Patent Application
20230132149
The present disclosure relates to organic compositions useful for absorbing electromagnetic radiation and devices (e.g., photodetectors and solar cells) comprising the same.
The active materials in organic optoelectronic devices have been rapidly developed so as to achieve high performance in combination with high-transmittance for next-generation integrated applications.[1-4] In particular, non-fullerene acceptors (NFAs) absorbing at near infrared (NIR) wavelengths have recently received considerable attention due to their potential application in thin-film-transistors, solar cells and sensors. Furthermore, the range of light absorption is selectable by tuning the bandgap of materials.[5-7] Applications of transparent light sensors include the Internet-of-Things (IoT) generation for vehicle windows, building smart exteriors, and E-Skin health devices.[8-9]
However, commercial applications require extension of the spectrum of NIR absorbing materials. Further research is needed to extend the benefits of non-fullerene solar cells, in terms of superior optoelectronic properties, over fullerene-based devices so as to realize more efficient NIR organic photodetectors and solar cells. The present disclosure satisfies this need.
Illustrative embodiments of the inventive subject matter according to embodiments of the present invention include, but are not limited to, the following examples.
D is independently one of the following:
wherein each R is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain.
wherein each R1 and R2 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain.
where each R4 and R7 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; and each R5 and R6 is independently hydrogen or a substituted or non-substituted alkyl or aryl chain.
wherein:
each Ar2 is independently a substituted or non-substituted aromatic functional group, or Ar2 is nothing and the valence of the ring is completed with hydrogen;
each Q is independently O, S Se, or N—R4;
each R and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain;
T is N, C—F, or C—Cl, and
X is C, Si, Ge, N or P or
the semiconducting compound of the structure:
wherein:
each Ar2 is independently a substituted or non-substituted aromatic functional group, or Ar2 is nothing and the valence of the ring is completed with hydrogen;
each Q is independently O, S Se, or N—R4;
each R and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain;
T is N, C—F, or C—Cl; and
X is C, Si, Ge, N or phosphorus (P),
or the semiconducting compound of the structure:
wherein:
each R is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain;
T is N, C—F, or C—Cl; and
X is C, Si, Ge, N or P,
or the organic semiconducting donor comprises the structure:
wherein:
each Ar1 is independently a substituted or non-substituted aromatic functional group, or each Ar1 is nothing and the valence of the ring is completed with hydrogen.
each Z is independently O, S, Se, or N—R4;
each R1, R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain; and
each Q is independently O, S Se, or N—R4, or
the organic semiconducting donor comprises the structure:
wherein:
each Z is independently O, S, Se, or N—R4;
each Q is independently O, S Se, or N—R4, and S is sulfur.
the anode coupled to the donor to receive the holes; and such that
the device outputs current in response to the electromagnetic radiation.
the device comprises the photodetector having an external quantum efficiency (EQE) above 2%, a responsivity of at least 0.01 A/W, and a specific detectivity of at least 1011 Jones across the entire wavelength range of 800-1200 nm of the electromagnetic radiation when the anode is biased at 0V with respect to the cathode.
a first electrode comprising the cathode;
a first carrier transport layer;
the active region comprising the composition of matter, wherein the first carrier transport layer is between the first electrode and the active region;
a second carrier transport layer, wherein the active region is between the first carrier transport layer and the second carrier transport layer; and
the second electrode comprising the anode on the second carrier transport layer.
an active region comprising the electron acceptor of example 1, wherein the active region outputs electrical current in response to absorbing electromagnetic radiation.
In one or more examples, the A-D-A′-D-A molecular structure of Non Fullerene Acceptor (NFA) has been tailored to achieve an enhanced intra-molecular charge transfer (ICT) effect resulting in an ultra-narrow bandgap of <1.0 eV useful for NIR absorber applications. In one or more examples, polymers including PM2, PTB7-Th and PBDTTT-C-T were chosen as the narrow bandgap donor material to combine with the NFAs. The NIR materials including PM2 donor and the NFAs exhibit NIR absorption (in a film) with narrow optical bandgaps of 1.41 eV (PM2), 0.86 eV (BCIC-4F), 0.99 eV (TCIC-4F) and 0.98 eV (TCIC-4Cl), respectively. Various compositions of donor:BCIC-4F and donor:TCIC-4X (X═F or Cl) were fabricated and characterized as NIR photon detecting devices. The resulting donor-acceptor blend consisting only of narrow bandgap materials is thereby characterized by a strong absorption of photons in the near infrared (NIR) region, resulting in an estimated value for specific detectivity of 1.6×1012 Jones at 1050 nm (for the PM2:TCIC-4F based device).
Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
1H NMR spectra of compound BCIC-4F (
In the following description of the preferred embodiment, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustrationa specific embodiment in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
1. Molecular Design, Synthesis and Characterization of NIR NFAs Cast in Films
The present disclosure reports on newly designed non-fullerene acceptor (NFA) materials utilizing the A-D-A′-D-A molecular structure tailored to promote the enhanced intra-molecular charge transfer (ICT) effect and thereby achieve ultra-narrow bandgap <1.0 eV NIR absorbers. The new NFAs were rationally designed and their molecular properties (HOMO, LUMO, optical gap, oscillator strength etc.) were determined by employing quantum chemistry calculations using density functional (DFT) calculations with the semi-empirically tuned ωB97XD/6-31G (d,p) functional and basis set where the bulky side chains were simplified to methyl or ethyl groups. The general principle of molecular design and DFT calculated frontier energy level results are shown in
The synthetic routes for the two targeted molecules are summarized in
To further examine the materials' optical properties, BCIC-4F, TCIC-4F and TCIC-4Cl chloroform (CF) solutions and thin-films (cast from the solutions of NFA (10 mg/mL) in chloroform (CF) at 1000 rpm) were measured by UV-Vis-NIR spectroscopy (
BCIC-4F is characterized by two main absorption peaks where the second peak lies around 1200 nm, and the TCIC-4F and TCIC-4Cl have a solid-state absorption peak at 1086 nm and 1095 nm respectively. With the onset absorption wavelength obtained from the absorption profile around 1200 nm, the optical gaps for TCIC-4F, TCIC-4Cl and BCIC-4F were estimated as 0.99 eV, 0.98 eV and 0.86 eV, respectively. TCIC-4F showed the maximum absorption peaks of around 1100 nm in NIR region.
A cyclic Voltammetry (CV) experiment was conducted using a CHI-730B electrochemistry workstation with the three-electrodes system consisting of glassy carbon disk, Pt wire, and Ag wire electrode which serve as the working electrode, counter electrode, and pseudo reference electrode, respectively. The measurement was performed in 0.1M tetrabutylammonium hexafluorophosphate (n-Bu4NPF6)-anhydrous acetonitrile solution at the potential scan rate of 40-100 mV s−1. Thin films of samples were deposited onto the glassy carbon working electrode from its 3-5 mg mL−1 chloroform solution. The electrochemical onsets were determined at the position where the current starts to differ from the baseline. The potential of Ag pseudo reference electrode was internally calibrated relative to Fc/Fc+ couple (−4.88 eV vs. vacuum). The HOMO level measured by CV for BCIC-4F is −5.4 eV and the calculated LUMO level is −4.5 eV. The HOMO level measured by CV for TCIC-4F is −5.6 eV and the calculated LUMO level is −4.6 eV.
aOptical band gap calculated from the absorption edge of thin film.
bHOMO energy level estimated from the onset oxidation potential.
cLUMO energy level estimated from the CVmeasured HOMO level and optical gap.
2. Device Fabrication and Characterization Method
In a first example, the NIR donor polymer PM2 with an optical band gap (Eopt) of 1.41 eV was selected to fabricate solar cell and photodetector devices with the newly designed ultra-narrow bandgap NFAs.
