MOLECULAR SEMICONDUCTORS CONTAINING DIKETOPYRROLOPYRROLE AND DITHIOKETOPYRROLOPYRROLE CHROMOPHORES FOR SMALL MOLECULE OR VAPOR PROCESSED SOLAR CELLS
Optoelectronic devices, such as photovoltaic devices, comprising a low band gap, solution processable diketopyrrolopyrrole or dithioketopyrrolopyrrole chromophore core or cores are disclosed. Also disclosed are methods of fabricating such optoelectronic devices.
This application is a continuation of U.S. patent application Ser. No. 12/748,266 filed Mar. 26, 2010, now abandoned, which claims priority benefit of U.S. Provisional Patent Application No. 61/163,789, filed Mar. 26, 2009. The entire contents of those applications are hereby incorporated by reference herein in their entirety.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENTThis invention was made with Government support under grants N000140510677 and N000140811226 awarded by the Office of Naval Research, and grant DE-FG02-06ER46324 awarded by the Department of Energy. The Government has certain rights in this invention.
BACKGROUND OF THE INVENTIONSolar cells based on organic semiconductors are evolving into a promising cost-effective alternative to silicon-based solar cells due to low-cost fabrication by solution-processing, ease of processing, light weight, and compatibility with flexible substrates. Gunes et al. Chem. Rev. 2007, 107, 1324; Roncali, J., Acc. Chem. Res. 2009, 42, 1719. Devices based on these materials were predicted to have an efficiency of 10% based on theoretical models. Scharber et al. J. Adv. Mater. 2006, 18, 789. For instance, solution processed bulk heterojunction (BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the electron donor and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as the electron acceptor have been reported to have efficiencies as high as 5.2%. Kim et al. Nature Mater. 2006, 5, 197. Although this system is capable of yielding some of the highest reported efficiencies among organic photovoltaics, it suffers from two significant shortcomings: i) the P3HT-PCBM mixture does not absorb light with wavelengths longer than about 650 nm, and thus a large fraction of sunlight is wasted in this system; and ii) the P3HT must have a relatively high molecular weight and very high regioregularity. Most commercially available P3HT yields BHJ devices with efficiencies much lower than 5%. Synthesizing “good” P3HT can be problematic as the consistency between different batches of P3HT can vary.
Recently, there has been a significant effort to address the light absorption problem, and a large number of materials have been designed which have low band gaps and are able to absorb light at wavelengths up to 800 or 900 nm. Although such materials are successfully able to absorb a large fraction of the solar spectrum, most of them do not yield efficient BHJ photovoltaics due to inadequate electrical properties such as low charge carrier mobilities, incorrectly aligned HOMO and LUMO levels, or poor solid state morphologies.
The most successful low bandgap material reported as of early 2009 has been poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2, 1-b;3,4-bldithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT). In this case, photovoltaics with efficiencies of close to 6% have been reported. However, the material is polymeric and there have been problems reproducing results using PCPDTBT from different sources.
The absorption problem can also be solved by fabricating “tandem” solar cells, in which two BHJ photovoltaics are stacked on top of each other, with each layer absorbing a different fraction of the solar spectrum. Efficiencies as high as 6.5% have been reported using this type of system; however, fabricating two photovoltaic layers on top of each other adds a significant amount of complexity to the device architecture and difficulty in processing.
One material that has been used as an organic semiconductor in electronic devices is a diketopyrrolopyrrole-based polymer; efficiencies as high as 4.7% were reported for this material. See U.S. Patent Application Publication No. 2007/0228359; see also WO 2008/000664.
Solution-processed solar cells based on conjugated small molecule donors and fullerene acceptors have also been investigated by a number of research groups. As of March 2009, small molecule-based solar cell devices have power conversion efficiencies ranging from 0.3% to 1.3%. Schmidt-Mende et al. Science 2001, 293, 1119. These efficiencies remain low when compared to either thermally deposited small molecule bilayer solar cells or polymer-based solar cells. Despite the lower performance attained thus far, conjugated small molecules can potentially offer several advantages over polymeric materials, making them promising materials for solution-processed solar cells. For example, molecular organic semiconductors, such as oligothiophenes and oligoacenes, display higher hole and electron mobilities than their polymeric analogues as a result of better molecular ordering. Most important, conjugated small molecules do not suffer from batch to batch variations, broad molecular weight distributions, end group contamination, and difficult purification methods, as is the situation for their polymeric counterparts.
These devices have distinct advantages over previous optoelectronic devices. First, the material is not a polymer, making the synthesis and purification easier and more repeatable than for similar conjugated polymers. Second, the material has desirable electronic properties such as favorable HOMO level, LUMO level, and hole mobility (˜104 cm2/Vs). Third, the material has desirable optical properties, including a very high optical density and good overlap with the solar spectrum in the solid state. Fourth, the efficiencies observed in photovoltaics fabricated using this system are higher than those previously reported for solution-processed, non-polymeric photovoltaics. Oligothiophene derivatives functionalized with a diketopyrrolopyrrolo core have been used in solution-processed field effect transistors (Tantiwiwat et al., J. Phys. Chem. C, 112:17402 (2008)).
BRIEF SUMMARY OF THE INVENTIONThe present invention is directed to an optoelectronic device comprising of a mixture of a non-polymeric electron-donating chromophore based on a diketopyrrolopyrrole (DPP) structure, as well as an electron-accepting material such as a fullerene or methanofullerene, and a method of fabricating the device by solution processing. Also disclosed are non-polymeric electron donating chromophores based on the DPP structure.
In one embodiment, the invention embraces an optoelectronic device comprising a) a first hole-collecting electrode; b) an optional hole-transporting layer; c) a layer comprising a mixture of an electron donor material and an electron acceptor material; and d) a second electron-collecting electrode, wherein the electron donor material comprises a compound of the following general Formula I:
wherein X is oxygen or sulfur;
A1 and A2 are independently selected from substituted and unsubstituted aryl or heteroaryl groups, wherein each individual A1 within the (A1)m moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group, and each individual A2 within the (A2)n moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group;
B1 is independently selected from substituted and unsubstituted aryl or heteroaryl groups;
m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
p is independently selected from 0 or 1;
E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group; and
R1, R2, R3, and R4 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
In one embodiment, the device is a photovoltaic device.
In one embodiment, X is oxygen. In another embodiment, X is sulfur.
In one embodiment, A1 and A2 are independently selected from the group consisting of thiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, indole, benzene, naphthalene, anthracene, indene, fluorene, pyrene, azulene, furan, pyrrole, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, pyridothiadiazole, and carbazole. In another embodiment, A1 and A2 are thiophene. In another embodiment, the thiophene moieties bonded to the diketopyrrolopyrrole core are bonded to the core via the 2-position of the thiophene. In another embodiment, the thiophene moieties bonded to the E1 and E2 moieties are bonded to the E1 and E2 moieties via the 5-position of the thiophenes. In another embodiment, the thiophene moieties bonded to the diketopyrrolopyrrole core are bonded to the remainder of the molecule via the 5-position of the thiophene, the thiophene moieties bonded to the E1 and E2 moieties are bonded to the remainder of the molecule via the 2-position of the thiophenes, and, if either or both of m and n are greater than 1, any thiophene-thiophene bond is bonded via a bond between the 2- and 5-positions of the thiophenes.
In one embodiment, m=n=1. In another embodiment, m=n=2. In another embodiment, m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In one embodiment, B1 is independently selected from the group consisting of thiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, indole, benzene, naphthalene, anthracene, indene, fluorene, pyrene, azulene, furan, pyrrole, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, pyridothiadiazole, carbazole,
where the bonds ending in wavy lines indicate the attachment of the B1 moiety to the remainder of the molecule.
In one embodiment, R1, R2, R3, and R4 are the same and are selected from hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl.
In one embodiment, the invention embraces an optoelectronic device comprising a) a first hole-collecting electrode; b) an optional hole-transporting layer; c) a layer comprising a mixture of an electron donor material and an electron acceptor material; and d) a second electron-collecting electrode, wherein the electron donor material comprises a compound of the following general Formula II:
wherein X is oxygen or sulfur; A1 and A2 are selected from substituted and unsubstituted aryl or heteroaryl groups, wherein each individual A1 within the (A1)m moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group, and each individual A2 within the (A2)n moiety can be independently selected from a substituted and unsubstituted aryl or heteroaryl group; m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group; and R1 and R2 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
In one embodiment, the device is a photovoltaic device.
In one embodiment, X is oxygen. In another embodiment, X is sulfur.
In one embodiment, A1 and A2 are independently selected from the group consisting of thiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, indole, benzene, naphthalene, anthracene, indene, fluorene, pyrene, azulene, furan, pyrrole, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, pyridothiadiazole, and carbazole. In another embodiment, A1 and A2 are thiophene. In another embodiment, the thiophene moieties bonded to the diketopyrrolopyrrole core are bonded to the core via the 2-position of the thiophene. In another embodiment, the thiophene moieties bonded to the E1 and E2 moieties are bonded to the E1 and E2 moieties via the 5-position of the thiophenes. In another embodiment, the thiophene moieties bonded to the diketopyrrolopyrrole core are bonded to the remainder of the molecule via the 5-position of the thiophene, the thiophene moieties bonded to the E1 and E2 moieties are bonded to the remainder of the molecule via the 2-position of the thiophenes, and, if either or both of m and n are greater than 1, any thiophene-thiophene bond is bonded via a bond between the 2- and 5-positions of the thiophenes.
In one embodiment, m=n=1. In another embodiment, m=n=2. In another embodiment, m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In one embodiment, R1 and R2 are the same and are selected from hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl.
In one embodiment, the invention embraces an optoelectronic device comprising a) a first hole-collecting electrode; b) an optional hole-transporting layer; c) a layer comprising a mixture of an electron donor material and an electron acceptor material; and d) a second electron-collecting electrode, wherein the electron donor material comprises a compound of the following general Formula IIa:
wherein X is oxygen or sulfur; m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group; and R1 and R2 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
In one embodiment, the device is a photovoltaic device.
In one embodiment, X is oxygen. In another embodiment, X is sulfur.
In one embodiment, m=n=1. In another embodiment, m=n=2. In another embodiment, m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In one embodiment, R1 and R2 are the same and are selected from hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl.
In one embodiment, the invention embraces an optoelectronic device comprising a) a first hole-collecting electrode; b) an optional hole-transporting layer; c) a layer comprising a mixture of an electron donor material and an electron acceptor material; and d) a second electron-collecting electrode, wherein the electron donor material comprises a compound of the following general Formula IIb:
wherein m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group; R1 and R2 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
In one embodiment, the device is a photovoltaic device.
