Field of the Invention

The present invention is in the field of materials for optoelectronic applications and in particular solar cells and light emitting diodes (LEDs).

Background to the Invention

In the technical field of optoelectronic devices, it is often required to prepare thin films of semiconducting materials. This is because creating films of uniform property and thickness is crucial for applications for large-area and flexible devices. The industrially scalable methods of spray coating, ink jet printing can be applied for this purpose but appropriate inks are needed.

Inkjet printing is a material-conserving deposition technique used for liquid inks, which consist of a material to be deposited, dissolved or dispersed in a solvent. The inkjet printing process consists in ejecting a given amount of ink in a chamber from a nozzle via piezoelectric action. The ejected drop falls on a substrate and spreads, and then dries through solvent evaporation. Inkjet printing offers a possibility of direct imaging, and thus provides more flexibility in designing optoelectronic devices.

Among several semiconducting materials, perovskites have received a lot of attention in recent years due to their flexibility, low weight and low cost.

Perovskites RMX ₃ (wherein R is an organic group such as methyl, butyl, phenyl etc., M are metal cations of Pb, Cs, and X are halide ions such as I, Cl, Br) are materials that are important for solar cells, LEDs and several optoelectronic applications, since these materials can be prepared as 2D or 3D materials. These materials have so far been used as bulk materials.

In high performance perovskite solar cell devices, Ti0 ₂ is used as the electron transport material or electron selective contact that transports electrons to the anode. This material is deposited using spin-coating deposition methods and so far there is no method to inkjet-print this material for high efficiency devices.

Cherrington et al. ([1]) discloses inkjet-printing of Ti0 ₂ , wherein the ink is composed of 14% DMF, 26% water and 25% PEG-400, 3% Ti0 ₂ nanoparticles and 3% dispersant.

Bernacka-Wojciket al. ([2]) discloses inkjet-printing of Ti0 ₂ , wherein the ink is composed of 87% of ethanol, 5% of ethylene glycol, 5% of Ti0 ₂ and 3% of dispersant.

Non-Patent Literature References

[1] Energy TechnoL 2015, 3, 866-870

[2] J. Colloid and interface Science, 2016, 465, 208-214

Summary of the Invention

The present invention aims at providing a composition which enables one to create films of uniform property and thickness, and to ensure reproducible fabrication of high quality Ti0 ₂ films outside of a glovebox and in ambient conditions, as well as stable inkjet printing at a variety of cartridge and substrate temperatures, from 21 °C to 50 °C, reducing the "coffee ring" effect upon ink drying/concentration.

The present ink formulation is intended for reproducible fabrication of high quality Ti0 ₂ films using scalable processing techniques, which has been a problem for previous reports of inkjet-printed perovskite films.

In one aspect, the present invention relates to a composition comprising:

(A) a titania source comprising:

(Al) Ti0 ₂ particles; and

(B) a solvent mixture comprising:

(Bl) a linear alcohol, an alicyclic alcohol, a benzyl alcohol or a mixture thereof; (B2) poly ethylene glycol, poly propylene glycol, poly(vinyl)alcohol, poly(vinyl)pyrrolidone, ethylcellulose or a mixture thereof; and

(B3) an N,N-dialkylamide, an alkyl sulfoxide or a mixture thereof.

The present invention also relates to a method for inkjet-printing the composition of the present invention, as well as its use and a solar cell comprising the composition of the present invention.

In another aspect, the present invention relates to a method of inkjetprinting comprising the following steps:

(1) printing the composition of the invention on a substrate to obtain a printed film;

(2) optionally dipping the printed film obtained in step (1) in an antisolvent, to obtain a dipped film; and

(3) annealing the dipped film obtained in step (2).

In still another aspect, the present invention relates to a use of the composition according to the present invention.