The electronic property and absorption spectra of devices comprising the NIR NFAs and NIR donor were measured.
Some example devices based on blends of PM2:BCIC-4F and PM2:TCIC-4F were fabricated in an inverted device structure of indium-tin-oxide (ITO)/zinc oxide (ZnO)/NIR D:A/MoO3/Ag, as illustrated in
Light-detecting characteristics measurements were carried out in the glove box using a solar simulator equipped with a Keithley 2635A source measurement unit. J-V curves were measured under AM 1.5G illumination at 100 mW cm−2. EQE measurements were conducted in ambient air condition using an EQE system.
3. Device Characterization and Analysis
External quantum efficiency (EQE), the ratio of the number of charge carriers collected by the device to the number of photons from incident light, was measured at 0 V to −5 V bias. Dark currents of the OPD devices were measured to calculate photodetector characterizations (e.g., responsivity and specific detectivity). Generally, Responsivity and specific detectivity(D*) are well-known figures of merit for photodetector. Responsivity is defined as photocurrent per incident unit of optical power, in other words, electrical output of photon input, which can be obtained from equation (1):
Specific detectivity (D*) is the sensitivity to monochromatic radiation at the wavelength for which the sensitivity is the highest. Larger D* means increased ability to detect a weak signal which is comparable with the detector's noise level. D* is given by equation (2):
where hv=photon energy, q=elementary charge, η=quantum efficiency, λ=wavelength, JD=the dark current density.
Table 2 in
While the photodiode comprising a PM2:TCIC-4F blend system without additives has a Jsc of 1.51 mA/cm2, a higher value of Jsc (2.26 mA/cm2) was obtained for the photodiode comprising a blend with 2% (v/v) 1-chloronaphthalene processing additive. Thus, the PM2:TCIC-4F based devices are characterized by two meaningful peaks at around 720-730 nm and around 1040-1050 nm as shown in their EQE spectra, which probably arise from the maximum absorption of PM2 and TCIC-4F, respectively. The PM2:BCIC-4F based device has just one maximum EQE peak at around 810 nm (at a longer wavelength as compared to the PM2:TCIC-4F based device). Maximum responsivities under photovoltaic mode (0 V bias) of 0.009 A/W and 0.042/0.039 A/W were determined for PM2:BCIC-4F, and PM2:TCIC-4F based devices at wavelengths of 810 nm and 730 nm/1050 nm, respectively. In addition, the maximum specific detectivity (D*, Jones) measured for PM2:BCIC-4F is 6.51×1011 Jones at the 810 nm wavelength, while PM2:TCIC-4F showed 1.82×1012 and 1.60×1012 Jones at each EQE peak wavelength.
Donor polymers P2, P2F, PTB7, PTB7-Th and PBDTTT-C-T (
PTB7:TCIC-4F and PBDTTT-C-T:TCIC-4F based OPDs were evaluated in both self-power mode (performance at zero bias) and in reverse bias mode (performance at −1V). As shown in Table 7, donor polymer PTB7 has −5.15 eV HOMO energy level and −3.31 eV LUMO energy level, while donor polymer PBDTTT-C-T has −5.11 eV HOMO energy level and −3.25 eV LUMO energy level.
ahttps://www.sigmaaldrich.com/US/en;
bhttps://www.ossila.com/products/pce10;
cU.S. Pat. No. 10,316,135;
dInternational Patent Application No. PCT/US20/39963. Structures of the polymers are listed in FIG. 2D.
PM2:TCIC-4F based organic solar cells with 2% (v/v) chloronaphthalene (CN) additive showed 0.44% of power conversion efficiency (PCE) with Jsc of 2.26 mA/cm2, Voc of 0.49 V and FF of 0.40 under 1 sun irradiation. On the other hand, organic solar cells comprising the PTB7:TCIC-4F blend system showed 0.73% PCE resulting from 4.18 mA/cm2 (Jsc) and 0.44 V (Voc) and a FT of 0.40. Peak responsivities under photovoltaic mode (0 V bias) were calculated as 0.042 A/W for the PM2:TCIC-4F device at around 730 nm wavelength, and 0.071 A/W for PTB7:TCIC-4F-based device at around 695 nm wavelength. The devices also showed peak responsivities of 0.039 A/W (PM2:TCIC-4F) and 0.049 A/W (PTB7:TCIC-4F) at around 1040-1050 nm wavelengths. It is possible that the peak responsivities at shorter wavelengths are more related to donor polymer absorption and the peak responsivities at longer wavelength (1050 nm) are related to photocurrent from TCIC-4F absorption. On the other hand, the peak specific detectivities (D*) of the best PM2:TCIC-4F device are 1.82-1012 Jones at 730 nm and 1.60×1012 Jones at 1050 nm and 0V bias. PTB7:TCIC-4F devices exhibited peak specific detectivities of 3.37×1012 Jones at 695 nm and 2.41×1012 Jones at 1040 nm and 0V bias.
Maximum responsivities around 1040 nm to 1050 nm under self-power mode (0 V) were calculated to be 0.049 A/W and 0.033 A/W for PTB7:TCIC-4F, and PBDTTT-C-T:TCIC-4F based devices, respectively. Responsivities of 0.094 A/W (PTB7:TCIC-4F) and 0.057 A/W (PBDTTT-C-T:TCIC-4F) were achieved at the bias of −1V.
Overall, broad EQE, responsivity and specific detectivity response in the 300 nm to 1200 nm region has been achieved. Furthermore, device EQE response over 10%, responsivity over 0.05 A/W and specific detectivity over 1012 Jones in the near IR region of 900-1100 nm has also been successfully demonstrated. Structural modification of BCIC-4F with longer and bulkier side chains may help improve its miscibility with donor polymers and the device performance.
Hole-only and electron-only devices with PBDTTT-C-T:TCIC-4F active layers were fabricated. Space charge limited current (SCLC) electron and hole mobilities were extracted using the Mott-Gurney equation from the SCLC region and are summarized in Table 8 (
Film morphologies of PTB7:TCIC-4F and PBDTTT-C-T:TCIC-4F blend films prepared under the device fabrication condition were examined by tapping mode Atomic Force Microscope (AFM) (
PTB7:TCIC-4F based OSC and OPD with the device configuration of ITO/Mg—ZnO (15%)/active layer/MoO3 (25 nm)/Ag and various donor to acceptor ratio (w/w 1:1, 1:1.5, 1.2) were fabricated and evaluated (
4. X-Ray diffraction Characterization
Grazing-incidence wide-angle X-ray scattering (GIWAXS) is sensitive to the crystalline phase and enables the determination of the molecular orientation. To investigate the molecular packing in pure PM2, BCIC-4F and TCIC-4F films, we carried out GIWAXS as shown in
5. Materials and Methods Used for the Synthesis and Testing of the Example Compositions Discussed in Sections 1-4 Using the Synthetic Route in
Materials All reagents and chemicals were purchased from commercial sources and used without further purification. All anhydrous organic solvents for the synthesis, characterization, and device fabrication steps were purchased from Sigma-Aldrich and TCI. Compounds 3, 8, 9 and 12 were purchased from SunaTech Inc. Compound 1 and 2 were prepared via a modified synthetic condition from literature.[1]
Characterizations of compounds 1H and 13C NMR spectra of intermediate monomers were recorded on a Varian Unity Inova 500 MHz spectrometer in deuterated chloroform solution (CDCl3) with 0.003% TMS as internal reference. Ultraviolet-Visible-Near-infrared (UV-Vis-NIR) absorption spectra were recorded on a Perkin Elmer Lambda 750 spectrophotometer. For the measurements of thin films, materials were spun coated onto precleaned glass substrates from chloroform solutions (10 mg mL−1). Optical band gap was determined from the absorption onset of the thin film samples.
