Parameters for the best fit of the impedance data for the different thickness. Measured in Figure 6.
This chapter has been mainly focused on the development and fabrication of various nanostructured materials for electrochemical energy conversion, specially, third generation (3rd) thin film photovoltaic system such as organic dye or perovskite -sensitized Solar Cells. Enormous efforts have been dedicated to the development of a variety of clean energy, capable of harvesting energy of various forms. Among the various energy forms, electrochemical devices that produce electric energy from chemical energy have received the most attention as the most promising power sources. In the majority of cases, researchers who come from the different background could engage on certain aspects of the components to improve the photovoltaic performances from different disciplines: (i) chemists to design and synthesize suitable donor–acceptor dyes and study structure–property relationships; (ii) physicists to build solar cell devices with the novel materials, to characterize and optimize their performances, and to understand the fundamental photophysical processes; and (iii) engineers to develop new device architectures. The synergy between all the disciplines will play a major role for future advancements in this area. However, the simultaneous development of all components such as photosensitizers, hole transport layer, photoanodes and cost effective cathode, combined with further investigation of transport dynamics, will lead to Photovoltaic cells, 30%. Herein, in this book, with taking optimized processing recipe as the standard cell fabrication procedure, imporant breakthough for each components is achieved by developing or designing new materials, concepts, and fabrication technique. This book report the following studies: (i) a brief introduction of the working principle, (ii) the detailed study of the each component materials, mainly including TiO2 photoanode under the category of 0D and 3D structures, strategies for co-sensitization with porphyrin and organic photosensitizers, and carbon catalytic material via controlled fabrication protocols and fundamental understanding of the working principles of electrochemical photovoltaic cell has been gained by means of electrical and optical modelling and advanced characterization techniques and (iii) new desgined stratages such as the optimization of photon confinement (iv) future prospects and survival stratagies for sensitizer assisted solar cell (especially, DSSC).
- photovoltaic cell
- photonic crystal
The search for grean sources of enegy is considered one of the priorities in today’s societies and occupies many policy makers’ agendas. Excitonic Solar cell such as organic dye or perovskite -sensitized solar cells (DSSC or PSC) is showing up as a promising solar harvesting technology that has bright future. Unlike conventional silicon p-n junction solar cell, an excitonic solar cell (ESC) can be modeled as a unipolar-junction cell and made from low-cost materials that do not need to be highly purified but still work well using simple manufacturing processes . For example, similar to the photosynthetic process in plants where chlorophyll absorbs photons but does not participate in charge transfer, the photoreceptor and charge carrier are implemented by different components in solar cell. This separation of functions leads to lower purity demands on raw materials and consequently makes exitonic solar cell a low-cost alternative. Nevertheless, to compete with the future PV market, ESC should foucus on the “Golden Triangle” issues, i.e., increasing light-to-electric energy conversion efficiency, enhancing long-term stability, and decreasing device cost .
Since the last third decades, scientists have devoted a great deal of effort on DSSCs’ four important components: photosensitizer, photoanodes, electrolytes, and counter electrodes; some significant processes have been achieved. The sensitization of semiconductors using dyes dates back to 19th century. It showed that the photosensitivity can be extended to longer wavelengths by adding a dye to silver halide emulsions [3, 4]. Grätzel has then extended the concept to the DSSC by adsorption of dye molecules on the nanocrystalline TiO2 electrodes . This breakthrough was due to large surface area of the mesoporous TiO2 that allowed anchoring significantly high amount of dye molecules (∼0.13 mmol/cm2) onto it; thereby increasing the absorption cross-section. Since the first successful demonstration of DSSC over three decades ago, a wealth of DSSC components have been investigated for enhancing energy conversion efficiency. State of the art DSSCs achieve more than 11% energy efficiency allied to good performance under any atmospheric condition and low irradiance. Moreover, the possibilities of transparency and multi-colored cells are truly a competitive advantages of DSSCs. However, for stimulating industrial market, performance of DSSCs must be improved close to the efficiency values of the conventioanl silicon solar cells.
Since 2012, organic–inorganic perovskites solar have attracted considerable research attention for photovoltaic device due to its superb light-harvesting characteristics and electrical properties. Within relatively a short time, this organic–inorganic lead halide perovskite has yielded photovoltaic efficiencies of 25.5%, being the highest-performing solution-processed solar cell on record and displacing technologies such as DSSCs and organic photovoltaics (OPVs) . In addition, the use of perovskite materials as light absorbers and hole transporting mateiral (HTM) in solid-state sensitized solar cells has opened up a new direction for the high-efficiency thin-film solar cells. Despite the best candidate at satisfying the need for high efficiencies, concerns surrounding the long-term stability in an ambient atmosphere as well as the water-soluble toxic lead components in the archetypal perovskite, APbX3 (A = methylammonium, formamidium, cesium, X = I−, Br−−, Cl−), have the potential risk for the environment issue. After around 10 years of intense PSC researches, several physical chemistry still have questions for the basic mechanism. In this aspect, the physical and chemical operation of DSSC has becom more clear and a good example of a ESC system where the function of the overall device is better than prodicted from the sum of the properties of its components. Therefore, this book address imporant breakthough’s our laboratory research for DSSC with taking optimized processing recipe as the standard cell fabrication procedure.
In order to meet this requiremnt, it will be necessary to alter at least two of the three major components simultaneously. In the majority of cases, however, researchers who come from the different background could engage on certain aspects of the components to improve the photovoltaic performances from different disciplines: (1) chemists or material scientists worked for developing photosensitizer and charge transport materials; (2) physicists to eluciate photovoltaic properties and working mechanism; and (3) engineers to develop process and device structure for module level production. However, the simultaneous development of all components such as new photosensitier or new classed strucutral perovskite materials with intrinsic stability and beneficial optoelectronic properties, solid state HTM and photoanodes, combined with further investigation of transport dynamics, will lead to ESCs with efficiencies exceeding 30%.
This report the following studies: (i) a brief introduction of the working principle, (ii) the detailed study of the each component materials, mainly including TiO2 photoanode under the category of 0D and 3D structures, strategies for co-sensitization with porphyrin and organic photosensitizers, and carbon catalytic material via controlled fabrication protocols and fundamental understanding of the working principles of electrochemical photovoltaic cell has been gained by means of electrical and optical modeling and advanced characterization techniques and (iii) new desgined stratages such as the optimization of photon confinement (iv) future prospects and survival stratagies for sensitizer assisted solar cell (especially, DSSC).
2. Fundamentals of dye-sensitized solar cells
2.1 Operation principle
The principle of operation of a DSSC is well documented in the literature . The simplified principle of the thin layer DSSC is shown in Figure 1. A light-harvesting Ru complex potosensitizers adsorbed on the surface of a porous nanocrystalline film composed of a wide bandgap metal oxide such as TiO2, ZnO or SnO2 absorb incident photon flux. The photosensitizers are exited from the ground state (D) to the excited state (D*) owing to the metal to ligand charge transfer (MLCT) transition (Eq. (1)). The exited electrons are injected into the conduction band of the TiO2 electrode, resulting in the oxidation of the photosensitizer (Eq. (2)).
Injected electrons in the conduction band of TiO2 are transported between TiO2 nanoparticles with diffusion toward the back contact (TCO) and consequently reach the counter electrode through the external load and wiring. The oxidized photosensitizer (D+) accepts electrons from the I− ion redox mediator, regenerationg the ground state (D), and I− is oxidized to the oxidized state, I3− (Eq. (3)). The injected eletrons may recombine either with oxidized sensitier at the TiO2 (Eq. (4)).
The oxidized redox mediator, I3−, diffuses toward the counter electrode and is rereduced to I− ions.
The primary energy conversion process in DSSCs is a photoinduced charge separation at the metal oxide/dye/electrolyte interface.
In order to elucidate DSSC working phenomenon, the physical kinetics and dynamics of charge transfer motion have been investigated in detail by many researchers, both experimentally and via computational modeling. Here, the electron transfer dynamics taking place at the oxide/dye/electrolyte interface for DSSCs are presented in Figure 2 [7, 8, 9]. This figure also contains the information for several competing loss pathways, shown as red arrows. These loss pathways include decay of the dye excited state to ground, and charge recombination of injected electrons whith dye cations and with the redox couple.
2.2 Dye/metal oxide interface
A monolayer dye molecules attached to the surace of the nanocrystalline film. The high surface area of nanocrystalline film ensured s a large concentration of the light absorber leading to good light haversting are critical to be efficient DSSCs. In addition, how and where the photosensitizer bound to the surface of TiO2 is another important issues since unexpected bonding between photosensitizer and the TiO2 surface lead to degrade electron injection performance. In the case of Ru complex, one carboxylic ligand provides good anchoring to metal oxide surface (Long-term stability against moisture condition can be improved by using phosphonic acid) as well as good electronic coupling of the excited states of photosensitizer with TiO2 conduction band states .