In still another aspect, the present invention relates to a solar cell wherein the composition according to the present invention and a composition comprising perovskite precursors are inkjet-printed. Brief Description of the Figures

Figure 1 presents scanning electron micrograph image of different film morphologies: a) spray-pyrolysis deposited compact ΊΊO2 (no particles) b) mesoporous Ti0 ₂ films deposited by inkjet printing (showing 30 nm nanoparticles) and c) mesoporous/compact hybrid Ti0 ₂ films deposited by inkjet printing with TAA additive (showing 5 nm and 30 nm nanoparticles).

Figure 2 presents J-V (current-voltage) curves, showing the fill factor, Jsc, and Voc of the devices, of cells using a) spin-coated Ti0 ₂ and MAPbI ₃ , b) inkjet- printed mesoporous Ti0 ₂ and MAPbI ₃ and c) inkjet-printed (FAo.i5MAo.85)Pb(I ₂ .55Bro.45)· Figure 3 presents a J-V curve of the best-performing cell with both inkjet-printed T1O2 and inkjet-printed perovskite layers. The cell was illuminated with 100 mWcm ² of a simulated solar spectrum.

Figure 4 presents a schematic structure of a typical solar cell, using both T1O2 and perovskite layers. Here, DP stands for inkjet-printed.

Detailed Description of the Invention

<Definitions>

The term "organic-inorganic hybrid perovskites", as used herein, refers to ABX3 materials with A = cation groups such as methylammonium (MA), butylammonium (BA), formamidinium (FA), Cs, and their mixtures; M is a metal such as Pb, Sn, Bi, Cu, Ag and their mixtures; and X are halides such as Cl, Br, I and their mixtures. Layered perovskites contain additional bulkier molecules such as phenethylamine (PEA) or phenyethylammomum, hexylammonium (HA) and longer chain ammonium species, which confine different perovskite domains into different repeating units. Specific examples given here comprise inorganic metal-halide multi-layered perovskites. These examples are nonlimiting.

The term "antisolvent", as used herein, refers to a solvent which precipitates the perovskite intermediate complex and induces nucleation while removing excess solvent. An anti-solvent treatment consists in, for example, introducing a volume of an anti-solvent, such as toluene, ethyl acetate, chlorobenzene, or ethyl ether onto the wet/drying/dry perovskite precursor film to supersaturate the precursor film and quickly induce nucleation and remove excess solvent to produce smooth perovskite films.

<Ink composition >

One aspect of the present invention relates to a composition comprising:

(A) a titania source comprising: (Al) Ti0 ₂ particles; and

(B) a solvent mixture comprising:

(Bl) a linear alcohol, an alicyclic alcohol, a benzyl alcohol or a mixture thereof;

(B2) poly ethylene glycol, poly propylene glycol, poly(vinyl)alcohol, poly(vinyl)pyrrolidone, ethylcellulose or a mixture thereof; and

(B3) an N,N-dialkylamide, an alkyl sulfoxide or a mixture thereof.

<Titania source (A)>

<TiC>2 particules (Al)>

The composition of the present invention comprises Ti0 ₂ particles (Al).

Ti0 ₂ particles (Al) used in the composition of the present invention are not particularly limited.

Preferably, Ti0 ₂ particles (Al) can be selected from the group consisting of dense, compact, textured, smooth, mesoporous, or amorphous Ti0 ₂ particles.

More preferably, the Ti0 ₂ particles are selected from the group consisting of mesoporous, textured, compact Ti0 ₂ particles.

In a particularly preferred embodiment, the Ti0 ₂ particles are mesoporous Ti0 ₂ particles.

The particle size of (Al) is 10 nm or more and 50 nm or less, preferably 20 nm or more and 40 nm or less and more preferably 25 nm or more and 35 nm or less, and most preferably about 30 nm, wherein the particle size is as measured by scanning electronic microscopy (SEM).

When the particle size of Ti0 ₂ particles is in the above range, charge collection is better.

In one preferred embodiment, the titania may have a formula of Ti0 ₂ .

If the titania is sub-stoichiometric, this is generally seen as deleterious for device functioning, but slightly extra oxygen should not be a large problem. In another preferred embodiment, the titania may be doped with a metallic or non-metallic elements such as the first and second row elements, transiton metals, and main group elements. Almost every element can be doped into titania.

In a preferred embodiment, Ti0 ₂ particles comprise 30 nm particles and 2-10 nm particles, with the small particles grown from molecular precursors in the ink, which improves charge collection.

<Ti0 ₂ precursors (A2)>

The composition may further comprise one or more Ti0 ₂ precursors (A2).

Ti0 ₂ precursors (A2) used in the composition of the present invention are not particularly limited.

Preferably Ti0 ₂ precursors (A2) can be selected from a group consisting of titanium bis(acetylacetone) diisopropoxide, titanium isopropoxide, titanium ethoxide, and titanium tetrachloride bis tetrahydrofuran.

More preferably Ti0 ₂ precursors (A2) is titanium bis(acetylacetone) diisopropoxide, since it is stable enough for ink storage and can be printed reliably.

< Linear alcohol, alicyclic alcohol, benzyl alcohol or mixture thereof (Bl)>

A linear alcohol, an alicyclic alcohol, a benzyl alcohol (Bl) used in the composition of the present invention is not particularly limited.

Preferably, (Bl) is selected from the group consisting of C5 to CIO linear alcohols, cyclic saturated alcohols, benzyl alcohol and mixtures thereof.

More preferably, (Bl) is selected from cyclopentanol, cyclohexanol and mixtures thereof.

The (Bl), such as cyclohexanol, is viscous, somewhat polar, and has a good surface tension. < Linear alcohol (Bl)>

Linear alcohol (Bl) used in the composition of the present invention is not particularly limited.

Preferably, linear alcohol (Bl) can be selected from the group consisting of methanol, ethanol and propanol.

< Alicyclic alcohol (Bl)>

Alicyclic alcohol (Bl) used in the composition of the present invention is not particularly limited.

Preferably, alicyclic alcohol (Bl) can be selected from the group consisting of cyclehexanol, a/p w-Campholenic alcohol, ara-Mentha-l^-dien-?- ol, and santalol ( alpha and beta).

<Poly ethylene glycol, poly propylene glycol, poly(vinyl)alcohol, poly(vinyl)pyrrolidone, ethylcellulose or a mixture thereof (B2)>

(B2) used in the composition of the present invention is not particularly limited.

In a preferred embodiment, (B2) has a molecular weight of 200 Da or more and 1000 Da or less, preferably of 250 Da or more and 600 Da or less, and more preferably 300 Da or more and 500 Da or less.

Preferably, (B2) is PEG-400, which acts as humectant, viscosity modifier, and density enhancer.

< N,N-dialkylamide, alkyl sulfoxide or mixture thereof (B3)>

(B3) used in the composition of the present invention is not particularly limited.

(B3) can be selected from the group consisting of N,N- dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide and N,N- diethylacetamide, lactams such as N-alkyl lactams and alkyl sulfoxides such as dimethyl sulfoxides, ethylmethyl sulfoxide, diethyl sulfoxide and mixtures thereof.

Preferably, (B3) is N,N-dimethylformamide, which has high polarity and surface tension and thus allows good drying after printing.

<Alkyl sulfoxide (B4)>

The present composition may further comprise an alkyl sulfoxide (A4). Alkyl sulfoxide (B4) is selected from the group consisting of dimethyl sulfoxide, cyclic or linear dialkyl sulfoxide, such as dimethyl sulfoxide, ethylmethyl sulfoxide, diethyl sulfoxide and other derivatives.

Preferably, alkyl sulfoxide (B4) is dimethyl sulfoxide.

It has been found that device performance can be enhanced with an alkyl sulfoxide.

Combination of (Bl), (B2) and (B3) >

Preferably, (Bl) is cyclohexanol, (B2) is PEG-400, and (B3) is N, N- dimethylformamide. In such a case, good drying with proper surface tension, proper density, proper viscosity, and humectant properties can be assured.

