以支持陶瓷片厚度来调节上陶瓷片和下陶瓷片之间的距离从而调控微小反应空间的大小，以平整的上陶瓷片和下陶瓷片作为纯铜箔的上下表面覆盖物，限制氧化亚铜在狭小的空间反应、结晶、生长，从而使得氧化亚铜在氧化结晶的过程中有更为稳定的环境，从而按一定取向生长出较大的晶粒，该方法得到的氧化亚铜晶 粒尺寸大，可至1.5mm，电化学性能优异，载流子迁移率可达到72cm 2/V·s，与一般方法相比，提升了一倍左右，且带隙小，为1.91eV，可作为吸光层材料用于太阳能电池领域。 1. In the present invention, a small reaction space is constructed by ceramic sheets to support the thickness of the ceramic sheet to adjust the distance between the upper ceramic sheet and the lower ceramic sheet to adjust the size of the small reaction space. The flat upper ceramic sheet and the lower ceramic sheet are used as pure The upper and lower surface coverings of the copper foil restrict the reaction, crystallization and growth of cuprous oxide in a small space, so that the cuprous oxide has a more stable environment during the oxidation and crystallization process, so that larger crystals can be grown in a certain orientation. The size of the cuprous oxide obtained by this method is large, up to 1.5mm, and the electrochemical performance is excellent. The carrier mobility can reach 72cm 2 /V·s, which is about twice as high as the general method. And the band gap is 1.91eV, which can be used as a light-absorbing layer material in the field of solar cells.
2.本发明通过普通的陶瓷材料作为辅助构筑微小反应空间，价格便宜，且可重复利用，工艺简单，重复性好，所用的设备要求简单，不需要昂贵的大型真空设备，不需要昂贵的原料，不需要复杂的刻蚀工艺，成本低，具有大工业生产的潜力。2. The invention uses ordinary ceramic materials as an auxiliary to construct a small reaction space, which is cheap, reusable, simple in process, good in repeatability, simple in equipment requirements, and does not require expensive large-scale vacuum equipment, and does not require expensive raw materials , No complicated etching process, low cost, and potential for large-scale industrial production.
附图说明Description of the drawings
图1为本发明实施例中构筑的微小反应空间的示意图，其中1-上陶瓷片、2-支撑陶瓷片、3-纯铜箔、4-下陶瓷片。Fig. 1 is a schematic diagram of a small reaction space constructed in an embodiment of the present invention, in which 1-upper ceramic sheet, 2-supporting ceramic sheet, 3-pure copper foil, 4-lower ceramic sheet.
图2为实施例1-2和6与对比例1-2中不同工艺时制备得到的氧化亚铜的扫描电镜图，其中，(a)和(b)实施例1，(c)实施例2，(d)实施例6，(e)对比例2，(f)对比例1。Figure 2 is a scanning electron micrograph of cuprous oxide prepared in different processes in Examples 1-2 and 6 and Comparative Example 1-2, in which (a) and (b) Example 1, (c) Example 2 , (D) Example 6, (e) Comparative Example 2, (f) Comparative Example 1.
图3为实施例1-2中以不同陶瓷片为衬底时制备得到的氧化亚铜的X射线衍射图，其中，(a)实施例1刚玉衬底，(b)实施例2氧化锆衬底。Figure 3 is an X-ray diffraction pattern of cuprous oxide prepared when using different ceramic sheets as substrates in Example 1-2, in which (a) Example 1 corundum substrate, (b) Example 2 zirconia lining end.
图4为实施例1和3中以不同厚度纯铜箔源制备得到的氧化亚铜的光学显微镜照片，其中(a)和(b)分别为实施例3中100μm厚度纯铜箔正面和截面，(c)和(d)分别为实施例1中200μm厚度纯铜箔正面和截面。Figure 4 is an optical microscope photograph of cuprous oxide prepared with pure copper foil sources of different thicknesses in Examples 1 and 3, where (a) and (b) are the front and cross sections of 100μm thick pure copper foil in Example 3, respectively. (c) and (d) are the front and cross section of the 200 μm thick pure copper foil in Example 1, respectively.
图5为实施例1中空间构筑法制备得到的氧化亚铜的(a)紫外可见吸收光谱图和(b)Taut-Plot图。Fig. 5 is (a) the ultraviolet-visible absorption spectrum and (b) the Taut-Plot diagram of the cuprous oxide prepared by the space structuring method in Example 1.