To be the effective electron transfer, the lowest unoccupied molecular orbital (LUMO) level of excited dye molecules is appropriately lower than the highest unoccupied molecular orbital (HUMO) level of the metal oxide. Under illumination, the photoxcited sensitizers are injected into the metal oxide and diffused from the dye/metal oxide interface to substrate. In an efficient DSSC, a time scale of femtoseconds to picoseconds nanoseconds of injection process is witnessed on the strong electronic coupling between photoexicted sensitizer and metal oxide. The injected electrons experience fast recombination process and thermalisation down to at the electron Fermi level of the electrode .
2.3 Dye/electrolyte interface
After ultrafast electron injection from the photoexcited dye into the conduction band of TiO2, the dye is in its oxidized state and must be reduced by an electron donor in the electrolyte for regeneration. The standard electron donor is iodide. For many typed dye, high value of regeneration efficiency, which give the probability that an oxidized dye is regenerated by an electron donor in the electrolyte rather than by recombination with an electron in the TiO2, have been estimated in iodide. The reaction mechanism from reduction of oxidized sensitizer (D+) by iodide follows:
Eq. (6) is most likely a one-electron transfer reaction between D+ and I−. (ε (I•/I−) = +1.33 V vs. NHE in aqueous solution.) The dye regeneration is firstly occured from the formation of a (D···I) complex since the redox potential (
The oxidized sensitizer (specially, the most commonly reported Ru complex dye, named as N719) is regeneated by the iodide/iodine redox couple in the liquid electrolyte in the range of 100 ns to 10 μs. The different regenation time can be explained by iodide concentration, the presence of additivies such as identity of caion salt (lithium ions) and tertbutylpyridine (tBP). To be the effective DSSC, the recombination process of electrons with either oxidized dye molecules or acceptors in the electrolyte must be minimized compared with regeneration process, which usually happens on a time scale of about 1 μs [7, 13, 14, 15].
2.4 TiO2 interface for electron transport
Unlike the typical the electron transport mechanism in bulk semiconductors, the electron transport mechanism of TiO2 in DSSC need to be extend from the properties of the individual nanoparticles to the particle connectivity or electronic coupling between the particles, and the geometrical configuration of the assembly. Interestingly, the mesoporous nanocrystalline TiO2 layer exhibit the highly efficient charge tranport through the nanocrystalline TiO2 layer, while the low inherent conductivity of the film ca. bulk mobility of TiO2 (1cm2/Vs), ZnO (200cm2/Vs), and SnO2 (250cm2/Vs) as well as the presence of disorder from randomly arranged metal . The main consequence of disorder in the electronic structure of the material is the appearance of localized states. This puzzling phenomenon has been explained by multiple-trapping model, in which the diffusion of conduction band electrons is affected by the trapping-detrapping events [17, 18, 19, 20]. Electron transport in nanostructured oxide films impregnated with a highly concentrated electrolyte is believed to occur mainly by diffusion. It is generally accepted that this diffusional transport is influenced by the existence of electron localized states or traps in the semiconductor.
In the TiO2 nanoparticles, electrons undergo a number of processes. A main process is the transport of electrons in the extended states of the conduction band (CB), where the concentration of free electrons
here is an equilibrium concentration in the effective density of states of the CB and
TiO2 nanoparticles exhibit numerous localized states in bandgap, which can capture and release electrons to the transport level. The position of Fermi level (
A localized state at energy
The carrier mobility is associated with random motion of free carriers, which is directed linked to the conductivity and resistivity. The expression of the electron conductivity
2.5 Electrolyte/counter electrode interface
In theory, the maximum photovoltage of the DSSC is determined by the energy difference between the redox potential and the Fermi level of the metal oxide semiconductor. However, the output voltage under load is usually less than the open circuit voltage the theorical expected. This voltage loss is mainly attributed the the overall overpotential of electrolyt and counter electrode (CE) interface. The mass-transfer overpotential is largely affected by the ionic conductivity of electrolytes and the transportation of mediator species from the CE to the photoanode. The kinetic overpotential or charge-transfer overpotential can be determined by electrocatalytic properties of the CE surface toward mediator reduction . To be effective CE, it should exhibit excellent conductivity and inhibit high electrocatalytic activity for reduction of the redox couple. The effect of electric field and transport by ionic migration can be negligible because of high ionic conductivity and ionic strength of liquid electrolyte. With increasing viscosity such as gel, quasi- solid and solid state electrolyte, an inadequate flux of redox components lead to sacrifice the photocurrent of the DSSC. In the case of the iodide/triiodide electrolyte, charge transport corresponds to formation and cleavage of chemical bonds:
The CE must exhibit catalytically fast reaction and low overpotential because the counter electrode reduces the redox species. (triiodide →iodide) Platinum (Pt) materials is widely used as a suitable catalyst for reaction 1.14 to replenish the reduced species in the redox electrolyte. However, Pt is very expensive and rare so they have limited potential for commercial use. Therefore substantial researches are under way to develop inexpensive alternatives materials for larger commercialisation prospects. The charge transfer reaction between the counter electrode surface and the electrolyte occurs the charge-transfer resistance (RCT) in the DSSCs. The small RCT will give a higher fill factor (FF), which lead to a high conversion efficiency.
3. Optimizing material and configuration for typical DSSCs
Numerous publications and review articles on DSSC have appeared in the literature for certain aspects of the DSSC fabrication or performance during the past three decades [26, 27, 28, 29, 30]. Proto-type module cells for manufacturing are actively under development [31, 32, 33, 34, 35]. This book reviews systematical parameters via controlled experiments (such as materials preparation, processing, device fabrication and assembly, measurements and device modeling) and the interfacial properties introduced by electrochemical impedance spectroscopy (EIS) for making better solar performance [36, 37, 38]. The inherent material properties such as impurity, surface properties in the DSSC are studied from this powerful tool for studying the kinetics of charge transport and electron–hole recombination. Furthermore, this book suggests other ways to improve cell efficiency externally from the photon confinement.
3.1 Understanding DSSC operation model by EIS
As mentioned in Section 1. diverse electrochemical processes take place in a DSSC during the cell operation. The I-V curves provide the information on the basic parameters such as short-circuit current (
In this book, for a deep comprehensive understanding of the device operation, Adachi model are employed to figure out the key parameters that control the efficiency of a DSSC [39, 40, 41, 42]. Figure 1 shows the schematic diagram of DSSC structure. In this system, the light comes from the indium or fluorine doped tin oxide (ITO or FTO) coated transparent conductive glass, the sheet resistance as small as 10 Ω/sq. is required, as an anode electrode (left) . An insulating blocking layer and mesoporous metal oxide film (TiO2 ZnO, SnO2 etc.) is deposited on top of bottom electrode. Next, dye molecules are covered by the surface of mesoporous metal oxide and iodine electrolyte is interpenetrated into metal oxide/dye layer. The platinum coated FTO substrate is used as a catalyst for iodide reduction as the counter electrode (right).
The kinetic behavior of charge trap and de-trap mechanism from electrochemical and photoelectrochemical processes affects the different capacitive and resistive element of faradaic impedance. EIS data generally shows Nyquist and Bode plots. An general plot shows x-axis the real impedance (Z’) versus the y-axis the imaginary impedance (Z”) in the complex plane. From EIS analysis, the complex impedance
Suppose the complex impedance is the same as its resistance. (
and using the following boundary conditions at
The equivalent impedance Z2 of Bisquert  is obtained as follows:
The total impedance (
From experimental (
3.2 Materials preparation
3.2.1 TiO2 nanoparticle
The highly crystalline anatase TiO2 nanoparticles (NPs) was synthesized by 2-step autoclaving technique (Figure 4(a)). A pH controlled TiO2 suspension was prepared by commercial TiO2 power. (P25, Degussa) The TiO2 suspension is placed in a total volume of 60 mL in a Teflon-lined stainless steel autoclave (125 mL volume, Parr Instrument Co.) and heated at 240°C for 12 h. The resulting powders are dried at ∼80°C in a conventional drying oven for 24 hour (Figure 4(b)). The pure Anatase colloidal TiO2 nanoparticle was obtained by autoclaving the low-pH titanate suspension at 240°C for 12h (Figure (4c)) .
