阅读说明：本技术 一种太阳能电池吸收层及其制备方法以及应用 (A kind of solar battery obsorbing layer and preparation method thereof and application ) 是由 高迪 陈涛 朱长飞 江国顺 于 2019-09-02 设计创作，主要内容包括：本发明提供了一种太阳能电池吸收层的制备方法,包括以下步骤：A)将酒石酸锑钾、硫代硫酸钠和硒代硫酸钠与水混合,得到沉积液；B)所述沉积液在衬底表面进行水热反应,得到复合于衬底表面的硫硒化锑薄膜；C)在惰性气体环境下将得到的硫硒化锑薄膜进行退火处理,得到太阳能电池吸收层。本发明使用水热法直接沉积出硫硒化锑薄膜,无需后续硒化,解决了溶液法大多需要后续硒化的问题。通过改变沉积液中硫代硫酸钠和硒代硫酸钠的浓度,可以方便地调节薄膜的带隙,得到带隙可调的硫硒化锑薄膜。与其他方法相比,本发明制备设备和工艺简单、薄膜结晶性好、薄膜成分和厚度容易控制,且薄膜的均匀性良好。(The present invention provides a kind of preparation methods of solar battery obsorbing layer, comprising the following steps: A) potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water, obtain deposition liquid；B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery obsorbing layer.The present invention goes out sulphur selenizing Sb film using hydro-thermal method Direct precipitation, is not necessarily to subsequent selenizing, solves the problems, such as that solwution method needs subsequent selenizing mostly.By changing the concentration of sodium thiosulfate and sodium thiosulfate in deposition liquid, adjusts the band gap of film with can be convenient, obtain the adjustable sulphur selenizing Sb film of band gap.It is compared with other methods, Preparation equipment of the present invention and simple process, crystalline property be good, thin film composition and thickness are easy to control, and film has good uniformity.)

1. a kind of preparation method of solar battery obsorbing layer, which comprises the following steps:

A potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water), obtain deposition liquid；

B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；

C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery obsorbing layer.

2. preparation method according to claim 1, which is characterized in that step A) specifically:

Potassium antimony tartrate and sodium thiosulfate are dissolved in water, obtain mixed solution；

Sodium thiosulfate aqueous solution is added into the mixed solution, obtains depositing liquid needed for deposition sulphur selenizing Sb film.

3. preparation method according to claim 2, which is characterized in that the sodium thiosulfate aqueous solution is molten by sodium sulfite Liquid and selenium powder flow back at 90~98 DEG C to be obtained；

The concentration of the sodium thiosulfate aqueous solution is 0.1M~0.4M.

4. preparation method according to claim 1, which is characterized in that it is described deposition liquid mesotartaric acid antimony potassium concentration be 0.015~0.04M, concentration of sodium thiosulfate are 0.06~0.16M, and the concentration of sodium thiosulfate is 0.00025~0.002M.

5. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 110~180 DEG C, Time is 1~5h.

6. preparation method according to claim 1, which is characterized in that the substrate is selected from FTO, transparent electro-conductive glass One of；The substrate surface is also deposited with CdS film.

7. preparation method according to claim 1, which is characterized in that the temperature of the annealing is 300~380 DEG C, annealing Time be 5~30min.

8. a kind of solar battery obsorbing layer that the preparation method as described in claim 1~7 any one is prepared, special Sign is, chemical formula Sb₂(S_xSe_1-x)₃, wherein 0 < x < 1.

9. a kind of solar battery, which is characterized in that including the preparation method preparation as described in claim 1~7 any one Obtained solar battery obsorbing layer.

Technical field

The invention belongs to technical field of solar batteries, and in particular to a kind of solar battery obsorbing layer and preparation method thereof And application.

Background technique

As a kind of inorganic light absorbing material, it is more and more that the application of sulphur antimony selenide in solar cells causes people Concern.The storage of element contained by this kind of material is very rich, nontoxic, has biggish absorption coefficient (≈ 10⁵cm^-1) and suitable light It learns band gap (1.03~1.8eV).Particular, it is important that the compound has good water, oxidative stability.Due to antimony trisulfide and selenium Change antimony crystal structure having the same, the flexible tune of material band gap can be realized by adjusting the ratio of two kinds of elements of sulphur and selenium Section, to obtain the light absorbing material with perfect optics band gap.Therefore, this kind of material has huge application prospect.