具体实施方案Specific implementation plan
本发明提供一种制备高结晶质量纯相氧化亚铜的薄膜的方法，为使本发明的目的、技术方案和效果更加清楚明白，以下结合具体实施例子，并参照附图，对本发明进一步详细说明。The present invention provides a method for preparing a thin film of pure phase cuprous oxide with high crystalline quality. In order to make the objectives, technical solutions and effects of the present invention clearer and clearer, the present invention will be further described in detail below in conjunction with specific implementation examples and with reference to the accompanying drawings. .
实施例1Example 1
提供一种高质量氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
1)将200μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；将纯铜箔置于微小反应空间内的下陶瓷片表面，如图1所示；上陶瓷片、下陶瓷片和2片支撑陶瓷片均为刚玉陶瓷片，上陶瓷片和下陶瓷片厚度为1mm，宽度为4cm，长度为12cm，支撑陶瓷片厚度为0.5mm。1) Cut the 200μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for later use; construct a small reaction space by ceramic sheets, take the upper ceramic sheet and the lower ceramic sheet , The two supporting ceramic sheets are placed between the upper ceramic sheet and the lower ceramic sheet, and a small space is supported between the upper ceramic sheet and the lower ceramic sheet, which is the constructed small reaction space; the pure copper foil is placed in the small The surface of the lower ceramic sheet in the reaction space is shown in Figure 1. The upper ceramic sheet, the lower ceramic sheet and the two supporting ceramic sheets are all corundum ceramic sheets. The thickness of the upper and lower ceramic sheets is 1mm, the width is 4cm, and the length It is 12cm, and the thickness of the supporting ceramic sheet is 0.5mm.
2)将步骤1)通过陶瓷片构筑的微小反应空间结构及内部的纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为50sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1010℃；在温度到达1010℃之后，关闭氩气阀门，打开氧气阀门，氧气体积流量设为100sccm，保温120min。2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, maintain the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
3)以0.5℃/min的速度将温度升至1015℃，在升温的过程中，关闭氧气阀门，抽空残余氧气，打开氩气阀门，氩气体积流量设为50sccm，然后于1015℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到高结晶质量的氧化亚铜。3) Raise the temperature to 1015°C at a rate of 0.5°C/min. During the heating process, close the oxygen valve, evacuate the residual oxygen, open the argon valve, set the argon volume flow to 50sccm, and then keep it at 1015°C for 90min; Finally, under the protection of argon, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the quenching of the cuprous oxide, and then naturally cooled to room temperature to obtain cuprous oxide with high crystalline quality.
实施例2Example 2
提供一种高质量氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
1)将200μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；将纯铜箔置于微小反应空间内的下陶瓷片表面，如图1所示；上陶瓷片和下陶瓷片为氧化锆陶瓷片，2片支撑陶瓷片为刚玉陶瓷片，上陶瓷片和下陶瓷片厚度为1mm，宽度为4cm，长度为12cm，支撑陶瓷片厚度为0.5mm。1) Cut the 200μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for later use; construct a small reaction space by ceramic sheets, take the upper ceramic sheet and the lower ceramic sheet , The two supporting ceramic sheets are placed between the upper ceramic sheet and the lower ceramic sheet, and a small space is supported between the upper ceramic sheet and the lower ceramic sheet, which is the constructed small reaction space; the pure copper foil is placed in the small The surface of the lower ceramic sheet in the reaction space is shown in Figure 1. The upper ceramic sheet and the lower ceramic sheet are zirconia ceramic sheets, and the two supporting ceramic sheets are corundum ceramic sheets. The thickness of the upper ceramic sheet and the lower ceramic sheet are 1mm and the width is 1mm. It is 4cm, the length is 12cm, and the thickness of the supporting ceramic sheet is 0.5mm.
2)将步骤1)通过陶瓷片构筑的微小反应空间结构及内部的纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为50sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1010℃；在温度到达1010℃之后，关闭氩气阀门，打开氧气阀门，氧气体积流量设为100sccm，保温120min。2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, maintain the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
3)以0.5℃/min的速度将温度升至1015℃，在升温的过程中，关闭氧气阀门，抽空残余氧气，打开氩气阀门，氩气体积流量设为50sccm，然后于1015℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到高结晶质量的氧化亚铜。3) Raise the temperature to 1015°C at a rate of 0.5°C/min. During the heating process, close the oxygen valve, evacuate the residual oxygen, open the argon valve, set the argon volume flow to 50sccm, and then keep it at 1015°C for 90min; Finally, under the protection of argon, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the quenching of the cuprous oxide, and then naturally cooled to room temperature to obtain cuprous oxide with high crystalline quality.