Grazing incidence wide angle X-ray scattering (GIWAXS) analysis 2D GIWAXS measurements were performed using Beamline 9A at the Pohang Accelerator Laboratory (PAL).
The photon energy is 11.055 keV (λ=1.1214 Å). The angle between the film surface and the incident beam was fixed at 0.12° for all of the samples. The measurements were obtained at scanning intervals of 2θ between 3° and 25°. The 2D GIWAXS images from the films were analyzed according to the relationship between the scattering vector q and the d spacing, q=2π/d. The GIWAXS images shown are normalized with respect to exposure time.
Material Synthesis[2-4]
Compound 4: A mixture of compound 3 (768 mg, 2 mmol), compound 2 (2.7 g, 4.8 mmol), Pd(PPh3)4 (47 mg) and anhydrous THF (20 mL) was added into a flame-dried and nitrogen-filled microwave tube in glovebox. The reactant was heated to 120° C. for 24 h. After the mixture was cooled to room temperature, DI water was added, and the mixture was extracted with dichloromethane (50 ml×3). The organic layer was dried over Na2SO4 and concentrated in vacuum. The crude product was purified by silica gel column chromatography (n-hexane:DCM, 9:1) to afford 4 as a deep blue solid (1.85 g, 90%). MS (MALDI-TOF): calculated m/z 1027.53; found m/z 1027.8.
1H NMR for compound 4 (500 MHz, CDCl3, ppm): δ 7.40 (t, 2H), 7.30 (d, 2H), 6.99 (m, 2H), 1.88-1.99 (m, 8H), 0.86-1.05 (m, 36H), 0.76-0.78 (m, 4H), 0.71-0.75 (m, 8H), 0.60-0.65 (m, 12H).
Compound 5: Compound 4 (740 mg, 0.72 mmol), Fe powder (504 mg, 9 mmol) and 20 mL Acetic Acid were added into a N2 purged 50 mL round bottom flask. The reaction was heated to 80° C. overnight then cooled to room temperature and diluted with 100 mL DI water. The mixture was extracted with dichloromethane (50 ml×3), dried over K2CO3 and concentrated in vacuum to afford 5 as a yellow brown solid that was relatively pure by 1H NMR and MALDI-TOF and used for the next step without further purification.
1H NMR for compound 5 (500 MHz, CDCl3, ppm): δ 7.15-7.28 (m, 2H), 7.17 (d, 2H), 6.97 (m, 2H), 4.48 (br, 4H), 1.90-1.99 (m, 8H), 1.00-1.10 (m, 36H), 0.85-0.90 (m, 4H), 0.71-0.80 (m, 8H), 0.62-0.68 (m, 12H). MS (MALDI-TOF): calculated m/z 966.48; found m/z 966.9.
Compound 6: Compound 5 (450 mg, 0.46 mmol) was dissolved in 5 mL anhydrous pyridine in a microwave tube, N-thionylaniline (131 mg, 0.94 mmol) and TMSCl (290 mg, 2.66 mmol) were added in the glovebox. The reaction was heated to 80° C. and stirred for 24 h. After cooling to room temperature, the reaction was diluted with DI water, extracted with dichloromethane (50 ml×3), dried over Na2SO4 and concentrated in vacuum. The crude product was purified by silica gel column chromatography (n-hexane:DCM, 6:1) to afford 6 as a yellow solid (260 mg, 56% for 2 steps).
1H NMR for compound 6 (500 MHz, CDCl3, ppm): δ 9.16 (m, 2H), 7.33 (d, 2H), 7.03 (m, 2H), 4.48 (br, 4H), 1.95-2.16 (m, 8H), 0.98-1.04 (m, 36H), 0.93-0.95 (m, 4H), 0.74-0.77 (m, 8H), 0.62-0.68 (m, 12H). MS (MALDI-TOF): calculated m/z 994.42; found m/z 995.6.
Compound 10: A mixture of compound 9 (240 mg, 0.2 mmol), compound 2 (284 mg, 0.5 mmol), Pd(PPh3)4 (11 mg) and anhydrous THF (10 mL) was added into a flame-dried and nitrogen-filled microwave tube in glovebox. The reactant was heated to 120° C. overnight. After the mixture cooled to room temperature, DI water was added, and the mixture was extracted with dichloromethane (50 ml×3). The organic layer was dried over Na2SO4 and concentrated in vacuum. The crude product was purified by silica gel column chromatography (n-hexane:DCM, 8:1) to afford 10 as a deep green solid (332 mg, 90%).
1H NMR for compound 10 (500 MHz, CDCl3, ppm): δ 9.17 (d, 2H), 7.83 (d, 4H), 7.22 (d, 2H), 7.01 (m, 4H), 6.99 (s, 2H), 3.94 (d, 4H) 1.93-2.09 (m, 8H), 1.82-1.87 (m, 6H), 1.2-1.44 (br, 74H), 0.93-1.06 (m, 32H), 0.74-0.89 (m, 26H), 0.60-0.65 (m, 16H). MS (MALDI-TOF): calculated m/z 1845.27; found m/z 1846.3.
The general procedure for the synthesis of bisaldehyde intermediate 7 and 11 is described as follows. To a flame-dried and nitrogen-filled one-neck round-bottom flask, POCl3 and DMF were added in anhydrous Chloroform (CF) solvent at 0° C. The solution was reacted at 0° C. for 30 min, then a solution of compound 6 (or 10) in CF was added. The reactants were heated to reflux overnight, giving a red solution. The reaction was quenched by DI water and stirred for 30 min at room temperature. The mixture was extracted with ether (50 ml×3), washed by DI water. The organic layer was dried over Na2SO4 and concentrated in vacuum. The residue was purified by silica gel column chromatography.
Compound 7: Compound 6 (260 mg, 0.26 mmol), POCl3 (0.50 mL), DMF (4.01 mL) and 10 mL of CF solvent were used for the reaction. The crude product was purified by using silica gel column chromatography (n-hexane:DCM, 6:4) to afford 7 as a deep yellow solid (260 mg, 94%).
1H NMR for compound 7 (500 MHz, CDCl3, ppm): δ 9.91 (s, 2H), 9.21 (m, 2H), 7.66 (t, 2H), 2.02-2.22 (m, 8H), 0.96-1.06 (m, 36H), 0.75-0.78 (m, 8H), 0.61-0.69 (m, 20H).
Compound 11: Compound 10 (266 mg, 0.144 mmol), POCl3 (0.333 mL), DMF (2.2 mL) and 10 mL of CF solvent were used for the reaction. The crude product was purified by using silica gel column chromatography (n-hexane:DCM, 6:4) to afford 11 as a deep yellow solid (222 mg, 80%).
1H NMR for compound 11 (500 MHz, CDCl3, ppm): δ 9.88 (s, 2H), 9.25 (d, 2H), 7.82 (m, 4H), 7.62 (d, 2H), 6.01 (m, 4H), 3.95 (d, 4H) 1.99-2.15 (m, 8H), 1.83-1.87 (m, 6H), 1.26-1.34 (br, 74H), 0.92-1.06 (m, 32H), 0.74-0.89 (m, 26H), 0.55-0.66 (m, 16H).
The general procedure for the synthesis of final products (BCIC-4F, TCIC-4F and TCIC-4Cl) is described as follows. A mixture of bisaldehyde intermediate 7 (or 11), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (compound 8), dry chloroform (20 mL), and pyridine was added into to a flame-dried and nitrogen-filled one-neck round-bottom flask. The flask was purged with N2 for 20 min and the reactant was heated to 60° C. for 12 h. After the mixture cooled to room temperature, the reaction mixture was concentrated in vacuum. The residue was purified by silica gel column chromatography.