3.2.2 Photosensitizer (purifed N719 dye)
For photosensitization studies, the calcined TiO2 nanoparticle electrode were immersed in the ethanol solution containing purified 3x10−4 M cis-di(thiocynato)-N,N′-bis(2,2′-bipyridyl-4-caboxylic acid-4′-tetrabutylammonium carboxy late) ruthenium (II) (N719, Solaronix) for 18 h at room temperature . Commercial N719 dye may not produce high efficiency because of impurities. Therefore, purification is required. The N719 complex is firstly dissolved in water with tertrabutylammonium hydroxide and then purified three times with chromatography. (Sephadex LH-20) The pH values below 4.5 is controlled by 0.02 M HNO3. The titration is carried out slowly over a period of three hours. Then, the solution is kept at -20°C for 15 hours. After allowing the flask to warm to 25°C, the precipitated complex is collected on a glass frit and air dried.
3.2.3 Liquid electrolyte
he liquid electrolyte was prepared by dissolving 0.6 M of 1- butyl-3-methylimidazolium iodide (
Even if tBP and Li+ ions play a different role for solar cell performance, both additives are widely used in liquid electrolyte. As another effective additive, adding GuSCN can be also good choice. It shifts the conduction band edge of TiO2 toward lower energies, suggesting adsorption of the cation onto the TiO2 surface. Coadsorbants, adsorbed onto the TiO2 during the dye adsorption procedure, can have similar effects as additives in the electrolytes .
3.2.4 Catalytic layer
The cathode-electrode was produced by coating F:SnO2 glass with a thin layer of a 5 mM solution of H2PtCl6 in isopropanol and was heated at 400°C for 20 min. Best performance and long-tern stability has been achieved with very low Pt-loadings (5 μg cm−2), so that the counter electrode remains transparent. Charge transfer resistances of less than 1 Ω cm2 can be achieved.
3.3 DSSC fabrication for conventional typed cell
A paste of anatase hydrothermal TiO2 powder was made by stirring with the mixture 0.5 g of anatase-TiO2 NPs, 100 μl of Triton X-100, 0.2 g of polyethylene glycol (PEG, Fluka, Mw = 20,000) into 3 ml acetic acid (0.1 M). The TiO2 paste is coated on a FTO glass by doctor blade technique. The thickness of the TiO2 film was measured by a surface profiler (TENCOR. P-10) [26, 51]. Figure 4(d) and (e) gives an illustrative sequence of steps that were used in the fabrication of our solar cells. The top and bottom electrodes were sandwiched together with thermal melt polymer film (Figure 4e).
3.3.1 TiO2 Nanoparticles prepared by 2-step hydrothermal treatment
Anatase TiO2 NPs were investigated by using a field-emission scanning electron microscope (SEM, S4800, Hitachi) and JEOL-2010 TEM (JEOL, Japan) equipped with an energy dispersive spectrometer (EDS) to investigate the TiO2 NPs and determine the compositions of the samples at 200 kV. The NPs were also characterized by x-ray diffraction (D/Max-A, Rigaku) measurements. Figure 5(a) shows a X-ray scan of the Anatase TiO2 NPs before and after sintering as described below. The inset shows a typical SEM photo of the NPs used in the experiment. These results reveal broad diffraction peaks at 25.3°, 37.8°, 48.2°, 53.9° and 55.2° were observed, which can be indexed to the (101), (004), (200), (105) and (211) reflections of anatase TiO2. Figure 5(b) provides the high resolution transmission microscopic (TEM) images and selected area electron diffraction pattern of the TiO2 NPs. It provides the corresponding electron diffraction pattern taken from the TiO2 NPs showing that the NPs are crystalline Anatase TiO2. Figure 5(b) gives the high-resolution TEM (HRTEM) image of NPs indicating that the TiO2 NPs are single-crystalline. Lattice of 0.189 nm and 0.243 nm corresponding to (200) and (103) planes of the tetragonal TiO2, respectively, have been resolved. The inset is the corresponding fast Fourier transform (IFFT) image of selected area in Figure 5(b)c. In Figure 5(b)d the EDS taken from TiO2 NPs shows that the NPs are composed of Ti and O. The Cu peak comes from the grid. From these measurements, we concluded that our starting materials were pure Anatase.
3.3.2 Study for the optimal TiO2 film thickness
To find the optimized condition for hydrothermal treated TiO2 film, the cell efficiency as a function of the TiO2 film thicknesses is studied. In Figure 6 (top), I give plots of
In Figure 7, AC impedance measurements with best-fit model curves of the cell is used for analyzing function on the different TiO2 NP film thicknesses. Form the Bode phase plots, the negative shift of the frequencies of the main peaks with an increase in the film thickness. In a simple equation, since
All cases of samples were equal in the total cell thicknesses (
|Film Thickness (μm)||Rk/Rw||EFF (%)|
3.4 Interfacial modification
There are numerous efforts to improve cell performance from different modifications techniques such as different semiconductors, dyes, or ionic conductors or on changing its nanostructures [53, 54]. Most of modification works show a tradeoff relation between the short-circuit current and open-circuit voltage. This can be explained the the modification of components affect sensibility of charge-transport and recombination dynamics . Therefore, this has been a big challenge in the field of DSSC design. In this book, effective surface passivation and treatment method provide on how it possible to contribute on the cell performance.
3.4.1 TiCl4 treatment
The best-known techiqnue to improve the performance of the solar cells is a post-treatment of the TiO2 film with a solution in TiCl4 is grown onto an extra layer of TiO2 nanoparticles constituting the film. The TiCl4 treatment results in an improvement in photocurrent, normally between 10% and 30%. Depending on the quality of the TiO2 used to make the initial film, the extrema of the improvement can be from <5% to >200% [35, 56]. The largest improvements come when using the poorest quality TiO2 films. Figure 8(a) show the SEM images and XRD patterns for TiCl4 treated TiO2 film. When the TiCl4 exposure condition is increased, the XRD intensity of the rutile peak increased . However, under well-controlled condition, no obvious different in the rutile content (20–25%) can be seen between treated and untreated TiO2 from XRD analysis., while an increased size of TiO2 NPs and densely packed TiO2 NPs film is observed. Figure 8(b) shows Brunauer–Emmett–Teller (
The 2-step HT-TiO2 NP show about 18.5% increased surface areas and 43.6% widened cumulative pore volume compared with the pristine TiO2 NP (P25). However, TiCl4 treated samples show ∼16.7% decreased surface area compared with pristine TiO2 film. However, the loss in actual electrode surface area after TiCl4 treatment is small because of the increase in mass of approximately 10.3% TiO2 volume on the electrode. From these observations it follows that, despite the substantial decrease in BET surface area, the film thickness is not affected. Therefore, the porosity must have decreased, as is shown in Table 2. In spite of the decreased surface area, the TiCl4 treated TiO2 film morphology is observed by about a 40% higher dye absorption at the 480 nm. (see Figure 9(a)) For more accurate experiment, the quantity of TiO2 NPs surface-bound sensitizers was measured by desorption process . UV–vis absorption spectra is used for calculating the number of desorbed sensitizer molecules (set as the extinction coefficient (
|BET & BJH||Absorption Properties||Electrical Properties||Solar Properties|
|Surface area (m2g−1)||Pore Volume (cm3g−1)||TiO2 mass (mg/cm2)||λmax (at 498 nm)||# of mole. (×10−8 mol /mg)||Rk/Rw||Rtotal (Ω)||EFF (%)|
|(d)||w CF4 (10 min)||—||—||2.3||0.390||3.48||3.45||3.13||5.15||29.3||0.852||10.29||76.0||6.67|
|*||w CF4 (30 min)||—||—||1.4||0.211||2.45||2.11||2.84||3.24||58.9||0.838||6.52||75.1||4.10|
3.4.2 Fuorine plasma etching
As mentioned above, the best efficiency of cell can be found at about 11.5 μm thicked TiO2 film. This resulting data shows mediately the importance of electrolyte’s infiltration all of the way into the TiO2 film. To minimize the effect on the panetration issues, plama etching techinque is introduced for widening the channels in TiO2 films . Figure 10(a) displays a schematic diagram of the plasma etching system. The detailed etching condition can be found in our eariler paper . Aa ehching gas, CF4/O2 of gas mixture (CF4 and O2) is used by generating the fluorine atoms in the plasma through complicated chemical reaction paths [58, 59, 60, 61, 62]. The plasma etching reaction is followed by:
TiO2 surface is subsequently ethced by free fluorine gas and several titanium fluoroxy compounds (ultimately TiF4) are developed [61, 63]. Along with the etching process, it was expected that the surface of the NP would be populated with fluorine atoms and bonded to Ti sites as discussed below.