In one embodiment, m=n=1. In another embodiment, m=n=2. In another embodiment, m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
here m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In one embodiment, R1 and R2 are the same and are selected from hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl.
In one embodiment, the invention embraces an optoelectronic device comprising a) a first hole-collecting electrode; b) an optional hole-transporting layer; c) a layer comprising a mixture of an electron donor material and an electron acceptor material; and d) a second electron-collecting electrode, wherein the electron donor material comprises a compound of the following general Formula IIc:
wherein m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group; and R1 and R2 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
In one embodiment, the device is a photovoltaic device.
In one embodiment, m=n=1. In another embodiment, m=n=2. In another embodiment, m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In another embodiment, A1 is selected from
where m is 1, 2, or 3. In another embodiment, A2 is selected from
where n is 1, 2, or 3. In another embodiment, A1 is selected from
where m is independently 1, 2, or 3, and A2 is selected from
where n is independently 1, 2, or 3. In another embodiment, A1 is selected from
where m is 1, and A2 is selected from
where n is 1; or where m=n=2, or where m=n=3.
In one embodiment, R1 and R2 are the same and are selected from hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl.
In one embodiment of any of the above devices, the first electrode comprises indium tin oxide.
In one embodiment of any of the above devices, the optional hole transporting layer is present and comprises poly(3,4-ethylene dioxythiophene:poly(styrenesufonate) (PEDOT:PSS).
In one embodiment of any of the above devices, the electron acceptor is a fullerene electron acceptor. In another embodiment of any of the above devices, the fullerene electron acceptor is [6,6]-phenyl C61-butyric acid methyl ester (PCBM). In another embodiment of any of the above devices, the fullerene electron acceptor is PC71BM.
In one embodiment of any of the above devices, the electron acceptor is a vinazene, a perylenetetracaroxylicacid-dianhydrides, or a perylenetetracaroxylicacid-diimide.
In one embodiment of any of the above devices, the electron acceptor is an inorganic acceptor selected from TiO2 (titanium dioxide) and ZnO (zinc oxide). In one embodiment of any of the above devices, the electron acceptor is TiO2 (titanium dioxide). In one embodiment of any of the above devices, the titanium dioxide is anatase. In another embodiment of any of the above devices, the titanium dioxide is rutile. In another embodiment of any of the above devices, the titanium dioxide is amorphous. In one embodiment of any of the above devices, the titanium dioxide is prepared by depositing a sol-gel precursor solution, for example by spincasting or doctorblading, and sintering at a temperature between about 300° C. and 500° C. The precursor can comprise titanium isopropoxide or another titanium alkoxide, or a mixture of titanium alkoxides.
In one embodiment of any of the above devices, the electron donor:electron acceptor ratio is between about 3:7 to about 7:3 parts by mass.
In one embodiment of any of the above devices, the layer comprising a mixture of an electron donor material and an electron acceptor material is about 50 nm to about 150 nm in thickness.
In one embodiment of any of the above devices, the second electrode comprises aluminum, silver or magnesium.
In one embodiment of any of the above devices, the first electrode can comprise Au or a material having a work function higher than the work function of the second electrode. In one embodiment of any of the above devices, the second electrode can comprise an ITO substrate modified using a self-assembled monolayer of 3-aminopropyltrimethoxysiloxane or a material having a work function lower than the work function of the first electrode. In one embodiment of any of the above devices, the first electrode can comprise Au or a material having a work function higher than the work function of the second electrode, and the second electrode can comprise an ITO substrate modified using a self-assembled monolayer of 3-aminopropyltrimethoxysiloxane or a material having a work function lower than the work function of the first electrode.
In one embodiment of any of the above devices, the device exhibits an external quantum efficiency of about 25% or greater between the wavelengths of about 550 nm to about 750 nm.
In one embodiment of any of the above devices, the electron donor:electron acceptor layer is cast from a solution comprising a solvent and the electron donor and the electron acceptor. In various embodiments of any of the above devices, the solvent can comprise chloroform, thiophene, trichloroethylene, or carbon disulfide, or a mixture of any of the foregoing solvents.
In another embodiment, the invention embraces a compound of Formula I.
In another embodiment, the invention embraces an electronic device comprising a compound of Formula I
In another embodiment, the invention embraces a compound of Formula I where p=0.
In another embodiment, the invention embraces an electronic device comprising a compound of Formula I where p=0.
In another embodiment, the invention embraces a compound of Formula I where p=1.
In another embodiment, the invention embraces an electronic device comprising a compound of Formula I where p=1.
In another embodiment, the invention embraces a compound of Formula II.
In another embodiment, the invention embraces an electronic device comprising a compound of Formula II.
In another embodiment, the invention embraces a compound of Formula IIa.
In another embodiment, the invention embraces an electronic device comprising a compound of Formula IIa.
In another embodiment, the invention embraces a compound of Formula IIb.
In another embodiment, the invention embraces an electronic device comprising a compound of Formula IIb.
In another embodiment, the invention embraces a compound of Formula IIc.
In another embodiment, the invention embraces an electronic device comprising a compound of Formula IIc.
In another embodiment, the invention embraces compound A:
In another embodiment, the invention embraces an electronic device comprising the compound A.
In another embodiment, the invention embraces 2,5-di-(2-ethylhexyl)-3,6-bis-(5″-n-hexyl-[2,2′;5′,2″ ]terthiophen-5-yl)-pyrrolo[3,4-c]pyrrole-1,4-dione (SMDPPEH):
In another embodiment, the invention embraces an electronic device comprising the compound SMDPPEH.
In another embodiment, the invention embraces compound (4):
In another embodiment, the invention embraces an electronic device comprising the compound 4.
In another embodiment, the invention embraces the compound C6PT1C6.
In another embodiment, the invention embraces an electronic device comprising the compound C6PT1C6.
In another embodiment, the invention embraces the compound C6PT2C6.
In another embodiment, the invention embraces an electronic device comprising the compound C6PT2C6.
In another embodiment, the invention embraces the compound C6PT3C6.
In another embodiment, the invention embraces an electronic device comprising the compound C6PT3C6.
In another embodiment, the invention embraces the compound EHPT2C6.
In another embodiment, the invention embraces an electronic device comprising the compound EHPT2C6.
In another embodiment, the invention embraces the compound C6PT2.
In another embodiment, the invention embraces an electronic device comprising the compound C6PT2.
In another embodiment, the invention embraces the compound 26 of Example 11.
In another embodiment, the invention embraces an electronic device comprising the compound 26 of Example 11.
In another embodiment, the invention embraces the compound 36 of Example 12.
In another embodiment, the invention embraces an electronic device comprising the compound 36 of Example 12.
Thiophene-based oligomers have not yet been investigated as donor materials in solar cells, as they do not absorb strongly in the red and near-infrared part of the solar spectrum where most photons are concentrated. Excellent overlap between the absorption of the semiconducting material and the terrestrial solar spectrum is a key requirement for increasing solar cell efficiencies. Another reason why oligothiophenes have not been as readily incorporated into solution-processed devices is due to their low solubility in common organic solvents, as a result of strong intermolecular π-π interactions. To make oligothiophenes that exhibit absorption at long wavelengths, electron donors (e.g., arylamines) and acceptors (e.g., cyano, benzothiadiazole) have been appended onto their backbone. The addition of these groups changes the redox properties of the materials and thereby their absorption properties.
To make oligothiophenes that can be solution-processed, a variety of functional groups have been incorporated as side chains such as charged groups, acyl groups, alkylsulfanyl groups, alkylsilyl groups, ether-based dendrons and straight and branched alkyl moieties. Other approaches include attaching solubilizing groups that can be thermally removed after film deposition and to partially disrupt the strong intermolecular π-π interactions by designing star-shaped or cross-shaped systems.
One potential strategy to make suitable donor materials using oligothiophenes is to incorporate highly absorbing chromophores that are used to make dyes and pigments. One such chromophore is 3,6-diaryl-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione, more commonly known as diketopyrrolopyrrole (DPP). DPP-containing materials are bright and strongly fluorescent with exceptional photochemical, mechanical and thermal stability and are therefore used in industrial applications as high performance pigments in paints, plastics, and inks. DPP-based molecular materials, however, are not soluble in most common organic solvents due to the concurrent strong H-bonding and π-π intermolecular interactions in the solid state. Soluble derivatives, however, can be made by attaching solubilizing groups including ionic groups, charged, or neutral long alkyl chains, and organic protecting groups such as t-Boc on the 3,4-positions (i.e., the lactam N atoms) and/or on the 2,5-positions of the DPP moiety. It has been shown that the solid state packing and optical properties of DPP containing materials are dependent on the nature of these substituents. DPP-containing oligothiophenes can self-assemble in the solid state forming unexpected nanostructures. The self-assembly process can be controlled by the number of thiophene rings and the nature of the aliphatic chains attached to N atoms.
ABBREVIATIONS AND DEFINITIONSAbbreviations used herein are as follows: 5-di-(2-ethylhexyl)-3,6-bis-(5″-n-hexyl-[2,2′;5′,2″ ]terthiophen-5-yl)-pyrrolo[3,4-c]pyrrole-1,4-di one (SMDPPEH); Atomic force microscopy (AFM); cyclic voltametry (CV); diketopyrrolopyrrole (DPP); external quantum efficiency (EQE); indium tin oxide (ITO); organic field-effect transistors (OFETs); poly(3-hexylthiophene) (P3HT); [6,6]-phenyl C61-butyric acid methyl ester (PCBM); poly(3,4-ethylene dioxythiophene:poly(styrenesufonate) (PEDOT:PSS); power conversion efficiency (PCE).
“(C1-C12)-alkyl” is intended to embrace a saturated linear, branched, cyclic, or a combination of linear and/or branched and/or cyclic hydrocarbon chain(s) and/or ring(s) of 1 to 12 carbon atoms. Examples of “(C1-C12)-alkyl” include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclobutyl, cyclopropyl-methyl, methyl-cyclopropyl, pentyl, or 2-ethylhexyl, where the point of attachment of the alkyl group to the remainder of the molecule can be at any chemically possible location.
Optoelectronic Device Structure and Fabrication
In one embodiment, the optoelectronic device of the invention comprises the following layers:
a) a first hole-collecting electrode, optionally coated onto a transparent substrate;
b) an optional layer or layers adjacent to the first electrode, such as a hole-transporting layer;
c) a layer comprising a mixture of an electron donor of the general Formula I, II, IIa, IIb, or IIc, and an electron acceptor (donor:acceptor);
d) an optional layer or layers such as hole-blocking, exciton-blocking, or electron-transporting layers; and
e) a second electron-collecting electrode.
Typically, the first electrode can be transparent, allowing light to enter the device, but in some embodiments, the second electrode can be transparent. In some embodiments, both electrodes are transparent.
