Molecular engineering of organic sensitizers for solar cell applications

Novel organic sensitizers comprising donor, electron-conducting, and anchoring groups were engineered at molecular level and synthesized. The functionalized unsymmetrical organic sensitizers 3-{5-[N,N-bis(9,9-dimethylfluorene-2-yl)phenyl]-thiophene-2-yl}-2-cyano-acrylic acid (JK-1) and 3-{5'-[N,N-bis(9,9-dimethylfluorene-2-yl)phenyl]-2,2'-bisthiophene-5-yl}-2-cyano-acrylic acid (JK-2), upon anchoring onto TiO2 film, exhibit unprecedented incident photon to current conversion efficiency of 91%. The photovoltaic data using an electrolyte having composition of 0.6 M M-methyl-N-butyl imidiazolium iodide, 0.04 M iodine, 0.025 M LiI, 0.05 M guanidinium thiocyanate, and 0.28 M tert-butylpyridine in a 15/85 (v/v) mixture of valeronitrile and acetonitrile revealed a short circuit photocurrent density of 14.0 +/- 0.2 mA/cm2, an open circuit voltage of 753 +/- 10 mV, and a fill factor of 0.76 +/- 0.02, corresponding to an overall conversion efficiency of 8.01% under standard AM 1.5 sunlight. DFT/TDDFT calculations have been performed on the two organic sensitizers to gain insight into their structural, electronic, and optical properties. Our results show that the cyanoacrylic acid groups are essentially coplanar with respect to the thiophene units, reflecting the strong conjugation across the thiophene-cyanoacrylic groups. Molecular orbitals analysis confirmed the experimental assignment of redox potentials, while TDDFT calculations allowed assignment of the visible absorption bands.     

Molecular engineering of organic sensitizers for dye-sensitized solar cell applications

Novel unsymmetrical organic sensitizers comprising donor, electron-conducting, and anchoring groups were engineered at a molecular level and synthesized for sensitization of mesoscopic titanium dioxide injection solar cells. The unsymmetrical organic sensitizers 3-(5-(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D5), 3-(5-bis(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D7), 5-(4-(bis(4-methoxyphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D9), and 3-(5-bis(4,4'-dimethoxydiphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D11) anchored onto TiO2 and were tested in dye-sensitized solar cell with a volatile electrolyte. The monochromatic incident photon-to-current conversion efficiency of these sensitizers is above 80%, and D11-sensitized solar cells yield a short-circuit photocurrent density of 13.90 +/- 0.2 mA/cm(2), an open-circuit voltage of 740 +/- 10 mV, and a fill factor of 0.70 +/- 0.02, corresponding to an overall conversion efficiency of 7.20% under standard AM 1.5 sun light. Detailed investigations of these sensitizers reveal that the long electron lifetime is responsible for differences in observed open-circuit potential of the cell. As an alternative to liquid electrolyte cells, a solid-state organic hole transporter is used in combination with the D9 sensitizer, which exhibited an efficiency of 3.25%. Density functional theory/time-dependent density functional theory calculations have been employed to gain insight into the electronic structure and excited states of the investigated species.     

Doubly ortho-linked quinoxaline/diphenylfluorene hybrids as bipolar, fluorescent chameleons for optoelectronic applications

The titled dipolar hybrids bearing a central quinoxaline-fused dibenzosuberene optoelectronic unit with functional C5 and C8 appendages and spiro-fluorene junction act as fluorescent bipolar OLED chameleons. The emission colors can be tuned from blue, green, yellow, to red with operation brightness of 205, 1268, 1542, and 1102 cd/m2, respectively, at 20 mA/cm2.     

Novel organic sensitizers containing a bulky spirobifluorene unit for solar cell

Three organic sensitizers JK-87, JK-88, and JK-89 containing a bulky spirobifluorene unit in the bridged group are designed and synthesized. Under standard global A.M. 1.5 solar condition, the JK-89 sensitized cell gave a short-circuit photocurrent density (J_sc) of 13.02 mA cm⁻², an open-circuit voltage (V_oc) of 0.75 V, and a fill factor of 0.70, corresponding to an overall conversion efficiency η of 6.83%. The η of JK-89 is higher than those of other two cells due to the larger J_sc. The improved J_sc value is mainly attributed to the broad and red-shifted absorption band.     