The evidence of etched TiO2 surface can be found by X-ray photon spectroscopy (XPS) measurement. The peak is located at binding energies 458.5 eV (Ti 2p3/2) and 464.2 eV (Ti 2p1/2), respectively, which correspond to the signals characteristic for the Ti4+ state of titanium [64, 65]. This indicates that TiO2 are formed. (see in Figure 10(b)). After plasma treatment the peak locations move to the somewhat higher binding-energies of 458.7 and 464.4 eV. The direct bonding with titanium and fluorine makes it possible to move higher binding-energy due to fluorine exhibit more electronegative than oxygen. From XPS analysis, the post-plasma F 1 s peak shows is also indicative of the fluorine being bonded directly to the titanium. The majority of the F 1 s peak (99%) is found at 684.8 eV which has been responsible for TiOF2. The minor (1%) energy shoulder at 686.8 eV is ascrbied to the replacement of oxygen lattice site in TiO2 by fluorine . The fluorine shows at ∼14% the oxygen level. Two O 1 s peaks are observed prior to plasma treatment. The major peak with ∼90% of the total oxygen is measured at a binding energy of 529.8 eV and 531.4 eV for Ti-O and Ti-OH bonding, respectively . The plasma treatment make the TiO2 peak move a little higher binding-energy of 529.9 eV.
Figure 11(a) shows SEM images of pre and post fluorine-treated films. It is clear from these images that fluorine effectively opens the channels among the NPs of the TiO2 film. The variance of film thickness and weight as a function of plasma etching time can be seen in Figure 11(b). With increased etching time, quantitative analysis (EDS) and morphology (SEM) of TiO2 surface reveal the plasma expand the pores of the TiO2 film surface. As the pore start to open up (∼10 min), the surface etching process of removed TiO2 and incorporated fluorine into the film is accelerated by active fluorine species. The detailed information can be found in our eailr paper .
As seen in Figure 12(a), the plasma etched TiO2 surface can rectify the interfacial property by decreased the electron-triiodine recombination rates taking place on the parts of the dye uncovered TiO2 surface. According to CF4 etching process, it function as diminishing the surface defects such as oxygen vacancies since fluorine atom comprised of stronger affinity for electrons compared with oxygen atom can enfeeble the bond in a titanium and oxygen . Therefore, the TiO2 surface comprised of less surface defects may play important role in a improvement of the open-circuit potential,
3.4.3 Cell properties for interfacial modification
The detailed solar cell research studied a series of five cells, each with a layer of 11.6 μm thick TiO2 NP film. Each of the four samples were treated differently prior to dye and electrolyte infiltration. As a first series of cells, TiO2 film prepared for cell (a) commercial and cell (b) hydrothermal treatment is studied. Next, for understanding the influence on interfacial modified TiO2 surface, post-treated cells with cell (c) with TiCl4 treatment and Tare cell (c) with fluorine etching are investigated. Figure 12(b) and (c) give, respectively, the
Cell (c) has a 25.5% increase in the
These changes show that the etching has significant effect on the electron recombination and transport properties of the cell, but the overall effect is not pronounced because the cell efficiency only increased by 8% with etching. As suggested in Figure 12(a), the fluorine etching can help to minimize the electron loss between TiO2 surface and reduced iodide, leading to the highest
Finally, we believe that combination of TiCl4 and fluorine etching post-treatment with the opposite physical properties make it possible to increase both the
4. Photon management using three-dimensional photonic crystals
Besides the interfacial modification, cell performance can be improved by external source (such as anti-reflection film and photonic crystal etc.) as reflecting passed photons back into the absorbing film [26, 70]. For the photon trapping, two approaches for geometrical or wave optics are employed . In this book, photon management concept using 3-dimensional photonic crystals (
4.1 Photon management effect on DSSCs
For 3D PhC layer, the vertical deposition technique for polystyrene (PS) opal templates is employed  (see in Figure 13(a)). The experimental procedures are reported in earlier work [82, 83]. Figure 13(b) is a SEM micrograph of a ZnO PhC (or inverse opal) layer showing both the side view (cross sectional, top) and top view (bottom).
The optical property can be estimated by using UV- vis- NIR spectrophotometer in a wavelength range of 185 ∼ 3300 nm. The quantum efficiency and transmission of the N719 cell with a thickness of about 11.5 μm as a function of the wavelength is shown in Figure 13(c) . N719 dye displays a broad absorption spectral coverage in the region 400 ∼ 700 nm, but a large proportion of infrared (IR) spectral range, which constitutes almost half the energy of the sun’s radiation, cannot be utilized.
To make up for insufficient photon absorption, a reflector by either using a Ag mirror or a stack of the PhC was simply attached to the bottom cell or cathode electrode (Figure 14(a) and (b)). As seen in this illustration, there are two physical mechanisms by which wave optics approaches (based on reflector and photonic crystals) can improve light-trapping: reflection and diffraction. Firstly, Ag film can provide high reflection property like a mirror. Distributed Bragg reflectors exhibit high index contrast and they can reflect light over a extensive wavelengths region and incident light angles . Likewise, a PhC can reflect incident light from broad range of angles for frequencies and polarizations within the photonic crystal in that it can reflect light within the bandgap incident from any angle or medium.
Secondly, wave optics-based devices was developed for diffracting incoming beams into indirect angles according to Bragg’s law . The diffraction originated from an interface improve light trapping with the distance increment that light must go forward to the front surface of the cell as well as diffracted beam are internal reflected back into the solar cell when the angle of critical angle overcome the diffracted beam .
Figure 14(c) shows the reflection spectra of Ag film and 3D PC with 198, 311, 375, and 410 nm diameters. The reflectivity of the Ag film is more than 80% in wavelengths ranging from 400 to 800 nm; clearly, this Ag film has better reflectivity than the 3D PC. The red line represents the spectrum from the 198 nm inverse opal sphere; a reflection peak can be observed at 410 nm corresponding to the lowest photonic band gap (
4.2 Measurements and modeling of DSSCs with 3D PhC
The effects of selective light trapping, which was caused by the reflection and diffraction by 3D PhCs, on the solar-to-electric conversion efficiencies and AC impedance measurements of the cell, are analyzed by measuring the photocurrent-density-voltage (
|τeff (ms)||Rk/Rw||EFF (%)|
|w 3D PhC|
In the case of the DSSCs with 3D PhCs, the solar-to-electric conversion efficiencies were enhanced by 1.94, 7.78, 10.7, 11.3 and 14.4% for the 198 nm, 311 nm, 375 nm, 410 nm, and double layer (375/410 nm), respectively, as compared to the traditional typed DSSC. The 3D PC with 198 nm sized PhC showed the lowest efficiency enhancements because the traditional DSSC absorbed most of the light, this corresponds to the reflection peak of this PhC, as shown in Figures 13(c) and 14(c). The 375 nm and 410 nm sized PhC showed high enhancements in the solar-to-electric conversion efficiencies because the traditional DSSC transmitted more than 50% of the light; this corresponds to the reflection peaks of these PhC. This enhancement in the solar-to-electric conversion efficiencies is higher than that in the Ag film even though the Ag film has a considerably higher reflection intensity; this can be explained by the diffraction effect of the PhC as shown in Figure 14(b). The PhC with 375/410 nm double layers showed highest enhancements in the solar-to-electric conversion efficiencies because the double layer PhC has a significant overlap with the quantum efficiency spectra of the ruthenium dye; moreover, the diffraction effect of the PhC is also present. From Table 3, the multilayer whose PBG has a large overlap with the quantum efficiency spectra of the ruthenium dye leads to larger enhancements in the photocurrent. Furthermore, the PhC -based DSSC exhibits considerably higher short circuit photocurrents than the traditional DSSC and is much more effective than the conventional Ag film.
The generation of photocurrent is primarily influenced by the light absorption of the dye. Therefore, when coupling PhC with the back surface of the DSSC, light absorption is increased attributed to the reflection and diffraction of light. This directly reflect the enhancement of the short-circuit current densities and the overall efficiency, while the open-circuit voltage, fill factor is unaffected. The DSSC with the PhC of 375, 410 nm and double layer diameters showed higher conversion efficiency than that with the Ag film; this can be explained not only by the reflection but also the diffraction effect in the DSSCs. As a result, we demonstrated here that recycling of photons by PhC is an effective way to increase the cell efficiency.
5. Nanostructures TiO2 electrode in DSSC from 0 to 3 dimensions
As the main core of DSSCs, the nanocrystalline morphology of the photoelectrode film is critical for the efficient operation. Large efforts have been paid to optimize the morphology of the nanostructured photoanodes with improved architectures for high dye loading and fast electron transport. Although 2-step HT-NPs films treated with the interfacial modification have been regarded as a paradigm of porous photoelectrode for use in DSSCs, there are still challenges to boost the photovoltaic performance or competitiveness. Therefore, the metal oxides in their nanoform can be synthesized under various morphologies with different shapes and sizes, thus offering the possibility for modulating their properties. In literature, a variety of preparation techniques, such as sol–gel,  hydrothermal/solvothermal,  electrochemical anodization,  electrospinning,  spray pyrolysis,  and atomic layer deposition , have been developed and applied to obtain different morphologies in photoanode materials. In this study, a variety of nanostructures from zero dimensional (0D) to three dimensional (3D) has been tested. Electro-spinning and spraying technique has been adopted to prepare the the different dimensional metal oxide semiconductor film by controlling the polymer host and solvents. The detailed results can be seen in followed section (Figure 16).
5.1 Titanium dioxide (TiO2) nanomaterials as a photoelectrode
Various typed metal oxide semiconductors such as TiO2, ZrO2, SnO2, ZnO, Nb2O5, Fe2O3, Al2O3, (binary compounds) and and ternary compounds such as SrTiO3 and Zn2SnO4 can all act as photoelectrodes in DSSC due to their electronic structures which are characterized by a filled valence band and an empty conduction band [7, 92]. Among these heterogenous semiconductors, TiO2 is the most widely used photoelectrode material because of the large amount of grain boundary and the large interface between the TiO2 surface, dye and the electrolyte in the solar cell, further defects in the crystal structure are expected. In TiO2, the Ti ions are in a distorted octahedral environment and formally have a Ti4+(3d0) electronic configuration. The different obital hybridized structure of valence band (VB) and conduction bands (CB) at Ti 3d states occur the decreased the transition probability of electrons to the VB when the electron–hole recombination probability is reduced . Therefore, in view of the electronic configuration and recombination probability TiO2 are the best choice as photoelectrodes among 3d transition metal oxides. TiO2 exsist naturally four commonly known crystalline polymorphs, i.e., anatase (tetragonal, Eg = 3.23 eV), rutile (tetragonal, Eg = 3.05 eV), brookite (orthorhombic, Eg = 3.26 eV) and metastable forms (monoclinic, orthrhombic, cotunnute) . These structures can be described in terms of chains of TiO6 octahedra. The crystal structures differ in the distortion of each octahedron and by the assembly pattern of the octahedra chains . The crystalline strucuture of TiO2 can be seen in Figure 17 . Both rutile and anatase have tetragonal structure with a = 0.46 nm and c = 0.29 nm (rutile); a = 0.3782 nm and c = 0.9502 nm (anatase). Brookite has orthorhombic structure with a = 0.5456 nm, b = 0.9182 nm, and c = 0.5143 nm and it is very hard to synthesize in the laboratory, while the rutile and anatase can be easily prepared. For solar cell application, anatase structure is more prferred because of ∼0.1 eV higher the Fermi level, lower recombination rate of electron–hole pairs and lower formation temperature .
Thermodynamic calculations based on calorimetric data predict that rutile is the stablest phase at all temperatures, exhibiting lower total lower total free energy than metastable phases of anatase and brookite. The small differences in the Gibbs free energy (4 ∼ 20 kJ/mole) between the three phases suggest that the metastable polymorphs are almost as stable as rutile at normal pressures and temperatures . The physical and chemical properties of TiO2 nanocrystals are affected not only by the intrinsic electronic structure, but also by their size, shape, organization, and surface properties. For example, if the particle sizes of the three crystalline phases are equal, anatase is most thermodynamically stable phase below 10 ∼ 15 nm, brookite is most stable between 11 ∼ 35 nm, and rutile is most stable at sizes greater than 35 nm . Herein, interesting morphologies and properties have recently attracted considerable attention and many nanostructured TiO2 materials, such as nanotubes, nanorods, nanofibers, nanosheets, and interconnected architectures, mesoporus material such as inverse opal and photonic crystal have been fabricated and applied in PV devices [35, 83, 99, 100]. In order to be effective photoelectode, several parameters such as morphologies, pore volume, and the crysltalinity of TiO2 influence the charge transport and recombination processes.
5.2 0-dimensional (0D) titanium dioxide (TiO2) Nanosphere
Particles which are more or less spherical in shape like fullerenes, quantum dots, nano-onions, nanoparticles, etc. are considered as 0D. These 0D nanomaterials are sized at nanoscale level in all three dimensions and must be amorphours or crystalline; single or polycrystalline; and composed of single- or multichemical element. Within 0D materials, all electrons are fully confined and their length equals the width. Due to confinement of both electrons and holes, the lowest energy optical transition from the valence to conduction band will increase in energy, effectively increasing the band gap. A 0D TiO2 nanosphere (
In this systmem, the formation of tight cluster sphere filled sphere is caused by the ultrafast evaporation of alcholic solvent under an electric field. For the desireable sphere typed TiO2 film, it is necessary to controll several parameters such as electric field, feed rate, a size of tip and a distance between the nozzle and FTO substrate. It is noted that the the sphere size is controlled by changing the TiO2 concentration and the mixture of solvent in the dispersion solution. In order to find the optimazed condition, TiO2 SPs with the different concentration are tested at 6 μm thick film. Figure 19(a) show the SEM results for E-sprayed film prepared from the different concentration at 1 wt%, 3 wt%, 5 wt% and 10 wt%. With increasing the concentration, the diameters of sphere are almost linearly increased, while the number of molecules calculated from UV–vis absorption spectra of desorbed sensitizers reveal that a TiO2 NSs with 5 wt% have about 11.6% and 13.9% higher value than that of 1 wt% and 10 wt% TiO2 NSs film, respectively (see Figure 19(b)).
Experiemntally, E-spraying at the low weight percent of TiO2 make it hard to achieve the competely formed sphere over 8 μm thick film. Therefore, in this reaserch, about 5 wt% TiO2 suspension in EtOH is used as the best condition. The detailed phase diagram accroding to the electrospraying parameters can be seen in the literature . Figure 19(c) displays the thickness profiler on the various thickness of TiO2 NSs photoelectrode film. In an E-spraying process, the film can control the feeding volume. Figure 19(c) shows the cross-sectional image of an E-sprayed TiO2 SPs film that demonstrates the uniform shape of the spheres from bottom to top. However, with increasing film thickness, TiO2 NSs photoelectrode tends to increase the film roughness since intrinsic insulator properties of TiO2 can influence on an electric field film during depositing process.
Figure 20(a) and (b) show SEM images of a distribution of mesoporous TiO2 NSs in the anode electrode of E-sprayed TiO2 NSs film. This film exhibits a range of diameters between 100 ∼ 800 nm, formed from nucleation and crystallization of 10 nm TiO2 particles. Also, the existence of such mesopores improved the electrolyte penetration. With the TiCl4 treatement, a filled sphere with a relatively rough surface is generated. (seen in Figure 20(b)) This is benefical for improving the interconnection between primary particles inside the TiO2 NSs. Figure 20(c) shows a TEM image of the spheres with the crystalline nano particles. The surface area and porosity of both TiO2 SPs and NPs film can be estimated by N2 adsorption–desorption isotherm at 77 K (see in Figure 20(d)). The SPs films show a type-IV isotherm as well as an increase in the adsorbed amount at high relative pressure, indicating the existence of mesopores in the sample . The measured specific surface area of TiO2 SPs is ∼188.47 m2g−1, ∼2.9 higher than that of similar amount of TiO2 NPs electrode (65.33 m2g−1). Furthermore, the cumulative BJH mesopore volume and maximum pore radius is 1.194 cm3g−1 and 10.05 nm, respectively, while hydrothermal nanoparticle film shows the pore volume of 0.607 cm3g−1 and maximum pore radius of 7.50 nm. In the case of TiCl4 treated SP, the surface area and the cumulative pore volume is decreased by as much as 65.3% and 65.2%, respectively compared with the non-treated SPs film. The amounts of dye adsorbed onto each of the pristine- and TiCl4 treated TiO2 SP layers at 11 μm were 5.80 × 10−6 and 8.19 × 10−5, respectively.