BCIC-4F: Compound 7 (170 mg, 0.162 mmol), compound 8 (124 mg, 0.54 mmol), pyridine (0.2 mL) and 30 mL of anhydrous CF solvent were used for the reaction. The crude product was purified by using silica gel column chromatography (n-hexane:DCM, 1:1) to afford BCIC-4F as a deep blue solid (160 mg, 67%).
1H NMR for BCIC-4F (500 MHz, CDCl3, ppm): δ 9.12 (s, 2H), 8.96 (s, 2H), 8.50 (m, 2H), 7.68 (m, 4H) 2.03-2.21 (m, 8H), 1.25 (s, 6H), 1.05 (br, m, 30H), 0.62-0.77 (m, 24H). MS (MALDI-TOF): calculated m/z 1475.93; found m/z 1475.48.
TCIC-4F: Compound 11 (200 mg, 0.103 mmol), compound 8 (80 mg, 0.35 mmol), pyridine (0.2 mL) and 40 mL of anhydrous CF solvent were used for the reaction. The crude product was purified by using silica gel column chromatography (n-hexane:DCM, 1:1) to afford TCIC-4F as a deep purple solid (175 mg, 72%).
1H NMR for TCIC-4F (500 MHz, CDCl3, ppm): 9.37 (t, 2H), 8.94 (s, 2H), 8.56 (q, 2H), 7.85 (t, 2H), 7.84 (t, 2H), 7.59 (t, 4H), 7.11 (m, 4H), 4.02 (d, 4H), 2.05-2.22 (m, 8H), 1.88-1.93 (m, 6H), 1.27-1.38 (br, 74H), 0.97-1.09 (m, 32H), 0.82-0.90 (m, 16H), 0.59-0.78 (m, 24H). MS (MALDI-TOF): calculated m/z 2325.3; found m/z 2326.3.
TCIC-4C: Compound 11(60 mg, 0.031 mmol), compound 12 (28 mg, 0.105 mmol), pyridine (0.07 mL) and 10 mL of anhydrous CF solvent were used for the reaction. The crude product was purified by using silica gel column chromatography (n-hexane:DCM, 1:1) to afford TCIC-4Cl as a deep purple solid (58 mg, 78%).
1H NMR for TCIC-4C (500 MHz, CDCl3, ppm): 9.36 (t, 2H), 8.94 (s, 2H), 8.77 (q, 2H), 7.93 (t, 2H), 7.83 (t, 2H), 7.81 (t, 4H), 7.08 (m, 4H), 4.00 (d, 4H), 2.01-2.20 (m, 8H), 1.86-1.92 (m, 6H), 1.20-1.37 (br, 74H), 0.91-1.01 (m, 32H), 0.78-0.90 (m, 16H), 0.57-0.67 (m, 24H).
Block 1000 represents optionally providing one or more donors (e.g., electron donors).
In one or more examples of this invention, the semiconductor donor compound comprises a conjugated main chain section, the conjugated main chain section having a repeating donor unit (D1) comprises a dithiophene structure.
In one or more embodiments, the repeating donor unit of the semiconductor compound comprises the structure:
wherein each Ar2 is independently a substituted or non-substituted aromatic functional group, or each Ar2 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar2 groups can be the same. Each R is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. X is C, Si, Ge, N or P. In some embodiments, the R comprising the substituted or non-substituted alkyl, aryl, alkoxy or thioether chain can be a C6-C50 substituted or non-substituted chain, —(CH2CH2O)n (n=2˜20), C6H5, —CnF(2n+1) (n=2˜20), —(CH2)nN(CH3)3Br (n=2˜20), 2-ethylhexyl, PhCmH2m+1 (m=1-20), —(CH2)nN(C2H5)2 (n=2˜20), —(CH2)nSi(CmH2m+1)3 (m, n=1 to 20), or —(CH2)nSi(OSi(CmH2m+1)3)x (CpH2p+1)y (m, n, p=1 to 20, x+y=3).
In one or more embodiments, the donor unit comprises:
In one or more embodiments, the semiconductor donor compound is a polymer.
In one or more embodiments, the semiconductor compound comprises a conjugated main chain section, the conjugated main chain section having a repeating acceptor unit (A) that comprises the structure:
wherein each Ar3 is independently a substituted or non-substituted aromatic functional group, or each Ar3 is nothing and the valence of the ring is completed with hydrogen. Each T is N, C—H, C—F or C—Cl.
In one or more embodiments, the semiconductor compound comprises a conjugated main chain section, the conjugated main chain section having an acceptor unit (A) that comprises the structure:
wherein each T is C—H, N, C—F or C—Cl, and Q is O, S, Se or N—R4, Each R4 is independently hydrogen or a substituted or non-substituted alkyl or aryl chain.
In one or more embodiments, the acceptor unit comprises:
In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section.
In one or more embodiments, the semiconductor donor compound is a polymer.
In one or more embodiments, the semiconductor compound comprises a conjugated main chain section, the conjugated main chain section further comprises a second donor unit (D2) that comprises the structure:
wherein each Ar1 is independently a substituted or non-substituted aromatic functional group, or each Ar1 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar1 groups can be the same. Each R1 and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R1 groups can be the same. Each Z is independently O, S, Se, or N—R4. In some embodiments, the Z groups can be the same. The R1 and R4 comprising the substituted or non-substituted alkyl, aryl, alkoxy or thioether chain can be a C6-C50 substituted or non-substituted chain, —(CH2CH2O)n (n=2˜20), C6H5, —CnF(2n+1) (n=2˜20), —(CH2)nN(CH3)3Br (n=2˜20), 2-ethylhexyl, PhCmH2m+1 (m=1-20), —(CH2)nN(C2H5)2 (n=2˜20), —(CH2)nSi(CmH2m+1)3 (m, n=1 to 20), or —(CH2)nSi(OSi(CmH2m+1)3)x(CpH2p+1)y (m, n, p=1 to 20, x+y=3).
In one or more embodiments, the second donor unit comprises:
In one or more embodiments, the second donor unit comprises:
wherein each Ar1 is independently a substituted or non-substituted aromatic functional group, or each Ar1 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar1 groups can be the same. Each R2, R3 and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R2 groups can be the same. In some embodiments, the R3 groups can be the same. Each Z and Z1 is independently O, S, Se, or N—R4. In some embodiments, the Z groups can be the same. In some embodiments, the Z1 groups can be the same.
In one or more embodiments, the second donor unit comprises:
In one or more embodiments, the second donor unit comprises.
In one or more embodiments, the second donor unit comprises:
In one or more embodiments, the second donor unit comprises:
In one or more embodiments, the semiconductor donor compound is a polymer.
In one or more embodiments, the semiconductor donor compound comprises a conjugated main chain section, the conjugated main chain section further comprises a second donor unit (D2) that comprises the structure:
wherein each Ar4 is independently a substituted or non-substituted aromatic functional group, or each Ar4 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar4 groups can be the same. Each Z is independently O, S, Se, or N—R4. Each R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain.
In one or more embodiments, the second donor unit comprises.
where R5 can be independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain, for example. In one or more embodiments, the semiconductor donor compound is a polymer.
In one or more embodiments, the semiconductor compound comprises a conjugated main chain section, the conjugated main chain section having a D1-A structure, where D1 is a first donor unit and A is an acceptor unit (e.g., having the compositions described herein in Block 1000).