实施例3Example 3
提供一种高质量氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
1)将100μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；将纯铜箔置于微小反应空间内的下陶瓷片表面，如图1所示； 上陶瓷片、下陶瓷片和2片支撑陶瓷片均为刚玉陶瓷片，上陶瓷片和下陶瓷片厚度为1mm，宽度为4cm，长度为12cm，支撑陶瓷片2厚度为0.5mm。1) Cut the 100μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for later use; construct a small reaction space by ceramic sheets, and take the upper ceramic sheet and the lower ceramic sheet , The two supporting ceramic sheets are placed between the upper ceramic sheet and the lower ceramic sheet, and a small space is supported between the upper ceramic sheet and the lower ceramic sheet, which is the constructed small reaction space; the pure copper foil is placed in the small The surface of the lower ceramic sheet in the reaction space is shown in Figure 1. The upper ceramic sheet, the lower ceramic sheet and the two supporting ceramic sheets are all corundum ceramic sheets. The thickness of the upper and lower ceramic sheets is 1mm, the width is 4cm, and the length is 4cm. The thickness of the supporting ceramic sheet 2 is 0.5 mm.
2)将步骤1)通过陶瓷片构筑的微小反应空间结构及内部的纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为50sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1010℃；在温度到达1010℃之后，关闭氩气阀门，打开氧气阀门，氧气体积流量设为100sccm，保温120min。2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, maintain the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
3)以0.5℃/min的速度将温度升至1015℃，在升温的过程中，关闭氧气阀门，抽空残余氧气，打开氩气阀门，氩气体积流量设为50sccm，然后于1015℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到高结晶质量的氧化亚铜。其霍尔测试结果如下表所示。3) Raise the temperature to 1015°C at a rate of 0.5°C/min. During the heating process, close the oxygen valve, evacuate the residual oxygen, open the argon valve, set the argon volume flow to 50sccm, and then keep it at 1015°C for 90min; Finally, under the protection of argon, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the quenching of the cuprous oxide, and then naturally cooled to room temperature to obtain cuprous oxide with high crystalline quality. The Hall test results are shown in the table below.
实施例4Example 4
提供一种高质量氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
1)将200μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；将纯铜箔置于微小反应空间内的下陶瓷片表面，如图1所示；上陶瓷片、下陶瓷片和2片支撑陶瓷片均为刚玉陶瓷片，上陶瓷片和下陶瓷片厚度为1mm，宽度为4cm，长度为12cm，支撑陶瓷片厚度为0.3mm。1) Cut the 200μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for later use; construct a small reaction space by ceramic sheets, and take the upper ceramic sheet and the lower ceramic sheet , The two supporting ceramic sheets are placed between the upper ceramic sheet and the lower ceramic sheet, and a small space is supported between the upper ceramic sheet and the lower ceramic sheet, which is the constructed small reaction space; the pure copper foil is placed in the small The surface of the lower ceramic sheet in the reaction space is shown in Figure 1. The upper ceramic sheet, the lower ceramic sheet and the two supporting ceramic sheets are all corundum ceramic sheets. The thickness of the upper and lower ceramic sheets is 1mm, the width is 4cm, and the length It is 12cm, and the thickness of the supporting ceramic sheet is 0.3mm.
2)将步骤1)通过陶瓷片构筑的微小反应空间结构及内部的纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为100sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1010℃；在温度到达1010℃之后，关闭打开氧气阀门，氧气体积流量设为100sccm，保温120min。2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 100sccm, keep the argon atmosphere in the tube furnace, set 90min to 800℃, and then 60min to 1010℃; after the temperature reaches 1010℃, close and open the oxygen valve, set the oxygen volume flow to 100sccm, keep the temperature for 120min .