It shows about 2.1 times increased dye absorption properties compared with the NP. This high density of dye molecules onto TiO2 NS can be explained by the high intrinsic surface area of each TiO2 NSs surface as well as the crack free surface morphology. In general, casting TiO2 NPs from a polymer supporter for the thick TiO2 layer onto substrates is by far the preferred method of depositing electrodes for DSSCs. Therefore, heating process at temperature ranging from 450–500°C is necessary to burn out the residual organic binder and to enhance the inter-particle connection between NPs. In this process, cracks are formed at the interface with TiO2 NPs, leading to deteriorate dye absorption. (see Figure 21(a)). In the case of E-sprayed TiO2 SPs from binder-free, the surface of the e-sprayed TiO2 layer is uniform and without cracks, unlike the surfaces produced using paste methods as shown in Figure 21(b).
|BET & BJH||Absorption Properties||Electrical Properties||Solar Properties|
|Surface area (m2g−1)||Pore Volume (cm3g−1)||λmax (at 498 nm)||# of mole. (×10−8 mol /mg)||Rk/Rw||D1 (×10−6 cm2s−1)||Rtotal (Ω)||EFF (%)|
|w TiCl4/ 3D||—||—||—||—||3.49||3.13||10.0||0.43||18.2||0.827||17.24||71.3||10.1|
5.3 1-dimensional (1D) titanium dioxide (TiO2) nanorod
One-dimensional (1D) nanostructures (e.g., nanowires, nanorods, nanotubes, nanobelts, cauliflower-shaped structures) have been widely considered to have superior electron transport characteristics compared to conventional nanorod (NP) -based systems. Eariler reported research have demonstrated that highly efficient TiO2 nanorod-based NR DSSCs and compare charge transport properties to those of typical TiO2 nanoparticle-based (NP, commercially available P-25) NP-DSSCs . The electrospun TiO2 NR based photoelectrodes exhibited about 2 times larger the pore volume and ∼2.5 times more dye coverages at the same weight than those of TiO2 NP. Therefore, NR based cell indicated about 40% higher efficiencies than NP-DSSCs attribied to ∼8 times slower electron–hole recombination in NR-DSSCs. With the TiCl4 post-treatment, further enhancement of electron diffusion coefficient, a charge collection efficiency and the efficiency can be demonstrated .
5.4 2-dimensional (2D) titanium dioxide (TiO2) nanosheets
Two-dimensional (2D) anisotropic nanostructures of metal oxides and semiconductor possess pronounced quantum surface effects and dramatic changes in electronic structures and thus in the physical and chemical properties, which are anticipated to inspire new fundamental and technological research . In my earlier research, TiO2 or ZnO nanofiber mat is used for employing DSSC. [108, 109] For empolying 2D TiO2 film for DSSCs, two different technique are used for TiO2 photoelectrode: (1) Nanofiber (NF) mats produced by electrospinning: (2) Nanotubes (NT) film from 2-step hydrothermal method. As see in Figure 22(a), TiO2/poly(vinly acetate, PVAc) composite fiber mats are directly electrospun onto a FTO glass and then polymer binders are removed by two step process: (i) a THF solvent tratement for melting PVAc polmyer, (ii) calcination this mat at 500°C for 30 min. With the post treatment, the adhesion issues between TiO2 NFs or NFs and FTO glass can be overcome. The TiO2 NTs film is prepared from adjusting pH values . Following this method, the well-growed NT poweders are deposited by mixing a mixture of PEO/PEG polymer binder as described in a section of “
The detailed surface and cross sectional images can be confirmed by the SEM images (1.22(b)). as can bmodified 2-step hydrothermal process. Figure 22(c) show the nitrogen adsorption–desorption isotherm and Barret–Joyner–Halenda (BJH) pore size distribution plot of the NF mats and NT film, respectively. The specific surface area and pore volume of both samples is very small and it is difficult to obtain a sufficient photocurrent density. In agreement with the BET analysis, the JV curve of all cells display an obviously low photocurrent density, leading to the poor cell efficiency.
5.5 3-dimensional (3D) titanium dioxide (TiO2)
In the section of “
Figure 23(b) shows the J-V curves for the different sized 3D PhC at liquid electrolyte. (as seen above) When the size of hole is increased from 198 nm to 410 nm, the
Moreover, large porosity structures of the inverted 3D TiO2 PhCs have enabled good infiltration for high-viscosity electrolytes. For solid state cell fabrication, we have chosen (P1,4I)-doped succinonitrile plastic crystal electrolyte [112, 113]. This electrolyte has the best performance for solid state DSSC as reported in the literature . At a room temperature, this compound electrolyte has a high conductivity of 3.3 mS/cm and fast ion transport of iodine and triiodine in its plastic phase of 3.7 × 10−6 and 2.2 × 10−6 cm2/Vs, respectively. The observed fast ion transport in this solid material can be seen as a decoupling of diffusion and shear relaxation times, which probably originates from local defect rotations in the succinonitrile plastic crystal [115, 116, 117]. Thus, this plastic electrolyte showed best high cell efficiency among other competing electrolyte materials. Figure 23(c) top shows the molecular structure of the compound. For better cell performance, we firstly injected the liquid state electrolyte into TiO2 NP film and evaporated this electrolyte by putting it in the dry oven at 80°C for 12 hour. Next, the plastic electrolyte was heated until it became a liquid (>70°C) and injected into the warmed sandwiched cells. After the cells included the plastic electrolyte was cooled down to room temperature, a waxy solid was obtained. Figure 23(c) shows the JV curve for solid state of 311 nm 3D PhC bilayer. Interestingly, no obvious efficiency change could be seen in all typed solid state electrolyte. The PCE of the solid state system is found to be 2% of that of the liquid electrolyte system. In conclusion, the design of 3D PhC bilayer film enables effective dye sensitization, electrolyte infiltration and charge collection because the layers are in direct physical and electronic contact, light harvesting in specific spectral regions was significantly increased by the 3D PhC effect and PC-induced resonances. This approach should be useful in solid-state devices where pore infiltration is a limiting factor as well as in weakly absorbing photovoltaic devices.
6. Photosensitizer for DSSC: state of the art.
6.1 Ruthenium (Ru) complex based photosensitizer
Since the advent of DSSCs, ruthenium-series dyes are considered as the most powerful photosensitizer because of the following reason: their strong metal to ligand charge transfer transition (MLCT) process, a broad absorption spectrum, suitable excited and ground state energy levels, relatively long excited-state lifetime, and good (electro) chemical stability and power conversion efficiency (PCE) >11% . In order to improve the efficiency of DSSCs, the sensitizer should be panchromatic, that is, absorb photons from the visible to near-infrared (NIR) region of the solar spectrum while maintaining sufficient thermodynamic driving force for the electron injection and dye regeneration process. Many efforts have been made to change the change the ligands of Ru complexes: [118, 119] As seen in Figure 24, ruthenium(II) – polypyridyl complexes such as the thiocyanato derivative,
However, the IPCE increases only gradually from the absorption onset to shorter wavelengths due to relatively low extinction coefficients (1.40 × 104 M−1 cm−1) [7, 47]. In addition, this class of compounds contains expensive ruthenium metal and requires careful synthesis and tricky purification steps. Therefore, efforts in the synthesis of sensitizers for DSSCs step forward to the metal-free organic donor–acceptor (D–A) dyes system.
6.2 Porphyrins based sensitizer
The idea for mimicking the light harvesting processes based on chlorophyll occurring photosynthetic reaction centres inspire the research for porphyrins based sensitizer. The porphyrin-based dyes exhibit large absorption coefficients in the visible and infrared region as well as their rigid molecular structures consisted of four meso and eight β reaction sites, which can control their properties [122, 123, 124]. The designed porphyrin dyes with a π-conjugated link at the β-position of the porphyrin ring enhance the electronic coupling of the dye with the surface of TiO2, reaching η =7.1% of a PCE . Numerous series of porphyrins are reported for the DSSC application as an effective sensitizer. of DSSC synthetized. Among them, a class of sensitizer consisting of a push–pull porphyrins with an electron-donating diarylamino group and an electron-withdrawing carboxyphenylethynyl anchoring group shows the outstanding solar properties. For example, advances in optimization of the device performance for a zinc porphyrin sensitizer (YD2-oC8) co-sensitized with an organic dye (Y123) using a cobalt-based electrolyte to enhance photovoltage of the device attained an unprecedented power conversion efficiency of
6.3 Tetrathienoacenes (TTAs) based sensitizers
Metal-free organic dyes have attracted much attention to researchers due to chemical or optical versatility, environmental compatibility and potential cost reductions . In spite of these attractions and efforts, a little lower cell performance and difficulty in synthesis cannot meet the requirement for commercialization.
