阅读说明：本技术 自支撑微纳结构TiO2薄膜及染料敏化太阳能电池制备方法 (Self-supporting micro-nano structure TiO2Thin film and preparation method of dye-sensitized solar cell ) 是由 张燕 于 2020-07-15 设计创作，主要内容包括：本发明公开了太阳能电池自支撑微纳结构TiO<Sub>2</Sub>薄膜的制备方法,包括以下步骤：(1)在衬底表面旋涂聚甲基丙烯酸甲酯溶液,在烘干箱内干燥,形成聚甲基丙烯酸甲酯薄膜；重复上述步骤1-2次。(2)将衬底置于射频磁控溅射镀膜设备的基座上,将锐钛矿型TiO<Sub>2</Sub>靶材、金红石型TiO<Sub>2</Sub>靶材相对安装在靶位上,对真空室抽真空,通入Ar、同时开启两个靶材电源,室温下溅射。(3)关闭电源以及Ar,取出衬底,在衬底表面获得微纳结构TiO<Sub>2</Sub>薄膜。(4)将衬底放入至丙酮中浸泡,从而将衬底与微纳结构TiO<Sub>2</Sub>薄膜分离,取出自支撑微纳结构TiO<Sub>2</Sub>薄膜。本发明公开了太阳能电池自支撑微纳结构TiO<Sub>2</Sub>薄膜制备的染料敏化太阳能电池。能够制备获得低粗糙度、微纳结构的TiO<Sub>2</Sub>薄膜,可以有效提高光电转化效率。(The invention discloses a self-supporting micro-nano structure TiO of a solar cell 2 The preparation method of the film comprises the following steps: (1) spin-coating a polymethyl methacrylate solution on the surface of the substrate, and drying in a drying oven to form a polymethyl methacrylate film; repeating the above steps 1-2 times. (2) Placing the substrate on a base of a radio frequency magnetron sputtering coating device, and adding anatase TiO 2 Target material and rutile type TiO 2 The target material is relatively arranged on the target position, the vacuum chamber is vacuumized, Ar is introduced, two target material power supplies are simultaneously started, and sputtering is carried out at room temperature. (3) Turning off the power supply and Ar, taking out the substrate, and obtaining the micro-nano structure TiO on the surface of the substrate 2 A film. (4) Soaking the substrate in acetone to ensure that the substrate and the micro-nano structure TiO are soaked 2 The separation of the thin film is carried out,taking out self-supporting micro-nano structure TiO 2 A film. The invention discloses a self-supporting micro-nano structure TiO of a solar cell 2 And (3) preparing the dye-sensitized solar cell by using the film. Can prepare TiO with low roughness and micro-nano structure 2 The film can effectively improve the photoelectric conversion efficiency.)

1. Self-supporting micro-nano structure TiO₂The preparation method of the film is characterized by comprising the following steps:

(1) spin-coating 5-10mg/mL polymethyl methacrylate solution on the surface of the substrate, drying for 5-10 minutes at 70-80 ℃ in a drying oven, and cooling to room temperature to form a polymethyl methacrylate film; repeating the steps for 1-2 times;

(2) placing the substrate on a base of a radio frequency magnetron sputtering coating device, and adding anatase TiO₂Target material and rutile type TiO₂The target material is relatively arranged on the target position, and the vacuum chamber is vacuumized to 1-5 multiplied by 10^-4Pa, introducing Ar while opening anatase type TiO₂Target material and rutile type TiO₂Sputtering the target material with a power supply at room temperature;

(3) turning off the power supply and Ar, taking out the substrate, and obtaining the micro-nano structure TiO on the surface of the substrate₂A film;

(4) putting the substrate into acetone for soaking, and dissolving the polymethyl methacrylate film, thereby putting the substrate and the micro-nano structure TiO₂Separating the film, taking out and obtaining the self-supporting micro-nano structure TiO of the solar cell₂A film.

2. The self-supporting micro-nano structure TiO according to claim 1₂The preparation method of the thin film is characterized in that the substrate is p-type single crystal Si or sapphire.

3. Self-supporting micro-nano structured TiO according to any one of claims 1 to 2₂The preparation method of the film is characterized in that the process parameters of the step (2) are as follows: ar flow rate of 100-₂Target power 600-₂The target material is 150-.