Currently, the method for preparing antimony trisulfide and selenizing Sb film mainly has vacuum method and solwution method.Vacuum method is to equipment More demanding, obtained film composition may be uneven.Traditional solwution method is easy to operate, but crystalline property is poor, and big Need subsequent selenizing, it is difficult to which a step prepares sulphur selenizing Sb film, complex process more.

Summary of the invention

In view of this, the technical problem to be solved in the present invention is that providing a kind of solar battery obsorbing layer and its preparation side Method and application, the present invention prepare sulphur selenizing Sb film using one step of hydro-thermal method, have Preparation equipment and simple process, film The advantages that good crystallinity, thin film composition and thickness are easy to control.

The present invention provides a kind of preparation methods of solar battery obsorbing layer, comprising the following steps:

A potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water), obtain deposition liquid；

B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；

C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery absorption Layer.

Preferably, step A) specifically:

Potassium antimony tartrate and sodium thiosulfate are dissolved in water, obtain mixed solution；

Sodium thiosulfate aqueous solution is added into the mixed solution, obtains depositing liquid needed for deposition sulphur selenizing Sb film.

Preferably, the sodium thiosulfate aqueous solution is flowed back at 90~98 DEG C by sodium sulfite solution and selenium powder and is obtained；

The concentration of the sodium thiosulfate aqueous solution is 0.1M~0.4M.

Preferably, the concentration of the deposition liquid mesotartaric acid antimony potassium is 0.015~0.04M, and concentration of sodium thiosulfate is 0.06~0.16M, the concentration of sodium thiosulfate are 0.00025~0.002M.

Preferably, the temperature of the hydro-thermal reaction is 110~180 DEG C, and the time is 1~5h.

Preferably, the substrate is selected from one of FTO, transparent electro-conductive glass；The substrate surface is also deposited with CdS film.

Preferably, the temperature of the annealing is 300~380 DEG C, and the time of annealing is 5~30min.

The present invention also provides a kind of solar battery obsorbing layer that above-mentioned preparation method is prepared, chemical formula Sb₂ (S_xSe_1-x)₃, wherein 0 < x < 1.

The present invention also provides a kind of solar batteries, absorb including the solar battery that above-mentioned preparation method is prepared Layer.

Compared with prior art, the present invention provides a kind of preparation methods of solar battery obsorbing layer, including following step It is rapid: A) potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water, obtain deposition liquid；B) the deposition liquid is serving as a contrast Bottom surface carries out hydro-thermal reaction, obtains the sulphur selenizing Sb film for being compound in substrate surface；C it) will obtain in an inert atmosphere Sulphur selenizing Sb film made annealing treatment, obtain solar battery obsorbing layer.The present invention goes out sulphur using hydro-thermal method Direct precipitation Selenizing Sb film is not necessarily to subsequent selenizing, solves the problems, such as that solwution method needs subsequent selenizing mostly.By changing sulphur in deposition liquid The concentration of sodium thiosulfate and sodium thiosulfate adjusts the band gap of film in which can be convenient, and it is thin to obtain the adjustable sulphur antimony selenide of band gap Film.It is compared with other methods, Preparation equipment of the present invention and simple process, crystalline property be good, thin film composition and thickness are easy control System, and film has good uniformity.

Detailed description of the invention

Fig. 1 is the uv-visible absorption spectra of sulphur selenizing Sb film and the forbidden bandwidth of fitting in embodiment 1；

Fig. 2 is the scanning electron microscope diagram piece of sulphur selenizing Sb film in embodiment 1；

Fig. 3 is the XRD spectrum of sulphur selenizing Sb film in embodiment 1；

Fig. 4 is the uv-visible absorption spectra of sulphur selenizing Sb film and the forbidden bandwidth of fitting in embodiment 2；

Fig. 5 is the scanning electron microscope diagram piece of sulphur selenizing Sb film in embodiment 2；

Fig. 6 is the XRD spectrum of sulphur selenizing Sb film in embodiment 2；

Fig. 7 is the uv-visible absorption spectra of sulphur selenizing Sb film and the forbidden bandwidth of fitting in embodiment 3；

Fig. 8 is the scanning electron microscope diagram piece of sulphur selenizing Sb film in embodiment 3；

Fig. 9 is the XRD spectrum of sulphur selenizing Sb film in embodiment 3；

Figure 10 is the corresponding profile scanning electron microscope of embodiment 4；

Figure 11 is the corresponding profile scanning electron microscope of embodiment 5.

Specific embodiment

The present invention provides a kind of preparation methods of solar battery obsorbing layer, comprising the following steps:

A potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water), obtain deposition liquid；

B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；

C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery absorption Layer.