Novel fluorene/carbazole hybrids with steric bulk as host materials for blue organic electrophosphorescent devices

The problem of self-quenching in organic electrophosphorescence devices has been extensively studied and partially solved by using sterically hindered spacers in phosphorescent dopants. This paper attempts to address this problem by using sterically hindered host materials. Novel fluorene/carbazole hybrids with tert-butyl substitutions, namely 9,9-bis[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]fluorene (TBCPF) and 9,9-bis[4-(carbazol-9-yl)phenyl]-2,7-di-tert-butylfluorene (CPTBF), have been synthesized and characterized. The compounds exhibit not only high triplet energy (>2.8 eV), but also high glass transition temperature (>160 °C) and thermal stability. The substitution of inert tert-butyl groups to the carbazole/fluorene rings of these host molecules has a remarkable effect on the corresponding properties of the host materials, i.e. enhancing the thermal and electrochemical stability, weakening the intermolecular packing, and tuning the solid-state emission. Blue electrophosphorescent devices with enhanced performance were prepared by utilizing the sterically hindered host materials. The devices based on the four tert-butyl substituted material TBCPF exhibit unusual tolerance of high dopant concentration up to 20% and marked reduction of efficiency roll-off at higher current, indicating significant suppression of self-quenching effect in organic electrophosphorescent devices by the substitution of steric bulks.     

Molecular engineering of sensitizers for dye‐sensitized solar cell applications

Dye‐sensitized solar cells (DSSCs) have attracted considerable attention in recent years as they offer the possibility of low‐cost conversion of photovoltaic energy. This account focuses on recent advances in molecular design and technological aspects of sensitizers based on metal complexes, metal‐free organics and tetrapyrrolic compounds which include porphyrins, phthalocyanines as well as corroles. Special attention has been paid to the design principles of these dyes, and co‐sensitization, an emerging technique to extend the absorption range, is also discussed as a way to improve the performance of the device. This account also focuses on recent advances of efficient ruthenium sensitizers as well as other metal complexes and their applications in DSSCs. Recent developments in the area of metal‐free organic and tetrapyrrolic sensitizers are also discussed. DOI 10.1002/tcr.201100044     

DFT-INDO/S modeling of new high molar extinction coefficient charge-transfer sensitizers for solar cell applications

A new ruthenium(II) complex, tetrabutylammonium [ruthenium (4-carboxylic acid-4'-carboxylate-2,2'-bipyridine)(4,4'-di(2-(3,6-dimethoxyphenyl)ethenyl)-2,2'-bipyridine)(NCS)(2)] (N945H), was synthesized and characterized by analytical, spectroscopic, and electrochemical techniques. The absorption spectrum of the N945H sensitizer is dominated by metal-to-ligand charge-transfer (MLCT) transitions in the visible region, with the lowest allowed MLCT bands appearing at 25 380 and 18 180 cm(-1). The molar extinction coefficients of these bands are 34 500 and 18 900 M(-1) cm(-1), respectively, and are significantly higher when compared to than those of the standard sensitizer cis-dithiocyanatobis(4,4'-dicarboxylic acid-2,2'-bipyridine)ruthenium(II). An INDO/S and density functional theory study of the electronic and optical properties of N945H and of N945 adsorbed on TiO(2) was performed. The calculations point out that the top three frontier-filled orbitals have essentially ruthenium 4d (t(2g) in the octahedral group) character with sizable contribution coming from the NCS ligand orbitals. Most critically the calculations reveal that, in the TiO(2)-bound N945 sensitizer, excitation directs charge into the carboxylbipyridine ligand bound to the TiO(2) surface. The photovoltaic data of the N945 sensitizer using an electrolyte containing 0.60 M butylmethylimidazolium iodide, 0.03 M I(2), 0.10 M guanidinium thiocyanate, and 0.50 M tert-butylpyridine in a mixture of acetonitrile and valeronitrile (volume ratio = 85:15) exhibited a short-circuit photocurrent density of 16.50 +/- 0.2 mA cm(-2), an open-circuit voltage of 790 +/- 30 mV, and a fill factor of 0.72 +/- 0.03, corresponding to an overall conversion efficiency of 9.6% under standard AM (air mass) 1.5 sunlight, and demonstrated a stable performance under light and heat soaking at 80 degrees C.     

Novel quinoxaline-based organic sensitizers for dye-sensitized solar cells

Novel quinoxaline-based organic sensitizers using vertical (RC-21) and horizontal (RC-22) conjugation between an electron-donating triphenylamine unit and electron-accepting quinoxaline unit have been synthesized and used for dye-sensitized solar cells (DSSCs), leading to the relatively high power conversion efficiencies of 3.30 and 5.56% for RC-21 and RC-22, respectively. This result indicates that the quinoxaline electron-accepting unit is quite a promising candidate in organic sensitizers.     

Anionic benzothiadiazole containing polyfluorene and oligofluorene as organic sensitizers for dye-sensitized solar cells

Anionic polyfluorene and oligofluorene derivatives were synthesized and utilized as organic dye sensitizers in dye sensitized solar cells to show a maximum power conversion efficiency of 1.39%.     

Dipolar organic pyridyl dyes for dye-sensitized solar cell applications

New dipolar dyes containing arylamine as the electron donor, 2-cyanoacrylic acid as the acceptor, and a conjugated spacer with incorporation of 2,5-pyridyl entity have been synthesized. Photophysical and electrochemical measurements, and theoretical computation were carried on these dyes. The solar cell devices using these dyes as the sensitizers exhibited light-to-electricity efficiencies in the range of 4.28–5.27%, which reaches 60–72% of N719-based device fabricated and measured under similar conditions. Better DSSC performance can be achieved with the dye where pyridine group is attached to thienyl or fluorenyl group because of favorable resonance energy and/or coplanarity for more effective charge transfer.     

Ru complexes of thienyl-functionalized dipyrrins as NCS-free sensitizers for the dye-sensitized solar cell

We report the first case of Ru(ii) dipyrrinates employed as dyes in dye-sensitized solar cells. These complexes exhibit panchromatic light harvesting that results in significant DSSC current densities, rendering them promising for photovoltaic applications. Adjustment of the lowest excited state energy is required to boost the power conversion efficiency.     

Synthesis and photovoltaic properties of novel organic sensitizers containing indolo[1,2-f]phenanthridine for solar cell

Organic dyes containing indolo[1,2-f]phenanthridine unit are a promising new class of sensitizers for dye-sensitized solar cells, as a result of their broad and intense visible absorptions. Under standard global AM 1.5 solar condition, the JK-61 sensitized cell gave a short circuit photocurrent density (J_sc) of 15.81 mA cm⁻², an open circuit voltage (V_oc) of 0.73 V, a fill factor of 0.72, corresponding to an overall conversion efficiency of 8.34%.     

Poly(o-phenylenediamine) thin film for organic solar cell applications

Poly(ortho phenylenediamine) (PoPDA) microrods with ladder-type structure are synthesized in acidic medium (pH?=?0.5) at room temperature based on a developed and facile method. The molecular structure, thermal stability, and surface morphology of the microrods-shaped PoPDA were described by different characterization techniques comprising FTIR, TGA, ¹HNMR, and SEM. Optimized thin films of PoPDA were successfully fabricated by thermal deposition method. The thin film was characterized by XRD and AFM. Au/PoPDA/p-Si/Al heterojunction diodes have been successfully fabricated. Dark current–voltage and capacitance–voltage characteristics were applied to get the particular parameters of the devices. Photovoltaic features of Au/PoPDA/p-Si/Al heterojunction at various intensities of white light illumination are studied. Under optimized conditions, the fabricated planar heterojunction solar cells utilizing a 95?±?10 nm of PoPDA film exhibited a power conversion efficiency (PCE) of ~?5.64% (J_SC?=?41.78 A/m², V_OC?=?0.36 V, and FF?=?28.11%). The relatively small FF (at room temperature with IP) and R_s of the devices designate that by increasing of the absolute temperature, the photovoltaic performance of the solar cells can be improved.     

Synthesis and characterization of organic dyes containing 4,5-diazafluorene as efficient sensitizers for dye-sensitized solar cells

Two dyes which are 4,5-diazafluoren-9-one-derived diimine ligands and their corresponding Ru(II) bipyridine complexes were synthesized. The structures of all compounds were determined by FTIR, UV–Vis, ¹H-NMR, ¹C-NMR, and MS spectroscopic data. The photovoltaic and electrochemical properties of these compounds were investigated and the applicability in DSSCs as photosensitizers was studied. The photovoltaic cell efficiencies (PCE) of the devices were 0.36–1.26% under simulated AM 1.5 solar irradiation of 100 mW/cm², and the highest open-circuit voltage (V_oc) reached 0.34 V. When comparing the photovoltaic performance of DSSC devices, efficiency increases L2 < L2-Ru < L1 < L1-Ru. The PCE value of 1.26% was obtained with a DSSC based on L1-Ru under AM irradiation (100 mW/cm²). DSSC based on L1-Ru produced efficiency of 1.26%, whereas DSSC-based L1 exhibited the device performance with efficiency of 0.84% under illumination. These results show that the availability of a π-conjugated bridge and a richer electron donor for photovoltaic performance of the DSSC provides increased efficiency.     

Molecular engineering of organic sensitizers containing indole moiety for dye-sensitized solar cells

Three organic dyes, JK-77, JK-78, and JK-79 containing indole unit are designed and synthesized. Nanocrystalline TiO₂ dye-sensitized solar cells were fabricated using these dyes. Under standard global AM 1.5 solar condition, the JK-79 sensitized solar cell gave a short circuit photocurrent density of 13.62 mA cm⁻², open-circuit voltage of 0.705 V, and a fill factor of 0.74, corresponding to an overall conversion efficiency η of 7.18%. We found that the η of JK-79 was higher than those of other two cells due to the higher V_oc. The improved V_oc value is attributed to the suppression of dark current owing to the blocking effect of a long alkyl chain.     

Novel organic dye sensitizers containing fluorenyl and biphenyl moieties for solar cells

Three novel triarylamine dyes(AFL1-AFL3) containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovoltaic performance of these dyes were investigated systematically through comparison of different π-bridges.The dye with a furan linker exhibited a higher open-circuit voltage(V_(OC)) and monochromatic incident photon-to-current conversion efficiency(IPCE) compared to thiophene and benzene linker.Thus,AFL3 containing a furan linker exhibited the maximum overall conversion efficiency of 5.81%(V_(OC) = 760 mV,J_(SC) = 11.36 mA cm~2 and ff=0.68) under standard global AM 1.5 G solar condition.     

Synthesis of new truxene based organic sensitizers for iodine-free dye-sensitized solar cells

Developing arylamine photosensitizers with high extinction coefficients, proper electronic structures, and steric properties is warranted for the dye-sensitized solar cells (DSCs) employing iodine-free redox shuttles. Two new organic sensitizers (M21 and M22) featuring unsymmetrical truxene-based triarylamine donor have been synthesized and compared to its reference sensitizer M4. The effects of unsymmetrical truxene-based triarylamine donors were investigated by their absorption spectra, electrochemical and photovoltaic properties. The incorporation of strong electron donor unit (i.e., dipropylfluorene and 4-methoxybiphenyl) has resulted in an improved light harvesting capacity, and thus photocurrent as well as efficiency of cells. M22 sensitized DSCs employing the Co(II/III)tris(1,10-phenanthroline)-based redox electrolyte affords a short circuit photocurrent of 13.1 mA cm⁻², an open circuit voltage of 861 mV, and a fill factor of 0.70, corresponding to an overall conversion efficiency of 7.89% under standard AM 1.5 sunlight.     

Functionalized organic dyes containing a phenanthroimidazole donor for dye-sensitized solar cell applications

Five functionalized organic dyes (H6-10) containing a phenanthroimidazole unit as an electron donor were synthesized and characterized for use in dye-sensitized solar cell (DSSC) applications. Under standard global AM 1.5 solar conditions, the DSSCs based on dye H6 displayed the best performance, with an incident photon-to-current conversion efficiency (IPCE) exceeding 70% at wavelengths of 400–530 nm, a short-circuit photocurrent density of 10.98 mA cm^?2, an open-circuit voltage of 0.68 V, a fill factor of 0.69, and an overall conversion efficiency of 5.12%. This efficiency is ～94% of that for JK2 cells (5.46%) and ～72% of that for N719 cells (7.07%) under the same conditions.