Method for inkjet printing an organic-inorganic perovskite

Patent metadata

Field	Value
Publication number	US-11177440-B2
Application number	US-201716322708-A
Country	US
Kind code	B2
Filing date	Aug 2, 2017
Priority date	Aug 2, 2016
Publication date	Nov 16, 2021
Grant date	Nov 16, 2021

Abstract

The present invention provides a method for depositing an organic-inorganic perovskite, the method comprising the step of depositing a perovskite precursor solution comprising one or more organic cation, wherein said precursor solution preferably deposited by inkjet printing. The method is particularly useful in the manufacture of perovskite solar cells. For depositing the perovskite, a perovskite precursor solution or ink is preferably used, which comprises an organic cation carrying an anchoring group, such as 5-ammonium valeric acid. Surprisingly, the presence of the latter compound renders the precursor solutions stable and suitable for inkjet printing.

First claim

The invention claimed is:

1. A method for depositing an organic-inorganic perovskite, the method comprising the step of depositing a perovskite precursor solution, wherein said precursor solution is deposited through a printing nozzle by inkjet printing, wherein said perovskite precursor solution comprises all components required to form said organic-inorganic perovskite, wherein said perovskite precursor solution comprises:
a first organic cation, said first organic cation being of formula (I):
Anc-R 1 —W +   (I),

wherein,
Anc is selected from —COOH, —CONH 2 , —PO 3 H 2 , —PO 2 H 2 R 2 , —PO 4 H 2 , —SO 3 H 2 , —CONHOH, salts thereof, and deprotonated forms thereof, R 2 is an organic substituent comprising from 1-20 carbon atoms and 0-10 heteroatoms,
W is a positively charged moiety comprising a positively charged nitrogen atom;
R 1 is an optionally substituted organic moiety comprising 1-20 carbons and 0-10 heteroatoms,
wherein R 1 and R 2 may be, independently, totally or partially halogenated
a second organic cation, wherein said second organic cation is comprised in said organic-inorganic perovskite and wherein said first organic cation is preferably associated with or comprised in said organic-inorganic perovskite; and
an inorganic metal cation and anions required for forming said organic-inorganic perovskite.

2. The method of claim 1 , wherein said positively charged nitrogen atom is selected from the group consisting of: —NH 3 + , —NH—C(NH 3 + )═NH, and —N═CH—NH 3 + .

3. The method of claim 1 , wherein R 2 is —(CH 2 )— n , with n being an integer of 1-10.

4. The method of claim 1 , wherein said first organic cations comprise a cation selected from the cations of formulae (1)-(3):

and salts of said cations (1)-(3),
wherein n is an integer of 1-10.

5. The method of claim 1 , wherein said first organic cation is added to or present in said precursor solution in the form of a salt comprising at least one anion selected from the group consisting of: halide anions, CN − , NCO − , NCS − , BF 4 − , and NCSe − .

6. The method of claim 1 , wherein said organic-inorganic perovskite to be deposited is a mixed organic cation perovskite.

7. The method of claim 1 , wherein said perovskite precursor solution is stable when stored for 1 day at room temperature (25° C.) or more in a glass vial or printer cartridge, wherein stable refers to the absence of precipitation of solutes during said 1 day.

8. The method of claim 1 , wherein said perovskite precursor solution has one or more of the properties selected from the group consisting of:
a density δ(kg/m 3 ) of >800;
a surface tension γ(dyne/cm) of 15-55; and
a solvent boiling point (° C.) of >80° C.

9. The method of claim 1 , wherein during depositing by printing, the temperature of said precursor solution is controlled to be in the range of 15-50° C.

10. The method of claim 1 , wherein during depositing by printing, the precursor solution is deposited with one or more selected from the group consisting of:
a drop spacing in the range of 1-50 μm;
by applying a customized waveform with 1-30 V amplitude and 0.1-50 kHz frequency.

11. The method of claim 1 , wherein said precursor solution is deposited in the form of droplets having a volume of 0.5-20 picolitres.

12. The method of claim 1 , wherein said precursor solution is deposited by drop-on-demand (DOD) inkjet printing and wherein said precursor solution is deposited by forcing the solution through a nozzle having an opening diameter of 10-100 μm.

13. A method for producing a solar cell comprising a light harvester that is an organic-inorganic perovskite, wherein said method comprises the step of depositing said perovskite precursor solution in accordance with claim 1 .

14. The method of claim 1 , which comprises printing said organic-inorganic perovskite layer on a surface of 90 cm 2 or larger in a continuous deposition process, where said printing nozzle operates continuously for covering the said surface.

15. The method of claim 14 , which comprises printing said organic-inorganic perovskite layer on a surface of 200 cm 2 or larger in said continuous deposition process.

16. A method for producing an inkjet printable ink solution, the method comprising providing an ink solution comprising a cation of formula (I):
Anc-R 1 —W +   (I),

wherein,
Anc is selected from —COOH, —CONH 2 , —PO 3 H 2 , —PO 2 H 2 R 2 , —PO 4 H 2 , —SO 3 H 2 , —CONHOH, salts thereof, and deprotonated forms thereof, R 2 is an organic substituent comprising from 1-20 carbon atoms and 0-10 heteroatoms,
W is a charged moiety comprising a positively charger quaternary ammonium group; selected from —NH 3 + , —NH—C(NH 3 + )═NH, —N═CH—NH 3 + ; and,
R 1 is an optionally substituted organic moiety comprising 1-20 carbons,
wherein R 1 and R 2 may be, independently, totally or partially halogenated, and
wherein said inkjet printable ink solution comprises all components required to form an organic-inorganic perovskite.

17. An inkjet ink for printing an organic-inorganic perovskite, said inkjet ink comprising a cation of formula (I):
Anc-R 1 —W +   (I),

wherein,
Anc is selected from —COOH, —CONH 2 , —PO 3 H 2 , —PO 2 H 2 R 2 , —PO 4 H 2 , —SO 3 H 2 , —CONHOH, and salts thereof, and deprotonated forms thereof, R 2 is an organic substituent comprising from 1-20 carbon atoms and 0-10 heteroatoms,
W is a charged moiety comprising a positively charged quaternary ammonium group; selected from —NH 3 + , —NH—C(NH 3 + )═NH, —N═CH—NH 3 +; and,
R 1 is an optionally substituted organic moiety comprising 1-20 carbons,
wherein R 1 and R 2 may be, independently, totally or partially halogenated,
wherein said inkjet ink comprises all components required to form said organic-inorganic perovskite.

18. A method for reducing and/or slowing down nucleation and/or precipitation of perovskite and/or perovskite intermediates in an inkjet ink comprising an organic-inorganic perovskite precursor solution, the method comprising adding a cation of formula (I) when preparing said inkjet ink:
Anc-R 1 —W +   (I),

wherein,
Anc is selected from —COOH, —CONH 2 , —PO 3 H 2 , —PO 2 H 2 R 2 , —PO 4 H 2 , —SO 3 H 2 , —CONHOH, salts thereof, and deprotonated forms thereof, R 2 is an organic substituent comprising from 1-20 carbon atoms and 0-10 heteroatoms,
W is a positively charged moiety comprising a positively charged nitrogen atom;
R 1 is an optionally substituted organic moiety comprising 1-20 carbons and 0-10 heteroatoms,
wherein R 1 and R 2 may be, independently, totally or partially halogenated, and
wherein said method further comprises adding all components required to form an organic-inorganic perovskite layer when preparing said inkjet ink.

Assignees

• Aalto Univ Foundation
• Ecole Polytechnique Fed Lausanne Epfl
• Solaronix S A

Inventors

• Hashmi Syed Ghufran
• Ozkan Merve
• Martineau David
• Li Xiong
• Zakeeruddin Shaik Mohammed
• Graetzel Michael

Classifications

• H10K85/50

  Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3 · CPC title

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H10K71/135

  using ink-jet printing · CPC title

• H10K30/151 Primary

  the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2 · CPC title

• Y02E10/549

  Organic PV cells · CPC title