Photodiode comprising fluropolymer compound

Patent metadata

Field	Value
Publication number	US-11903304-B2
Application number	US-202017119153-A
Country	US
Kind code	B2
Filing date	Dec 11, 2020
Priority date	Dec 11, 2020
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

The invention relates to a photodiode, like an photovoltaic (OPV) cell or photodetector (OPD), comprising, between the photoactive layer and an electrode, a hole selective layer (HSL) for modifying the work function of the electrode and/or the photoactive layer, wherein the HSL comprises a fluoropolymer and optionally a conductive polymer, and to a composition comprising such a fluoropolymer and a conductive polymer.

First claim

What is claimed is:

1. A photodiode comprising
a photoactive layer,
a hole collecting electrode and an electron collecting electrode located on opposite sides of the photoactive layer,
a first hole selective layer (HSL) which is located between the photoactive layer and the hole collecting electrode, and which comprises a fluoropolymer of formula I

wherein
X is selected from the group consisting of H, Li, Na and K,
x is 0.01 to 0.99,
y is 0.99 to 0.01, and x+y=1,
n is an integer >1.

2. The photodiode according to claim 1 , which is a photovoltaic (OPV) or photodetector (OPD) device.

3. The photodiode according to claim 1 , wherein the first HSL further comprises a conductive polymer.

4. The photodiode according to claim 3 , wherein the conductive polymer comprises one or more repeating units selected from the group consisting of the following formulae

wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
X 1 , X 2 is O, S or Se,
R 1-6 is selected from the group consisting of H, F, Cl, CN, and straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are each optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —Si R 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C═C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are each optionally replaced by F, Cl, Br, I or CN, and in which one or more CH 2 or CH 3 groups are each optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
L is selected from the group consisting of F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , O R 0 , S R 0 , —C(═O)X0, —C(═O) R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 3 R 0 , —OH, —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,
R 0 , R 00 are H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,
X 0 is halogen.

5. The photodiode according to claim 4 , wherein the conductive polymer comprises one or more repeating units selected from the group consisting of the following formulae

wherein R 1 is as defined in claim 4 , and R 7 and R 8 denote, independently of each other and on each occurrence identically or differently, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more H atoms are each optionally replaced by F.

6. The photodiode according to claim 5 , wherein the conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedithiathiophene) (PEDTT) or poly(3-alkyl)thiophene wherein “alkyl” is C 1-12 alkyl or poly(thieno[3,4-b]thiophene).

7. The photodiode according to claim 1 , wherein the photodiode further comprises, between the photoactive layer and the hole collecting electrode, a second HSL comprising the conductive polymer.

8. The photodiode according to claim 1 , wherein the photoactive layer comprises, or is formed from, a p-type semiconductor which is selected from conjugated polymers, and an n-type semiconductor which is selected from the group consisting of fullerenes, fullerene derivatives and small molecules not containing a fullerene moiety.

9. The photodiode or process according to claim 8 , wherein the p-type semiconductor and the n-type semiconductor form a bulk heterojunction.

10. The photodiode according to claim 1 , which comprises the following sequence of layers from bottom to top:
optionally a first substrate ( 110 ),
a hole collecting electrode ( 120 ),
a hole selective layer (HSL) ( 130 ),
a photoactive layer ( 140 ) containing an n-type organic semiconducting (OSC) compound and a p-type OSC compound,
optionally an electron selective layer (ESL) ( 150 ),
an electron collecting electrode ( 160 ),
optionally a second substrate ( 170 ),
wherein the HSL ( 130 ) comprises a fluoropolymer of formula I as defined in claim 1 .

11. The photodiode according to one or more of claim 1 , which comprises the following sequence of layers from bottom to top:
optionally a first substrate ( 110 ),
an electron collecting electrode ( 160 ),
optionally an electron selective layer (ESL) ( 150 ),
a photoactive layer ( 140 ), containing an n-type organic semiconducting (OSC) compound and a p-type OSC compound,
a hole selective layer (HSL) ( 130 ),
a hole collecting electrode ( 120 ),
optionally a second substrate ( 170 ),
wherein the HSL ( 130 ) comprises a fluoropolymer of formula I as defined in claim 1 .

12. A process of manufacturing an photodiode according to claim 1 , comprising the following steps in the order from a) to h)
a) depositing a high work function electrode material onto a substrate ( 110 ) to form a hole collecting electrode ( 120 ),
b) optionally depositing a conductive polymer onto the hole collecting electrode ( 120 ) by a liquid-based process, to form a second HSL ( 180 ),
c) depositing a polymer of formula I or a composition or polymer blend according to the present invention as described above and below onto the hole collecting electrode ( 120 ) or, if present, onto the second HSL ( 180 ), to form a first HSL ( 130 ),
d) depositing an electron donor material and an electron acceptor material onto the first HSL ( 130 ) to form a photoactive layer ( 140 ),
e) optionally subjecting the photoactive layer ( 140 ) to thermal treatment, such as annealing, to form a randomly organized bulk heterojunction (BHJ),
f) optionally depositing an electron selective material onto the photoactive layer ( 140 ) to form an ESL ( 150 ), for example by a sputtering, vapour deposition or liquid-based process depending on the material used,
g) depositing a low work function electrode material onto the photoactive layer ( 140 ) or, if present, onto the ESL ( 150 ) to form an electron collecting electrode ( 160 ),
h) optionally applying a second substrate ( 170 ) onto the low work function electrode ( 160 ).

13. The process according to claim 12 , comprising steps a) to h) in reverse order.

14. The process according to claim 12 , wherein the photoactive layer comprises, or is formed from, a p-type semiconductor w

Assignees

• Raynergy Tek Inc

Inventors

• Chang Yi-Ming
• Liao Chuang-Yi
• Li Wei-Long
• Tsai Kuen-Wei
• Tan Huei Shuan
• Blouin Nicolas
• Lucera Luca
• Poertner Tim
• Morse Graham
• Tiwana Priti

Classifications

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H10K30/30

  comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains · CPC title

• H10K85/1135 Primary

  Polyethylene dioxythiophene [PEDOT]; Derivatives thereof · CPC title

• C09D165/00 Primary

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• C08G61/126

  with a five-membered ring containing one sulfur atom in the ring · CPC title