In one or more embodiments, the semiconductor compound comprises a conjugated main chain section, the conjugated main chain section having a D1-A structure that comprises the structure:
wherein each Ar2 and Ar3 is independently a substituted or non-substituted aromatic functional group, or each Ar2 and Ar3 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar2 groups can be the same. In some embodiments, the Ar3 groups can be the same. Each R is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. X is C, Si, Ge, N or P. T is C—H, N, C—F or C—Cl.
In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section.
In one or more embodiments, the conjugated main chain section comprises:
wherein the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
wherein each Ar2 is independently a substituted or non-substituted aromatic functional group, or each Ar2 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar2 groups can be the same. Each R and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. X is C, Si, Ge, N or P. T is C—H, N, C—F or C—Cl. Q is O, S, Se or N—R4.
In one or more embodiments, the conjugated main chain section comprises:
wherein the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
Each R is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. X is C, Si, Ge, N or P. T is C—H, N, C—F or C—Cl.
In one or more embodiments, the conjugated main chain section comprises:
In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section.
In one or more embodiments, the conjugated main chain section comprises:
In one or more embodiments, the conjugated main chain section comprises:
In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section.
In one or more embodiments, the semiconductor compound is a semiconductor polymer.
In one or more embodiments, the semiconductor polymer comprises the structure:
wherein each Ar2 s independently a substituted or non-substituted aromatic functional group, or each Ar2 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar2 groups can be the same. Each R and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. X is C, Si, Ge, N or P. T is C—H, N, C—F or C—Cl. Q is O, S, Se or N—R4. n is an integer.
In one or more embodiments, the acceptor unit is regioregularly arranged along the semiconductor polymer backbone.
In one or more embodiments, the semiconductor polymer comprises the structure:
Wherein each R is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. X is C, Si, Ge, N or P. T is C—H, N, C—F or C—Cl.
In one or more embodiments, the acceptor unit is regioregularly arranged along the semiconductor polymer backbone.
In one or more embodiments, the semiconductor polymer comprises the structure:
In one or more embodiments, the acceptor unit is regioregularly arranged along the semiconductor polymer backbone.
In one or more embodiments, the semiconducting compound further comprising the structure:
wherein:
each Ar1 is independently a substituted or non-substituted aromatic functional group, or each Ar1 is nothing and the valence of the ring is completed with hydrogen. each Z is independently O, S, Se, or N—R4; each R1, R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. each Q is independently O, S Se, or N—R4: T is C—H, N, C—F, or C—Cl.
In one or more embodiments, the semiconducting compound further comprising the structure:
In one or more embodiments, the semiconductor compound comprises a conjugated main chain section, the conjugated main chain section having a DI-A-D2-A structure, while D1 is a first donor unit, D2 is a second donor unit, A is an acceptor unit.
In one or more embodiments, the semiconductor compound comprises a conjugated main chain section, the conjugated main chain section having a D1-A-D2-A structure that comprises the structure:
wherein each Ar1 and Ar2 is independently a substituted or non-substituted aromatic functional group, or each Ar1 and Ar2 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar1 groups can be the same. In some embodiments, the Ar2 groups can be the same. Each R, R1 and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. In some embodiments, the R1 groups can be the same. Each Z is independently O, S, Se, or N—R4. In some embodiments, the Z groups can be the same. X is C, Si, Ge, N or P; T is C—H, N, C—F, or C—Cl, and Q is O, S, Se or N—R4. In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
wherein the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
wherein each Ar1 and Ar2 is independently a substituted or non-substituted aromatic functional group, or each Ar1 and Ar2 is nothing and the valence of the ring is completed with hydrogen. In some embodiments, the Ar1 groups can be the same. In some embodiments, the Ar2 groups can be the same. Each R, R2, R3 and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. In some embodiments, the R2 groups can be the same. In some embodiments, the R3 groups can be the same. Each Z and Z1 is independently O, S, Se, or N—R4. In some embodiments, the Z groups can be the same. In some embodiments, the Z1 groups can be the same. X is C, Si, Ge, N or P, and Q is O, S, Se or N—R4. In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
In one or more embodiments, the conjugated main chain section comprises:
wherein each R, R1 and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. In some embodiments, the R1 groups can be the same. Each Z is independently O, S, Se, or N—R4. In some embodiments, the Z groups can be the same. X is C, Si, Ge, N or P, and Q is O, S Se, or N—R4. In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
wherein the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
In one or more embodiments, the conjugated main chain section comprises:
wherein each R, R2 and R3 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. In some embodiments, the R2 groups can be the same. In some embodiments, the R3 groups can be the same. X is C, Si, Ge, N or P. In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
wherein the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the conjugated main chain section comprises:
In one or more embodiments, the semiconductor compound is a semiconductor polymer.
In one or more embodiments, the semiconductor polymer comprises.
wherein each R and R1 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. In some embodiments, the R1 groups can be the same. X is carbon (C), silicon (Si), germanium (Ge), nitrogen (N) or phosphorus (P). In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the semiconductor polymer comprises:
wherein each R, R2 and R3 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In some embodiments, the R groups can be the same. In some embodiments, the R2 groups can be the same. In some embodiments, the R3 groups can be the same. In one or more embodiments, the acceptor unit is regioregularly arranged along the conjugated main chain section as shown in the structure.
In one or more embodiments, the semiconductor polymer comprises:
In one or more embodiments, the semiconductor donor polymer comprises a conjugated main chain section, the conjugated main chain section having a repeating unit of D1-A-D2-A structure, while D1 is a first donor unit with strong electron donating capability, D2 is a second donor unit with weaker electron donating capability, A is a strong acceptor unit. Such backbone structures can tune the optical bandgap, HOMO-LUMO levels and yield well-ordered polymer crystallite phases in thin films.
In one or more embodiments, the semiconductor donor compound is a small molecule donor comprises the structure of E-A-(D1-A)n-E, while D1 can be selected from any of the above listed first donor units, and A can be selected from any of the above listed acceptor units. n=1-10. E is a terminal end group which can be independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy group.
In one or more embodiment, the small molecule donor comprises the structure of E-A-(D1-A)n-E, while D1 is
wherein each R and R4 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. X is C, Si, Ge, N or P. T is C—H, N, C—F or C—Cl, and Q is O, S, Se or N—R4, E is an alkylated bithiophene, n=1, 2, 3, 4 or 5. Each T can be the same or different. Each X can be the same or different.
In one or more embodiment the small molecule donor comprises the structure:
wherein each R1 and R2 is independently hydrogen or a substituted or non-substituted alkyl, aryl, alkoxy or thioether chain. In one or more embodiments, R1 is 2-ethylhexyl, and R2 is hexyl. In another embodiment, R2 is 2-ethylhexyl, and R1 is hexyl.
The R, R1, R2, R3 and R4 groups can be a linear or branched side-chain comprising a C3-C50, C5-C50, C8-C50, or C9-C50 substituted or non-substituted alkyl chain. Examples of alkyl chains include isopropyl, sec-butyl, t-butyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, dimethyloctyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, 1-2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1-, 2-pentylheptyl, branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonoadecyl, eicosyl with one or more branch points at any carbon of the alkyl chain, such as 2 (or 1, or 3, or 4)-ethylhexyl, 2 (or 1, or 3, or 4)-hexyldecyl, 2 (or 1, or 3, or 4)-octyldodecyl, 2 (or 1 or 3, or 4)-butyloctyl, 4 (or 1, or 2, or 3, or 5, or 6)-butyldecyl, 5 (or 1, or 2, or 3, or 4, or 6, or 7)-butylundecyl, 6 (or 1, or 2, or 3, or 4, or 5, or 7, or 8)-butyldodecyl, 12 (or 1, or 2, or 3, or 4, or 5, or 6, or 7, or 8, or 9, or 10, or 11, or 13, or 14)-butyloctadecyl, and the like.
