Method for manufacturing perovskite-based devices in ambient air

Abstract

A method for manufacturing perovskite-based devices, such as solar cells. In ambient air includes steps of forming a perovskite film on a substrate by spin-coating, the perovskite film having a turbid point when the perovskite film transitions from transparent to turbid in appearance, and dropping an antisolvent on the perovskite film during an antisolvent window having a start time five seconds before the turbid point and an end time one second before the turbid point. The method also includes the step of measuring the current relative humidity of the ambient air at the time of manufacture and adjusting the antisolvent window or optimum drop time of the antisolvent based upon the current relative humidity.

Claims

1. A method for manufacturing of a perovskite-based device in ambient air, comprising: forming a perovskite film on a substrate by spin-coating, the perovskite film having a turbid point when the perovskite film transitions from transparent to turbid in appearance; and dropping an antisolvent on the perovskite film during an antisolvent window having a start time 3-8 seconds before the turbid point and a stop time one second before the turbid point.

2. The method of claim 1, wherein the turbid point of the perovskite film has a time that is based on a current relative humidity of the ambient air.

3. The method of claim 2, including measuring the current relative humidity of the ambient air at a current time of the manufacturing of the perovskite-based device and basing timing of the antisolvent window upon the time of the turbid point for the current relative humidity.

4. The method of claim 3, wherein the time of the turbid point is measured from the start of the spin-coating.

5. The method of claim 4, including dropping the antisolvent onto the perovskite film between 4-8 seconds after the starting of the spin-coating when the current relative humidity is 0%.

6. The method of claim 4, including dropping the antisolvent onto the perovskite film between 10-14 seconds after the starting of the spin-coating when the current relative humidity is 50%.

7. The method of claim 4, including dropping the antisolvent onto the perovskite film between 14-18 seconds after the starting of the spin-coating when the current relative humidity is 70%.

8. The method of claim 4, including dropping the antisolvent onto the perovskite film between 15-19 seconds after the starting of the spin-coating when the current relative humidity is 90%.

9. The method of claim 1, including dropping the antisolvent onto the perovskite film between 4-8 seconds after starting of the spin-coating when the current relative humidity is 0%.

10. The method of claim 1, including dropping the antisolvent onto the perovskite film between 10-14 seconds after starting of the spin-coating when the current relative humidity is 50%.

11. The method of claim 1, including dropping the antisolvent onto the perovskite film between 14-18 seconds after starting of the spin-coating when the current relative humidity is 70%.

12. The method of claim 1, including dropping the antisolvent onto the perovskite film between 15-19 seconds after starting of the spin-coating when the current relative humidity is 90%.

13. A perovskite-based device made in accordance with the method of claim 1.

14. A perovskite-based device made in accordance with the method of claim 2.

15. A perovskite-based device made in accordance with the method of claim 3.

16. A perovskite-based device made in accordance with the method of claim 4.

17. A perovskite-based device made in accordance with the method of claim 5.

18. A perovskite-based device made in accordance with the method of claim 6.

19. A perovskite-based device made in accordance with the method of claim 7.

20. A perovskite-based device made in accordance with the method of claim 8.

Description

BRIEF DESCRIPTION OF THE DRAWING FIGURES

(1) The accompanying drawing figures incorporated herein and forming a part of the patent specification, illustrate several aspects of the method and together with the description serve to explain certain principles thereof.

(2) FIG. 1 is a schematic illustration of a perovskite solar cell incorporating a spin-coated perovskite film on a support substrate.

(3) FIG. 2 is a graph of the turbid point in seconds as a function of the relative humidity of the ambient air.

DETAILED DESCRIPTION

(4) Reference is now made to FIGS. 1 and 2 which illustrate one possible embodiment of a perovskite solar cell 10 of the type made in accordance with the new and improved method 20 for manufacturing perovskite solar cells in ambient air.

(5) As illustrated in FIG. 1, the perovskite cell 10 includes a spin-coated perovskite film 12 on a support substrate 14. The support substrate 14 may comprises any number of materials known to be useful as a support substrate for a solar cell, including, for example, indium tin oxide (ITO) glass. Other useful substrate materials include, but are not necessarily limited to FTO glass, metal, tin oxide, silicon and flexible materials.

(6) A layer 16 of electron transport material is provided on the surface 18 of the support substrate 14 between the support substrate and the outer perovskite film 12. The electron transport layer 16 may be applied or deposited by spin-coating or other means known to those skilled in the art of solar cell manufacture. Useful materials for the electron transport layer 16 include tin oxide (SnO.sub.2), titanium oxide (TiO.sub.2), mesoporous titanium oxide (m-TiO.sub.2) or combinations thereof.

(7) A new and improved method for making the perovskite solar cell 10, such as illustrated in FIG. 1, or other perovskite-based devices, such as transistors, detectors and light emitting diodes will now be described.

(8) That method includes the step of cleaning the support substrate 14 in accordance with a manner known in the art. For example, the support substrate 14 may be cleaned in a detergent aqueous solution, rinsed one or more times with deionized water and then undergo sequential sonication in acetone and ethanol for a predetermined period of time such as fifteen minutes. After the ethanol evaporates, the substrate may be treated by UV-ozone for a predetermined period of time such as 20 minutes.