4. Self-supporting micro-nano structured TiO according to any one of claims 1 to 2₂The method for producing a film is characterized by further comprising the step (5): making self-supporting micro-nano structure TiO₂Placing the film in deionized water, ultrasonically cleaning for 2-5min, taking out, and drying at 40-60 deg.C for 5-10 min.

5. Self-supporting micro-nano structured TiO according to any one of claims 1 to 2₂The preparation method of the film is characterized in that the self-supporting micro-nano structure TiO₂The thickness of the film is 5-10 μm.

6. Self-supporting micro-nano structured TiO according to any one of claims 1 to 2₂A method for producing a thin film, characterized in that,the self-supporting micro-nano structure TiO₂The film is made of 80-90wt.% anatase TiO₂

And 10-20wt.% rutile TiO₂And (4) forming.

7. Self-supporting micro-nano structured TiO according to any one of claims 1 to 2₂The preparation method of the film is characterized in that the self-supporting micro-nano structure TiO₂The roughness Ra of the surface of the film contacting the polymethyl methacrylate film is 300-400 nm.

8. Self-supporting micro-nano structure TiO₂The dye-sensitized solar cell prepared from the film is characterized in that the solar self-supporting micro-nano structure TiO₂The film is prepared by the method of any one of claims 1 to 7.

9. The self-supporting micro-nano structure TiO according to claim 8₂The dye-sensitized solar cell prepared from the thin film is characterized in that the short-circuit current density (Jsc) of the dye-sensitized solar cell is 15-17mA/cm²The open-circuit voltage (Voc) is 0.65-0.75V, the Fill Factor (FF) is 67-70%, and the photoelectric conversion efficiency (eta) is 9-12%.

Technical Field

The invention relates to the field of solar cells, in particular to a self-supporting micro-nano structure TiO₂A film and a method for preparing a dye-sensitized solar cell.

Background

The dye-sensitized solar cell has high performanceSpecific surface area and photoelectric conversion rate, simple manufacturing process, stability, long service life and the like, and TiO₂Is a semiconductor thin film with relatively high conversion efficiency, and the research on the semiconductor thin film has made a certain technical breakthrough in recent years.

Chinese patent CN101857966A discloses a self-supporting Ti0₂A nanotube array film made by the method of: a) performing primary anodic oxidation on the titanium foil to form Ti0 on the titanium foil₂A nanotube array film; b) then annealing and crystallizing the titanium foil obtained by the step a); c) performing secondary anodic oxidation on the treated titanium foil to obtain titanium foil and Ti0₂An amorphous oxide layer with a certain thickness is formed between the nanotube array films: d) finally, stripping the Ti02 nanotube array film from the amorphous oxide layer. Chinese patent CN109136831A, the mass thickness of which is 700-²The preparation method of the self-supporting germanium film comprises the following steps: (1) depositing a sodium chloride release agent on the surface of the substrate; (2) depositing an alumina buffer film on the surface of the substrate by adopting a 90-degree magnetic Filtration Cathode Vacuum Arc (FCVA) system; (3) rotating the sample by 180 degrees, and depositing the germanium film again by using a straight tube magnetic Filtration Cathode Vacuum Arc (FCVA) system; (4) placing the obtained substrate into a container containing ethanol solution for demoulding treatment; (5) fishing out the germanium film by using a fishing plate to obtain the germanium film with the mass thickness of 700-²A self-supporting germanium film. By preparing alumina as a buffer layer between the germanium film and the substrate, the self-supporting germanium film can be prevented from cracking due to the release of residual stress in the demolding process.

The surface morphology of the substrate or the release agent can be replicated by the self-supporting film, the performance of the self-supporting film can be influenced by the roughness of the self-supporting film, and how to prepare the self-supporting film with low roughness is also a bottleneck in the technical field. Self-supporting TiO₂The application of the film in solar cells is much less studied, as for self-supporting TiO₂The structure and roughness of the film are not used for reference on the performance of the solar cell.

Disclosure of Invention

The invention aims to provide a method for solving the defects in the prior artSelf-supporting micro-nano structure TiO of solar cell₂Preparation method of film and dye-sensitized cell, and TiO with low roughness and micro-nano structure can be prepared₂The film can effectively improve the photoelectric conversion efficiency.