In one or more examples of this invention, the electron donor compounds can be but are not limited to those listed in FIG. 20A-F of U.S. patent application Ser. No. 16/792,000 incorporated by reference herein.
Block 1002 represents providing, synthesizing and/or combining the donor(s) of Block 1000 with, one or more non-fullerene acceptor (NFA), e.g., to form a blend of the one or more donors and the one or more NFAs.
In one or more examples of the present invention, the non-fullerene acceptor (electron acceptor) comprises an A-D-A′-D-A structure, where D is any strong electron donating unit, group or moiety; A and A′ are any strong electron accepting unit, group or moiety, and A and A′ can be the same or different.
In one or more embodiments, D can be, but is not limited to, the following strong electron donating units:
where each R, R1, R3 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; X is C, Si, Ge, N or P; Y is O, S, Se or N—R3; each Ar is independently a substituted or non-substituted aromatic functional group, or each Ar is independently nothing and the valence of its respective thiophene ring is completed with hydrogen. Each Ar may comprise one, two, three or more 5-membered or 6-membered aromatic rings.
In one or more embodiments, examples of D include, but are not limited to, the following strong electron donating units:
where each R1, R3 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; X is C, Si, Ge, N or P; and Y is O, S, Se or N—R3.
Further examples of D include, but are not limited to, the following strong electron donating units:
where each R, R1, R2, R3 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; X is C, Si, Ge, N or P; Y is O, S, Se or N—R3.
In one or more embodiments, examples of D include, but are not limited to, the following strong electron donating units:
where each R2, R3, R4, R5, R6 and R7 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; in some embodiments, R4 is either a hydrogen or the same as Z—R2; R5 is either a hydrogen or the same as R3; Y is O, S, Se, or N—R6, Z is O, S, Se or N—R7.
Examples of dithiophene units further include those illustrated in Table B (
In one or more examples, A can be but not limited to those electron accepting units listed in FIG. 19A-H of U.S. patent application Ser. No. 16/792,000, and those listed in FIGS. 22a-g of U.S. patent application Ser. No. 16/179,294, which applications are incorporated by reference herein.
Examples of A′ include, but are not limited to, the following strong electron accepting units:
wherein each Y or Z can be CH, CF, CCl, N, C—CN, C—COR, C—COOR, C—OR, C—SR, C—NO2; each X is O, S, Se or N—R3; each Ar is independently a substituted or non-substituted aromatic functional group, preferred to be an electron withdrawing aromatic functional group, or each Ar is independently nothing; each X1 and X2 is halogen, CN or alkoxy, alkylthio, or N-annulated, or S-annulated; each Y1, Y2, Y3 and Y4 is S or O; each R, R1, R2, and R3 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain.
In one or more embodiments, the A-D-A′-D-A semiconductor comprises the general structure:
wherein each R1 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; X is O, S, Se or N—R1; each Ar is independently a substituted or non-substituted aromatic functional group, preferred to be an electron withdrawing aromatic functional group, or each Ar is independently nothing and the valence of the adjacent ring is completed with hydrogen. Each Ar may comprise one, two, three or more 5-membered or 6-membered aromatic rings, for example. Each D can be any strong electron donating unit, group or moiety; each A can be any strong electron accepting unit, group or moiety. The two A units in the A-D-A′-D-A semiconductor can be the same or different. The two D units in the A-D-A′-D-A semiconductor can be the same or different. In one or more embodiments, each D can be a dithiophene unit.
In one or more examples, each Ar can be, but is not limited to, the following aromatic units:
wherein each R is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; X is O, S, Se or N—R1.
As described above, A is an electron accepting unit (electron acceptor group or moiety). Examples of A include, but are not limited to, those electron accepting units listed in FIG. 19A-H of U.S. patent application Ser. No. 16/792,000, and those listed in FIGS. 22a-g of U.S. patent application Ser. No. 16/179,294, which applications are incorporated by reference herein.
In one or more embodiments, each A can be an electron acceptor group, moiety or unit of the following structure:
where
EWG=any electron withdrawing group, examples of EWG including, but not limited to, F, Cl, Br, I, CN, CF3, NO2, sulfonate, ketone, ester, n=1, 2, 3 or 4. Examples of Ar′ include, but are not limited to, the following:
In one or more embodiments, the A-D-A′-D-A semiconductor comprises the general structure:
wherein each Ar is independently a substituted or non-substituted aromatic functional group, preferred to be an electron withdrawing aromatic functional group, or each Ar is independently nothing and the valence of the adjacent ring is completed with hydrogen. In one or more examples, each Ar may comprise one, two, three or more 5-membered or 6-membered aromatic rings. X is O, S, Se or N—R1; Y is O, S, Se, or N—R2; Z is C, Si, Ge, N or P; Each R, R1 and R2 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; In some embodiments, the R, R1 and R2 groups can be the same. The R, R1 and R2 comprising the substituted or non-substituted alkyl, aryl or alkoxy chain can be a C6-C50 substituted or non-substituted alkyl or alkoxy chain, —(CH2CH2O)n (n=2˜30), C6H5, —CnF(2n+1) (n=2˜50), —(CH2)nN(CH3)3Br (n=2˜50), 2-ethylhexyl, PhCmH2m+1 (m=1-50), —(CH2)nN(C2H5)2 (n=2˜50), —(CH2)nSi(CmH2m+1)3 (m, n=1 to 50), or —(CH2)nSi(OSi(CmH2m+1)3)x(CpH2p+1)y (m, n, p=1 to 50, x+y=3). In one or more examples, R is 2-ethylhexyl. In some more examples, R is n-octyl.
The R, R1, R2 and R3 groups described herein can be a branched side-chain comprising a C3-C50, C5-C50, C8-C50, or C9-C50 substituted or non-substituted alkyl chain. Examples of branched alkyl chains include isopropyl, sec-butyl, t-butyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, dimethyloctyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3- 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1-, 2-pentylheptyl, branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonoadecyl, eicosyl with one or more branch points at any carbon of the alkyl chain, such as 2 (or 1, or 3, or 4)-ethylhexyl, 2 (or 1, or 3, or 4)-hexyldecyl, 2 (or 1, or 3, or 4)-octyldodecyl, 2 (or 1 or 3, or 4)-butyloctyl, 4 (or 1, or 2, or 3, or 5, or 6)-butyldecyl, 5 (or 1, or 2, or 3, or 4, or 6, or 7)-butylundecyl, 6 (or 1, or 2, or 3, or 4, or 5, or 7, or 8)-butyldodecyl, 12 (or 1, or 2, or 3, or 4, or 5, or 6, or 7, or 8, or 9, or 10, or 11, or 13, or 14)-butyloctadecyl, and the like.
In some embodiments, the A-D-A′-D-A semiconductor comprise the structure:
wherein X is O, S, Se or N—R1, Y is O, S; Z is C, Si, Ge, N; each R and R1 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; each Ar1 and Ar2 is independently a substituted or non-substituted aromatic functional group, preferred to be an electron withdrawing aromatic functional group, or each Ar1 and Ar2 is independently nothing and the valence of its respective adjacent ring is completed with hydrogen. In one or more examples each Ar1 and Ar2 may comprise one, two, three or more 5-membered or 6-membered aromatic rings.
In some embodiments, the A-D-A′-D-A semiconductor comprises the structure:
wherein X is O, S, Se or N—R3; Z is C, Si, Ge, N; each R1, R2 and R3 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain;
EWG=any electron withdrawing group, wherein EWG can be, but is not limited to F, Cl, Br, I, CN, CF3, NO2, sulfonate, ketone, ester, n=1, 2, 3 or 4. Examples of Ar include, but are not limited to, the following:
In one or more examples, R1 is ((2-decyltetradecyl)oxyl)phenyl and R2 is 2-ethylhexyl.