3)以0.5℃/min的速度将温度升至1015℃，在升温的过程中，关闭氧气阀门，抽空残余氧气，打开氩气阀门，氩气体积流量设为100sccm，然后于1015℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到高结晶质量的氧化亚铜。3) Raise the temperature to 1015°C at a rate of 0.5°C/min. During the heating process, close the oxygen valve, evacuate the residual oxygen, open the argon valve, set the argon volume flow to 100sccm, and then keep it at 1015°C for 90min; Finally, under the protection of argon, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the quenching of the cuprous oxide, and then naturally cooled to room temperature to obtain cuprous oxide with high crystalline quality.
实施例5Example 5
提供一种高质量氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
1)将200μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将 两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；将纯铜箔置于微小反应空间内的下陶瓷片表面，如图1所示；上陶瓷片、下陶瓷片和2片支撑陶瓷片均为刚玉陶瓷片，上陶瓷片和下陶瓷片厚度为1mm，宽度为4cm，长度为12cm，支撑陶瓷片2厚度为0.5mm。1) Cut the 200μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for later use; construct a small reaction space by ceramic sheets, take the upper ceramic sheet and the lower ceramic sheet , The two supporting ceramic sheets are placed between the upper ceramic sheet and the lower ceramic sheet, and a small space is supported between the upper ceramic sheet and the lower ceramic sheet, which is the constructed small reaction space; the pure copper foil is placed in the small The surface of the lower ceramic sheet in the reaction space is shown in Figure 1. The upper ceramic sheet, the lower ceramic sheet and the two supporting ceramic sheets are all corundum ceramic sheets. The thickness of the upper and lower ceramic sheets is 1mm, the width is 4cm, and the length The thickness of the supporting ceramic sheet 2 is 0.5 mm.
2)将步骤1)通过陶瓷片构筑的微小反应空间结构及内部的纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为50sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1050℃；在温度到达1050℃之后，关闭氩气阀门，打开氧气阀门，氧气体积流量设为100sccm，保温120min。2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set to 50sccm, keep the argon atmosphere in the tube furnace, set the temperature to 800°C for 90 minutes, and then to 1050°C for 60 minutes; after the temperature reaches 1050°C, close the argon valve, open the oxygen valve, and set the oxygen volume flow rate to 100sccm, heat preservation for 120min.
3)以0.5℃/min的速度将温度升至1055℃，在升温的过程中，关闭氧气阀门，抽空残余氧气，打开氩气阀门，氩气体积流量设为50sccm，然后于1055℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到高结晶质量的氧化亚铜。3) Raise the temperature to 1055°C at a rate of 0.5°C/min. During the heating process, close the oxygen valve, evacuate the residual oxygen, open the argon valve, set the argon volume flow to 50sccm, and then keep it at 1055°C for 90min; Finally, under the protection of argon, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the quenching of the cuprous oxide, and then naturally cooled to room temperature to obtain cuprous oxide with high crystalline quality.
实施例6Example 6
提供一种高质量氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing high-quality cuprous oxide film is provided. The specific steps are as follows:
1)将200μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；将纯铜箔置于微小反应空间内的下陶瓷片表面，如图1所示；上陶瓷片、下陶瓷片和2片支撑陶瓷片均为刚玉陶瓷片，上陶瓷片和下陶瓷片厚度为1mm，宽度为4cm，长度为12cm，支撑陶瓷片厚度为0.5mm。1) Cut the 200μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for later use; construct a small reaction space by ceramic sheets, take the upper ceramic sheet and the lower ceramic sheet , The two supporting ceramic sheets are placed between the upper ceramic sheet and the lower ceramic sheet, and a small space is supported between the upper ceramic sheet and the lower ceramic sheet, which is the constructed small reaction space; the pure copper foil is placed in the small The surface of the lower ceramic sheet in the reaction space is shown in Figure 1. The upper ceramic sheet, the lower ceramic sheet and the two supporting ceramic sheets are all corundum ceramic sheets. The thickness of the upper and lower ceramic sheets is 1mm, the width is 4cm, and the length It is 12cm, and the thickness of the supporting ceramic sheet is 0.5mm.
2)将步骤1)通过陶瓷片构筑的微小反应空间结构及内部的纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为50sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1010℃；在温度到达1010℃之后，关闭氩气阀门，打开放气阀门，通入空气，保温120min。2) Put the small reaction space structure constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1), use a mechanical pump to extract the air in the tube furnace, and then open the argon valve, the argon volume flow rate Set it to 50sccm, keep the argon atmosphere in the tube furnace, set it to rise to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the vent valve, and breathe in air. Keep for 120min.