A donor-π-acceptor (D-π-A) structure is a promising strategy for metal-free organic sensitizers because of the effective photoinduced intramolecular charge transfer property [7, 130]. Thanks to support from Chen’s group, a new series of organic dye based on tetrathienoacene are applied for DSSC [105, 131]. In this design, triphenylamine electron-donor (D) unit and cyanoacrylic acid electron-acceptor (A) unit is connected to an electron rich a lipophilic dihexyloxy-substituted thiophene-based fused tetrathienoacene. (
Several fused thiophene derivatives have already been demonstrated to have excellent charge transport performance. For example, dithienothiophene (DTT) and tetrathienoacene (TTA) based OTFTs exhibited mobilities up 0.42 (p-channel) and 0.30 (n-channel) cm2V−1 s−1, respectively . Relative to organic semiconductors, the potential of fused thiophene-based DSSCs has not been well explored until recently, and only for a limited range of TT and DTT materials. To the best of our knowledge, the first example of a TT-based small molecule DSSC with a PCE of 7.8% was reported by
The effects of thiophene introduction between the bridge and the donor and/or acceptor moieties can be systematically understood. Starting from the simplest
The optical absorption spectra of the five organic dyes are displayed in Figure 27(c), indicating the presence of two strong absorptions from a charge-transfer band (∼482 nm (
|Dye||λmax (nm)||Eg (eV)||Energy level (eV)||Energy level (eV)||Photoexcited Electron Dynamics||Electron injection efficiency (%)||Solar Performance|
|EHOMOa||ELUMOa||EHOMOb||ELUMOb||τ1 (ps)||τ2 (ps)||τ3 (ps)||Voc (V)||Jsc (mA/cm2)||FF (%)||EFF(%)|
To understand the exciton dynamics in dyes, femtosecond time-resolved photoluminescence (FTR-PL) was used [140, 141]. The electron injection efficiency can be calculated by the followed equation, η = (1/τ1)/(1/τ2 + 1/τ3), where τ 1 is the electron injection time from the dye to TiO2, τ2 is the exaction-exciton annihilation time, and τ3 is the lifetime of an exciton in the dye . The calculated time constants and electron injection efficiency for the dye coated TiO2 film are summarized in Table 5. The electron injection efficiency of 5 dyes shows almost 97% at λ = 420 nm, which is well matched results for IPCEs data (>93%) at the same wavelength.
6.4 Multi-sensitized DSSC
Designed sensitizers with higher molar extinction coefficient have allowed significant improvement of cell performance. Nevertheless, possible efficiency boosts can be obtained by extending the dye absorption range while simultaneously avoiding a negative impact on other parameters, such as ground- and excited-state redox potential, intensity of absorption, or stability. Many series of dyes have been developed to find an efficient absorber with high extinction coefficients particularly in the solar spectrum from 350 ∼ 1,000 nm that is also environmentally benign and inexpensive to use. However, it’s a big challenge. Therefore, scientists are tried to mix two or more dyes with different absorption range [142, 143, 144]. Although this concept is very sensible, the multi-sensitizers system should meet some essential conditions: (i) strong molar extinction coefficients to minimize the thickness of the mesoscopic TiO2 film; (ii) a suitable structure to avoid unfavorable dye aggregation; (iii) to reduce the recombination of electrons in the TiO2 film with I3− and other acceptors materials through the formation of a compact molecule monolayer covering the bare TiO2 surface. With the continuous efforts, the co-sensitized DSSC has achieved an 11.5% efficiency record with the liquid state electrolyte,  but the energy conversion efficiency of mixed sensitizer still lags behind a champion cell made from the single dye. The reason is that the formation of molecular aggregates onto the TiO2 surface having a finite number of anchoring sites as well as the deactivation of dye excited states due to energy or electron transfer processes between the different sensitizers .
In this book, three sensitizers with the different main absorption position and D-π-A framework (a Zn based porphyrin dye (YD2-oC8)  and the more conjugated TTA-based small molecules (TTAR) , which hold records of solar performance as a single dye) are applied by modified stepwise approach. For the efficient cosensitizaion, a good understadning of the intermolecular interactions such as matchable size, shape, and orientations as well as compensating light-harvest between or among the coadsorbed dyes must take precedence. In addition dye aggregation on the surface of TiO2 significantly must be avoided because the formation of dye aggregates significantly decrease the efficiency of electron injection. Attached long alkoxyl chains at phenyl group is plausible strategies to suppress effectively the dye aggregation. The key structural feature of YD2-oC8 involves long alkoxyl chains in the
For supporting the lack of light-harvesting ability beyond 700 nm, near-IR dyes, named as YDD6, is employed . The ortho-substituted alkoxyl chains in YDD6 can be contributed as not only a light-harvesting ability extending beyond 800 nm but also failed to prevent dye aggregation for this porphyrin. A weakly absorption around
The possibility of dye aggregation of TTAR are test with various amounts of chenodeoxycholic acid (CDCA) co-adsorbed on the photoanodes. The effect of CDCA concentration on the photovoltaic properties of the DSSCs fabricated with
For the effective co-sensitization deposition, there are two well known approaches: (i) the cocktail approach uses a mixture of dye solutions with certain molar ratios of the two dyes, [147, 150] and (ii) the stepwise approach accomplishes sequential adsorptions of the two sensitizers [151, 152]. In our experiement, the fabrication of a co-sensitized onto the TiO2 sphere film is performed by the modified stepwise deposition method. (see Figure 28(b)) Considering the enegetic band position, the TiO2 electrode is firstly immersed into a 1 M
Figure 29(a) and (b) show the current–voltage characteristics and the corresponding IPCE action for the TTAR, YD2-oC8, YDD6 and Multiple (TTAR/YD2-oC8/YDD6) sensitized DSSC, respectively. The photovoltaic parameters are listed in Table 6. An impressive cell performance of ca 11.2% (
|τeff (ms)||Rk||Rw||Rk/Rw||RIR (Ω)||EFF (%)|
7. Electrolyte and solid state hole transport material
The liquid electrolytes possess some important features such as easy preparation, high conductivity, low viscosity, and good interfacial wetting between electrolytes and electrodes and thus high conversion efficiency for the DSSCs [153, 154]. Today, the best working redox-couple known so far is the iodide/triiodide system. The unique performance of I− /I3− based liquid electrolytes is mainly attributed to the favorable penetration into the nanoporous semiconductor film, very fast dye regeneration, and relatively slow recombination losses through reaction with injected photoelectrons. Cobalt based redox mediators bring the concomitant improvements in the
In our research, three different classes of solid state electrolyte are investigated (i) iodide based plastic crystal electrolyte prepared by mixing synthesized N-methyl-N-butylpyrrolidinium iodide (P1,4I), I2, and succinonitrile ; (ii) a novel cross-linkable organiosiloxane cross-linkable molecule, 4,4′-bis((
As an organic molecule system, several different systems have been proposed including melt processing,  in-situ polymerizastion,  use of low
Figure 30(b) shows a scheme on the possible change of electronic structure by additive treatment by the UPS spectra of P3HT before and after additive treatment. The detailed information can be seen in Table 7. In HOMO emission regions, the HOMO band onsets also show no significant difference, corresponding to IPs of 4.94 and 4.98 eV for P3HT before and after additive treatment, respectively. This result is in perfect agreement with CV data (Table 7). However, for TPDSi2 films, the additive treatment result in a clear shift both in high binding energy cutoff (HBEC) and HOMO emission regions. In particular, the HBEC position shifts to lower binding energy after additive treatment, whereas the HOMO cutoff shifts close to 0 eV. This effect could indicate a strong p-doping effect of additives on TPDSi2. Scholin et al.  observed a similar effect of Fermi level shift to move closer to the HOMO level on Spiro-OMeTAD by Li-TFSI doping. Here, by using the same substrates and a common vacuum level, the shift of Fermi energy to the move closer to the HOMO position is confirmed. In addition, IPs also shift from 5.36 to 5.12 eV after additive treatment, which is in excellent agreement with CV-derived HOMO energies.
|Sample||EHOMOa (eV)||IPb (eV)||Eopt,gapc (eV)||ELUMOd (eV)||μTFT (cm2/Vs)||μSCLC (cm2/Vs)||Voc (V)||Jsc (mA/cm2)||FF (%)||PCE (%)|
|P3HT||?||−4.94||1.91||−3.03||4.3 × 10−3||1.0 × 10−3||0.166||0.38||32.1||0.02|
|P3HT + additives||?||−4.98||1.90||−3.08||1.1 × 10−2||2.3 × 10−3||0.497||1.69||39.4||0.33|
|TPDSi2||−5.31||−5.37||2.90||−2.47||NA||4.6 × 10−4||0.485||2.81||46.7||0.64|
|TPDSi2 + additives||−5.09||−5.11||2.90||−2.22||NA||2.8 × 10−3||0.683||4.97||60.3||2.05|
The overall energy alignment including all DSSC device components, specifically, FTO/TiO2/Z907/HTMs (P3HT + additives or TPDSi2 + additives)/Au is presented as Figure 30(b).