The method comprises the steps of firstly, preparing deposition liquid to obtain mixing molten specifically, potassium antimony tartrate and sodium thiosulfate are dissolved in water Liquid；

Sodium thiosulfate aqueous solution is added into the mixed solution, obtains depositing liquid needed for deposition sulphur selenizing Sb film.

The sodium thiosulfate aqueous solution is flowed back at 90~98 DEG C by sodium sulfite solution and selenium powder and is obtained；

The concentration of the sodium thiosulfate aqueous solution is 0.1~0.4M, preferably 0.2~0.3M.

In the deposition liquid, the concentration of potassium antimony tartrate is 0.015~0.04M, preferably 0.02~0.035M；It is thio Sodium sulfate concentration is 0.06~0.16M, and preferably 0.08~0.13M, the concentration of sodium thiosulfate is 0.00025~0.002M, Preferably 0.001~0.0015M.

Then, the deposition liquid carries out hydro-thermal reaction in substrate surface, and the sulphur antimony selenide for obtaining being compound in substrate surface is thin Film.

The substrate is selected from one of FTO, transparent electro-conductive glass；The substrate surface is also deposited with CdS film.

Specifically, first carrying out pre-treatment to substrate, wherein the substrate is one of FTO, transparent electro-conductive glass.

Substrate ultrapure water, ethyl alcohol, isopropanol, acetone are successively cleaned by ultrasonic 10~60min, oxygen plasma cleaning 10 ~30min.

Then in substrate surface CdS thin films.

Then, the deposition liquid is poured into hydrothermal reaction kettle, the substrate for being deposited with CdS film is put into hydrothermal reaction kettle In, control temperature is at 110~180 DEG C, and preferably 120~160 DEG C；Time is 1~5h, preferably 2~4h, obtains sulphur antimony selenide Film.It carries out in hydrothermal reaction process, substrate is completely immersed in deposition liquid, and the angle of substrate surface and deposition liquid level is 0~90 Degree.Substrate is horizontally or diagonally or to be disposed vertically in hydrothermal reaction kettle.

Then, substrate is taken out with being dried with nitrogen.

Obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery absorption Layer.

The inert gas environment is preferably nitrogen or argon gas.

The temperature of the annealing is 300~380 DEG C, and preferably 340~360 DEG C, the time of annealing is 5~30min, preferably For 10~20min.

The annealing is selected from heating plate annealing or tube annealing.

The present invention also provides a kind of solar battery obsorbing layer that above-mentioned preparation method is prepared, chemical formula Sb₂ (S_xSe_1-x)₃, wherein 0 < x < 1.

The present invention also provides a kind of solar batteries, absorb including the solar battery that above-mentioned preparation method is prepared Layer.The present invention is not particularly limited the structure and preparation method of solar battery, and well known to a person skilled in the art the sun It can battery structure and preparation method.

The principle of the present invention is:

It 1) the use of potassium antimony tartrate is antimony source, sodium thiosulfate is sulphur source, and sodium thiosulfate is selenium source, takes water as a solvent and matches System deposition liquid, the high quality sulphur selenizing Sb film of smooth densification is obtained using hydro-thermal reaction on substrate.

2) by changing the concentration of sodium thiosulfate and sodium thiosulfate, to control sulphur member in hydro-thermal reaction institute deposition film The content of element and selenium element obtains the adjustable sulphur selenizing Sb film of band gap to adjust the band gap of film.

The invention has the following advantages:

1) there is patent report to cross and obtain precursor thin-film using solwution method, obtain the side of selenizing Sb film through high temperature selenizing Method.The present invention directly obtains sulphur selenizing Sb film using hydro-thermal method, and manufacturing process is simpler, and preparation cost is low, is suitble to industry Change large-scale production.

2) it is found through patent retrieval, this patent directly prepares sulphur selenizing Sb film using hydro-thermal method for the first time.

3) compared with the method reported, the sulphur antimony selenide crystalline property that the present invention obtains is good, the smooth cause of surface topography Close, uniformity is good, can be used for preparing the photoelectric device of high quality.

4) by adjusting the dosage of sodium thiosulfate and sodium thiosulfate, the element of sulphur and selenium in film can flexibly be controlled Ratio obtains the continuously adjustable sulphur selenizing Sb film of band gap.It, can be easily by adjusting dosage and the reaction time of each raw material Control the ingredient and thickness of film.

For a further understanding of the present invention, below with reference to embodiment to solar battery obsorbing layer provided by the invention and its Preparation method and application are illustrated, and protection scope of the present invention is not limited by the following examples.