3)以0.5℃/min的速度将温度升至1015℃，在升温的过程中，关闭放气阀门，用机械泵抽出残余空气，再打开氩气阀门，氩气体积流量设为50sccm，然后于1015℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到高结晶质量的氧化亚铜。3) Raise the temperature to 1015°C at a rate of 0.5°C/min. During the heating process, close the vent valve, extract the residual air with a mechanical pump, and then open the argon valve. The argon volume flow is set to 50sccm, and then Keep the temperature at 1015°C for 90 minutes; finally, under the protection of argon, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the sudden cooling of cuprous oxide, and then naturally cooled to room temperature to obtain high crystalline quality oxide copper.
对比例1Comparative example 1
提供一种氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing a cuprous oxide film is provided, and the specific steps are as follows:
1)将200μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；将清洗后的纯铜箔直接放置于刚玉陶瓷片上，不采用构筑空间的方法；1) Cut the 200μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for later use; place the cleaned pure copper foil directly on the corundum ceramic sheet without using The method of constructing the space;
2)将上述刚玉陶瓷片与纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为50sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1010℃；在温度到达1010℃之后，关闭氩气阀门，打开氧气阀门，氧气体积流量设为100sccm，保温120min。2) Put the above corundum ceramic sheet and pure copper foil in a tube furnace, use a mechanical pump to extract the air in the tube furnace, then open the argon valve, set the argon volume flow to 50sccm, and keep the tube furnace In an argon atmosphere, set the temperature to 800°C for 90 minutes and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, set the oxygen volume flow rate to 100 sccm, and keep the temperature for 120 minutes.
3)以0.5℃/min的速度将温度升至1015℃，在升温的过程中，关闭氧气阀门，打开氩气阀门，氩气体积流量设为50sccm，然后于1015℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到氧化亚铜薄膜。3) Raise the temperature to 1015°C at a rate of 0.5°C/min. During the heating process, close the oxygen valve and open the argon valve. Under the protection of air, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the quenching of cuprous oxide, and then naturally cooled to room temperature to obtain a cuprous oxide film.
对比例2Comparative example 2
提供一种氧化亚铜薄膜的制备方法，具体步骤如下：A method for preparing a cuprous oxide film is provided, and the specific steps are as follows:
1)将200μm厚度纯铜箔裁剪为2cm*2cm大小，分别使用去离子水，丙酮，乙醇超声清洗10min，用氮气吹干备用；与对比例1不同的是，将清洗后的纯铜箔直接放置于石英片上，不采用构筑空间的方法；1) Cut the 200μm thick pure copper foil into a size of 2cm*2cm, use deionized water, acetone, and ethanol to clean ultrasonically for 10 minutes, and dry it with nitrogen for use; the difference from Comparative Example 1 is that the cleaned pure copper foil is directly Placed on a quartz plate, without using the method of constructing space;
2)将上述石英片与纯铜箔一起置于管式炉中，用机械泵抽出管式炉中的空气，然后打开氩气阀门，氩气体积流量设为50sccm，保持管式炉内为氩气氛围，设定90min升至800℃，再60min升至1010℃；在温度到达1010℃之后，关闭氩气阀门，打开氧气阀门，氧气体积流量设为100sccm，保温120min；2) Put the above quartz plate and pure copper foil together in a tube furnace, use a mechanical pump to extract the air in the tube furnace, then open the argon valve, set the argon volume flow to 50sccm, and keep the tube furnace filled with argon Atmosphere, set the temperature to 800°C for 90 minutes, and then to 1010°C for 60 minutes; after the temperature reaches 1010°C, close the argon valve, open the oxygen valve, set the oxygen volume flow rate to 100sccm, and keep the temperature for 120min;
3)以0.5℃/min的速度将温度升至1015℃，在升温的过程中，关闭氧气阀门，打开氩气阀门，氩气体积流量设为50sccm，然后于1015℃保温90min；最后，在氩气的保护下，以5℃/min的速度降温至500℃，防止氧化亚铜骤冷导致的应力破碎，然后自然冷却至室温，得到氧化亚铜薄膜。3) Raise the temperature to 1015°C at a rate of 0.5°C/min. During the heating process, close the oxygen valve and open the argon valve. Under the protection of air, the temperature is lowered to 500°C at a rate of 5°C/min to prevent stress breakage caused by the quenching of cuprous oxide, and then naturally cooled to room temperature to obtain a cuprous oxide film.
