Efficient And Stable Inorganic Lead-Free Perovskite Solar Cell And Method For Preparing The Same

Abstract

The disclosure provides an efficient and stable inorganic lead-free perovskite solar cell and a method for preparing the same. The solar cell includes a conductive substrate, a PEDOT: PSS layer, an inorganic lead-free CsSnI.sub.3 perovskite layer, a C60 layer, a BCP layer, and a metal counter electrode layer arranged in order from bottom to top, wherein the inorganic lead-free CsSnI.sub.3 perovskite layer is a CsSnI.sub.3 perovskite layer passivated by a thioureas small-molecule organic compound.

Claims

1. An efficient and stable inorganic lead-free perovskite solar cell, comprising a conductive substrate, a poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) layer, an inorganic lead-free CsSnI.sub.3 perovskite layer, a fullerene layer, a bathocuproine layer, and a metal counter electrode layer arranged in order from bottom to top, wherein the inorganic lead-free CsSnI.sub.3 perovskite layer is a CsSnI.sub.3 perovskite layer passivated by a thioureas small-molecule organic compound.

2. The efficient and stable inorganic lead-free perovskite solar cell of claim 1, wherein the conductive substrate is an indium tin oxide conductive glass substrate.

3. The efficient and stable inorganic lead-free perovskite solar cell of claim 1, comprising one or more of the following features: i. the conductive substrate has an electrical resistance of less than 6 ohm/sq, and a thickness of 140-160 nm; ii. the poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) layer has a thickness of 20-40 nm; iii. the inorganic lead-free CsSnI.sub.3 perovskite layer has a thickness of 400-500 nm; iv. the fullerene layer has a thickness of 30-50 nm; v. the bathocuproine layer has a thickness of 5-10 nm; and vi. the metal counter electrode layer has a thickness of 50-70 nm.

4. The efficient and stable inorganic lead-free perovskite solar cell of claim 1, wherein the thioureas small-molecule organic compound is selected from the group consisting of thiourea, thiosemicarbazide, and thioacetamide.

5. The efficient and stable inorganic lead-free perovskite solar cell of claim 1, wherein the inorganic lead-free CsSnI.sub.3 perovskite layer is prepared by a process comprising: sequentially depositing SnI.sub.2, the thioureas small-molecule organic compound, and CsI on the poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) layer, and then annealing to obtain the inorganic lead-free CsSnI.sub.3 perovskite layer.

6. The efficient and stable inorganic lead-free perovskite solar cell of claim 1, wherein a metal counter electrode in the metal counter electrode layer is copper counter electrode or gold counter electrode.

7. A method for preparing the efficient and stable inorganic lead-free perovskite solar cell of claim 1, comprising the following steps: (1) pretreating the conductive substrate; (2) spin-coating a poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) aqueous solution on the conductive substrate, and annealing to obtain the poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) layer; (3) using SnI.sub.2, the thioureas small-molecule organic compound and CsI as raw materials, depositing SnI.sub.2, the thioureas small-molecule organic compound, and CsI on the poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) layer in sequence by a vacuum thermal evaporation, and then annealing to obtain an inorganic lead-free CsSnI.sub.3 perovskite layer; and (4) sequentially depositing a fullerene layer, a bathocuproine layer and a metal counter electrode layer on the inorganic lead-free CsSnI.sub.3 perovskite layer by a vacuum thermal evaporation to obtain an inorganic lead-free perovskite solar cell.

8. The method of claim 7, wherein the method is conducted under conditions comprising one or more of the following items: i. in step (1), the conductive substrate is pretreated as follows: etching, washing, and drying the conductive substrate, and finally subjecting the conductive substrate to an ultraviolet ozone treatment; ii. in step (2), the poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate)aqueous solution is spin coated on the conductive substrate using a spin coater at a spin-coating speed of 2000-3000 rpm for 30-40 s; and iii. in step (2), the annealing is conducted at a temperature of 80-120° C. for 5-15 min.