In another embodiment, the optoelectronic device of the invention comprises the following layers:
a) indium tin oxide (ITO) coated glass (a first electrode),
b) poly(3,4-ethylene dioxythiophene:poly(styrenesufonate) (PEDOT:PSS),
c) a mixture of electron-donating chromophores of the general Formula I, II, IIa, IIb, or IIc, and an electron-acceptor (donor:acceptor), and
e) a metal electrode (a second electrode);
where layer (d) in the previous embodiment is absent.
In one configuration, where light passes though a transparent first electrode (such as ITO-coated glass), it is absorbed by the donor:acceptor mixture, which results in the separation of electrical charges and migration of the charges to the electrodes, yielding a usable electrical potential (
The first electrode can be made of materials such as indium-tin oxide, indium-magnesium oxide, cadmium tin-oxide, tin oxide, aluminum- or indium-doped zinc oxide, gold, silver, nickel, palladium and platinum. Preferably the first electrode has a high work function (4.3 eV or higher).
The optional layer adjacent to the first electrode is preferably polystyrenesulfonic acid-doped polyethylenedioxythiophene (PEDOT:PSS). Other hole transporting materials, such as polyaniline (with suitable dopants), or N,N′-diphenyl-N,N′-bis(3-methylphenyl) [1,1′-biphenyl]-4,4′-diamine (TPD), can be used.
One method of fabricating the optoelectronic device is as follows: A conductive, transparent substrate is prepared from commercially available indium tin oxide-coated glass and polystyrenesulfonic acid doped polyethylenedioxythiophene using standard procedures. A solution containing a mixture of the donor and acceptor materials is prepared so that the ratio of donor to acceptor is between 1:99 and 99:1 parts by mass; more preferably between 3:7 and 7:3 parts by mass. The overall concentration of the solution may range between 0.1 mg/mL and 100 mg/mL, but is preferably in the range of 10 mg/mL and 30 mg/mL.
The electron acceptor is preferably [6,6]-phenyl C61-butyric acid methyl ester (PCBM), but may be a different fullerene (including, but not limited to, C71-PCBM), a tetracyanoquinodimethane, a vinazene, a perylene tetracarboxylic acid-dianhydride, a perylene tetracarboxylic acid-diimide, an oxadiazole, carbon nanotubes, or any other organic electron acceptor, such as those compounds disclosed in U.S. 2008/0315187.
In other embodiments, the electron acceptor is an inorganic acceptor selected from TiO2 (titanium dioxide) and ZnO (zinc oxide). The titanium dioxide can anatase, rutile, or amorphous. A titanium dioxide layer can be prepared by depositing a sol-gel precursor solution, for example by spincasting or doctorblading, and sintering at a temperature between about 300° C. and 500° C. When an inorganic layer is used, component (c) of the optoelectronic device described above can be comprised of a layer of electron-donating chromophores of the general Formula II and an inorganic electron-acceptor layer. Alternatively, the inorganic material can be dispersed in the electron-donating chromophores to create a single layer. Preparation of TiO2 for use in solar cells is described in Brian O'Regan & Michael G{umlaut over (r)}atzel Nature 353:737 (1991) and Serap Günes et al., 2008 Nanotechnology 19 424009.
Useful solvents include chloroform, toluene, chlorobenzene, methylene dichloride and carbon disulfide. However, the solvent used may be any solvent which dissolves or partially dissolve both donor and acceptor materials and has a non-zero vapor pressure.
The solution of donor and acceptor is deposited onto the transparent conductive substrate by spin casting, ink-jet printing, roll-to-roll coating or any process which yields a continuous film of the donor-acceptor mixture such that the thickness of the film is within the range of 10 to 1000 nm, more preferably between 50 and 150 nm.
In certain embodiments, the layer of the donor and acceptor is cast from a solution comprising a solvent and the electron donor and the electron acceptor. The solvent can comprise chloroform, thiophene, trichloroethylene, or carbon disulfide, or a mixture of any of the foregoing solvents. The solvent can also include processing additives, such as those disclosed in US Patent Application Publication Nos. 2009/0032808, 2008/0315187, or 2009/0108255. For example, 1,8-octanedithiol can be added to the solvent/donor/acceptor mixture in an amount of about 1% or at least about 1%, about 2% or at least about 2%, about 3% or at least about 3%, about 4% or at least about 4%, about 5% or at least about 5%, about 8% or at least about 8%, or about 10% or at least about 10%. The additive, such as 2% 1,8-octanedithiol, can be added to any organic solvent used to cast the layer of donor/acceptor, such as chloroform.
An additional layer or layers of material (i.e., the layer(s) adjacent to the second electrode) may optionally be deposited on top of the donor-acceptor film in order to block holes or excitons, act as an optical buffer, or otherwise benefit the electrical characteristics of the device. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline can act as a hole-blocking or exciton-blocking material, while 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine and polyethylene dioxythiophene can act as exciton-blocking materials.
Finally, a metal electrode is deposited on top of the structure by thermal evaporation, sputtering, or some other process. The metal is preferably aluminum, silver or magnesium, but may be any metal. In some embodiments, the device is annealed before and/or after evaporation of the metal electrode.
Hole and electron mobilities are important parameters to consider in the fabrication/function of bulk heterojunction solar cells. For optimal device performance, a balance in the mobility of both charge carriers is desirable. Preferably, the electron and hole mobilities are both on the order of 10−4 cm2/Vs or higher. More preferably, the electron mobilities are on the order of 10−3 cm2/Vs or higher. In some embodiments, the electron mobilities are on the order of 10−4 cm2/Vs or higher, and the hole mobilities are between 10−8 cm2/Vs and 104 cm2/Vs or higher. In other embodiments, the electron mobilities are on the order of 10−3 cm2/Vs or higher, and the hole mobilities are between 10−8 cm2/Vs and 104 cm2/Vs or higher.
Optoelectronic devices of the present invention have excellent photovoltaic properties. In some embodiments, the power conversion efficiency (PCE) is at least 0.5%, at least 1.0%, at least 2.0%, at least 3.0%, or at least 4.0%. In some embodiments, the short circuit current density is greater than 3.0 mA/cm2, and preferably greater than 8 mA/cm2. In some embodiments, the open circuit voltage is between 0.6 and 1.0 V or higher. In some embodiments, the device exhibits an external quantum efficiency of approximately 25% or greater between 550-750 nm.
The morphological properties of the donor:acceptor films can be measured using atomic force microscopy or other surface-sensitive techniques. Preferably, the films will have a root-mean-squared surface roughness of less than 1.0 nm, more preferably less than 0.5 nm.
For embodiments of the devices using an inverted device architecture, the first electrode can comprise Au or another material having a work function higher than the work function of the second electrode, while the second electrode can comprise an ITO substrate modified using a self-assembled monolayer of 3-aminopropyltrimethoxysiloxane or another material having a work function lower than the work function of the first electrode.
Electron-Donating Chromophores
Electron-donating chromophores useful in fabricating the devices described herein can be of the formulas I, II, IIa, IIb, or IIc as described herein. For example, the electron-donating chromophores can be of the following general Formula II:
wherein
X is oxygen or sulfur;
A1 and A2 are selected from substituted and unsubstituted aryl or heteroaryl groups, wherein each individual A1 within the (A1)m moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group, and each individual A2 within the (A2)n moiety can be independently selected from a substituted and unsubstituted aryl or heteroaryl group;
m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group;
and
R1 and R2 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
In certain embodiments, X is sulfur. In other embodiments, X is oxygen.
In certain embodiments, the one or more substituted or unsubstituted aryl or heteroaryl groups A1 and A2 are independently selected from the group consisting of thiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, indole, benzene, naphthalene, anthracene, indene, fluorene, pyrene, azulene, furan, pyrrole, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, pyridothiadiazole, and carbazole. Each individual Am group in an (A1)m chain, and each individual A2 in an (A2)n chain, can be independently selected. Thus, for example, when m=3, the (A1)3 chain can be:
The aryl or heteroaryl groups are directly connected to each other at any valence where a bond to another group is chemically possible, and in a manner so as to allow conjugation of the delocalized electrons between the aryl or heteroaryl groups and any other aryl or heteroaryl groups to which they are bonded, such as the diketopyrrolopyrrole core moieties.
In certain embodiments, the moieties E1 and E2 are independently selected from n-hexyl (—C6H13) and benzofuran
In other embodiments, when E1 and/or E2 is benzofuran, the benzofuran moiety is attached to the remainder of the molecule at the 2-position of the benzofuran ring.
In certain embodiments, m=n=3. In other embodiments, m=n=2. In other embodiments, m=n=1.
In certain embodiments, the moieties R1 and R2 are independently selected from the group consisting of hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl. In another embodiment, the same group selected for R1 is also used for the R2 group.
In certain embodiments, the electron-donating chromophore comprises compound A, which has the following formula:
In other embodiments, the electron-donating chromophore comprises 2,5-di-(2-ethylhexyl)-3,6-bis-(5″-n-hexyl-[2,2′;5′,2″ ]terthiophen-5-yl)-pyrrolo[3,4-c]pyrrole-1,4-dione (SMDPPEH), which has the following formula:
In other embodiments, the electron-donating chromophore comprises compound (4), which has the following formula:
In other embodiments, the electron-donating chromophore comprises C6PT1C6. In other embodiments, the electron-donating chromophore comprises C6PT2C6. In other embodiments, the electron-donating chromophore comprises C6PT3C6. In other embodiments, the electron-donating chromophore comprises EHPT2C6. In other embodiments, the electron-donating chromophore comprises C6PT2. The structures of C6PT1C6, C6PT2C6, C6PT3C6, EHPT2C6, and C6PT2 are described in Example 10 below. In other embodiments, the electron-donating chromophore comprises compound 26 of Example 11. In other embodiments, the electron-donating chromophore comprises compound 36 of Example 12.
Excellent solubility and high thermal stability of the electron-donating chromophores leads to a more robust optoelectronic device. In some embodiments, the electron-donating chromophore has a solubility of >20 mg/mL in chloroform, chlorobenzene or toluene. In some embodiments, the electron-donating chromophore is thermally stable up to 250° C.
Conversion of Diketopyrrolopyrroles to Dithioketopyrrolopyrroles
Syntheses of diketopyrrolopyrroles are presented in the Examples below. Once the diketopyrrolopyrroles have been prepared, reaction with Lawesson's reagent or other thiation agents converts the diketopyrrolopyrroles into dithioketopyrrolopyrroles. Exemplary protocols are provided in Closs and Gompper, Angew. Chem. Int. Ed. Engl. 26(6):552 (1987), and in Thomsen et al., Organic Syntheses, Coll. Vol. 7, p. 372 (1990); Vol. 62, p. 158 (1984).
Use of Diketopyrrolopyrroles and Dithioketopyrrolopyrroles as Electron Acceptors
While the diketopyrrolopyrroles and dithioketopyrrolopyrroles described herein are described primarily as electron donors, compounds of the formula I, II, IIa, IIb, and IIc can also be used as electron acceptor materials. For use as an electron acceptor, the diketopyrrolopyrrole or dithioketopyrrolopyrrole should have a relatively low LUMO level, about 0.3 eV or more lower than the LUMO of the electron donor it will be used with. It should also have a reasonably high electron mobility to serve as an acceptor, such as an electron mobility about or on the order of 10−6 cm2/Vs or higher, preferably about or on the order of 104 cm2/Vs or higher, more preferably about or on the order of 10−3 cm2/Vs or higher. Lowering the LUMO and increasing electron mobility can be accomplished by using electron withdrawing groups (such as fluoro, chloro, cyano, trifluoromethyl, etc.) attached to the conjugated system, or by using electron deficient aryl groups (such as pyridine or benzothiadiazole); see Prashant Sonar, J. Mater. Chem., 2010, DOI: 10.1039/b924404b.
Inverted Device Architecture
In some cases, it can be advantageous to have the substrate act as a cathode, while the top electrode acts as the anode. For example, using the substrate to collect electrons can allow a stable, high work function metal such as gold or nickel to be used as the top electrode. This can be achieved by modifying the work function of the substrate or using an n-type substrate.
Compound 4 was synthesized according to the following synthetic procedure:
Part A. The parent 2,5-dihydro-1,4-dioxo-3,6-dithienylpyrrolo[3,4-c]-pyrrole (1) was prepared in 55% yield following a previously reported procedure which comprises the reaction of 2-thiophenecarbonitrile with 0.5 eq of di-n-butyl succinate ester and an excess of potassium t-butoxide using 2-methyl-2-butanol as solvent. See Tamayo et al., J. Phys. Chem. C 112:15543 (2008) and references therein.
Part B. Compound (2) was synthesized according to a modified literature procedure. Zambounis et al. Nature 1997, 388, 131. In a three-necked, oven-dried 100 mL round bottom flask, 1 (3.0 g, 10.0 mmol) was dissolved in 150 mL of anhydrous tetrahydrofuran (THF) and the resulting solution was purged with argon for ten minutes. Dimethylaminopyridine (DMAP 3.0 g, 25 mmol) was added and the reaction mixture was stirred for 15 minutes under argon at room temperature. Di-tert-butyl-dicarbonate (11.0 g, 50 mmol) was then added and the mixture was stirred for 24 hours, after which the solvent was removed in vacuo to obtain a brownish red solid. Petroleum ether (250 mL) was poured into the crude product and the resulting suspension was stirred for 1 hour. The solids were then collected by vacuum filtration and further washed with several portions of petroleum ether. The crude product was purified by flash chromatography using chloroform as eluent and the solvent was removed in vacuo giving 4.0 g of pure product as a shiny crystalline red powder. (yield: 4.0 g, 80.2%).
Analysis: NMR (400 MHz, CDCl3, ppm) δ=8.28 (dd, J=4.0 Hz, 1.2 Hz, 2H), 7.68 (dd, J=4.0 Hz, 1.2 Hz, 2H), 7.19 (dd, J=8.0 Hz, 4.0 Hz, 4.0 Hz, 2H), 1.60 (s, 18H). MS (ESI-TOF): Calculated for C24H24N2O6S2: 500.11. Found: 501 (M++H). CHN Analysis: Calcd. C, 57.58; H, 4.83; N, 5.60. Found: C, 57.23; H, 4.88; N, 5.73.
Part C. Compound (3) was synthesized according to a modified literature procedure. Zhang et al. J. Mater. Chem. 2006, 16, 736. In a three-necked, oven-dried 150 mL round bottom flask covered with aluminum foil, 2 (2.623 g, 4.0 mmol) was dissolved in 150 mL of anhydrous CHCl3, covered with aluminum foil and stirred at room temperature under argon for 15 minutes. N-bromosuccinimide (1.500 g, 8.4 mmol) was then added and the reaction mixture was kept at room temperature and stirred for 48 hours. The reaction mixture was poured into 400 mL of methanol and the resulting suspension was stirred at room temperature for 15 minutes. The solid was then collected by vacuum filtration and was washed with several portions of hot distilled water and hot methanol to obtain 1.98 g of pure product as shiny dark purple powder (yield: 1.98 g, 60.2%).
Analysis: 1H NMR (400 MHz, CDCl3, ppm) δ=8.08 (d, J=4.0 Hz, 2H), 7.15 (d, J=4.0 Hz, 2H), 1.63 (s, 18H). MS (ESI-TOF): Calculated for C30H38Br2N2O2S2: 655.93. Found 656 (M++H). CHN Analysis: Calcd. C, 43.78; H, 3.37; N, 4.25. Found: C, 43.67; H, 3.30; N, 4.21.
Part D. Compound (4) was synthesized according to a modified literature procedure. Zrig et al. J. Org. Chem. 2007, 72, 5855. In an three-necked, oven-dried 100 mL round bottom flask, 3 (0.6825 g, 1.00 mmol) and 5′-hexyl-2,2′-bis-thiophene boronic acid pinacol ester (2.25 mmol) were dissolved in 15 mL of anhydrous toluene and 20 ml of anhydrous 1,2-dimethoxyethane and the resulting solution degassed for ten minutes. Tris(dibenzylideneacetone)dipalladium(0) (14 mg, 0.0153 mmol), and tri-tert-butylphosphonium tetrafluoroborate (18 mg, 0.0620 mmol) were then added and the mixture degassed for another five minutes. A degassed 2.0 molar solution of potassium phosphate (5 mL) was then added and the reaction mixture stirred and heated to 90° C. under argon overnight. The reaction mixture was allowed to cool down to room temperature after which it was poured into 400 mL of methanol and was then stirred for 30 minutes. The precipitated solid was then collected by vacuum filtration and was washed with several portions of distilled water, methanol, isopropanol and petroleum ether. The crude product was purified by flash chromatography using chloroform as eluent and the solvent removed in vacuo giving a shiny green crystalline powder (yield: 0.65 g, 65.0%).
Analysis: 1H NMR (400 MHz, CDCl3, ppm) δ=8.28 (d, J=4.0 Hz, 2H), 7.21 (dd, J=4.0 Hz, 4H), 7.04 (dd, J=4.0 Hz, 4H), 6.71 (d, J=4.0 Hz, 2H), 2.81 (t, J=8.0 Hz, 4H), 1.68-1.72 (m, 4H), 1.66 (s, 18H), 1.22-1.46 (m, 10), 0.90 (t, J=7.2 Hz, 6H). MS (FAB): Calculated for C52H56N2O6S6: 996.25. Found 996. MS (FAB): Calculated for C52H56N2O6S6: 996.25. Found 996. Calcd. C, 62.62; H, 5.66; N, 2.81. Found: C, 62.30; H, 5.64; N, 2.85.
Example 2 Device FabricationIndium tin oxide (ITO)-coated glass substrates (Thin Film Devices) were cleaned with detergent and de-ionized water after which the substrates were sonicated for 10 minutes in soap solution, de-ionized water, acetone and isopropanol. The ITO substrates were then treated in a UV ozone cleaner for 30 minutes followed by spin coating a solution of poly(3,4-ethylene dioxythiophene:poly(styrenesulfonate) (PEDOT:PSS, Baytron P) (5000 rpm for 40 seconds). The PEDOT:PSS film was dried at 140° C. inside a glovebox for 15 minutes which yielded a film 60 nm thick. A 2% (w/v) blend solution of compound (4) and PCBM (Nano-C, USA) in chloroform (CHCl3) was filtered through a 0.45 μm poly(tetrafluoroethylene) (PTFE) filter and spin coated at 1500 rpm for 60 seconds on top of the PEDOT:PSS layer. Subsequently, aluminum (1200 Å) was thermally evaporated at a pressure of 1×10−7 Torr at room temperature using a shadow mask. Illumination was done through the glass slide using light from 150 W Newport-Oriel AM 1.5 G light source operating at 100 mW/cm2. Mobility measurements were done using the following diode structures: ITO/PEDOT:PSS/active material/Au for holes and Al/active material/Al for electrons. Au (1000 Å) and Al (500 Å) electrodes were thermally evaporated at a pressure of 1×10−7 Torr at room temperature using a shadow mask (Angstrom Engineering, Inc.). The active layer thicknesses in all devices obtained by AFM were approximately 100-110 nm. All fabrications and characterization were performed under nitrogen.
Example 3 Electrochemical and Photophysical Characterization of (4)Cyclic voltammetry (CV) was performed using an EG&G potentiostat/galvanostat model 283. Anhydrous dichloromethane was used as the solvent under an inert atmosphere, and 0.1 M solution tetra-butyl ammonium hexafluorophosphate was used as the supporting electrolyte. A glassy carbon rod was used as the working electrode, a platinum wire was used as the counter electrode, and a silver wire was used as a pseudo reference electrode. The redox potentials are obtained by taking the average of anodic and cathodic waves and are reported relative to a ferrocenium/ferrocene (Cp2Fe+/Cp2Fe, 0.475 V versus SCE in dichloromethane) redox couple used as an internal reference. UV-visible absorption spectra were recorded on a Shimadzu UV-2401 PC dual beam spectrometer. Steady-state fluorescence experiments at room temperature were performed using a PT1 (Lawrenceville, N.J.) Quantum Master fluorimeter equipped with a Xenon lamp excitation source and a Hamamatsu (Japan) 928 PMT using 90° angle detection for solution samples.
The CV of (4) exhibits one reversible oxidation process and one reduction process at 0.43 V and at −1.61 V, respectively. Based on the measured oxidation and reduction potentials, (4) has HOMO and LUMO energy levels of −5.03 eV and −3.0 eV, respectively. These values are within the required electronic levels for BHJ solar cells when PCBM is used as the electron acceptor.
Tapping mode atomic force microscopy (AFM) topographic and phase images of pure (4) and the blends were obtained using the Multi-Mode microscope and the controller NanoScope IIIa (Veeco Inc.). Images were collected in air using silicon probes with a typical spring constant of 1-5 nN/m and a resonant frequency of 75 kHz (Budget Sensors).
To demonstrate the potential of (4) as an electron donor in photovoltaic devices, BHJ devices were fabricated by spin-coating from 2% (w/v) chloroform solutions comprising a mixture of (4) and PCBM in different blend ratios (30:70, 50:50, and 70:30).