分析实施例1-6和对比例1-2的测试结果如下：The test results of analysis examples 1-6 and comparative examples 1-2 are as follows:
图2为实施例1-2和6与对比例1-2中不同工艺时制备得到的氧化亚铜的扫描电镜图，其中，(a)和(b)实施例1，(c)实施例2，(d)实施例6，(e)对比例2，(f)对比例1。如图(a)和(b)(实施例1)所示，使用刚玉陶瓷衬底构筑空间的方法制备得到的氧化亚铜薄膜具有较大的晶粒，且表面非常平整，图2b中可以看到晶粒大小达到了1.5mm，氧化亚铜尺寸可达至毫米级。图c(实施例2)和图d(实施例6)分别为使用氧化锆陶瓷构筑空间方法和使 用空气作为氧源制备得到的氧化亚铜，其结晶质量同样较高。但当我们不使用空间构筑的方法，如图e(对比例2)和图f(对比例1)，无论衬底是石英片还是刚玉坩埚，结晶质量均不如前面的结果。Figure 2 is a scanning electron micrograph of cuprous oxide prepared in different processes in Examples 1-2 and 6 and Comparative Example 1-2, in which (a) and (b) Example 1, (c) Example 2 , (D) Example 6, (e) Comparative Example 2, (f) Comparative Example 1. As shown in Figures (a) and (b) (Example 1), the cuprous oxide film prepared by using a corundum ceramic substrate to build a space has large crystal grains and a very flat surface, as can be seen in Figure 2b By the time the grain size has reached 1.5mm, the size of the cuprous oxide can reach the millimeter level. Figure c (Example 2) and Figure d (Example 6) respectively show the use of zirconia ceramics to construct the space and the use of air as an oxygen source to prepare cuprous oxide. The crystal quality is also relatively high. But when we do not use the space construction method, as shown in Figure e (Comparative Example 2) and Figure f (Comparative Example 1), no matter whether the substrate is a quartz plate or a corundum crucible, the crystal quality is not as good as the previous results.
图3为实施例1-2中不同陶瓷片为衬底时制备得到的氧化亚铜的X射线衍射图，其中，(a)实施例1刚玉衬底，(b)实施例2氧化锆衬底。图中显示，实施例1与实施例2均能制备出纯相的氧化亚铜，且主要沿(110)和(220)晶面取向生长。Figure 3 is an X-ray diffraction pattern of cuprous oxide prepared when different ceramic sheets are used as substrates in Example 1-2, in which (a) Example 1 corundum substrate, (b) Example 2 zirconia substrate . The figure shows that both Example 1 and Example 2 can prepare pure phase cuprous oxide, and it mainly grows along the (110) and (220) crystal plane orientations.
图4为纯铜箔源厚度为100μm(实施例3)和200μm(实施例1)时用空间构筑法制备得到氧化亚铜的光学显微镜照片，放大倍率均为10倍，其中(a)100μm正面，(b)100μm截面，(c)200μm正面，(d)200μm截面。图中显示：当纯铜箔厚度为100μm时，制备得到的氧化亚铜晶粒要小于厚度为200μm，但是从截面图可以看到，整个氧化亚铜晶体贯穿整个厚度，这对于在电池方面的应用是一个优势。Figure 4 is an optical micrograph of the cuprous oxide prepared by the space construction method when the thickness of the pure copper foil source is 100μm (Example 3) and 200μm (Example 1), the magnification is both 10 times, of which (a) 100μm front , (B) 100μm cross-section, (c) 200μm front side, (d) 200μm cross-section. The figure shows that when the thickness of the pure copper foil is 100μm, the prepared cuprous oxide crystal grains are smaller than the thickness of 200μm. However, it can be seen from the cross-sectional view that the entire cuprous oxide crystal penetrates the entire thickness. Application is an advantage.
图5为实施例1中空间构筑法制备得到的氧化亚铜的(a)紫外可见吸收光谱图和(b)Taut-Plot图。图中显示，本实施例1制备得到的Cu 2O带隙较小，为1.91eV，更适合作为吸光层材料用于太阳能电池领域。 Fig. 5 shows (a) the ultraviolet-visible absorption spectrum and (b) the Taut-Plot diagram of the cuprous oxide prepared by the space structuring method in Example 1. The figure shows that the Cu 2 O prepared in Example 1 has a relatively small band gap of 1.91 eV, and is more suitable for use as a light-absorbing layer material in the field of solar cells.