(9) Next, the method includes the step of applying the electron transport layer 16 on the surface 18 of the support substrate 14. Thus, for example, a compact layer of tin oxide or other electron transport material may be deposited by spin-coating diluted tin oxide aqueous solutions (e.g. SnO.sub.2 colloid precursor and deionized water, 1/6 v/v) at 4,000 revolutions per minute for 20 seconds followed by annealing at 165° C. for 30 minutes in air and UV-ozone treatment for 15 minutes.

(10) Here, it should be appreciated that processes, other than spin-coating, that are known to those skilled in the art of perovskite-based device production may be used for applying or depositing the electron transport layer 16 on the surface 18 of the support substrate 14.

(11) Next, the method includes the step of forming a perovskite film 12 on the support substrate 14. More particularly, in the illustrated embodiment, the perovskite film 12 is formed by spin-coating the perovskite film overlying the electron transport layer 16 on the surface 18 of the support substrate 14. The perovskite film 12 has a turbid point when the perovskite film transitions from transparent to turbid in appearance.

(12) Next, the method includes the step of dropping an antisolvent on the perovskite film 12 during an antisolvent window having a start time 3-8 seconds before the turbid point and an end time one second before the turbid point. In another possible embodiment of the method, the antisolvent window has a start time 3-5 seconds before the turbid point and an end time one second before the turbid point. In another possible embodiment of the method, the antisolvent window has a start time of four seconds before the turbid point and an end time of one second before the turbid point. In yet another possible embodiment of the method, the antisolvent window has a start time of three seconds before the turbid point and an end time of one second before the turbid point. Antisolvents useful in the method include, but are not necessarily limited to diethyl ether (DE), chlorobenzene (CBZ), toluene (TL), isopropyl alcohol (IPA) and combinations thereof.

(13) Toward this end, in at least one possible embodiment of the method, a MAPbI.sub.3 film is prepared by spin-coating a perovskite precursor solution (1.5 mol. methylammonium iodide (MA)I and lead (II) iodide (PbI.sub.2) in 1 ml mixed solvent of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), 9:1 v/v) at 4,000 revolutions per minute for 25 seconds followed by dropping 300 ul antisolvent (diethyl ether (DE) or chlorobenzene (CBZ) approximately 1-5 seconds before the turbid point. The perovskite film 12 may then be heated to 100° C. for a predetermined period of time such as five minutes.

(14) The method may further include the step of identifying the timing of the turbid point for the ambient air at different relative humidities. See FIG. 2 illustrating the turbid point in seconds as a function of the relative humidity of the ambient air. This Figure allows one to identify the antisolvent timing window for dropping the antisolvent at any current relative humidity shown in FIG. 2.

(15) Thus, it should be appreciated that the method may also include the step of measuring the current relative humidity of the ambient air at the time of the manufacturing of the perovskite-based device and basing timing of the antisolvent window (and, therefore, the dropping of the antisolvent) upon the identified timing of the turbid point for the current relative humidity as illustrated in FIG. 2. In this regard, the method may include the step of measuring the timing of the turbid point from the starting of the spin-coating.

(16) Thus, in accordance with the data presented in FIG. 2, the method may include the step of dropping the antisolvent onto the perovskite film between 4-8 seconds after the starting of the spin-coating when the current relative humidity is 0%. Alternatively, the method may include the step of dropping the antisolvent onto the perovskite film between 10-14 seconds after the starting of the spin-coating when the current relative humidity is 50%.

(17) In yet another possible embodiment, the method may include the step of dropping the antisolvent onto the perovskite film between 14-18 seconds after the starting of the spin-coating when the current relative humidity is 70%. In yet another possible embodiment, the method may include the step of dropping the antisolvent onto the perovskite film between 15-19 seconds after the starting of the spin-coating when the current relative humidity is 90%.

(18) In summary, the method of manufacturing of a perovskite-based device in ambient air set forth herein may be broken down into two steps: (1) spin-coating-induced crystallization of a perovskite precursor film and (2) enhanced nucleation through solvent extraction by dropping antisolvent.

(19) For best results, it is necessary to determine the optimum point of time at which to drop the antisolvent. As indicated above, the optimum time point or antisolvent window is closely related to the turbid point and usually several seconds before the turbid point. Dropping the antisolvent too early or too late leads to bad morphology of the perovskite film and a reduction in the power conversion efficiency of the manufactured perovskite solar cell.

(20) As illustrated in FIG. 2, as the relative humidity of the ambient air rises, the turbid point is delayed. Thus, in order to determine and drop the antisolvent at the optimum time, it is necessary to measure the current relative humidity of the ambient air at the time of manufacture and then adjust the time at which to drop the antisolvent based upon the effect of the current relative humidity on the turbid point as indicated in FIG. 2.

(21) Advantageously, the method allows for the production of perovskite-based devices, including perovskite solar cells, having a relatively high power conversion efficiency at a substantially reduced cost. This is accomplished by eliminating the need for manufacture in a glove box under an inert atmosphere as currently required by state-of-the-art manufacturing methods used to manufacture perovskite solar cells having similar levels of power conversion efficiency.

(22) The foregoing has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the embodiments to the precise form disclosed. Obvious modifications and variations are possible in light of the above teachings. All such modifications and variations are within the scope of the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled.