# US 2021/0280787 A1 · Hole Transporting Material and Photovoltaic Device that Uses it

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- Number: US 2021/0280787 A1
- Document ID: US20210280787A1
- Status: Published application
- Kind: A1
- Application number: 16/466,100
- Filed: 2017-12-22
- Published: 2021-09-09
- Earliest claimed: 2016-12-27
- Assignees: ENI S.p.A.
- Applicants: Eni S.P.A.
- Inventors: Riccardo Po'; Alessandra Cominetti
- Web page: https://patentgrep.com/patent/US20210280787A1

## CPC

- H10K 85/361: {Polynuclear complexes, i.e. complexes comprising two or more metal centers}
- H10F 77/211: {for photovoltaic cells}
- H10K 30/81: Electrodes
- H10K 85/1135: {Polyethylene dioxythiophene [PEDOT]; Derivatives thereof}
- H10K 85/40: Organosilicon compounds, e.g. TIPS pentacene
- H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K 30/50: Photovoltaic [PV] devices
- H10K 50/15: Hole transporting layers
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K 85/151: {Copolymers}
- H10K 2101/30: Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
- H10K 2102/103: {comprising indium oxides, e.g. ITO}
- Y02E 10/549: Organic PV cells
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Hole transporting material obtained through a process comprising: reacting at least one heteropoly acid containing at least one transition metal belonging to group 5 or 6 of the Periodic Table of the Elements; with an equivalent amount of at least one salt or one complex of a transition metal belonging to group 5 or 6 of the Periodic Table of the Elements with an organic anion, or with an organic ligand; in the presence of at least one organic solvent selected from alcohols, ketones, esters. Said hole transporting material can be advantageously used in the construction of photovoltaic devices (or solar devices) such as, for example, photovoltaic cells (or solar cells), photovoltaic modules (or solar modules), either on a rigid support, or on a flexible support. Furthermore, said hole transporting material can be advantageously used in the construction of Organic Light Emitting Diodes (OLEDs), or of Organic Field Effect Transistors (OFETs). In particular, said hole transporting material can be advantageously used in the construction of a polymer photovoltaic cell (or solar cell) with an inverted structure.

## Claims

### Claim 1

Hole transporting material obtained by reacting:
at least one heteropoly acid containing at least one transition metal belonging to group 5 or 6 of the Periodic Table of the Elements; with
an equivalent amount of at least one salt or one complex of a transition metal belonging to group 5 or 6 of the Periodic Table of the Elements with an organic anion, or with an organic ligand;
in the presence of at least one organic solvent selected from alcohols, ketones, esters.

### Claim 2 (depends on 1)

Hole transporting material according to claim 1, wherein said heteropoly acid is selected from heteropoly acids having general formula (I):
Hx[A(MO3)yOz] (I)
in which:
A represents a silicon atom, or a phosphorus atom;
M represents an atom of a transition metal belonging to group 5 or 6 of the Periodic Table of the Elements;
x is an integer that depends on the valence of A;
y is 12 or 18;
z is 4 or 6.

### Claim 3 (depends on 1)

Hole transporting material according to claim 1, wherein said heteropoly acid is selected from heteropoly acids having general formula (II):
Hx[A(Mo)p(V)qO40] (II)
in which:
A represents a silicon atom, or a phosphorus atom;
x is an integer that depends on the valence of A;
p is 6 or 10;
q is 2 or 6.

### Claim 4 (depends on 2)

Hole transporting material according to claim 2, wherein said heteropoly acids having general formula (I) and said heteropoly acids having general formula (II) are selected from: phosphomolybdic acid hydrate {H3[P(MoO3)12O4].nH2O}, phosphomolybdic acid in alcoholic solution {H3[P(MoO3)12O4]}, phosphotungstic acid hydrate {H3[P(WO3)12O4].nH2O}, phosphotungstic acid in alcoholic solution {H3[P(WO3)12O4]}, silicomolybdic acid hydrate {H4[Si(MoO3)12O4].nH2O}, silicomolybdic acid in alcoholic solution {H4[Si(MoO3)12O4]}, silicotungstic acid hydrate {H4[Si(WO3)12O4].nH2O}, silicotungstic acid in alcoholic solution {H4[Si(WO3)12O4]}, phosphomolybdic vanadic acid hydrate {H3[P(Mo)6(V)6O40].nH2O}, phosphomolybdic vanadic acid in alcoholic solution {H3[P(Mo)6(V)6O40]}, phosphomolybdic vanadic acid hydrate {H3[P(Mo)10(V)2O40].nH2O}, phosphomolybdic vanadic acid in alcoholic solution {H3[P(Mo)10(V)2O40]}, and mixtures thereof.

### Claim 5 (depends on 1)

Hole transporting material according to claim 1, wherein said at least one salt or a complex of a transition metal belonging to group 5 or 6 of the Periodic Table of the Elements with an organic anion, or with an organic ligand, is selected from: bis(acetylacetonato)dioxomolybdenum(VI) (Cas No. 17524-05-9), molybdenum(VI) dioxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate) (Cas No. 34872-98-5), bis(tert-butylimido)(bis)(dimethylamino)molybdenum(VI) (Cas No. 923956-62-1), 2,6-di-iso-propylphenylimido-neophilidene molybdenum(VI) bis(tert-butoxide) (Cas No. 126949-65-3), 2,6-di-iso-propylphenylimidoneophilidene molybdenum(VI) bis(hexafluoro-tert-butoxide) (“Schrock's catalyst”) (Cas No. 139220-25-0), adduct of 2,6-di-iso-propylphenylimidoneophylidene molybdenum(VI) bis(trifluoromethanesulfonate)-dimethoxyethane (Cas No. 126949-63-1), 2,6-di-iso-propylphenylimidoneophylidene-[racemic-BIPHEN] molybdenum(VI) (“rac-Schrock's-Hoveyda catalyst”) (Cas No. 300344-02-9), 2,6-di-iso-propylphenylimidoneophylidene[R-(+)-BIPHEN]molybdenum(VI) [“(R) Schrock's-Hoveyda catalyst” ] (Cas No. 329735-77-5), 2,6-di-iso-propylphenylimidoneophylidene [S-(−)BIPHEN]molybdenum(VI) [“(S) Schrock's-Hoveyda catalyst” ] (Cas No. 205815-80-1), vanadium(V) oxytriisopropoxide (Cas No. 5588-84-1), vanadium(IV) oxide acetylacetonate (Cas No. 3153-26-2), acetylacetonate of vanadium(III), tetrakis(dimethylamino)vanadium(IV) (Cas No. 19824-56-7), tetrakis (diethylamino)vanadium(IV) (Cas No. 219852-96-7), and mixtures thereof.

### Claim 6 (depends on 1)

Hole transporting material according to claim 1, wherein the organic solvent is an alcohol selected from: methanol, ethanol, trifluoroethanol, n-propanol, iso-propanol, hexafluoro-iso-propanol, n-butanol, and mixtures thereof.

### Claim 7 (depends on 1)

Hole transporting material according to claim 1, wherein the organic solvent is a ketone selected from: cyclohexanone, acetone, methyl ethyl ketone, and mixtures thereof.

### Claim 8 (depends on 1)

Hole transporting material according to claim 1, in which the organic solvent is an ester selected from: butyrolactone, ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, and mixtures thereof.

### Claim 9 (depends on 1)

Hole transporting material according to claim 1, wherein said process is carried out at a temperature ranging from 25° C. to the boiling point of the solvent used, and for a time ranging from 15 minutes to 8 hours.

### Claim 10 (depends on 1)

Polymer photovoltaic cell (or solar cell) with an inverted structure comprising:
an anode;
an anode buffer layer;
an active layer comprising at least one photoactive organic polymer as the electron donor and at least one electron acceptor organic compound;
a cathode buffer layer;
a cathode;
wherein said anode buffer layer comprises the hole transporting material of claim 1.

### Claim 11 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, wherein said anode is made of metal or is constituted by grids of conductive material and by a transparent conductive polymer or is constituted by a metal nanowire-based ink.

### Claim 12 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, wherein said photoactive organic polymer is selected from:
(a) polythiophenes;
(b) conjugated alternating or statistical copolymers comprising:
at least one benzotriazole unit (B) having general formula (Ia) or (Ib):
in which group R is selected from alkyl groups, aryl groups, acyl groups, thioacyl groups, said alkyl, aryl, acyl and thioacyl groups being optionally substituted;
at least one conjugated structural unit (A), in which each unit (B) is connected to at least one unit (A) in any of positions 4, 5, 6, or 7;
(c) conjugated alternating copolymers comprising benzothiadiazole units;
(d) conjugated alternating copolymers comprising thieno[3,4-b]pyrazidine units;
(e) conjugated alternating copolymers comprising quinoxaline units;
(f) conjugated alternating copolymers comprising monomeric silica units;
(g) conjugated alternating copolymers comprising condensed thiophene units;
(h) conjugated alternating copolymers comprising benzothiadiazole or naphtothiadiazole units substituted with at least one fluorine atom and thiophene units substituted with at least one fluorine atom;
(i) conjugated copolymers comprising thieno[3,4-c]pyrrole-4,6-dione units;
(l) conjugated copolymers comprising thienothiophene units;
(m) polymers comprising a derivative of indacen-4-one having general formula (III), (IV) or (V):
in which:
W and W1, identical or different, represent an oxygen atom; a sulfur atom; an N—R3 group wherein R3 represents a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups;
Z and Y, identical or different, represent a nitrogen atom; or a C—R4 group in which R4 represents a hydrogen atom, or is selected from linear or branched C1-C20alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups, optionally substituted heteroaryl groups, linear or branched, C1-C20 alkoxy groups, R5—O—[CH2—CH2—O]n-polyethylenoxyl groups in which R5 is selected from linear or branched C1-C20 alkyl groups, and n is an integer ranging from 1 to 4, —R6—OR7 groups in which R6 is selected from linear or branched C1-C20 alkyl groups, and R7 represents a hydrogen atom or is selected from linear or branched C1-C20 alkyl groups, or is selected from polyethylenoxyl groups R5—[OCH2—CH2-]n— in which R5 has the same meanings reported above and n is an integer ranging from 1 to 4, —COR8 groups wherein R8 is selected from linear or branched C1-C20 alkyl groups —COOR9 groups in which R9 is selected from linear or branched C1-C20 alkyl groups; or represent a —CHO group, or a cyano group (—CN);
R1 and R2, identical or different, are selected from linear or branched C1-C20 alkyl groups; optionally substituted cycloalkyl groups; optionally substituted aryl groups; optionally substituted heteroaryl groups; linear or branched C1-C20 alkoxy groups; R5—O—[CH2—CH2—O]n-polyethylenoxyl groups—in which R5 has the same meanings reported above and n is an integer ranging from 1 to 4; —R6—OR7 groups in which R6 and R7 have the same meanings reported above; —COR8 groups in which R8 has the same meanings reported above; or —COOR9 groups in which R9 has the same meanings reported above; or represent a —CHO group, or a cyano group (—CN);
D represents an electron-donor group;
A represents an electron acceptor group;
n is an integer comprised from 10 to 500.

### Claim 13 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, wherein said organic electron acceptor compound is selected from derivatives of the fullerene.

### Claim 14 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, wherein said organic electron acceptor compound is selected from non-fullerene compounds, optionally polymeric; indacenothiophene with terminal electron-poor groups; compounds having an aromatic core able to symmetrically rotate.

### Claim 15 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, wherein said cathode buffer layer comprises zinc oxide, indium oxide, tin oxide, cerium oxide, or titanium oxide.

### Claim 16 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, wherein said cathode is made of a material selected from: indium tin oxide (ITO), tin oxide doped with fluorine (FTO), zinc oxide doped with aluminum (AZO), zinc oxide doped with gadolinium oxide (GZO); or is constituted by grids of conductive material, said conductive material being selected from silver (Ag), copper (Cu), graphite, graphene, and by a transparent conductive polymer, said conductive transparent polymer being selected from PEDOT: PSS [poly(3,4-ethylenediossithiophene): poly(styrene sulfonate)], (PEDOT:PANI) [poly(3,4-ethylenediossithiophene): polyaniline]; or it is constituted by a metal nanowire-based ink, said metal being selected from silver (Ag), and copper (Cu).

### Claim 17 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, wherein said cathode is associated with a support layer made of a rigid transparent material or of a flexible material selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethyleneimine (PI), polycarbonate (PC), polypropylene (PP), polyimide (PI), triacetyl cellulose (TAC), or their copolymers.

### Claim 18 (depends on 10)

Process for the preparation of a polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10, comprising:
forming the cathode through sputtering; or through electron beam assisted deposition; or through deposition of a conductive transparent polymer through spin coating, or gravure printing, or flexographic printing, or slot die coating, preceded by the deposition of grids of conductive material through evaporation, or screen-printing, or spray-coating, or flexographic printing; or through deposition of said metal nanowire-based ink through spin coating, or gravure printing, or flexographic printing, or slot die coating;
forming the cathode buffer layer through spin coating, or gravure printing, or flexographic printing, or slot die coating;
forming the active layer through spin coating, or gravure printing, or slot-die coating;
forming the anode buffer layer through spin coating, or gravure printing, or screen-printing, or flexographic printing, or slot-die coating;
forming the anode through vacuum evaporation, or screen-printing, or spray-coating, or flexographic printing; or through deposition of a conductive transparent polymer through spin coating, or gravure printing, or flexographic printing, or slot die coating, followed by deposition of grids of conductive material through evaporation, or screen-printing, or spray-coating, or flexographic printing; or through deposition of metal nanowire-based ink through spin coating, or gravure printing, or flexographic printing, or slot die coating.

### Claim 19 (depends on 10)

Polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 10 wherein:
the anode has a thickness ranging from 50 nm to 150 nm;
the anode buffer layer has a thickness ranging from 1 nm to 100 nm;
the active layer has a thickness ranging from 50 nm to 500 nm;
the cathode buffer layer has a thickness ranging from 10 nm to 100 nm;
the cathode has a thickness ranging from 50 nm to 150 nm.

### Claim 20 (depends on 12)

The polymer photovoltaic cell (or solar cell) with an inverted structure according to claim 12 wherein said photo active organic polymer is selected from the group consisting of poly(3-hexylthiophene) (P3HT), PffBT4T-2OD {poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3′″-di(2-octyldodecyl)-2,2′,5′,2″;5″,2′″-quaterthiophene-5,5′″-diyl)]}, PBDTTPD {poly[[5-(2-ethylhexyl)-5,6-dihydro-4,6-dioxo-4H-thieno[3,4-c]pyrrole-1,3-diyl] [4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]}; PTB7 {poly({4,8-bis[(2-ethylhexyl)oxo]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyll)carbonyl]thieno[3,4-b]thiophenediyl})}.