In one or more embodiments, the A-D-A′-D-A semiconductor comprises the structure:
wherein each R, and R′ is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain. In one or more examples, R is 2-ethylhexyl, R′ is ((2-decyltetradecyl)oxyl)phenyl. X can be any electron withdrawing group, can be but is not limited to F, Cl, Br, I, CN, CF3, NO2, sulfonate, ketone.
In one or more examples of the present invention, the non-fullerene acceptor comprises an A-D-A′-D′-A′-D-A structure, where D′ and D is any strong electron donating unit, including but not limited to, electron donating units, groups and moieties described herein; A and A′ are any strong electron accepting unit, including but not limited to the electron accepting units, groups and moieties described herein; and D and D′, A and A′ can be the same or different.
In one or more embodiments, the A-D-A′-D′-A′-D-A semiconductor comprise the structure:
wherein each R1, R2, R3, R4, R5 and R6 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; each X is independently O, S, Se or N—R1; each Y is independently O, S, Se or N—R2; each E is independently O, S, Se, or N—R3; each Ar1 and Ar2 is independently a substituted or non-substituted aromatic functional group, preferably an electron withdrawing aromatic functional group, or each Ar1 and AR2 is independently nothing and the valence of its respective adjacent ring is completed with hydrogen. In one or more examples, each Ar1 and AR2 may comprise one, two, three or more 5-membered or 6-membered aromatic rings. Each A can be any strong electron accepting unit, group or moiety. The two A units in the A-D-A′-D′-A′-D-A semiconductor can be the same or different.
In one or more examples, each Ar1 can be, but is not limited to, the following aromatic units:
wherein each R and R1 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; and each X is independently O, S, Se or N—R1.
As described above, A is an electron accepting unit (electron acceptor moiety). Examples of A include, but are not limited to, those electron accepting units listed in FIG. 19A-H of U.S. patent application Ser. No. 16/792,000, and those listed in FIGS. 22a-g of U.S. patent application Ser. No. 16/179,294 incorporated by reference herein
In one or more embodiments, each A can be an electron acceptor group, moiety or unit of the following structure:
where
EWG=any electron withdrawing group, where examples of EWG include but are not limited to F, Cl, Br, I, CN, CF3, NO2, sulfonate, ketone, ester, n=1, 2, 3 or 4. Examples of Ar′ can be but not limited to the following:
In one or more embodiments, D can be, but is not limited to, the following electron donating units:
where each R2, R3, R4, R5, R6 and R7 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; in some embodiments, R4 is either a hydrogen or the same as Z—R2; R5 is either a hydrogen or the same as R3; Y is O, S, Se, or N—R6, Z is O, S, Se or N—R7.
Examples of A include, but are not limited to, those electron accepting units listed in FIG. 19A-H of U.S. patent application Ser. No. 16/792,000, and those listed in FIGS. 22a-g of U.S. patent application Ser. No. 16/179,294, which applications are incorporated by reference herein.
In one or more embodiments, the A-D-A′-D′-A′-D-A semiconductor comprises the structure:
where each R4 and R7 is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; and each R5 and R6 is independently hydrogen or a substituted or non-substituted alkyl or aryl chain.
Block 1004 represents the end result, a composition of matter comprising the NFA and the donor. In one or more examples, a film comprising the composition of matter may have an absorptivity of at least 0.7 across the entire wavelength range of 1000-1200 nm, wherein the electron acceptor has a bandgap less than 1.0 eV and the donor compound has a bandgap less than 1.45 eV.
Block 1006 represents optionally processing the composition of matter in a device.
In one or more embodiments, the device comprises a heterojunction between the electron acceptor and the organic semiconducting donor compound.
In one or more examples, the device comprises an active region comprising the electron acceptor, wherein the active region outputs electrical current in response to absorbing electromagnetic radiation.
In one or more embodiments, the active region (e.g., in the solar cell or the photodetector) is sensitive to infrared wavelengths (i.e., the bandgap of the acceptor molecule and/or donor molecule are sufficiently low to absorb infrared radiation).
In one or more embodiments, the semiconductor donor compound has a Highest occupied molecular orbital (HOMO) in a range of −4.8 eV to −5.5 eV, a lowest un-occupied molecular orbital (LUMO) in a range of −3.2 eV to −4.0 eV, and a bandgap in a range of 1.0 eV to 2.0 eV.
In one or more embodiments, the semiconductor donor compound has a HOMO in a range of −4.8 eV to −5.5 eV, a LUMO in a range of −3.5 eV to −4.0 eV, and a bandgap in a range of 1.0 eV to 1.4 eV.
In one or more embodiments, the semiconductor donor compound has HOMO in a range of −5.0 eV to −5.3 eV, a LUMO in a range of −3.5 eV to −3.9 eV, and a bandgap in a range of 1.0 eV to 1.3 eV.
In one or more embodiments, the semiconductor donor compound has a bandgap narrower than 1.5 eV.
In one or more embodiments, the semiconductor donor compound has a bandgap narrower than 1.4 eV or narrower than 1.1 eV.
In one or more embodiments, the semiconductor donor compound has a main absorption band between 600 and 1200 nm.
In one or more embodiments, the semiconductor donor compound has a main absorption band between 600 and 900 nm.
In one or more embodiments, the semiconductor donor compound has a main absorption band between 700 and 1100 nm.
In one or more embodiments, the semiconductor donor compound has a maximum extinction coefficient in solution of at least 1×105 M−1 cm−1.
In one or more embodiments, the organic electron acceptor (NFA) has a HOMO in a range of −5.3 eV to −5.7 eV, a LUMO in a range of −4.3 eV to −4.7 eV, and a bandgap less than of 1.0 eV or in a range of 0.8 to 0.99 eV.
In one or more embodiments, the organic electron acceptor (NFA) has a main absorption band between 800 and 1400 nm.
In one or more embodiments, the organic electron acceptor (NFA) has a maximum extinction coefficient in solution of at least 1×105 M−1 cm−1.
In one or more examples, an energetic offset between the donor and acceptor HOMO levels (HOMOD-HOMOA, ΔEHOMO) is no more than 0.3 eV, 0.2 eV or 0.1 eV.
In one or more examples, the device comprising an active region comprising the NFA and the donor has an external quantum efficiency (EQE) over 2% in the wavelength range of 600-1100 nm and a short circuit current density JSC over 3 mA cm−2.
In one or more embodiments (e.g., as illustrated in
In one or more examples, the device comprises a photodetector having an external quantum efficiency (EQE) above 2%, a responsivity of at least 0.01 A/W, and a specific detectivity of at least 1011 Jones across the entire wavelength range of 800-1200 nm of the electromagnetic radiation when the anode is biased at 0V with respect to the cathode.
In one or more embodiments, the device:
The photovoltaic device may have a standard or inverted structure. It may comprise a substrate, a first electrode deposited on the substrate, a second electrode, an optional electron conducting/hole blocking layer deposited either between the first electrode and the active layer, or between the active layer and the second electrode, and an optional hole conducting/electron blocking layer deposited either in between the first electrode and the active layer, or between the active layer and the second electrode.
In one or more examples (e.g., as used to obtain the results shown in
holes and electrons are generated in the active region in response to electromagnetic radiation incident on the active region,
the electrons are collected in the electron acceptor and are transmitted through to the cathode, and
the holes are collected in the electron donor and transmitted through to the anode.
Also illustrated is a hole blocking layer 1108 between the cathode and the active region, and an electron blocking layer 1110 between the anode and the active region.