The exact energetic alignment of HTMs are carefully derived from optical absorption, cyclic voltammetry and ultraviolet photoemission spectroscopy and is discussed below. To carefully investigate the charge transport properties of HTMs, both TFT and space charge limited current (SCLC) measurements are performed. For TFT mobility measurements, bottom-gate/top-contact configurations were employed for all devices fabricated by spin-coating of a 5 mg/mL chlorobenzene solution onto Si/SiO2 substrates using Au source and drain contacts. All TFT and SCLC mobilies are summarized in Table 7. For P3HT, typical p-type TFT behavior was observed both in pristine films and films treated with additives. A noticeable increase in p-type mobility from 4.3 × 10−3 to 1.1 × 10−2 is observed. However, TPDSi2 exhibit relatively low TFT performance, as a result of disconnected domains in the lateral direction. In real DSSC condition, hole transport through the HTMs to the counter electrode can significantly influence charge recombination and device performance. Therefore, SCLC method which directly measures the charge transport in the direction perpendicular to substrate can be employed as a good indicator mimicking real device conditions . For the cross-linked TPDSi2 HTM, it show about 2.8 time higher p-type hole mobility than that of pristine, which is indicative of favorable charge transport properties in DSSCs. Therefore, power conversion efficiency (PCE) of DSSCs of >2% is achieved when using standard amphiphilic dye and TPDSi2 as HTM (see Figure 30(c)).
8. Carbonaceous cathode for DSSC
In this part, we show our effort on developing the counter electrode (CE). Generally, CE mainly functions as reducing the redox species from I3− to I2. A suitable redox charge mediator should effectively perform the function of shuttling the generated positive charge away from the light absorbing sensitizer residing on the semiconductor surface to the CE, thus completing the electrical circuit. For being an effective CE, it exhibit high electrical conductivity and electrocatalytic activity toward I3−reduction and corrosion resistant to iodide/triiodide electrolyte . To date, a platinum (Pt) is the most common catalyst material for DSSC . However, its cost remains a concern for the large-scale commercialization of the DSSC. Therefore, numerous researchers are trying to find new CE materials. Carbonaceous materials such as graphite [166, 167] carbon black [168, 169], activated carbon , hard carbon sphere , carbon nanotube , fullerene and graphene , conductive polymers , metal compounds  and composites have been developed and tested as promising counter electrodes. So far, carbonaceous materials are regarded as the most attractive option.
In this book, we introduce large-effective-surface-area polyaromatic hydrocarbon (LPAH) for DSSC. A detailed description for generating LPAH species has been reported in an earlier publication . The catalytic properties of LPAH can be calculated by EIS method. Device symmetric structure and the Randles-typed equivalent circuit model consisting of charge transfer resistance (
In general, the equivalent circuit of the complete solar cell may be represented as indicated in Figure 31(b) [37, 176]. From right to left, it demonstrates impedance for charge transfer at electrolyte/catalytic materials-FTO interface, diffusion of I3− species in the electrolyte, electron transport and electron capture by the I3− at the TiO2/electrolyte interface and the electron transport at the FTO/TiO2 interface, respectively. These components can be simplified from proposed in DSSC model:
The catalytic activity described the exchange current density (
Figure 31(c).b described fitted Nyquist plot and
|sample||BET & BJH analysis||Symmetric Cell||Compete DSSC (w/o mask)|
|Surface area (m2/g)||Pore Volume (cm3/g)||Pore diameter (nm)||CPE:B (S.s β)||CPE: β||RCT (Ωcm2)||Jo (mA/cm2)||VOC (V)||Jsc (mA/cm2)||FF (%)||EFF (%)||RIR* (Ohm)|
|(a) pt||—||—||—||2.9 × 10−5||0.87||0.61||22.0||0.824||13.4||73.8||8.12||17.1|
|(b) CB||7.5 ± 0.8||69.6||0.094||5.93||2.3 × 10−5||0.76||70.3||0.190||0.804||11.5||68.9||6.35||111|
|(c)LPAH||3.2 ± 0.6||216.8||0.474||13.3||2.3 × 10−3||0.85||2.12||6.31||0.820||13.1||73.2||7.89||21.9|
9. Optimization of the DSSC performance for having maximum performance
Based on these fundamental achievements, our efforts are headed for achieving an energy efficiency of over 12.3% by combining new materials and concept. For a photoanode, the ITO NR array with over 3 μm spacing and 10 μm thickness is used as the 3D cell . In this design, it is very important how well the TiO2 nanoparticles have infiltrated among the ITO nanowire. In our earlier research, TiO2 solution including polymer binder is air-sprayed into ITO NWs. Although this method is easy and efficient enough to fill TiO2 NPs into ITO NW, it formed surface defect (such as crack) on the surface of TiO2 film during sintering process (see Figure 32). Through Electro-spraying process, crack free TiO2 film is deposited into ITO NW. For an electro-spraying, aqueous solvent in the hydrothermal treated TiO2 nanoparticle solution is replaced by ethanol and then alpha-terpineol is added into the ethanol solution of TiO2 particles. The replaced solution was loaded into a syringe equipped with a 27-gauge stainless steel needle. The spaying rate (25 μL/min) was controlled using a syringe pump. The electric field (12–15 kV) was applied between a metal orifice and the aluminum foil at a distance of 10 cm using a power supply and was electrosprayed onto ITO NWs substrate. The TiO2 coated electrode was gradually calcined under an air flow at 150°C for 15 min, at 320°C for 10 min, at 500°C for 30 min. As seen in Figure 32(a), TiO2 sphere solution prepared from pure EtOH formed the film on the top of ITO NWs, which make it difficult to penetrate into the ITO NWs. Therefore, adding alpha-terpineol solvent with viscous and low evaporation rate into TiO2 solution, TiO2 solution is directly dropped into highly charged ITO NWs in between and spreading through x-y-z moving robot system. As a result, completely filled and crack free TiO2 film in ITO NWs can be obtainable (see Figure 32(b)). A
Figure 33(a) presents the solar performance for the best cell. Form an effective approach to enhance the light-harvesting ability and to retard the charge recombination, the maximum PCE is about 13.26%, with short-circuit current density (
10. Future prospects of ESC
Compared with traditional silicon solar cells, the DSSC device promises to be less expensive (the ease of fabrication and cost effectiveness of materials, which do not need to be highly purified process), thinner, more flexible, and amenable to a wide range of lighting conditions, all of which makes it viable and efficient solar cells for the future. Therefore, they said that ESC along with its good performance will definitely replace c-Si dominated photovoltaic markets very sooner. However, although each material is extremely inexpensive, the cost of silicon continues to fall as well. Silicon photovoltaics module are a mature technology and their costs have continued to reduce from US $1.52 W−1 in 2010 to just US$ 0.39 W−1 in 2018, with module efficiencies ranging from 15–20% and lifetime guaranteed to 25 years . Unfortunately, the ESC technology is not so trivial that the highest module efficiency, the fastest production methods, or the lowest materials cost necessarily provides the best module solution. In addition, long term stability is the big challenge. Therefore, for surviving the future photovoltaic market, we believe ESCs have to develop the system of transparency with esthetics ability.
Building integrated photovoltaic (BIPV) technology has become an emerging research hotspot of solar PV technology because it intends to achieve “zero energy building (ZEB)” consumption through transformations of buildings from energy consumers to sustainable energy producers . A sustainable building can minimize energy consumption, while at the same time supplying its own energy demand through self-generation. PV was generally installed on building’s roofs, but it’s very harsh to meet strict requirements of ZEB regulation. The potential power of rooftop in the United States is approximately estimated as 1400 TWh/yr. (0.16TW) at about 16% of module efficiency cell, nearly 40% of the total electricity generation of the US . In buildings rooftop system with conventional PV application, the available area for PV installation is limited and it cannot fulfill the building’s energy needs. On the other hands, transparent or semi-transparent PV windows have a tremendous potential to increase harvesting area as well as reduce the annual electricity consumption for cooling and heating. Therefore, we believe transparent PV is the most promising future energy system and research efforts for minimizing the tradeoff relation between the average visible transparency (AVT) and power conversion efficiency (PCE) can decide ESC’s fate .
The main aim of this book is to put a comprehensive review how to improve and what kind of factors are influence on cell performance. Fundamental and professional understanding of the DSSC has been gained by means of experimental, electrical and optical modeling and advanced characterization techniques. In this book, TiO2 photoanode under the category of 0D and 3D structures, organic photosensitizer, solid state transporting materials and catalytic carbon as a material field was studied by using various optical and electrical tools. The combined research efforts have led to the important technical achievements: by controlling the nanocrystal structure, size, shape, organization and interface of titanium dioxide, we have made great progress in controlling the light harvesting, charge transfer and transport properties in the devices and have greatly boosted the performance of the devices. By using specially designed photonic crystals to confine the photons in the cells, the overall cell efficiency can reach to about 13.26%.
The Northwestern University authors acknowledge the support of the Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) under Award Number DE-SC0001059. This work made use of the EPIC, Keck-II, and SPID facilities of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS), the MRSEC program (NSF DMR-1121262 and 1542205) at the Materials Research Center, the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois,