A series of novel porphyrin materials with pushpull framework were designed and synthesized for organic solar cells (OSCs). To start with, a brief overview on the background of OSC, including dye-sensitized solar cells (DSSCs) and bulk heterojunction (BHJ) solar cells, and the porphyrin based materials for OSC applications was presented in Chapter 1. In Chapter 2, an efficient panchromatic light harvesting was demonstrated by the co-adsorption of a porphyrin molecule HD18 or HD19 and N719 in dye-sensitized solar cells. It is apparent that the porphyrin sensitizers show strong absorption in the Soret (400500 nm) and Q bands (600700 nm), while N719 shows efficient spectral response in the 500600 nm (between the Soret and Q bands), and the combination of these two kinds of dye molecules might display strong spectral response in the full-colour region. Mechanistic investigations were carried out by various spectral and electrochemical characterizations. The best co-sensitized device based on HD18 + N719 shows considerably enhanced power conversion efficiency of 8.27%, while those individually sensitized by HD18 and N719 display efficiencies of 6.74% and 6.90%, respectively. Subsequently, an optimized co-sensitized device based on the porphyrin HD18 and organic dye PT-C6 was fabricated by a stepwise adsorption of HD18 and PT-C6. The best performance of JSC/mA cm-2 =19.61, VOC/V = 0.74, FF = 0.69 and η = 10.1%, is superior to that of the individual device made from either HD18 (η = 7.4%) or PT-C6 (η = 8.2%) under the same conditions of fabrication. The post-adsorption of PT-C6 on the porphyrin-sensitized TiO2 anode surface not only enhances the spectral response of solar cells, but also greatly retards the back reaction between conduction-band electrons in TiO2 and the oxidized species ( I_3^-) in the electrolyte. In Chapter 3, a series of new donor-π-acceptor (DπA) porphyrin sensitizers with extended π-conjugation units were designed and synthesized for DSSC applications. Appending a phenothiazine (PTZ) donor moiety to the well-investigated porphyrin core and a variety of acceptors with electron deficient property at the opposite side can significantly red shift the absorption spectra to 700 nm in dyes (24). These different acceptor groups exert a significant influence on the electrochemical and photovoltaic properties of these sensitizers. These dyes have been evaluated in dye-sensitized solar cells, showing efficiencies of 0.90~7.29% with I^-/I_3^- based electrolytes. A detailed investigation on their physical, photophysical and electrochemical properties provided some important information on the factors affecting the main photovoltaic parameters. In Chapter 4, we designed and synthesized another series of dyes based on the rigid 2-aryl-1H-imidazo[4,5-b]porphyrin donors, in which an electron-accepting group was incorporated at the position 2 of imidazo unit via an aromatic spacer. Their photophysical and electrochemical properties, theoretical calculations and dye-sensitized solar cell performances have been investigated. The spectroelectrochemical data suggests the 1H imidazo unit can extend the conjugation length and lower the optical gap. As expected, the π conjugated substituents in all these dyes produced panchromatic absorption spectra over a wide range of wavelengths and IPCE spectra featuring a broad plateau in the region 430650 nm. In addition, both DFT computational and electrochemical data indicate a smaller HOMOLUMO energy gap for HD31Zn than that for dye 1, suggesting that a slightly more facile conjugation between the porphyrin core and the diketopyrrolopyrrole (DPP) unit through the 1H imidazo unit in HD31. Both Dye 1 and HD31Zn exhibited strong solvation effect in different solvents. The effects of solvents and their structures on the photophysical and photochemical properties and device performance have been studied in detail. The results indicate that porphyrin fused heterocycle as an effective electron donor and a suitable spacer between the donor and the acceptor can reduce the molecular aggregation through solvation effects. In Chapter 5, a series of conjugated DπA small molecules (YJ1YJ6, YJ13YJ15 and YJ16YJ19) for bulk heterojunction solar cells (BHJSCs) were prepared by the Sonogashira cross coupling of the electron rich porphyrin units with electron deficient benzothiadiazole (BT), DPP, or 3-ethylrhodanine moieties. The peripheral side chains on the porphyrin units like alkoxyl phenyl, alkyl, and (triisopropylsilyl)ethynyl (TIPS) can alter the solubility, conformation, and electronic properties of the obtained DπA small molecules, allowing the tuning of their photovoltaic properties when blended with fullerene derivatives. The presence of these side chains groups on porphyrin donor units affects the torsion angles between the side chains and the conjugated main chain, but resulting in only slightly different energy levels for the highest occupied molecular orbital (HOMO) for these molecules. Their performance in solution-processed solar cells is under studying. In Chapter 6, we reported the synthesis, electrochemical properties, and optical properties of seven novel BODIPY based π-conjugated materials. These dyes were synthesized via the Stille coupling reactions between the BODIPY units and electron donating groups (EDGs), such as 4,8-bis(5-(2-ethylhexyl)thiophen-2- yl)benzo[1,2-b:4,5-b′]dithiophene (BDT), 9,9-dioctyl-9H-fluorene (FL) or thieno[3,2-b]thiophene (TH). These donors were rationally chosen based on their gas phase ionization potential (IP) values estimated by density functional theory (DFT) calculations. Cyclic voltammetry of these dyes in dichloromethane solutions reveals that HOMOs of the resulting dyes correlated well with the ionization potentials (donor strength) of the donors. On the contrary, the lowest unoccupied molecular orbital (LUMO) energy levels of all dyes are fairly invariant, independent of the donors used. This suggests that the BODIPY moiety provides the primary influence on the LUMO levels of the materials. Two series of YJ9YJ11 and YJ21YJ23 show strong visible absorption in the red region. In addition, we presented the first example of a donor-acceptor BODIPY- containing conjugated copolymers, HDP6 and HDP7, with absorption over the entire spectrum of visible light and part of near infrared region (300900nm) making them suitable as additive for light-harvesting antenna. These dyes provide us with a toolset to tune the frontier molecular orbital energy levels, while retaining the low band gap and broad absorption of these dyes. Overall, these BODIPY molecules exhibited appropriate lower lying LUMO levels (3.70 ~ 3.86 eV) when compared with that of the P3HT, indicating their potential as acceptors for many donor materials in BHJSCs.

Bulk heterojunction organic solar cells (BHJ OSCs) have been fascinated in recent years for the future green energy generation due to their most promising results of low-cost fabrication, great flexibility, and lightweight properties. Very recently small molecule donors in the BHJ active layers have shown prominent attention due to the synergistic advantages over the polymer counterparts, which possess easy purification, highly facile synthesis, and negligible batch-batch variations. To construct push-pull molecules for p-type semiconductors, acceptor-donor-acceptor (A-D-A) based backbone exalted so far. In addition, the most impressive small molecule electron-donor units (D) are like benzodithiophene (BDT), oligothiophene, 3-dithienosilole (DTS), and indacenedithiophene (IDT) and so on. Likewise, electron-acceptors (A), such as 3-alkylrhodanine, diketopyrrolopyrrole (DPP), and perylenediimide (PDI) have been utilized. Porphyrin derivatives show excellent photochemical and electrochemical properties. Interestingly, porphyrins can be easily modified by different substituents at the peripheral positions (meso- and β-) and metal insertions at the center of the porphyrin core. In this work, we design, synthesize and characterize visible-near infrared absorbing new porphyrin dimer based small molecules with acceptor-donor-acceptor (A-D-A) configuration for bulk heterojunction organic solar cells, and investigate their structure-property relationships, specifically the effect of conjugation and planarity of the backbone central units on the charge mobility, film morphology, and solar cell performances. Chapter 1 deals with an overview of the past and recent development of BHJ OSCs, particularly the key principles and photovoltaic characteristics. Furthermore, we focus on the detailed classification of porphyrin-based small molecules and their performances in OSCs. In chapter 2, two promising near-IR absorbing porphyrin-based dimeric small molecules were designed and synthesized, in which diketopyrrolopyrrole-ethynylene-bridged porphyrin dimers are capped with electron-deficient 3-ethylrhodanine (A2) via a π-bridge of phenylene ethynylene, with an optimal A2-π-D-A1-D-π-A2 architecture affording porphyrin dimers DPP-2TTP and DPP-2TP. They possess strong absorption in ranges of 400-550 (Soret bands) and 700-900 nm (Q bands). Their intrinsic absorption deficiency between the Soret and Q bands could be perfectly compensated by a wide bandgap small molecule DR3TBDTTF with absorption in 500-700 nm. Impressively, the optimal ternary device based on the blend films of DPP-2TPP, DR3TBDTTF (20 wt.%) and PC71BM, shows a PCE of 11.15%, while the binary devices based on DPP-2TTP/PC71BM and DPP-2TP/PC71BM blend films exhibit PCEs of 9.30% and 8.23%, respectively. The high compatibility of the low bandgap porphyrin dimers with the wide bandgap small molecule provides a new threesome with PC71BM for highly efficient panchromatic ternary organic solar cells. Chapter 3 describes another two new A-π-D-π-A structural porphyrin small molecules denoted as TDPP-2P and TDPPE-2P which are constructed from dimeric porphyrin linked by 2,5-bis(2-butyloctyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (TDPP), and 2,5-bis(2-butyloctyl)-3,6-bis(5-ethynyl-2-thienyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (TDPPE), respectively, further π-extended symmetrically with electron-deficient 4-[(3-ethyl-4-oxo-2-thioxo-5-thiazolidinylidene)methyl]-phenylethynyl fragments. Compared to the absorption spectra of TDPP-2P, astonishingly TDPPE-2P improves the range of near-infrared over 1000 nm due to the enhanced coplanarity of the central core. Moreover, the intrinsic absorption deficiency (500-700 nm) is perfectly compensated by IT-M small molecule acceptor. Remarkably the blend film TDPPE-2P:IT-M accomplished panchromatic photo-current absorption from 400-900 nm, as a result, the device exhibits a prominent PCE of 5.69%. Whereas, the film TDPP-2P:IT-M shows comparatively low PCE of 4.12%. Finally, we believe that such a combination of TDPPE-2P:IT-M device demonstrates synergetic compatibility of donor/acceptor domain to promote the complementary absorption spectrum and enhances through higher hole mobilities and better crystallinity of the surface and interface for non-fullerene small-molecule organic solar cells. In Chapter 4, we further modified and synthesized a new series of A*-π-D2-D1-D2-π-A* based porphyrin dimer (2P) (D2) small molecules flanked by 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-2,6-diethynylbenzo[1,2-b:4,5-b']dithiophene (TBDTE) and 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (TBDT) as TBDTE-2P and TBDT-2P respectively, in which benzodithiophene (BDT) (D1) based analog was constructed as a central unit because of extended coplanarity conjugation length. Finally, TBDTE and TBDT units end-capped with 3-ethylrhodanine (A*) via a π-bridge of phenyl ethynyl linker and 2-octyldodecan-1-al long alkyl chain was used on vertical meso-porphyrins to improve the material solubility for the solution-processed OSCs. The compound TBDTE-2P accomplishes absorption range from 400-800 nm in the vis-near-infrared region, whereas TBDT-2P compound absorbs 400-700 nm range. The higher absorption range of TBDTE-2P arises from more planar backbone orientation and strong intramolecular charge transfer (ICT) within the donor molecules. Further, we focus on the OPV performances of binary devices TBDTE-2P / TBDT-2P: IDIC under AM 1.5G 1-Sun and 300 lux LED illuminations. The champion device TBDTE-2P: IDIC was accumulated a PCE of 7.46% under 1-Sun whereas a PCE of 12.34% was obtained under indoor light illuminations. The exploit of superior properties, charge generation and collection, hole and electron mobilities, and atomic force microscopy (AFM) were also examined. In Chapter 5, we synergistically designed and synthesized two new porphyrin dimers triply fused at meso-meso, β-β and βꞌ-βꞌ positions, from the corresponding meso-meso singly-linked porphyrin arrays. These fused porphyrin tapes differ by two metal atoms at the porphyrin core, such as zinc and nickel, termed as F-C19ZnP and F-C19NiP, respectively. With the purpose for design new acceptor-donor-acceptor small molecules for OSCs, the two fused porphyrin tapes were investigated in detail on the photophysical and electrochemical properties. Both fused porphyrins exhibit a strong and wide Soret-band absorption from 400-570 nm. Interestingly, the compound F-C19ZnP is recorded a larger red-shift absorption than the compound F-C19NiP consistent with cyclic voltammetry (CV) measurements, because the Zn-porphyrin attains more planar conjugated geometry. Finally, the dissertation was completed with a summary in chapter 6

Bulk heterojunction organic solar cells (BHJ OSCs) have been fascinated in recent years for the future green energy generation due to their most promising results of low-cost fabrication, great flexibility, and lightweight properties. Very recently small molecule donors in the BHJ active layers have shown prominent attention due to the synergistic advantages over the polymer counterparts, which possess easy purification, highly facile synthesis, and negligible batch-batch variations. To construct push-pull molecules for p-type semiconductors, acceptor-donor-acceptor (A-D-A) based backbone exalted so far. In addition, the most impressive small molecule electron-donor units (D) are like benzodithiophene (BDT), oligothiophene, 3-dithienosilole (DTS), and indacenedithiophene (IDT) and so on. Likewise, electron-acceptors (A), such as 3-alkylrhodanine, diketopyrrolopyrrole (DPP), and perylenediimide (PDI) have been utilized. Porphyrin derivatives show excellent photochemical and electrochemical properties. Interestingly, porphyrins can be easily modified by different substituents at the peripheral positions (meso- and β-) and metal insertions at the center of the porphyrin core. In this work, we design, synthesize and characterize visible-near infrared absorbing new porphyrin dimer based small molecules with acceptor-donor-acceptor (A-D-A) configuration for bulk heterojunction organic solar cells, and investigate their structure-property relationships, specifically the effect of conjugation and planarity of the backbone central units on the charge mobility, film morphology, and solar cell performances. Chapter 1 deals with an overview of the past and recent development of BHJ OSCs, particularly the key principles and photovoltaic characteristics. Furthermore, we focus on the detailed classification of porphyrin-based small molecules and their performances in OSCs. In chapter 2, two promising near-IR absorbing porphyrin-based dimeric small molecules were designed and synthesized, in which diketopyrrolopyrrole-ethynylene-bridged porphyrin dimers are capped with electron-deficient 3-ethylrhodanine (A2) via a π-bridge of phenylene ethynylene, with an optimal A2-π-D-A1-D-π-A2 architecture affording porphyrin dimers DPP-2TTP and DPP-2TP. They possess strong absorption in ranges of 400-550 (Soret bands) and 700-900 nm (Q bands). Their intrinsic absorption deficiency between the Soret and Q bands could be perfectly compensated by a wide bandgap small molecule DR3TBDTTF with absorption in 500-700 nm. Impressively, the optimal ternary device based on the blend films of DPP-2TPP, DR3TBDTTF (20 wt.%) and PC71BM, shows a PCE of 11.15%, while the binary devices based on DPP-2TTP/PC71BM and DPP-2TP/PC71BM blend films exhibit PCEs of 9.30% and 8.23%, respectively. The high compatibility of the low bandgap porphyrin dimers with the wide bandgap small molecule provides a new threesome with PC71BM for highly efficient panchromatic ternary organic solar cells. Chapter 3 describes another two new A-π-D-π-A structural porphyrin small molecules denoted as TDPP-2P and TDPPE-2P which are constructed from dimeric porphyrin linked by 2,5-bis(2-butyloctyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (TDPP), and 2,5-bis(2-butyloctyl)-3,6-bis(5-ethynyl-2-thienyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (TDPPE), respectively, further π-extended symmetrically with electron-deficient 4-[(3-ethyl-4-oxo-2-thioxo-5-thiazolidinylidene)methyl]-phenylethynyl fragments. Compared to the absorption spectra of TDPP-2P, astonishingly TDPPE-2P improves the range of near-infrared over 1000 nm due to the enhanced coplanarity of the central core. Moreover, the intrinsic absorption deficiency (500-700 nm) is perfectly compensated by IT-M small molecule acceptor. Remarkably the blend film TDPPE-2P:IT-M accomplished panchromatic photo-current absorption from 400-900 nm, as a result, the device exhibits a prominent PCE of 5.69%. Whereas, the film TDPP-2P:IT-M shows comparatively low PCE of 4.12%. Finally, we believe that such a combination of TDPPE-2P:IT-M device demonstrates synergetic compatibility of donor/acceptor domain to promote the complementary absorption spectrum and enhances through higher hole mobilities and better crystallinity of the surface and interface for non-fullerene small-molecule organic solar cells. In Chapter 4, we further modified and synthesized a new series of A*-π-D2-D1-D2-π-A* based porphyrin dimer (2P) (D2) small molecules flanked by 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-2,6-diethynylbenzo[1,2-b:4,5-b']dithiophene (TBDTE) and 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (TBDT) as TBDTE-2P and TBDT-2P respectively, in which benzodithiophene (BDT) (D1) based analog was constructed as a central unit because of extended coplanarity conjugation length. Finally, TBDTE and TBDT units end-capped with 3-ethylrhodanine (A*) via a π-bridge of phenyl ethynyl linker and 2-octyldodecan-1-al long alkyl chain was used on vertical meso-porphyrins to improve the material solubility for the solution-processed OSCs. The compound TBDTE-2P accomplishes absorption range from 400-800 nm in the vis-near-infrared region, whereas TBDT-2P compound absorbs 400-700 nm range. The higher absorption range of TBDTE-2P arises from more planar backbone orientation and strong intramolecular charge transfer (ICT) within the donor molecules. Further, we focus on the OPV performances of binary devices TBDTE-2P / TBDT-2P: IDIC under AM 1.5G 1-Sun and 300 lux LED illuminations. The champion device TBDTE-2P: IDIC was accumulated a PCE of 7.46% under 1-Sun whereas a PCE of 12.34% was obtained under indoor light illuminations. The exploit of superior properties, charge generation and collection, hole and electron mobilities, and atomic force microscopy (AFM) were also examined. In Chapter 5, we synergistically designed and synthesized two new porphyrin dimers triply fused at meso-meso, β-β and βꞌ-βꞌ positions, from the corresponding meso-meso singly-linked porphyrin arrays. These fused porphyrin tapes differ by two metal atoms at the porphyrin core, such as zinc and nickel, termed as F-C19ZnP and F-C19NiP, respectively. With the purpose for design new acceptor-donor-acceptor small molecules for OSCs, the two fused porphyrin tapes were investigated in detail on the photophysical and electrochemical properties. Both fused porphyrins exhibit a strong and wide Soret-band absorption from 400-570 nm. Interestingly, the compound F-C19ZnP is recorded a larger red-shift absorption than the compound F-C19NiP consistent with cyclic voltammetry (CV) measurements, because the Zn-porphyrin attains more planar conjugated geometry. Finally, the dissertation was completed with a summary in chapter 6

Organic donor and acceptor have promised the better future energy technologies to alleviate global energy demand and environmental issues. And nowadays they begin to come true in bulk heterojunction organic solar cells (BHJ OSCs) with advantages of low-cost, light-weight, large-area, flexibility, and with high efficiencies (PCEs) of over 14% for converting solar energy to electricity. Porphyrins are unique potential for artificial photocatalysis but their application in BHJ OSCs are still limited by the PCEs less than 10%. This complicacy comes from their inadequate spectral absorptions and the imperfect morphologies. In this thesis, we devote to chemical modification of acceptor-π-porphyrin-π-acceptor (A-π-Por-π-A) structural molecules to enhance their spectral absorptions and phase-separation functions with fullerene acceptor. Firstly, chemically driving J-aggregates have been studied on the new A-π-Por-π-A porphyrin molecule, which could improve the phase-separation of its blend film with PC71BM and and enhance its performance in BHJ OSCs with PCE up to 8.04%. Secondly, two new benzodithiophene (BDT) π-bridged A-π-Por-π-A molecules have been prepared with complementary absorption between the Soret and Q bands. The devices based on the blend fims of the porphyrin donor and PC71BM acceptor exhibit full spectral photocurrent generation and impressive PCEs up to 7.92%. Thirdly, we further extended the π-conjugation of the above BDT π-brigded A-π-Por-π-A molecules by inserting alkyl chain substituted thiophene derivatives into their backbones, resulting in new porphyrin molecules with UV-visible-near-infraed absorption spectra. Using those porphyrin molecules as donor and PCBM as acceptor, the devices show full spectra photocurrent generatoion and appropriate film morphology, resulting in high PCE up to 8.59%. Besides, photocatalysis is also a new promising technology to generate renewable energy. We herein develop new low-cost and noble-metal-free photocatalysts based on Co(OH)2 modified CdS nanowires and applied them for visible light driven hydrogen production from water-splitting. The optimum H2 production rate reaches 14.43 mmol·h−1·g−1 under (λ ≥ 420 nm) upon visible light irradiation, which is 206 and 3 times larger than that of the pristine CdS NWs and 1 wt% Pt-CdS NWs, respectively. The results indicate the promising application of earth-abundant Co(OH)2 as alternative cocatalysts of noble metals.

Title from first page of PDF document. Includes bibliographical references (p. 154-156).