表1为实施例1和3及对比例1制备得到的氧化亚铜的霍尔测试的结果，表中显示，实施例1中得到的氧化亚铜载流子迁移率可达72cm 2/V·s，与对比例1采用一般方法得到的氧化亚铜相比，提升了一倍左右，电学性质非常优异。 Table 1 shows the results of the Hall test of the cuprous oxide prepared in Examples 1 and 3 and Comparative Example 1. The table shows that the carrier mobility of the cuprous oxide obtained in Example 1 can reach 72 cm 2 /V· s. Compared with the cuprous oxide obtained by the general method in Comparative Example 1, it is doubled, and the electrical properties are very excellent.
表1实施例1和3及对比例1制备得到的氧化亚铜的霍尔测试的结果Table 1 The results of the Hall test of the cuprous oxide prepared in Examples 1 and 3 and Comparative Example 1
Figure PCTCN2021073525-appb-000001
Figure PCTCN2021073525-appb-000001
综上所述，本发明通过使用平整的陶瓷片作为纯铜箔的上下表面覆盖物，限制氧化亚铜在狭小的空间反应、结晶、生长，从而使得氧化亚铜在氧化结晶的过程中有更为稳定的环境，从而按一定取向生长出较大的晶粒。所述制备方法简单可控，重复性强，制备得到的材料拥有良好的结构性能和电学性能，适用于制备太阳能电池。In summary, the present invention uses flat ceramic sheets as the upper and lower surface coverings of pure copper foil to limit the reaction, crystallization, and growth of cuprous oxide in a small space, so that the cuprous oxide has a better effect in the process of oxidation and crystallization. For a stable environment, larger crystal grains are grown in a certain orientation. The preparation method is simple and controllable, has strong repeatability, and the prepared material has good structural properties and electrical properties, and is suitable for preparing solar cells.
应当理解的是，本发明的应用不限于上述的实例，对本领域普通技术人员来说，可以根据上述说明加以改进或者变换，所有这些改进和变换都应属于本发明权利要求的保护范围。It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or changes can be made based on the above description, and all these improvements and changes should fall within the protection scope of the claims of the present invention.

Claims (8)

  1. 一种高质量氧化亚铜薄膜的制备方法，其特征在于，通过陶瓷片构筑微小反应空间，以纯铜箔为铜源，氧气或者空气作为反应气源采用热氧化法制备得到高质量氧化亚铜薄膜；其中：A method for preparing high-quality cuprous oxide film, which is characterized in that a small reaction space is constructed by ceramic sheets, pure copper foil is used as a copper source, oxygen or air is used as a reactive gas source, and a high-quality cuprous oxide film is prepared by thermal oxidation. ;in:
    微小反应空间的构筑方法为：取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于所述上陶瓷片和所述下陶瓷片之间，在所述上陶瓷片和所述下陶瓷片之间撑起微小空间，即为构筑的微小反应空间；The method for constructing the small reaction space is: take the upper ceramic sheet and the lower ceramic sheet, and place the two supporting ceramic sheets between the upper ceramic sheet and the lower ceramic sheet, respectively, between the upper ceramic sheet and the lower ceramic sheet. The small space between the ceramic pieces is the small reaction space constructed;
    所述纯铜箔置于构筑得到的所述微小反应空间内的所述下陶瓷片表面；The pure copper foil is placed on the surface of the lower ceramic sheet in the small reaction space obtained by the structure;
    所述支撑陶瓷片厚度为0.1-1mm，所述纯铜箔厚度为0.05-0.2mm，所述支撑陶瓷片厚度至少是所述纯铜箔厚度的1.5倍。The thickness of the supporting ceramic sheet is 0.1-1 mm, the thickness of the pure copper foil is 0.05-0.2 mm, and the thickness of the supporting ceramic sheet is at least 1.5 times the thickness of the pure copper foil.