AFM topographical and phase images collected in the areas between the Al electrodes of the devices are shown in
The hole and electron mobilities were measured for 30:30, 50:50 and 70:30 blend ratios using the hole-only and electron-only diode structures. The mobility values were extracted using the SCLC model. Blom et al. Phys. Rev. B 1997, 55, 656. It was found that the electron mobilities do not change significantly as the donor concentration increases. The electron mobilitites are 3, 5 and 6×104 cm2/Vs for 30%, 50% and 70% acceptor contents, respectively. In contrast, the hole mobilities exhibited a more pronounced dependence on the concentration of donor material, increasing by more than an order of magnitude from 2×10−8 to 5×10−7 cm2/Vs as the concentration of donor material was decreased from 30% to 70%. It is evident that the charge transport properties are more balanced at high donor concentration, resulting in improved device efficiency. From these results, the electron and hole mobilities are different by three orders of magnitudes. Thus, higher efficiency can be achieved if one can further improve the hole mobility.
The optimal donor concentration in this system is much larger than optimal blend ratios previously observed for solution-processed conjugated polymer/PCBM mixtures. This may be because large concentrations of (4) do not disrupt the percolation of the PCBM phase as polymers do. In this system, a high donor concentration is not seen to adversely affect device properties as with polymers, but allows for enhanced light absorption by the chromophore and increased order in film morphology, in addition to balancing charge transport properties.
Example 6 Electrochemical and Photophysical Characterization of SMDPPEH and SMDPPEH:PCBM BlendThe optical properties of SMDPPEH in solution (dotted line) and in film (solid line) together with that of C71-PCBM (dashed line) are shown in
From the external quantum efficiency (EQE) spectra shown in
The hole and electron mobilities for all the blends are given in Table 2. The hole mobilities are of the order of 10−4-10−5 cm2/V·s and are not significantly different from the measured hole mobility of the pure donor film irrespective of the blend ratio. Similarly, the electron mobilities are also of the order of 10−4 cm2/V's. These carrier mobilities are comparable to those measured for high performance BHJs solar cells based on P3HT:PCBM blends. Importantly, the electron and hole mobilities of the blends are quite balanced which may help explain the high PCEs observed for this donor-acceptor system.
The AFM images of the as-cast films of SMDPPEH:C71-PCBM with different blend ratios are given in
In a three-necked, oven-dried 100 mL round-bottom flask, 3,6-bis-(5-bromo-thiophen-2-yl)-2,5-di-n-octyl-pyrrolo[3,4-c]pyrrole-1,4-dione (0.683 g, 1.00 mmol) (Wienk, M. M., Turbiez, M., Gilot, J. & Janssen, R. A. J., Adv. Mater. 20, 2556-2560 (2008)) was mixed with 15 mL of anhydrous toluene and 10 ml of 2.0 M potassium phosphate and the resulting mixture was degassed for 10 min. Benzofuran-2-boronic acid (0.375 g, 2.25 mmol), tris(dibenzylideneacetone)dipalladium(0) (14 mg, 0.0153 mmol), and tri-tert-butylphosphonium tetrafluoroborate (18 mg, 0.0620 mmol) were then added to the mixture and then degassed again for 5 minutes. The reaction mixture was stirred and heated to 90° C. under argon overnight. The reaction mixture was allowed to cool down to room temperature, after which it was poured into 300 mL of methanol and then stirred for 30 min. The precipitated solid was then collected by vacuum filtration and washed with several portions of distilled water, methanol, isopropanol, and petroleum ether. The crude product was purified by flash chromatography using chloroform as eluent, and the solvent was removed in vacuo to obtain a pure product. 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione is formed as a shiny, dark-green powder (yield: 67.2%). mp 233° C. 1H NMR (250 MHz, CDCl3, ppm) δ=9.01 (d, J=4.0 Hz, 2H), 7.48-7.61 (m, 6H), 7.20-7.36 (m, 6H), 7.05 (s, 2H), 4.85 (dd, J=4.0 Hz, 0.5 Hz, 4H) 1.98 (m, 2H), 1.20-1.50 (m, 20H), 0.80-1.00 (m, 12H). MS (LR-EI) m/z: [M+] calculated for C38H44N22N2O2S4: 756.31. found 756.03. CHN analysis: calcd: C, 72.89; H, 6.39; N, 3.70. found: C, 72.35; H, 6.33; N, 3.88.
Example 9 Fabrication of Solar Cells Incorporating SMBFuSolar cells were fabricated by spin-casting the active bulk heterojunction layer onto a 50 nm layer of H.C. Stark Baytron P 4083 poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) on Corning 1737 active-matrix liquid-crystal-display glass patterned with 140 nm of indium tin oxide by Thin Film Devices. An 80-nm-thick aluminum cathode was deposited (area 20 mm2) by thermal evaporation with no heating of the sample. Unless otherwise stated, the bulk heterojunction layer was spin-cast at 2,500 r.p.m. from a solution of SMBFu and PC71BM in chloroform at a total solids concentration of 20 mgml−1. PC71BM was purchased from Nano-C. The active layers were determined to be approximately 95 nm thick using an Ambios XP-100 Stylus profilometer. Device efficiencies were measured with a 150WNewport-Oriel AM 1.5 G light source operating at 100 mWcm−2 and independently cross-checked using a 300WAM 1.5 G source operating at 100 mWcm-2 for verification. Solar-simulator illumination intensity was measured using a standard silicon photovoltaic with a protective KG5 filter calibrated by the National Renewable Energy Laboratory. IPCE spectra measurements were made with a 250 W Xe source, a McPherson EU-700-56 monochromater, optical chopper and lock-in amplifier, and a National Institute of Standards and Technology traceable silicon photodiode for monochromatic power-density calibration. AFM images were taken on a Veeco Innova AFM. Ultraviolet-visible absorption spectroscopy was measured on a Shimadzu 2401 diode array spectrometer. For ultraviolet photoelectron spectroscopy (UPS) measurements, a 75 nm thick Au film was deposited on a precleaned Si substrates with a thin native oxide.
Absorption characteristics of as-cast SMBFu:PC71BM films at various blend ratios are shown in
Blend (or pure) solutions were then spin coated at spin speeds of 2,000 rpm and concentration of 0.1%. All films were fabricated inside a N2 atmosphere glovebox and were transferred via an airtight sample holder to the UPS analysis chamber. Samples were also kept in a high vacuum chamber overnight to remove solvent residues. The UPS analysis chamber was equipped with a hemispherical electron energy analyzer (Kratos Ultra Spectrometer) and was maintained at 1×10−9 Torr. The UPS measurements were carried out using the He I (hv=21.2 eV) source. During UPS measurements, a sample bias of −9 V was used in order to separate the sample and the secondary edge for the analyzer. In order to confirm reproducibility of UPS spectra, the measurements were repeated twice on each set of samples. Thin film XRD spectra were recorded using an X'Pert Phillips Material Research Diffractometer (MRD) at 45 kV and 40 mA with a scanning rate of 0.004 degree per second, and Cu Kα radiation (with wavelength λ=1.5405 Å) with a 2theta-omega configuration. Carrier mobilities were measured using the space charge limited current technique where J-V curves were measured for devices with the architecture ITO/PEDOT:PSS/SMBFu:PC71BM/Au for holes and Mg/SMBFu:PC71BM/Mg for electrons. Electron mobility measurements were repeated using the architecture Al/SMBFu:PC71BM/Ba/Al. Electron mobilities were measured using electrodes with different work functions to ensure that the built-in potential of the devices did not affect the results. Mobilities were extracted by fitting the current density-voltage curves using the Mott-Gurney relationship.
One of the primary reasons that small molecules have not been investigated more extensively as solution processable semiconductors is that they tend to either be insoluble or form rough films. Until now, morphologies have not been achieved which allow efficient charge separation and collection such as those observed in P3HT:PCBM systems. Since it is known that the morphology of the active layer in BHJ solar cells significantly affects the performance, the morphologies of pure SMBFu films and blends with PC71BM were investigated using tapping mode atomic force microscopy (AFM). SMBFu is soluble in chloroform at 60° C. up to ˜20 mg/mL and forms smooth films with an average surface roughness of 0.7 nm when spin cast onto indium tin oxide (ITO) coated glass substrates with a 45 nm layer of poly(styrenesulfonic acid) doped poly(ethylenedioxythiophene) (PEDOT:PSS). Annealing pure SMBFu at ˜100° C. increases surface roughness to ˜1.0 nm.
The solid state structure of mixed donor-acceptor films influences how the material will perform as a BHJ solar cell. The donor and acceptor films should phase separate into an interpenetrating network of donor and acceptor domains, where the ideal domain size of a donor or acceptor material depends largely on the exciton diffusion length in each material. When the domain size of the material is smaller than the exciton diffusion length, this allows many excitons to diffuse to a donor-acceptor interface and undergo charge separation.
AFM was used to examine the surface structure of SMBFu:PC71BM films as a function of annealing temperature. SMBFu forms good quality films when spin cast with PC71BM. Mixtures of SMBFu and PC71BM at 20 mg/mL overall concentration in chloroform, spin cast at 2,500 rpm yield films approximately 95 nm thick.
Next, the effect of donor:acceptor ratio on film morphology was examined. The as-cast SMBFu:PC71BM films at various blend ratios are smooth with a surface roughness of less than 1 nm similar to those of
The charge carrier mobilities of BHJ films have a large affect on how a material will perform in a solar cell. Low charge carrier mobilities result in charge accumulation and inefficient charge collection while un-balanced charge carrier mobilities decrease the fill factor (FF) and efficiency of BHJ devices by promoting excessive charge recombination. In order to quantify carrier mobilities for the materials, current density-voltage (J-V) characteristics of single-carrier diodes were measured for pure and blended films. The hole and electron mobilities were extracted using the space-charge limited current (SCLC) model. Pure SMBFu films exhibit hole mobilities on the order of ˜1×10−5 cm2/Vs before and after annealing at 100° C. s. The average measured hole mobilities for as-cast 30:70, 50:50, 60:40 and 70:30 films were found to be 0.9×10−5 cm2/Vs, 2×10−5 cm2/Vs, 3×10−5 cm2/Vs and 3×10−5 cm2/Vs, respectively. The hole mobilities did not change significantly upon annealing. Electron mobilities were found to increase from 2×10−5 cm2/Vs to 70×10−5 cm2/Vs to 200×10−5 cm2/Vs for the 30:70, 50:50 and 70:30 blend ratios, respectively, increasing with the acceptor concentration. The electron mobilities increased after annealing at 100° C. to 90×10−5 cm2/Vs to 200×10−5 cm2/Vs to 300×10−5 cm2/Vs for 30:70, 50:50 and 70:30 blend ratios, respectively. The dramatic increase of the electron mobility at low acceptor concentration suggests that percolation pathways for electron transport do not exist in as-cast films with low fullerene concentrations, but are developed after thermal annealing. The charge carrier mobilities for all different blend ratios before and after annealing were compared. The carrier mobilities were found to be more balanced at high donor concentrations, consistent with the observed increase in fill factor at high donor concentrations. The measured hole mobilities for this series of materials were somewhat surprising, as they did not increase after annealing despite an obvious increase in the crystallinity of the donor material.