9. The method of claim 7, wherein step (3) is conducted under conditions comprising one or more of the following items: i. the thermal vacuum evaporation is conducted at a vacuum degree of less than 1×10.sup.−5 Pa, during which SnI.sub.2 is evaporated at a heating temperature of 300-350° C. and an evaporation rate of 0.1-0.2 nm/s, the thioureas small-molecule organic compound is evaporated at a heating temperature of 70-100° C. and an evaporation rate of 0.1-0.2 nm/s, and CsI is evaporated at a heating temperature of 550-600 ° C. and an evaporation rate of 0.2-0.5 nm/s; ii. a molar ratio of CsI to SnI.sub.2 is in a range of 1: (1-1.3), a molar ratio of the thioureas small-molecule organic compound to CsI is in a range of 1: (45-55), a molar ratio of CsI to SnI.sub.2 is 1:1.2, and a molar ratio of the thioureas small-molecule organic compound to CsI is 1:50; iii. CsI has a purity of 99.9%, and SnI.sub.2 has a purity of 99.99%; and iv. the annealing is conducted at a temperature of 120-140° C. for 10-20 min.

10. The method of claim 7, wherein step (4) is conducted as follows: under a vacuum degree of less than 1×10.sup.−5 Pa, evaporating fullerene at an evaporation rate of 0.1-0.3 nm/s, preferably 0.2 nm/s, and depositing on the inorganic lead-free CsSnI.sub.3 perovskite layer to obtain a fullerene layer; then evaporating bathocuproine at an evaporation rate of 0.05-0.3 nm/s, preferably 0.1 nm/s, and depositing on the fullerene layer to obtain a bathocuproine layer; finally evaporating a metal at an evaporation rate of 0.2-0.7 nm/s, preferably 0.5 nm/s, and depositing on the bathocuproine layer to obtain an inorganic lead-free perovskite solar cell.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG. 1 is a diagram showing X-ray diffraction (XRD) patterns of the inorganic lead-free CsSnI.sub.3 perovskite layers prepared in Example 1, Example 5 and Comparative Examples 1-3 of the present disclosure.

[0045] FIG. 2 is a diagram showing XRD patterns of the inorganic lead-free CsSnI.sub.3 perovskite layers prepared in Example 1 and Comparative Examples 4-5 of the present disclosure.

[0046] FIG. 3 shows scanning electron microscope (SEM) images of the inorganic lead-free CsSnI.sub.3 perovskite layers prepared in Example 1 (panel b) and Comparative Example 4 (panel a) of the present disclosure, in which the panels have a scale length of 500 nm.

[0047] FIG. 4 is a diagram showing X-ray photoelectron spectroscopy (XPS) patterns of element Sn of the inorganic lead-free CsSnI.sub.3 perovskite layers prepared in Example 1 (thiosemicarbazide) and Comparative Example 4 (Comparative Example) of the present disclosure.

[0048] FIG. 5 shows a diagram (panel a) illustrating the structure model of the solar cell prepared in Example 1 of the present disclosure, and a diagram (panel b) illustrating the current density-voltage curves of the solar cells prepared in Example 1 (thiosemicarbazide) and Comparative Example 4 (Comparative Example) of the present disclosure.

[0049] FIG. 6 is a diagram showing the stability test results of the solar cells prepared in Example 1 (thiosemicarbazide) and Comparative Example 4 (Comparative Example) of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0050] The present disclosure will be further illustrated below through specific examples, but it is not limited thereto.

[0051] The raw materials used in examples, unless otherwise specified, are conventional raw materials, which are commercially available; the methods used in the examples, unless otherwise specified, are all prior art.

[0052] In the examples, the ITO conductive glass used has a resistance of less than 6 ohm/sq.

EXAMPLE 1

[0053] A method for preparing an efficient and stable inorganic lead-free perovskite solar cell is conducted as follows:

[0054] (1) A conductive surface of an ITO conductive glass was partially etched by an etching process as follows: a dilute hydrochloric acid with a concentration of 2 mol/L was added to a surface of the ITO glass with a half of the surface covered with zinc powder at ambient temperature, and then reacted for 5 min; after that, the etching was completed. Then, the partially etched ITO glass was ultrasonically cleaned in a cleaning agent, acetone and ethanol in sequence at ambient temperature, 20 min for each cleaning material. The cleaned ITO glass was dried, and then placed in an ultraviolet-ozone processor and treated at ambient temperature for 30 min, obtaining an ITO conductive glass substrate with a thickness of 150 nm.