  2. 根据权利要求1所述的制备方法，其特征在于，包括如下步骤：The preparation method according to claim 1, characterized in that it comprises the following steps:
    1)通过陶瓷片构筑微小反应空间，取上陶瓷片和下陶瓷片，将两片支撑陶瓷片分别置于上陶瓷片和下陶瓷片之间，在上陶瓷片和下陶瓷片之间撑起微小空间，然后将纯铜箔置于构筑得到的所述微小反应空间内的下陶瓷片表面；1) Construct a small reaction space by ceramic sheets, take the upper ceramic sheet and the lower ceramic sheet, and place the two supporting ceramic sheets between the upper ceramic sheet and the lower ceramic sheet, and prop up between the upper ceramic sheet and the lower ceramic sheet. A small space, and then pure copper foil is placed on the surface of the lower ceramic sheet in the constructed small reaction space;
    2)将步骤1)通过陶瓷片构筑的微小反应空间及内部的纯铜箔一起置于管式炉中，在惰性气体氛围中，升至800-850℃，降低升温速率继续升至1010-1050℃，然后将惰性气体氛围置换成氧气或空气氛围，保温60-180min进行热氧化反应，Cu生成Cu 2O； 2) Put the small reaction space constructed by the ceramic sheet and the pure copper foil inside the tube furnace together in step 1). In an inert gas atmosphere, raise it to 800-850℃, reduce the heating rate and continue to rise to 1010-1050 ℃, then replace the inert gas atmosphere with oxygen or air atmosphere, keep for 60-180min for thermal oxidation reaction, Cu generates Cu 2 O;
    3)在步骤2)热氧化反应结束后将氧气或空气氛围置换成氩气氛围，继续保温一段时间后降温至500-600℃，自然冷却至室温，即得高结晶质量的氧化亚铜薄膜。3) After the step 2) the thermal oxidation reaction is completed, the oxygen or air atmosphere is replaced with an argon atmosphere, the temperature is kept for a period of time and then cooled to 500-600°C, and naturally cooled to room temperature, to obtain a cuprous oxide film with high crystalline quality.
  3. 根据权利要求2所述的制备方法，其特征在于，所述步骤2)中，800-850℃之前升温速率应控制在6-10℃/min，800-850℃之后控制在6℃/min之内。The preparation method according to claim 2, characterized in that, in the step 2), the heating rate before 800-850°C should be controlled at 6-10°C/min, and after 800-850°C, it should be controlled at 6°C/min. Inside.
  4. 根据权利要求2所述的制备方法，其特征在于，所述步骤2)中，氧气的体积流量为100-200sccm。The preparation method according to claim 2, wherein in the step 2), the volume flow rate of oxygen is 100-200 sccm.
  5. 根据权利要求2所述的制备方法，其特征在于，所述步骤3)中，将氧气或空气氛围置换成氩气氛围后继续保温60-180min，然后以3-5℃/min的速度降温至500-600℃。The preparation method according to claim 2, characterized in that, in the step 3), the oxygen or air atmosphere is replaced with an argon atmosphere, and then the temperature is kept for 60-180 minutes, and then the temperature is reduced to a temperature of 3-5°C/min. 500-600°C.
  6. 根据权利要求2所述的制备方法，其特征在于，所述步骤3)中，热氧化反应结束后，在热氧化反应温度基础上继续上升5-10℃，在升温过程中，将氧 气或空气氛围置换成氩气氛围。The preparation method according to claim 2, characterized in that, in the step 3), after the thermal oxidation reaction is completed, the temperature of the thermal oxidation reaction is continued to rise by 5-10°C, and during the heating process, oxygen or air The atmosphere is replaced with an argon atmosphere.
  7. 根据权利要求2所述的制备方法，其特征在于，所述步骤3)中，所述惰性气体为氩气或氮气，体积流量为50-100sccm。The preparation method according to claim 2, wherein in the step 3), the inert gas is argon or nitrogen, and the volume flow rate is 50-100 sccm.
  8. 根据权利要求1或2所述的制备方法，其特征在于，所述陶瓷片为刚玉、氧化锆或氮化铝，其中上陶瓷片和下陶瓷片材质相同，上陶瓷片和下陶瓷片与支撑陶瓷片的材质可相同也可不同。The preparation method according to claim 1 or 2, wherein the ceramic sheet is corundum, zirconia or aluminum nitride, wherein the material of the upper ceramic sheet and the lower ceramic sheet are the same, and the upper ceramic sheet and the lower ceramic sheet are compatible with the support The material of the ceramic sheet can be the same or different.
PCT/CN2021/073525 2020-06-22 2021-01-25 Preparation method for pure phase cuprous oxide thin film having high crystalline quality WO2021258728A1 (en)

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