Finally, the performance of SMBFu:PC71BM films in solar cells was examined.
The IPCEs of a 60:40 blend ratio at various annealing temperatures are shown in
The photovoltaic characteristics for different blend ratios and annealing temperatures are summarized in Table 3. The highest performance observed occurred for a 60:40 blend annealed for 3 minutes at 110° C., yielding a short circuit current of 10.0 mA/cm2, a Voc of 0.92 V, a FF of 0.48 and a power conversion efficiency of 4.4%. It is apparent that the annealing temperature which yields the highest efficiency results in donor-rich domain sizes on the order of ˜100 nm, higher than expected for efficient exciton diffusion and is slightly higher than annealing temperatures which yield the highest optical absorption. This suggests that percolation paths are underdeveloped at lower temperatures.
Table 3 below compares the device characteristics of different SMBFu:PC71BM blend ratios annealed at different temperatures. JSC is the short circuit current density, Voc is the open circuit voltage, FF is the fill factor and η is the overall power conversion efficiency. The architecture is ITO/PEDOT:PSS/SMBFu:PC71BM/Al for all devices.
Conditions: (i) Cesium carbonate, alkylbromide, DMF, 40° C.; (ii) appropriate thiophene bronic acid pinacol ester, Pd2(dba)3, HP(tBu)3BF4, K3PO4, THF; (iii) 2-bromothiophene, Pd2(dba)3, HP(tBu)3BF4, K3PO4, THF; (iv) n-BuLi, 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.
Material Synthesis.
5-Hexyl-2-thiophene boronic acid pinacol ester, 2,2′-bithiophene-5-boronic acid pinacol ester, and 5-hexyl-2,2′-bithiophene-5′-boronic acid pinacol ester were purchased from Sigma-Aldrich Chemical Co. and used as received. Other chemicals and solvents were used as received from commercial sources without further purification. Tetrahydrofuran (THF) was distilled over sodium/benzophenone. 3,6-bis(4-bromophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrolo-1,4-dione, 11, was synthesized following the procedure in D. Cao et al. J. Poly. Sci. A 2006, 44, 2395.
2,5-Dihexyl-3,6-bis(4-bromophenyl)pyrrolo[3,4-c]-pyrrole-1,4-dione (12a)To a solution of 11 (5.0 g, 11, mmol) in N,N-dimethylformamide (DMF) (50 mL), 1-bromohexane (7.4 g, 45 mmol) and cesium carbonate (11 g, 34 mmol) were added at 40° C. After stirring 24 hr, the reaction mixture was filtered to remove solid. The filtrate was extracted with chloroform and recrystallized from methanol to yield red needle-like crystal (4.1 g, 60%). 1H NMR (200 MHz, CDCl3): 7.67 (s, 8H), 3.71 (t, 4H), 1.58 (m, 4H), 1.19 (m, 12H), 0.82 (t, 6H).
2,5-Dihexyl-3,6-bis(4-bromophenyl)pyrrolo[3,4-c]-pyrrole-1,4-dione (12b)The procedure for the synthesis of 12a was followed to prepare 12b using 2-ethylhexyl bromide (3.5 g, 18 mmol) instead of 1-bromohexane. The crude product was purified by gradient column chromatography on a silical gel with using gradient solvent with dichloromethane/hexane from 1/1 to 2.5/1 (v/v) to yield in 22% (0.66 g). 1H NMR (200 MHz, CDCl3): 7.65 (s, 8H), 3.70 (d, 4H), 1.45 (m, 2H), 1.09 (m, 16H), 0.74 (m, 12H).
5-hexyl-2,2′:5′,2″-terthiophene, (15)To a mixture of 2-bromothiophene (1.56 g, 9.57 mmol), 5-hexyl-2,2′-bithiophene-5′-boronic acid pinacol ester (3.0 g, 8.0 mmol), tri (dibenzylidene-acetone)palladium (0) (Pd2(dba)3) (0.15 g, 0.17 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.18 g, 0.65 mmol), and potassium phosphate (14 g, 64 mmol), degassed THF/water (30 mL/3 mL) was added. After stirring under argon at 80° C. overnight, the reaction mixture was poured into methanol. The crude product was collected by filtration and purified by column chromatography on a silica gel with hexane to obtain 15 (2.1 g, 81%). 1H NMR (200 MHz, CDCl3): 7.20 (m, 2H), 7.04 (m, 4H), 6.68 (d, 1H), 2.79 (t, 2H), 2.64 (m, 2H), 1.33 (m, 6H), 0.89 (t, 3H).
5-hexyl-2,2′:5′,2″-terthiophene-5″-boronic acid pinacol ester, (16)To a solution of 15 (1.8 g, 5.4 mmol) in 45 mL of THF, n-BuLi (2.6 mL, 6.5 mmol, 2.5 M in hexane) was added dropwise at −78° C. After stirred for 30 min at −78° C., the solution was warmed to room temperature and stirred for 1 hr. Then, the mixture was cooled down to −78° C. and add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dixoaborolane (1.5 g, 8.1 mmol) at once. The mixture was warmed up to room temperature and stirred overnight. After reaction was quenched with water, the organic layer was extracted by ethyl acetate and dried over magnesium sulfate. After solvent was removed under reduced pressure, the crude product was purified by column chromatography to obtain 16 (1.9 g, 77%). 1H NMR (200 MHz, CDCl3): 7.51 (d, 1H), 7.22 (d, 1H), 7.11 (d, 1H), 6.99 (m, 2H), 6.68 (d, 1H), 2.79 (t, 2H), 1.68 (m, 2H), 1.35 (m, 20H), 0.89 (t, 3H).
2,5-Dihexyl-3,6-bis[4-(5-hexylthiophene-2-yl)phenyl]pyrrolo[3,4-c]-pyrrole-1,4-dione, C6PT1C6To a mixture of 12a (0.75 g, 1.2 mmol), 5-hexyl-2-thiophene boronic acid pinacol ester (0.79 g, 2.7 mmol), Pd2(dba)3 (0.056 g, 0.061 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.11 g, 0.37 mmol), and potassium phosphate (3.11 g, 14.7 mmol), degassed THF/water (30 mL/3 mL) was added. After stirring under argon at 80° C. overnight, the reaction mixture was poured into methanol. The crude product was collected by filtration and purified by gradient column chromatography on a silica gel with chloroform/hexane from 2/1 to 5/1 (v/v) to obtain C6PT1C6 (0.40 g, 42%). 1H NMR (200 MHz, CDCl3): 7.83 (d, 4H), 7.68 (d, 4H), 7.24 (d, 2H), 6.78 (d, 2H), 3.79 (t, 4H), 2.84 (4H), 1.68 (m, 8H), 1.23-1.35 (m, 24H), 0.87 (m, 12H).
2,5-Dihexyl-3,6-bis[4-(5-hexyl-2,2′-bithiophene-5-yl)phenyl]pyrrolo[3,4-c]-pyrrole-1,4-dione, C6PT2C6The procedure for the synthesis of C6PT1C6 was followed using 5-hexyl-2,2′-bithiophene-5′-boronic ester pinacol ester (0.92 g, 2.4 mmol), instead of 5-hexyl thiophene boronic acid pinacol ester to yield in 91% (0.85 g). 1H NMR (200 MHz, CDCl3): 7.87 (d, 4H), 7.73 (d, 4H), 7.33 (d, 2H), 7.10 (d, 2H), 7.05 (d, 2H), 6.71 (d, 2H), 3.80 (t, 4H), 2.81 (t, 4H), 1.70 (m, 8H), 1.23-1.43 (m, 24H), 0.87 (m, 12H).
2,5-Dihexyl-3,6-bis[4-(5-hexyl-2,2′:5′,2″-terthiophene-5″-yl)phenyl]pyrrolo[3,4-c]-pyrrole-1,4-dione, C6PT3C6The procedure for the synthesis of C6PT1C6 was followed using 5-hexyl-2,2′:5′,2″-terthiophene-5″-boronic acid pinacol ester (0.90 g, 2.0 mmol), instead of 5-hexyl thiophene boronic acid pinacol ester to yield in 78% (0.68 g). 1H NMR (200 MHz, CDCl3): 7.83 (d, 4H), 7.69 (d, 4H), 7.31 (d, 2H), 7.14 (m, 4H), 6.98 (m, 4H), 6.62 (d, 2H), 3.78 (t, 4H), 2.88 (t, 4H), 1.61 (m, 8H), 1.10-1.40 (m, 24H), 0.82 (m, 12H).
2,5-Dihexyl-3,6-bis[4-(2,2′-bithiophene-5-yl)phenyl]pyrrolo[3,4-c]-pyrrole-1,4-dione, C6PT2The procedure for the synthesis of C6PT1C6 was followed using 2,2′-bithiophene-5′-boronic acid pinacol ester (0.89 g, 3.1 mmol), instead of 5-hexyl thiophene boronic acid pinacol ester to yield in 78% (0.75 g). 1H NMR (200 MHz, CDCl3): 7.88 (d, 4H), 7.74 (d, 4H), 7.35 (d, 2H), 7.27 (m, 4H), 7.19 (d, 2H), 7.06 (m, 2H), 3.80 (t, 4H), 1.66 (m, 4H), 1.24 (m, 12H), 0.84 (t, 6H).
2,5-Dihexyl-3,6-bis[4-(5-hexyl-2,2′-bithiophene-5-yl)phenyl]pyrrolo[3,4-c]-pyrrole-1,4-dione, EHPT2C6The procedure for the synthesis of C6PT1C6 was followed using 12b (0.58 g, 0.87 mmol) and 5-hexyl-2,2′-bithiophene-5′-boronic ester pinacol ester (0.81 g, 2.2 mmol), instead of 12a and 5-hexyl thiophene boronic acid pinacol ester to yield in 86% (0.75 g). 1H NMR (200 MHz, CDCl3): 7.83 (d, 4H), 7.70 (d, 4H), 7.31 (d, 2H), 7.08 (d, 2H), 7.04 (d, 2H), 6.70 (d, 2H), 3.80 (d, 4H), 2.81 (t, 4H), 1.71 (m, 4H), 1.34 (m, 14H), 1.11 (m, 16H), 0.90 (t, 6H), 0.77 (m, 12H).
Example 11 Synthesis of Two-Core Diketopyrrolopyrrole Compounds with Electron-Rich Bridge MoietyTo a solution of 21 (10 g, 33 mmol) in N,N-dimethylformamide (DMF) (100 ml), 1-bromohexane (17 g, 99 mmol) and potassium carbonate (12 g, 83 mmol) were added at 90° C. After stirring 8 hr, the reaction mixture was filtered to remove solid. The filtrate was extracted with chloroform and recrystallized from methanol to yield 2 (9.0 g, 58%). 1H NMR (200 MHz, CDCl3): 8.94 (d, 2H), 7.65 (d, 2H), 7.29 (d, 2H), 4.08 (t, 4H), 1.75 (m, 4H), 1.22-1.50 (m, 12H), 0.89 (t, 6H).
2,5-Dihexyl-3-bromothienyl-6-thienylpyrrolo[3,4-c]-pyrrole-1,4-dione (23)To the solution of 22 (4.5 g, 9.6 mmol) in chloroform (140 ml), N-bromosuccinimide (NBS) (1.14 g, 6.4 mmol) was added. After stirring overnight at room temperature, the reaction mixture was washed with water. The organic layer was dried over magnesium sulfate and solvent was removed by reduced pressure. The crude product was purified by gradient column chromatography on silica gel with chloroform/hexane (from 2/1 to 4/1, v/v) to yield 23 (3.2 g, 91%). 1H NMR (200 MHz, CDCl3): 8.95 (d, 1H), 8.67 (d, 1H), 7.67 (d, 1H), 7.29 (d, 1H), 7.23 (d, 1H), 4.02 (m, 4H), 1.71 (m, 4H), 1.22-1.50 (m, 12H), 0.89 (t, 6H).
2,5-Dihexyl-3-thienyl-6-(5-hexyl-2,2′:5′,2″-terthienylpyrrolo[3,4-c]-pyrrole-1,4-dione (24)To a mixture of 23 (1.0 g, 1.8 mmol), 5-hexyl-2,2′-bithiophene-5′-boronic acid pinacol ester (0.82 g, 2.2 mmol), tri (dibenzylidene acetone)palladium (0) (Pd2(dba)3) (0.084 g, 0.091 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.16 g, 0.55 mmol), and potassium phosphate (3.1 g, 15 mmol), degassed THF/water (35 ml/2 ml) was added. After stirring under reflux overnight, the reaction mixture was poured into methanol. The crude product was collected by filtration and purified by column chromatography on a silica gel with chloroform/hexane (5/1, v/v) to obtain 24 (1.3 g, 99%). 1H NMR (200 MHz, CDCl3): 8.98 (d, 1H), 8.95 (d, 1H), 7.64 (d, 1H), 7.32 (d, 2H), 7.24 (d, 1H), 7.06 (t, 2H), 6.74 (d, 1H), 4.08 (t, 4H), 2.83 (t, 2H), 1.75 (m, 6H), 1.23-1.53 (m, 18H), 0.90 (m, 9H).
2,5-Dihexyl-3-bromothienyl-6-(5-hexyl-2,2′:5′,2″-terthienylpyrrolo[3,4-c]-pyrrole-1,4-dione (25)To the solution of 24 (1.3 g, 1.7 mmol) in chloroform (45 ml), NBS (0.34 g, 1.9 mmol) was added. After stirring overnight at room temperature, the reaction mixture was washed with water. The organic layer was dried over magnesium sulfate and solvent was removed by reduced pressure. The crude product was purified by column chromatography on silica gel with chloroform/hexane (4/1, v/v) to yield 5 (1.3 g, 92%). 1H NMR (200 MHz, CDCl3): 8.99 (d, 1H), 8.64 (d, 1H), 7.32 (d, 1H), 7.24 (d, 2H), 7.05 (t, 2H), 6.74 (d, 1H), 4.08 (m, 4H), 2.83 (t, 2H), 1.75 (m, 6H), 1.23-1.50 (m, 18H), 0.92 (m, 9H).
9,9-Dihexylfluorene-2,7-bis(2,5-dihexyl-3-thienyl-6-(5-hexyl-2,2′:5′,2″-terthienyl pyrrolo[3,4-c]-pyrrole-1,4-dione) (26)To a mixture of 25 (0.80 g, 1.0 mmol), 9,9-dihexylfluroene-2,7-bis(boronic ester pinacol ester) (0.26 g, 0.44 mmol), Pd2(dba)3 (0.070 g, 0.028 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.053 g, 0.18 mmol), and potassium phosphate (1.1 g, 5.2 mmol), degassed THF/water (25 ml/2 ml) was added. After stirring under reflux overnight, the reaction mixture was poured into methanol. The crude product was collected by filtration and purified by gradient column chromatography on a silica gel with chloroform/hexane (from 1/1 to 4/1, v/v) to obtain 26 (0.40 g, 52%). 1H NMR (200 MHz, CDCl3): 9.02 (d, 2H), 8.95 (d, 2H), 7.73 (d, 2H), 7.68 (d, 2H), 7.63 (s, 2H), 7.55 (d, 2H), 7.31 (d, 2H), 7.23 (d, 2H), 7.05 (t, 4H), 6.72 (d, 2H), 4.15 (m, 8H), 2.83 (t, 4H), 2.08 (m, 4H), 1.82 (m, 8H), 1.70 (m, 4H), 1.50 (m, 8H), 1.30-1.45 (m, 28H), 1.10 (m, 12H), 0.90 (m, 9H), 0.75 (m, 10H).
Example 12 Synthesis of Two-Core Diketopyrrolopyrrole Compounds with Electron-Deficient Bridge MoietyTo a solution of 31 (5.0 g, 17 mmol) in DMF (70 ml), 2-ethylhexyl bromide (13 g, 67 mmol) and potassium carbonate (6.9 g, 50 mmol) were added at 90° C. After stirring 8 hr, the reaction mixture was filtered to remove solid. The filtrate was extracted with chloroform and dried over magnesium sulfate. Upon evaporating solvent under reduced pressure, the crude product was purified by column chromatography with chloroform/hexane (4/1, v/v) to yield 32 (2.7 g, 32%). 1H NMR (200 MHz, CDCl3): 8.90 (d, 2H), 7.63 (d, 2H), 7.29 (d, 2H), 4.04 (d, 4H), 1.83 (m, 2H), 1.22-1.50 (m, 16H), 0.88 (m, 12H).
2,5-Bis(2-ethylhexyl)-3-bromothienyl-6-thienylpyrrolo[3,4-c]-pyrrole-1,4-dione (33)To the solution of 32 (2.0 g, 3.8 mmol) in chloroform (60 ml), NBS (0.45 g, 2.5 mol) was added. After stirring overnight at room temperature, the reaction mixture was washed with water. The organic layer was dried over magnesium sulfate and solvent was removed by reduced pressure. The crude product was purified by gradient column chromatography on silica gel with chloroform/hexane (from 2/1 to 4/1, v/v) to yield 33 (1.7 g, 75%). 1H NMR (200 MHz, CDCl3): 8.94 (d, 1H), 8.67 (d, 1H), 7.67 (d, 1H), 7.29 (d, 1H), 7.24 (d, 1H), 4.02 (m, 4H), 1.90 (m, 2H), 1.25-1.52 (m, 16H), 0.89 (m, 12H).
2,5-Bis(2-ethylhexyl)-3-thienyl-6-(5-hexyl-2,2′:5′,2″-terthienylpyrrolo[3,4-c]-pyrrole-1,4-dione (34)To a mixture of 33 (1.0 g, 1.7 mmol), 5-hexyl-2,2′-bithiophene-5′-boronic acid pinacol ester (0.8 g, 2.0 mmol), Pd2(dba)3 (0.076 g, 0.083 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.14 g, 0.50 mmol), and potassium phosphate (2.8 g, 13 mmol), degassed THF/water (30 ml/3 ml) was added. After stirring under reflux overnight, the reaction mixture was poured into methanol. The crude product was collected by filtration and purified by column chromatography on a silica gel with chloroform/hexane (5/1, v/v) to obtain 34 (1.2 g, 94%). 1H NMR (200 MHz, CDCl3): 8.98 (d, 1H), 8.92 (d, 1H), 7.63 (d, 1H), 7.32 (d, 2H), 7.24 (d, 1H), 7.06 (t, 2H), 6.74 (d, 1H), 4.08 (d, 4H), 2.83 (t, 2H), 1.90 (m, 2H), 1.70 (m, 2H), 1.20-1.54 (m, 22H), 0.89 (m, 15H).
2,5-Bis(2-ethylhexyl)-3-bromothienyl-6-(5-hexyl-2,2′:5′,2″-terthienylpyrrolo[3,4-c]-pyrrole-1,4-dione (35)To the solution of 34 (1.2 g, 1.6 mmol) in chloroform (25 ml), NBS (0.30 g, 1.7 mmol) was added. After stirring overnight at room temperature, the reaction mixture was washed with water. The organic layer was dried over magnesium sulfate and solvent was removed by reduced pressure. The crude product was purified by column chromatography on silica gel with chloroform/hexane (4/1, v/v) to yield 35 (1.2 g, 91%). 1H NMR (200 MHz, CDCl3): 9.00 (d, 1H), 8.66 (d, 1H), 7.32 (d, 1H), 7.25 (d, 2H), 7.07 (t, 2H), 6.74 (d, 1H), 4.08 (m, 4H), 2.83 (t, 2H), 1.90 (m, 2H), 1.70 (m, 2H), 1.20-1.55 (m, 22H), 0.92 (m, 15H).
2,1,3-Benzothiadiazole-4,7-bis(2,5-dihexyl-3-thienyl-6-(5-hexyl-2,2′:5′,2″-terthienyl pyrrolo[3,4-c]-pyrrole-1,4-dione) (36)To a mixture of 35 (0.86 g, 1.0 mmol), 2,1,3-benzothiadiazole-4,7-bis(boronic acid pinacol ester), (0.17 g, 0.44 mmol), Pd2(dba)3 (0.028 g, 0.031 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.053 g, 0.18 mmol), and potassium phosphate (0.745 g, 3.51 mmol), degassed THF/water (20 ml/1 ml) was added. After stirring under reflux overnight, the reaction mixture was poured into water and extracted with chloroform. The solution was dried over magnesium sulfate, followed by evaporating the solvent under reduced pressure. The crude product was purified by gradient column chromatography on a silica gel with chloroform/hexane (from 1/1 to 5/1, v/v) to obtain 36 (0.67 g, 91%). 1H NMR (200 MHz, CDCl3): 9.05 (d, 2H), 8.99 (d, 2H), 7.90 (d, 2H), 7.70 (s, 2H), 7.07 (d, 2H), 7.00 (d, 2H), 6.88 (d, 2H), 6.82 (d, 2H), 6.60 (d, 2H), 3.95 (m, 8H), 2.83 (t, 4H), 1.90 (m, 4H), 1.70 (m, 4H), 1.20-1.55 (m, 44H), 0.92 (m, 30H).