In order to solve the problems in the prior art, one of the technical schemes provided by the invention is as follows: self-supporting micro-nano structure TiO of solar cell₂The preparation method of the film comprises the following steps:

(1) spin-coating 5-10mg/mL polymethyl methacrylate solution on the surface of the substrate, drying for 5-10 minutes at 70-80 ℃ in a drying oven, and cooling to room temperature to form a polymethyl methacrylate film; repeating the above steps 1-2 times.

(2) Placing the substrate on a base of a radio frequency magnetron sputtering coating device, and adding anatase TiO₂Target material and rutile type TiO₂The target material is relatively arranged on the target position, and the vacuum chamber is vacuumized to 1-5 multiplied by 10^-4Pa, introducing Ar while opening anatase type TiO₂Target material and rutile type TiO₂And (4) sputtering the target material at room temperature by using a power supply.

(3) Turning off the power supply and Ar, taking out the substrate, and obtaining the micro-nano structure TiO on the surface of the substrate₂A film.

(4) Putting the substrate into acetone for soaking, and dissolving the polymethyl methacrylate film, thereby putting the substrate and the micro-nano structure TiO₂Separating the film, taking out and obtaining the self-supporting micro-nano structure TiO of the solar cell₂A film.

Further, the substrate is p-type single crystal Si or sapphire.

Further, the process parameters of the step (2) are as follows: ar flow rate of 100-₂Target power 600-₂The target material is 150-.

Further, the method also comprises the step (5): self-supporting micro-nano structure TiO of solar cell₂Placing the film in deionized water, ultrasonically cleaning for 2-5min, taking out, and drying at 40-60 deg.C for 5-10 min.

Further, the solar cell is self-supportingTiO with micro-nano structure₂The thickness of the film is 5-10 μm.

Further, the solar cell is self-supporting and micro-nano TiO structure₂The film is made of 80-90wt.% anatase TiO₂And 10-20wt.% rutile TiO₂And (4) forming.

Further, the solar cell is self-supporting and micro-nano TiO structure₂The surface of the film in contact with the polymethyl methacrylate film (hereinafter referred to as the surface in contact with PMMA) had a roughness Ra of 300-400 nm.

The second technical scheme provided by the invention is as follows: self-supporting micro-nano structure TiO of solar cell₂Dye-sensitized solar cell prepared from thin film and solar self-supporting micro-nano structure TiO₂The films were prepared by the above method.

Further, the short-circuit current density (Jsc) of the dye-sensitized solar cell is 15-17mA/cm²The open-circuit voltage (Voc) is 0.65-0.75V, the Fill Factor (FF) is 67-70%, and the photoelectric conversion efficiency (eta) is 9-12%.

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

(1) in the prior art, copper foil and sodium chloride are generally adopted as release agents, and the surface roughness of the self-supporting film can be reduced by spin coating the polymethyl methacrylate film, wherein the surface roughness Ra is 300-400 nm.

(2) The Applicant has found that TiO in the anatase or rutile form alone₂The electrochemical performance of the dye-sensitized solar cell composed of the film is not as good as that of anatase or rutile mixed crystal TiO₂Thin film, so the present invention uses anatase type TiO₂Target material and rutile type TiO₂Preparing self-supporting micro-nano structure TiO of anatase type and rutile type mixed crystal type by co-sputtering target material at room temperature₂The film avoids the melting of polymethyl methacrylate at high temperature, and on the other hand, avoids the self-supporting micro-nano structure TiO₂Stress warping and cracking of the film caused by subsequent high temperature heat treatment of the film.

(3) The dye-sensitized solar cell prepared by the method has excellent electrochemical performance.

Drawings

FIG. 1 shows a self-supporting micro-nano structure TiO prepared by the embodiment of the invention₂Scanning electron micrographs of both surfaces of the film.

FIG. 2 shows a self-supporting micro-nano structure TiO prepared by the embodiment of the invention₂X-ray diffraction patterns of both surfaces of the film.

Fig. 3 is a J-V curve of a dye-sensitized solar cell prepared according to an embodiment of the present invention.

Detailed Description

The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.