[0055] (2) 100 μL of PEDOT: PSS conductive coating (with a concentration of 1.3-1.7%) was spin-coated on the ITO conductive glass substrate by a spin coater at a speed of 3000 rpm for 30 s, then placed on a hot plate with a temperature 100° C. and heated in air for 10 min, obtaining a PEDOT: PSS layer with a thickness of 30 nm.

[0056] (3) The three precursors, i.e. 1.2 mmol of SnI.sub.2 (with a purity of 99.99%), 0.02 mmol of thiosemicarbazide and 1 mmol of CsI (with a purity of 99.9%), were respectively placed in three evaporation chambers of a vacuum thermal evaporation equipment, and under a pressure of less than 1×10.sup.−5 Pa, SnI.sub.2 was firstly evaporated at a heating temperature of 350° C. and an evaporation rate of 0.2 nm/s until SnI.sub.2 was exhausted, thiosemicarbazide was then evaporated at a heating temperature of 100° C. and an evaporation rate of 0.2 nm/s until thiosemicarbazide was exhausted, and finally, CsI was evaporated at a heating temperature of 600° C. and an evaporation rate of 0.5 nm/s until CsI was exhausted. The deposited product was transferred from the vacuum thermal evaporation equipment to a heating plate, and annealed at a temperature of 120° C. for 15 min, obtaining an inorganic lead-free CsSnI.sub.3 perovskite layer with a thickness of 500 nm.

[0057] (4) Finally, the sample prepared in step (3) was placed in a vacuum thermal evaporation chamber, and under a pressure in the evaporation chamber of lower than 1×10.sup.−5 Pa, C60 was evaporated at an evaporation rate of 0.2 nm/s and deposited on the inorganic lead-free CsSnI.sub.3 perovskite layer, obtaining a C60 layer with a thickness of 40 nm, BCP was then evaporated at an evaporation rate of 0.1 nm/s and deposited on the C60 layer, obtaining a BCP layer with a thickness of 8 nm, and finally Cu was evaporated at an evaporation rate of 0.5 nm/s and deposited on the BCP layer, obtaining a Cu counter electrode layer with a thickness of 60 nm, thus obtaining an inorganic lead-free perovskite solar cell.

[0058] XRD patterns of the inorganic lead-free CsSnI.sub.3 perovskite layer prepared in step (3) of this example are shown in FIG. 1 and FIG. 2. It can be seen from FIG. 1 that as the annealing temperature increases, the diffraction peaks of the precursors CsI and SnI.sub.2 gradually weaken, while the diffraction peaks of CsSnI.sub.3 gradually increase; moreover, the prepared inorganic lead-free CsSnI.sub.3 perovskite shows B-γ-CsSnI.sub.3 perovskite crystal phase. It can be seen from FIG. 2 that the inorganic lead-free CsSnI.sub.3 perovskite with an addition of 2% thiosemicarbazide (percentage of a molar amount of thiosemicarbazide accounts for the molar amount of CsSnI.sub.3, i.e. the molar amount of CsI) is the most fully reacted and shows the best crystal structure.

[0059] An SEM image of the inorganic lead-free CsSnI.sub.3 perovskite layer prepared in step (3) of this example is shown in FIG. 3. It can be seen from FIG. 3 that the inorganic lead-free CsSnI.sub.3 perovskite added with thiosemicarbazide shows an increased grain size, which is about 500 nm.

[0060] An XPS pattern of the inorganic lead-free CsSnI.sub.3 perovskite layer prepared in step (3) of this example is shown in FIG. 4. The CsSnI.sub.3 perovskite film passivated by thiosemicarbazide shows a significantly reduced vibration peak of Sn.sup.4+, indicating that thiosemicarbazide could effectively inhibit the oxidation of divalent tin.

[0061] A structure model and a current density-voltage curve of the solar cell prepared in this example are shown in FIG. 5. It can be seen from FIG. 5 that the perovskite cell after thiosemicarbazide passivation has a significantly increased voltage, and an increased photoelectric conversion efficiency of 8.20%, which is much higher than that of

Comparative Example 4 (5.06%).