During operation, either or both the electron donor and the electron acceptor absorb photons to create electron-hole pairs, the electron acceptor (interfacing with the electron donor) receives or collects the electron in the electron hole pair and transports the electron to the cathode interface layer/hole blocking layer and the cathode. The hole is transported by the electron donor to the anode interface layer/electron blocking layer and then the anode.
In one or more examples, the device 1100 comprises an infrared photodetector, comprises a first electrode 1102 (e.g., anode or cathode); a first carrier transport layer 1108; an active layer 1106, wherein the first carrier transport layer (e.g., hole blocking layer or electron blocking layer) is between the first electrode and the active layer; a second carrier transport layer 1110, wherein the active layer is between the first carrier transport layer and the second carrier transport layer; and a second electrode 1104 (e.g., anode or cathode) on the second carrier transport layer (e.g., hole blocking layer or electron blocking layer).
Examples of a substrate include, but are not limited to, a flexible substrate, a plastic substrate, a polymer substrate, a metal substrate, a silicon substrate, or a glass substrate. In one or more embodiments, the flexible substrate is at least one film or foil selected from a polyimide film, a polyether ether ketone (PEEK) film, a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a polytetrafluoroethylene (PTFE) film, a polyester film, a metal foil, a flexible glass film, and a hybrid glass film. Examples of cathode interface layer include, but are not limited to ZnO and/or ITO. The ZnO can include multiple layers (e.g., two layers) and have a surface roughness of less than 5 nm over an area of 0.2 cm2.
Examples of anode interface layer include, but are not limited to MoOx having a thickness in a range of 5-150 nm. Further examples include, but are not limited to, the hole transporting/conducting layer material selected from, but not limited to, the group comprising or consisting of poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS), p-type organic small molecule semiconductors such as Spiro-MeOTAD, pentacene, biscarbazolylbenzene, oligomer semiconductors, polymer semiconductors such as PTAA, poly(3-hexylthiophene-2,5-diyl) (P3HT), donor-acceptor copolymer semiconductors such as PCPDTBT, PCDTBT, conjugated small molecule electrolytes, conjugated oligomer electrolytes, conjugated polymer electrolytes, metal oxides such as CuI, CuBr, CuSCN, Cu2O, CuO or CIS. VOx, NbOx, MoOx, WOx, NiOx, where x is 3 or less than 3, or other main group or transition metal oxides and a compound as shown in FIG. 1 of U.S. Ser. No. 14/954,131.
Examples of cathode material include, but are not limited to, ITO. In further examples, the electron transporting/conducting layer material is selected from, but not limited to, the group comprising or consisting of TiO2, ZnO, SnO, SnO2, SiO2, CeO2, ZrO2, CdSe, WO3, ZnSnO4, PbI2, SrTiO3, LiF, Li2CO3, fullerene based electron acceptors (C60, C70, PC61BM, PC71BM, ICBA), borane based electron acceptors (3TPYMB), Bathocuproine (BCP), bathophenanthroline (Bphen), ITIC type of non-fullerene acceptors, NDI and PDI based non-fullerene acceptors, and the combination of above (double layer). The electron transporting layer may have a thickness of 2 nm to 500 nm, preferably a thickness of 20 nm to 200 nm, more preferably a thickness of 20-50 nm, or 50 nm to 100 nm.
Examples of cathode and anode materials include, but are not limited to, a metal or at least one material selected from gold, aluminum, copper, silver, silver paste, palladium, platinum, nickel, a combination/bilayer of metal and molybdenum oxide or molybdenum (wherein the MoOx is an interlayer), a liquid metal (e.g., mercury alloy, eutectic gallium indium), a transparent conductive layer, carbon nanotubes, graphene, carbon paste, PEDOT:PSS, and a conjugated polyelectrolyte.
In one or more embodiments, the electrodes, anode, cathode, interface layers, electron transporting/hole blocking layers, hole transporting/electron blocking layers of the electronic device can be transparent or semitransparent.
The active layer, electron transporting/hole blocking layers, hole transporting/electron blocking layers of the electronic device may be deposited by solution casting or vapor deposition. Illustrative thin film deposition methods include a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a blade coating method, a wire bar coating method, a dip coating method, a spray coating method, a free span coating method, a dye coating method, a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method, a dispenser printing method, a nozzle coating method and a capillary coating method, for forming a film from a solution.
Possible Modifications and Variations
Non-fullerene acceptor materials were designed and synthesized with different chemical structures to tune chemical properties for narrower bandgaps and higher device performance. In addition, the device performance can be improved through further morphology control of the active layer. Further device optimization includes, but is not limited to, optimizing the donor/acceptor ratio, the solvent solution concentration, processing additive types and amounts, film deposition methods (spin coating, blade coating, drop casting etc.), film deposition temperature, film thickness, buffer layers (electron transporting layer, hole transporting layer).
In addition, the above systems can be applied to various organic electronic devices including organic solar cells, organic field effect transistor and organic sensor. Organic photodetectors (OPDs) with NIR responsivity have plenty of applications such as image sensing, night surveillance, optical communication, and health monitoring.
Advantages and Improvements
Conventional photodetectors are based on crystalline inorganic semiconductor materials such as silicon and epitaxial semiconductors grown on planar and rigid substrates (wafers).[10-11] On the other hand, organic semiconductors (n-conjugated molecules and polymers) have high extinction coefficients, arise from the large wavefunction overlap between the electronic ground state and the lowest excited state, which result in strong light absorption in thin films.[14]
NIR non-fullerene acceptors are a strategy key to achieve high-transparent device and high-detectivity in range of NIR wavelength (over 780 nm). The present disclosure describes desirable compositions of NIR donors and NIR non-fullerene acceptors for organic solar cells and photodetectors with demonstration of their device performance. In the examples described herein, NIR absorbing donor (PM2) and ultra-narrow bandgap NIR-non fullerene acceptors (BCIC-4F, TCIC-4F and TCIC-4Cl) were synthesized and characterized for organic solar cell and organic photodetector structures based on a donor:acceptor heterojunction which can separate excitons and generate charges.[15]. Since PM2 polymer has narrow energy bandgap of ˜1.41 eV and absorbs the sunlight at wavelengths up to ˜900 nm, compositions with NIR non-fullerene acceptors exhibit broader NIR light absorption coupled with high transparency at wavelengths detectable by the human naked eye and superior performance in NIR range. NIR organic optoelectronic applications that can leverage this strong absorption in the near-infrared region include state of the art internet of things (IoT) applications, health monitoring (e.g., unobtrusive photodetectors that can be integrated in/on the human body, such as healthcare devices operating by continuous detection of physiological signals or small electronic chips[12-13]), and lightweight and conformal image sensors with color or infrared sensitivity for applications in wearable electronics, prosthetics, robotics, and automotive applications.
The following references are incorporated by reference herein.
This concludes the description of synthesis route, the optical and electrical properties of NIR absorbing materials; donor polymer and three ultra-narrow bandgap NIR-NFAs (e.g., BCIC-4F and TCIC-4F). Also, this describes the device structure and methods of the device fabrication, with photovoltaic and photodetector performances. The foregoing description of one or more embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
This application claims the benefit under 35 U.S.C. Section 119(e) of co-pending and commonly assigned U.S. Provisional Application Ser. No. 63/224,097, filed on Jul. 21, 2021, by Guillermo Bazan, Seyeong Song, Ziyue Zhu, and Hengbin Wang, entitled “ULTRA NARROW BANDGAP NON-FULLERENE ACCEPTOR-BASED ORGANIC ELECTRONICS,” attorneys' docket number G&C 30794.0801USP1 (UC 2021-876-1), which application is incorporated by reference herein.
| Number | Date | Country | |
|---|---|---|---|
| 63224097 | Jul 2021 | US |