<Relative amount of (Al), (Bl), (B2) and (B3) >

In terms of the relative amounts of (Al), for the total weight amount of the composition summing to 100% by weight, the weight amount of (Al) is preferably comprised between 0.323 % and 0.418 %: weight of (Al)

0.323 < * 100 < 0.418

total weight of the composition

In one preferred embodiment, for the total weight amount of the composition summing to 100% by weight, the weight amount of (Al) is 0.399%. weight of (Al)

* 100 0.399

total weight of the composition

When the amount of (Al) is comprised in the above range, this will allow good formation of open Ti0 ₂ pores.

In terms of the relative amounts of the four solvents (Bl), (B2) and (B3), for a total amount of added volume of solvents (Bl), (B2) and (B3) summing to 100% by volume, the amount of (Bl) is preferably 58% by volume or more and 68% by volume or less, the amount of (B2) is preferably 16% by volume or more and 26% by volume or less, and the amount of (B3) is preferably 11% by volume or more and 21% by volume or less:

When the amount of (Bl) is comprised in the above range, this will allow good formation of open Ti0 ₂ pores.

More preferably, for a total amount of added volume of solvents (Bl), (B2) and (B3) summing to 100% by volume, the amount of (Bl) is 61% by volume or more and 65% by volume or less, the amount of (B2) is 19% by volume or more and 23% by volume or less, and the amount of (B3) is 14% by volume or more and 18% by volume or less:

When the amount of (Bl), (B2) and (B3) is comprised in the above range, this will allow good formation of open Ti0 ₂ pores.

In one preferred embodiment, for a total amount of added volume of solvents (Bl), (B2) and (B3) summing to 100% by volume, the amount of (Bl) is 60% by volume, the amount of (B2) is 20% by volume, and the amount of (B3) is 15% by volume.

When the amount of (Bl), (B2) and (B3) is comprised in the above range, this will allow very good formation of open Ti0 ₂ pores.

In one particularly preferred embodiment, (Bl) is cyclohexanol, (B2) is PEG-400 and (B3) is N,N-dimethylformamide, and the volume ratio between (Bl), (B2) and (B3) is 60 : 20 : 15. < Other additive >

< Dispersant (C)>

The present composition may further comprise a dispersant (C) selected from any non-ionic dispersant such as TWEEN, polidocanol, decyl polyglucose, glycerol monostrearate, monolaurin, stearyl alcohol, polyoxamer.

The amount of (C) is not particularly limited.

Preferably, the amount of the dispersant (C) is 0.001% to 5% by volume, for the total amount of the composition summing to 100% by volume.

In one preferred embodiment, the amount of the dispersant is 0.8% by volume, for the total amount of the composition summing to 100% by volume. <Method of inkjet printing>

One aspect of the present invention relates to a method of inkjet printing comprising the following steps:

(1) printing the composition as set out above on a substrate to obtain a printed film;

(2) optionally, dipping the printed film obtained in step (1) in an anti ^¬ solvent, to obtained a dipped film; and

(3) annealing the dipped film obtained in step (2).

<Substrate>

The substrate can be selected from the group consisting of metal-oxide semiconductors such as ZnO, T1O2, SnC>2, Al-doped ZnO (AZO), NiO _x , vanadium oxide, Si0 ₂ , Al ₂ 0 ₃ , Si, graphene; and other 2D transition metal chalcogenides, such as M0S2, MeSe2, FeS2, VS2; glass coated with fluorine doped tin oxide, glass titanium dioxide surfaces on glass. lnkjet printing (1)> The inkjet-printing step can be realized by using a printing machine appropriate for inkjet-printing.

For example, Dimatix 2831, Dimatix 2850, Ceradrop inkjet printer, commercially available, can be used for inkjet- printing.

<Anti-solvent treatment (2)>

An optional anti-solvent treatment consists in dipping the printed film obtained in step (1) in an anti-solvent.

The anti-solvent can be any organic solvent.

Preferably, the anti-solvent can be selected from the group consisting of benzene, substituted benzenes, such as toluene, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, toluene, xylene, mesitylene, ethyl acetate, ethyl propionate, metyl propionate, ethyl ether, diethyl ether, propyl ether, butyl ether, pentane, hexane, heptane, cyclohexane, cycloheptane, octane and octene.

Preferably, the anti-solvent is selected from the group consisting of diethyl ether, ethyl acetate, toluene, and hexane.

<Annealing (3)>

In one particular embodiment, anti-solvent treatment step (3) is carried out in an ambient atmosphere, at 120°C, for 30 seconds to 1 minute.

In a preferred embodiment, the method of inkjet-printing further comprises the following step (4) after step (3):

(4) spray-depositing a solution or dispersion comprising perovskite precursors selected from the group consisting of MAI, Pbl2, MABr, PbBr2, MACI, PbCI ₂ , PEAI, PEABr, PEACI, Csl, SrCI ₂ , CaCI ₂ , KI, CsBr, CsCI, NaCI, Nal, GUAI, GUABr, GUACI, FAI, FABr, FACI wherein MA stands for methylammonium, PEA for phenylethylammonium, GUA for guanidinium, and FA for formamidinium. IB

<Film processi ng>

In the film processing, the film is transported from the platen of the inkjet printer to the anti-solvent bath for some time, then placed on a hotplate set to 120° C. Technical effect of the present invention

By using the composition of the present invention, it is possible to create films of uniform property and thickness, and to ensure reproducible fabrication of high quality ΊPO2 films outside of a glovebox and in ambient conditions, as well as stable inkjet-printing at a variety of cartridge and substrate temperatures, from 21°C to 50°C, reducing the "coffee ring" effect upon ink drying/concentration. The present ink composition also has concentration flexibility: Ti0 ₂ can be dispersed at a variety of concentrations from 0.323 to 0.418 % by weight, for the total amount of the composition summing to 100% by weight. Such concentration flexibility facilitates its application in inkjetprinting. The present ink composition is further compatible with anti-solvent treatment.

<Applications>

The present composition can be used in inkjet printing, especially, in order to produce an optoelectronic device, and more specifically, in order to produce a solar cell or a light emitting diode (LED).

As shown in Figure 4, a solar cell can comprise a substrate layer (in Figure 4, a glass substrate is used), a transparent conducing film layer (in Figure 4, fluorine-doped tin oxide (FTO) is used), an electron extraction layer (a spray coated compact Ti0 ₂ (in Figure 4, c-Ti0 ₂ ) layer is used), an electron transport layer (in Figure 4, an inkjet-printed mesoporous Ti0 ₂ (m-Ti0 ₂ ) layer is used), a spin-coated hole transport material (in Figure 4, spiro-OMeTAD is used), and an electrode (in Figure 4, a thermally evaporated Au layer is used). In advantageous embodiments of the present application, the perovskite inkjet printing ink composition is based on a binary solvent mixture comprising:

(A) at least one perovskite precursor(s); and

(B) a mixture of solvents comprising:

(Bl) a lactone, an ester or a carbonate; and

(B2) a linear N,N-dialkylamide.

The composition may further comprise lactam (B3), which is preferably is selected from the group consisting of N-alkyl lactams, and preferably is N- methylpyrrolidone.

For a total amount of added volume of solvents (Bl), (B2), (B3) and (B4) summing to 100% by volume, the amount of (Bl) is preferably28% by volume or more and 43% by volume or less, the amount of (B2) is 28% by volume or more and 43% by volume or less, the amount of (B3) is 0.001% by volume or more and 15% by volume or less and the amount of (B4) is 0% by volume or more and 33% by volume or less:

43

43 volume of (B3)

0.001 < * 100 < 15

sum of the volume of (Bl), (B 2), (B3) and (BA) and more preferably, for a total amount of added volume of solvents (Bl), (B2), (B3) and (B4) summing to 100% by volume, the amount of (Bl) is 30% by volume or more and 40% by volume or less, the amount of (B2) is 30% by volume or more and 40% by volume or less, the amount of (B3) is 0.01% by volume or more and 10% by volume or less and the amount of (B4) is 26% by volume or more and 30% by volume or less: volume of (Bl)

30 < * 100 < 40

sum of the volume of (51), (52), (53) and (54)

Examples

1) Ink Synthesis:

1)-1: Preparation of perovskite ink

The following starting materials were mixed to prepare an ink composition: 0.417 mL gamma-butyrolactone;

0.062 mL N-methylpyrrolidone;

0.352 mL dimethyl sulfoxide;

0.417 mL N,N'-dimethylformamide;

with Pbl (1.15 mmol, 0.53 g), FAI (1.033 mmol, 0.177 g), PbBr ₂ (0.19 mmol, 0.071 g), MABr (0.18 mmol, 0.020 g), Csl (0.115 mmoln 0.02988 g), Gul (0.063 mmol, 0.012 g), and phosphatidylcholine (0.001 g)

The solvents are added to the dry powder chemicals in each case.

The obtained ink composition comprised 0.9 M of Pb precursors.

The solvent in the anti-solvent bath is diethyl ether, and the film is wet after printing and dry after the bath and before heat treatment. A high performance ink was obtained with 0.6 M Pbl , 0.6 M methylammonium iodide, and 0.2 M methylammonium chloride in the previously mentioned solvent blend.

1)-2: Preparation of Ti0 ₂ ink

PEG-400 (0.20 ml_), cyclohexanol (0.65 mL), N,N-dimethylformamide (0.15 mL), and TWEEN-60 (0.008 g) and GreatCell Solar Italia-NRT 30 T1O2 paste (0.028 g), comprising 19% by weight (i.e. 0.00532 g) of Ti0 ₂ particles, were mixed, sonicated, and stirred at room temperature until thoroughly mixed. The suspension was then filtered with a 1.2 pm filter.

A Ti0 ₂ ink formulation was prepared as a ternary solvent blend with proportions of 60% cyclohexanol, 20% PEG-400, 15% DMF, 2.1% Ti0 ₂ paste, 2.1% titanium bis(acetylacetonate) diisopropoxide solution, 0.8% dispersant.

2) Device fabrication

2)-l: Substrate Preparation before printing Ti0 ₂

Electrode preparation with compact Ti0 ₂ : Chemically etched FTO glass (Nippon Sheet Glass) was sequentially cleaned by sonication in a 2 % Helmanex solution, deionized water, acetone and isopropanol for 8 min each. To form a 30 nm thick Ti0 ₂ blocking layer, titanium di-isopropoxide bis(acetylacetonate) (TAA, 75% in isopropanol) solution (Sigma-Aldrich) diluted in ethanol 3% (v/v) was deposited by spray pyrolysis at 450 °C.

2)-2: Inkjet printing of mesoporous Ti0 ₂

The Ti0 ₂ ink was added to a disposable Dimatix (DMP-2800) 1.5 mL printer cartridge of nominally 10 pL jetted droplet volume and containing 16 nozzles (21 pm orifice) and nozzle spacing of 254 pm. The cartridge head was warmed to 70°C and the substrate was warmed to 35°C. After printing, the substrate was warmed to 100°C for 10 min and then baked at 500°C for 30 min. The annealed substrates were then scored with glass scorer/cutter to yield 1.35 x 2.35 cm ² areas.

The ink was printed on a thin layer of titanium dioxide which was deposited on fluorine-doped tin oxide deposited on a glass substrate.

When fabricating spin-coated perovskite layers on these electrodes, the substrate was broken along the scored lines. When inkjet-printing the perovskite layer on these electrodes, the substrate was not broken along the scored lines until the perovskite was deposited.

2)-3: Ti0 ₂ film processing

For Ti0 ₂ film processing, the printed ink is allowed to dry at room temperature for a period of time of minutes to hours, then annealed on a hot plate up to 500 °C.