[0062] The solar cell prepared in this example was subjected to continuous light (AM1.5G) in the air to test its stability, and the test result is shown in FIG. 6. It can be seen from FIG. 6 that the perovskite cell passivated by thiosemicarbazide could still maintain about 90% of the initial photoelectric conversion efficiency after testing for 500 h, indicating that it has good long-term working stability.

EXAMPLE 2

[0063] A method for preparing an efficient and stable inorganic lead-free perovskite solar cell was conducted as described in Example 1, except that:

[0064] The metal counter electrode layer was an Au layer, which was prepared by a process as follows: under a pressure of lower than 1×10.sup.−5 Pa, Au was evaporated at an evaporation rate of 0.5 nm/s and deposited on the BCP layer, obtaining the Au counter electrode layer with a thickness of 50 nm.

EXAMPLE 3

[0065] A method for preparing an efficient and stable inorganic lead-free perovskite solar cell was conducted as described in Example 1, except that:

[0066] In step (3), thiosemicarbazide was replaced with thiourea; the inorganic lead-free CsSnI.sub.3 perovskite layer was prepared by a process as follows: three precursors, i.e. 1.2 mmol of SnI.sub.2 (with a purity of 99.99%), 0.02 mmol of thiourea, and 1 mmol of CsI (with a purity of 99.9%), were respectively placed in three evaporation chambers of a vacuum thermal evaporation equipment, and under a vacuum degree of less than 1×10.sup.−5 Pa, SnI.sub.2 was firstly evaporated at a heating temperature of 350° C. and an evaporation rate of 0.2 nm/s until SnI.sub.2 was exhausted, thiourea was then evaporated at a heating temperature of 100° C. and an evaporation rate of 0.2 nm/s until thiourea was exhausted, and finally, CsI was evaporated at a heating temperature of 600° C. and an evaporation rate of 0.5 nm/s until CsI was exhausted. The deposited product was transferred from the vacuum thermal evaporation equipment to a heating plate, and annealed at a temperature of 120° C. for 15 min, obtaining the inorganic lead-free CsSnI.sub.3 perovskite layer with a thickness of 500 nm.

EXAMPLE 4

[0067] A method for preparing an efficient and stable inorganic lead-free perovskite solar cell was conducted as described in Example 1, except that:

[0068] In step (3), thiosemicarbazide is replaced with thioacetamide; the inorganic lead-free CsSnI.sub.3 perovskite layer was prepared by a process as follows: three precursors, i.e. 1.2 mmol of SnI.sub.2 (with a purity of 99.99%), 0.02 mmol of thioacetamide, and 1 mmol of CsI (with a purity of 99.9%), were respectively placed in three evaporation chambers of a vacuum thermal evaporation equipment, and under a vacuum degree of less than 1×10.sup.−5 Pa, SnI.sub.2 was firstly evaporated at a heating temperature of 350° C. and an evaporation rate of 0.2 nm/s until SnI.sub.2 was exhausted, thioacetamide was then evaporated at a heating temperature of 100° C. and an evaporation rate of 0.2 nm/s until thiourea was exhausted, and finally, CsI was evaporated at a heating temperature of 600° C. and an evaporation rate of 0.5 nm/s until CsI was exhausted. The deposited product was transferred from the vacuum thermal evaporation equipment to a heating plate, and annealed at a temperature of 120° C. for 15 min, obtaining the inorganic lead-free CsSnI.sub.3 perovskite layer with a thickness of 500 nm.

EXAMPLE 5

[0069] A method for preparing an efficient and stable inorganic lead-free perovskite solar cell was conducted as described in Example 1, except that:

[0070] In step (3), the annealing was conducted at a temperature of 140° C. for 15 min.

Comparative Example 1

[0071] A method for preparing a solar cell was conducted as described in Example 1, except that:

[0072] In step (3), the annealing is conducted at a temperature of 60° C. for 15 min

Comparative Example 2

[0073] A method for preparing a solar cell was conducted as that described in Example 1, except that:

[0074] In step (3), the annealing was conducted at a temperature of 80° C. for 15 min.

[0075] The other steps and conditions were the same as those in Example 1.

Comparative Example 3

[0076] A method for preparing a solar cell was conducted as that described in Example 1, except that:

[0077] In step (3), the annealing was conducted at a temperature of 100° C. for 15 min.

Comparative Example 4

[0078] A method for preparing a solar cell was conducted as described in Example 1, except that:

[0079] In step (3), only CsI and SnI.sub.2 were deposited (i.e. the step of depositing thiosemicarbazide was omitted), and an unpassivated CsSnI.sub.3 perovskite layer was prepared by a process as follows: two precursors, i.e. 1.2 mmol of SnI.sub.2 (with a purity of 99.99%) and 1 mmol of CsI (with a purity of 99.9%), were respectively placed in two evaporation chambers of a vacuum thermal evaporation equipment, and under a vacuum degree of less than 1'10.sup.−5 Pa, SnI.sub.2 was firstly evaporated at a heating temperature of 350° C. and an evaporation rate of 0.2 nm/s until SnI.sub.2 was exhausted, and finally, CsI was evaporated at a heating temperature of 600° C. and an evaporation rate of 0.5 nm/s until CsI was exhausted. The deposited product was transferred from the vacuum thermal evaporation equipment to a heating plate, and annealed at a temperature of 120° C. for 15 min, obtaining the unpassivated CsSnI.sub.3 perovskite layer.

[0080] An SEM image of the CsSnI.sub.3 perovskite layer without thiosemicarbazide passivation prepared in this comparative example is shown in FIG. 3 (panel a). It can be seen from FIG. 3 (panel a) that the inorganic CsSnI.sub.3 perovskite without thiosemicarbazide has a smaller crystal grain size than that of the CsSnI.sub.3 perovskite treated with thiosemicarbazide in Example 1 of the present disclosure.

[0081] An XPS pattern of the CsSnI.sub.3 perovskite layer without thiosemicarbazide passivation prepared in this comparative example is shown in FIG. 4. It can be seen from FIG. 4 that the CsSnI.sub.3 perovskite layer without thiosemicarbazide treatment shows a very obvious vibration peak of tetravalent tin, indicating an obvious oxidation.

[0082] A current density-voltage curve of the CsSnI.sub.3 perovskite solar cell without thiosemicarbazide passivation prepared in this comparative example is shown in FIG. 5. It can be seen from FIG. 5 that this device has a photoelectric conversion efficiency of 5.06%, which is lower than that of the solar cell prepared in Example 1 of the present disclosure, further demonstrating the importance of surface passivation by a thioureas molecular in the present disclosure.

[0083] A result of stability test of the CsSnI.sub.3 perovskite solar cell prepared in this comparative example without thiosemicarbazide passivation is shown in FIG. 6. It can be seen from FIG. 6 that after testing for 500 h, the photoelectric conversion efficiency of this device decays to less than 70% of the initial value, which is significantly lower than that of the solar cell prepared in Example 1 of the present disclosure, demonstrating that the surface passivation by a thioureas molecular in the present disclosure plays an important role in the stability of the CsSnI.sub.3 perovskite solar cell.

Comparative Example 5

[0084] A method for preparing a solar cell was conducted as described in Example 1, except that:

[0085] In step (3), thiosemicarbazide is used in an amount of 0.01 mmol, i.e. the amount of thiosemicarbazide accounts for 1% of CsSnI.sub.3 (i.e. a molar amount of CsI).

[0086] An XRD pattern of the CsSnI.sub.3 perovskite layer passivated with a small amount of thiosemicarbazide (1% of thiosemicarbazide) prepared in this comparative example is shown in FIG. 2. It can be seen from FIG. 2 that the inorganic CsSnI.sub.3 perovskite treated with a small amount of thiosemicarbazide has not been completely reacted, and a few of unreacted perovskite precursors SnI.sub.2 and CsI are still present.

Comparative Example 6

[0087] A method for preparing a solar cell was conducted as described in Example 1, except that:

[0088] In step (3), thiosemicarbazide is used in an amount of 0.05 mmol, i.e. the amount of thiosemicarbazide accounts for 5% of CsSnI.sub.3 (i.e. a molar amount of CsI).

[0089] An XRD pattern of the CsSnI.sub.3 perovskite layer passivated with excess thiosemicarbazide (5% of thiosemicarbazide) prepared in this comparative example is shown in FIG. 2. It can be seen from FIG. 2 that the inorganic CsSnI.sub.3 perovskite treated with excess thiosemicarbazide is not formed.