To a mixture of 2,5-dibutyl-3,6-bis(4-bromophenyl)pyrrolo[3,4-c]-pyrrole-1,4-dione (0.40 g, 0.72 mmol), 5-hexyl-2,2′-bithiophene boronic acid pinacol ester (0.67 g, 1.8 mmol), Pd2(dba)3 (0.033 g, 0.036 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.062 g, 0.22 mmol), and potassium phosphate (2.4 g, 12 mmol), degassed THF/water (22 mL/2 mL) was added. After stirring under reflux overnight, the reaction mixture was poured into methanol. The crude product was collected by filtration and purified by gradient column chromatography on a silica gel with chloroform/hexane from 2/1 to 5/1 (v/v) to obtain C4PT2C6 (0.55 g, 86%). 1H NMR (200 MHz, CDCl3): 7.83 (d, 4H), 7.68 (d, 4H), 7.28 (d, 2H), 7.03 (d, 2H), 7.00 (d, 2H), 6.67 (d, 2H), 3.78 (t, 4H), 2.76 (t, 4H), 1.61 (m, 8H), 1.18-1.46 (m, 16H), 0.83 (m, 12H).
Example 13 Characteristics of Devices with Two-Core Diketopyrrolopyrrole Compounds2,1,3-Benzothiadiazole-4,7-bis(2,5-dihexyl-3-thienyl-6-(5-hexyl-2,2′:5′,2″-terthienyl pyrrolo[3,4-c]-pyrrole-1,4-dione) (36) has a band gap of approximately 1.3 eV and an absorption spectrum which extends beyond 900 nm. 9,9-Dihexylfluorene-2,7-bis(2,5-dihexyl-3-thienyl-6-(5-hexyl-2,2′:5′,2″-terthienyl pyrrolo[3,4-c]-pyrrole-1,4-dione) (26) has a band gap of approximately 1.6 eV and an absorption spectrum which extends to 800 nm.
One example of a device using compound 36 is shown in Device 1 of
In another example (Device 2 of
In another example (Device 3 of
Current-voltage characteristics under 100 mW/cm2 simulated solar radiation of these Devices 1-3 are plotted in
In some cases, it can be advantageous to select new or different solvents for the fabrication of the active layer. Any volatile solvent which adequately dissolves both donor and acceptor material may be used to fabricate the active layer, so long as the concentration and processing conditions are adjusted to achieve films with thickness in the range of 50 to 300 nm, preferably 75-125 nm, and the annealing temperature is optimized for the solvent being used.
The devices described below were prepared using the method described for the devices in Example 13. In one example (Device 4), a 60:40 mixture of SMBFu and PC71BM were dissolved in chloroform at a concentration of 16.7 mg/mL, spincast on a substrate at 1500 rpm and annealed at 130° C. for 10 minutes, yielding a device with a Jsc of 10.1 mA/cm2, a Voc of 0.88V, a FF of 48% and a power conversion efficiency of 4.3%.
In another example (Device 5 of
In another example (Device 6 of
In another example (Device 7 of
Current-voltage characteristics under 100 mW/cm2 simulated solar radiation of these Devices 4-7 are plotted in
Although fullerenes typically yield significantly higher efficiencies than other electron accepting materials when used in BHJ solar cells, they are very expensive to synthesize and refine. Additionally, it can be difficult to adjust the ionization potential (HOMO) and electron affinity (LUMO) of fullerene derivatives in order to adjust device characteristics such as Voc. Specifically, the Voc of optimized devices is often found to be about 0.3 V less than the difference between the LUMO of the acceptor and the HOMO of the donor (A). For these reasons, it may be advantageous to use electron accepting materials other than fullerenes.
In one example, the DPP based electron donating material C4PT2C6 (indicated as Material 3 of
An energy level diagram comparing HOMO and LUMO values of C4PT2C6 (Material 3) with PCBM is shown at left in
In one example (Device 8 of
Devices having inverted architecture were prepared. In one example (Device 9), the work function of an ITO substrate is modified using a self-assembled monolayer of 3-aminopropyltrimethoxysiloxane and measured to be 4.3 eV by UPS. A 60:40 mixture of SMBFu and PC71BM were dissolved in chloroform at a concentration of 16.7 mg/mL and spincast on the modified substrate at 2000 rpm. A layer of PEDOT:PSS was then deposited on top by spincasting a 2:1 mixture of isopropanol:Baytron Clevios P4083 at 3000 rpm. The resulting film was annealed at 110° C. for 30 minutes, followed by the evaporation of Au anodes at a base pressure of 10−6 torr and a rate of less than 1 Angstrom/second. This device had a Jsc of 6.4 mA/cm2, a Voc of 0.74 V, a FF of 43% and a power conversion efficiency of 2.0%.
In another example (Device 10), an ITO substrate was modified by spincasting a solution consisting of 4% titanium isopropoxide, 10% dimethoxyethanol and 86% isopropanol by volume at 3000 rpm in an atmosphere with 20 ppm water concentration. This substrate was then annealed at 200° C. for 30 minutes in the same atmosphere. A 60:40 mixture of SMBFu and PC71BM were dissolved in chloroform at a concentration of 16.7 mg/mL and spincast on the modified substrate at 2000 rpm. A layer of PEDOT:PSS was then deposited on top by spincasting a 2:1 mixture of isopropanol:Baytron Clevios P4083 at 3000 rpm. The resulting film was annealed at 110° C. for 30 minutes, followed by the evaporation of Au anodes at a base pressure of 10−6 torr and a rate of less than 1 Angstrom/second. This device had a Jsc of 8.8 mA/cm2, a Voc of 0.88 V, a FF of 36% and a power conversion efficiency of 2.8%.
The disclosures of all publications, patents, patent applications and published patent applications referred to herein by an identifying citation are hereby incorporated herein by reference in their entireties.
Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is apparent to those skilled in the art that certain changes and modifications will be practiced. Therefore, the description and examples should not be construed as limiting the scope of the invention.
Claims
1. A optoelectronic device comprising:
- a) a first hole-collecting electrode;
- b) an optional hole-transporting layer;
- c) a layer comprising a mixture of an electron donor material and an electron acceptor material; and
- d) a second electron-collecting electrode,
- wherein the electron donor material comprises a compound of Formula (I):
- wherein X is oxygen or sulfur;
- A1 and A2 are independently selected from substituted and unsubstituted aryl or heteroaryl groups, wherein each individual A1 within the (A1)m moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group, and each individual A2 within the (A2)n moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group;
- B1 is independently selected from substituted and unsubstituted aryl or heteroaryl groups;
- m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
- n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
- p is independently selected from 0 or 1;
- E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group; and
- R1, R2, R3, and R4 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
2. The device of claim 1, wherein X is oxygen.
3. The device of claim 1, wherein p is 1.
4. The device of claim 1, wherein A1 and A2 are independently selected from the group consisting of thiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, indole, benzene, naphthalene, anthracene, indene, fluorene, pyrene, azulene, furan, pyrrole, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, pyridothiadiazole, and carbazole.
5. The device of claim 1, wherein B1 is independently selected from the group consisting of thiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, indole, benzene, naphthalene, anthracene, indene, fluorene, pyrene, azulene, furan, pyrrole, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, pyridothiadiazole, carbazole,
6. The device of claim 1, wherein A1 is selected from where m is independently 1, 2, or 3, and A2 is selected from here n is independently 1, 2, or 3.
7. The device of claim 1, wherein m=n=1, m=n=2, or m=n=3.
8. The device of claim 1, wherein R1, R2, R3, and R4 are the same and are selected from hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl.
9. The device of claim 1, wherein the first electrode comprises indium tin oxide and the second electrode comprises aluminum, silver or magnesium.
10. The device of claim 1, wherein the optional hole transporting layer is present and comprises poly(3,4-ethylene dioxythiophene:poly(styrenesufonate) (PEDOT:PSS).
11. The device of claim 1, wherein the electron acceptor is selected from the group consisting of fullerene electron acceptors, [6,6]-phenyl C61-butyric acid methyl ester (PCBM), PC71BM, titanium dioxide, and zinc oxide.
12. A optoelectronic device comprising:
- a) a first hole-collecting electrode;
- b) an optional hole-transporting layer;
- c) a layer comprising a mixture of an electron donor material and an electron acceptor material;
- and
- d) a second electron-collecting electrode,
- wherein the electron donor material comprises a compound of Formula (II):
- wherein
- X is oxygen or sulfur;
- A1 and A2 are selected from substituted and unsubstituted aryl or heteroaryl groups, wherein each individual A1 within the (A1)m moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group, and each individual A2 within the (A2)n moiety can be independently selected from a substituted and unsubstituted aryl or heteroaryl group;
- m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
- n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;
- E1 and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group;
- and
- R1 and R2 are independently selected from H, C1-C12 alkyl, and —C(═O)—O—C1-C12 alkyl.
13. The device of claim 12, wherein X is oxygen.
14. The device of claim 12, wherein A1 and A2 are independently selected from the group consisting of thiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, indole, benzene, naphthalene, anthracene, indene, fluorene, pyrene, azulene, furan, pyrrole, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, pyridothiadiazole, and carbazole.
15. The device of claim 12, wherein A1 is selected from where m is independently 1, 2, or 3, and A2 is selected from where n is independently 1, 2, or 3.
16. The device of claim 12, wherein m=n=1, m=n=2, or m=n=3.
17. The device of claim 12, wherein R1 and R2 are the same and are selected from hexyl, 2-ethylhexyl, t-butoxycarbonyl, and trimethylsilyl.
18. The device of claim 12, wherein the first electrode comprises indium tin oxide and the second electrode comprises aluminum, silver or magnesium.
19. The device of claim 12, wherein the optional hole transporting layer is present and comprises poly(3,4-ethylene dioxythiophene:poly(styrenesufonate) (PEDOT:PSS).
20. The device of claim 12, wherein the electron acceptor is selected from the group consisting of fullerene electron acceptors, [6,6]-phenyl C61-butyric acid methyl ester (PCBM), PC71BM, titanium dioxide, and zinc oxide.
Type: Application
Filed: Apr 8, 2016
Publication Date: Oct 13, 2016
Inventors: Thuc-Quyen NGUYEN (Santa Barbara, CA), Arnold Bernarte TAMAYO (Glendale, CA), Bright WALKER (Goleta, CA), Tyler KENT (Newport Beach, CA), Chunki KIM (Goleta, CA), Mananya TANTIWIWAT (Goleta, CA)
Application Number: 15/094,576