Room-temperature drying followed by thermal annealing was then carried out at 500 °C for round 90 nm. It is dried before the perovskite ink is added during the thermal annealing step mentioned previously.

2)-4 (A): Inkjet- printing of perovskite

The perovskite ink was loaded into a disposable Dimatix (DMP-2800) 1.5 ml_ printer cartridge of nominally 10 pL jetted droplet volume and containing 16 nozzles (21 pm orifice) and nozzle spacing of 254 pm. The cartridge head and substrate were not warmed prior to printing. Once printed, the wet film was immersed in diethylether for 5-10 s, removed, and annealed at 120 °C in ambient conditions.

The ink was used in a Fujifilm Dimatix DMP printer with a 16 nozzle printhead, 21 micron spacing between nozzles at a cartridge temperature of 45 °C. The ink formulation allows for stable printing and reduces coffee ring effect upon ink drying/concentration. 2)-4 (B): Perovskite Deposition by spin-coating:

Mixed-perovskite precursor was prepared by mixing 1.15 M Pbk, 1.10 M FAI, 0.2 M PbBr2, 0.2 M MABr in a mixed solvent of DMF:DMSO = 4:1 (volume ratio). Mixed perovskite solutions were successively spin-coated in the glovebox as follows: first, 2000 rpm for 10 s with a ramp-up of 200 rpnrs ^-1 ; second, 6000 rpm for 30 s with a ramp-up of 2000 rpnrs ^-1 . Toluene (110 pi) was dropped on the spinning substrate during the second spin-coating step 20 s before the end of the procedure. Then films were annealed at 100 °C for 90 min.

The pure MaPbl3 precursor solution contained 1.3 M Pbl2 and 1.3 M MAI in anhydrous DMSO. The perovskite films were prepared by spin-coating on the substrates at 1000 rpm for the first 10 s and 4000 rpm for the following 30 s. Chlorobenzene (0.1 ml_, CB) was slowly dropped on the film 10 s before the spin-coating program finished, then the samples were heated at 100°C for 1 hour.

2)-5: Perovskite film processing

For perovskite film processing, the wet ink is submerged in an antisolvent bath for a period of time of seconds to minutes and then the dry film is annealed on a hot plate at 120 °C.

After printing the perovskite precursor ink, the films were dipped in anti-solvent bath of diethyl ether, then dried, and annealed in ambient atmosphere at 120 °C for 30s - 1 min.

2)-6: Hole Transport Material (HTM) Deposition and gold evaporation

HTM solution (40 pL) containing 91 mg Spiro-OMeTAD and additives (21 pL of Li-bis(trifluoromethanesulfonyl)imide from a stock solution of 520 mg in 1 mL of acetonitrile, 16 mI_ of FK209, tris(2-(lH-pyrazol-l-yl)-4-tert-3 butyl pyridine)-cobalt(III) tris(bis(trifIuoromethylsulfonyl)imide from a stock solution of 375 mg in 1 mL of acetonitrile, and 36 pL of 4-tertbutylpyridine in 1 mL of CB was spin-coated on the samples at 4000 rpm for 20 s, and followed by the evaporating Au electrode with thickness of 70 nm.

Photovoltaic Characterization

The photovoltaic performance was analyzed using a VeraSol LED solar simulator (Newport) coupled with a Keithley 2400 source/meter giving light with AM 1.5G (100 W/cm ² ) spectral distribution. A black mask with an aperture 0.16 cm ² was applied on top of the cell. The light intensity was calibrated with an NREL certified KG5 filtered Si reference diode.

Table 1 presents photovoltaic performance of perovskite solar cells utilizing inkjet- printed mesoporous TΊO2 layers and spin-coated perovskite films under 100 mW-crrf ² simulated solar irradiation. Each value is an average of measurements from at least two devices. For these cells, drop spacing = 30 pm, passes = two. Asterisk denotes reference devices.

Table 1