The influence of dye structure on charge recombination in dye-sensitized solar cells

Replacing the nonyl groups on the solar cell dye Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-dinonyl-2,2'-bipyridine)(NCS)(2) (Z-907) with amino groups results in a marked decrease in solar cell performance. This is despite the fact that the amino derivative (Z-960) has more favourable light absorption characteristics than Z-907 when used with thick nanocrystalline TiO(2) layers. Electron transfer to the electrolyte from the exposed fluorine-doped tin oxide (FTO) substrate is particularly fast in cells employing the Z-960 dye if a compact TiO(2) blocking layer is not used. The kinetics of electron transfer from the nanocrystalline TiO(2) layer in DSCs employing Z-960 are comparable to those of bare TiO(2) and ca. 2 to 5 times faster than for cells employing Z-907. The faster charge recombination in cells employing Z-960 lowers open-circuit photovoltage and results in very significant charge collection losses that lower short-circuit photocurrent. Voltammetric measurements show that surface modification of FTO electrodes with Z-960 results in slightly more facile charge transfer to acceptor species in triiodide/iodide electrolytes in the dark. A simpler molecule, p-aminobenzoic acid, more dramatically catalyses this charge transfer reaction. Conversely, chemical modification of FTO electrodes with Z-907 or p-toluic acid retards charge transfer kinetics. Similar results are obtained for nanocrystalline TiO(2) electrodes modified with these benzoic acid derivatives. These results strongly imply that surface adsorbed molecules bearing amino groups, including dye molecules, can catalyse charge recombination in dye-sensitized solar cells.     

Significant efficiency improvement of the black dye-sensitized solar cell through protonation of TiO2 films

This paper describes the influence of acid pretreatment ofTiO2 mesoporous films prior to dye sensitization on the performance of dye-sensitized solar cells based on [(C4H9)4N]3[Ru(Htcterpy)(NCS)3] (tcterpy = 4,4',4"-tricarboxy- 2,2',2"-terpyridine), the so-called black dye. The HCl pretreatment caused an increase in overall efficiency by 8%, with a major contribution from photocurrent improvement. It is speculated, from the analysis of incident photon-to-electron conversion efficiency, UV-vis absorption spectra, redox properties of the dye and TiO2, and the impedance spectra of the dye-sensitized solar cells, that photocurrent enhancement is attributed to the increases in electron injection and/or charge collection efficiency besides the improvement of light harvesting efficiency upon HCl pretreatment. Open-circuit photovoltage (V(oc)) remained almost unchanged in the case of significant positive shift of flat band potential for TiO2 upon HCl pretreatment. The suppression of electron transfer from conduction band electrons to the I3- ions in the electrolyte upon HCl pretreatment, reflected by the increased resistance at the TiO2/dye/electrolyte interface and reduced dark current, resulted in a V(oc) gain, which compensated the V(oc) loss due to the positive shift of the flat band. Using the HCl pretreatment approach, 10.5% of overall efficiency with the black dye was obtained under illumination of simulated AM 1.5 solar light (100 mW cm(-2)) using an antireflection film on the cell surface.     

Double-layer coating of SrCO3/TiO2 on nanoporous TiO2 for efficient dye-sensitized solar cells

Surface modification plays a crucial role in improving the efficiency of dye-sensitized solar cells (DSSCs), but the reported surface treatments are in general superior to the untreated TiO(2) but inferior to the typical TiCl(4)-treated TiO(2) in terms of solar cell performance. This work demonstrates a two-step treatment of the nanoporous titania surface with strontium acetate [Sr(OAc)(2)] and TiCl(4) in order, each step followed by sintering. An electronically insulating layer of SrCO(3) is formed on the TiO(2) surface via the Sr(OAc)(2) treatment and then a fresh TiO(2) layer is deposited on top of the SrCO(3) layer via the TiCl(4) treatment, corresponding to a double layer of Sr(OAc)(2)/TiO(2) coated on the TiO(2) surface. As compared to the typical TiCl(4)-treated DSSC, the Sr(OAc)(2)-TiCl(4) treated DSSC improves short-circuit photocurrent (J(sc)) by 17%, open-circuit photovoltage (V(oc)) by 2%, and power conversion efficiency by 20%. These results indicate that the Sr(OAc)(2)-TiCl(4) treatment is better than the often used TiCl(4) treatment for fabrication of efficient DSSCs. Charge density at open circuit and controlled intensity modulated photocurrent/photovoltage spectroscopy reveal that the two electrodes show almost same conduction band level but different electron diffusion coefficient and charge recombination rate constant. Owing to the blocking effect of the SrCO(3) layer on electron recombination with I(3)(-) ions, the charge recombination rate constant of the Sr(OAc)(2)-TiCl(4) treated DSSC is half that of the TiCl(4)-treated DSSC, accounting well for the difference of their V(oc). The improved J(sc) is also attributed to the middle SrCO(3) layer, which increases dye adsorption and may improve charge separation efficiency due to the blocking effect of SrCO(3) on charge recombination.     

Novel fluorous amphiphilic heteroleptic Ru-based complexes for a dye-sensitized solar cell: the first fluorous bis-ponytailed amphiphilic Ru complexes

A new series of amphiphilic heteroleptic ruthenium(II) sensitizers with a fluorous bis-ponytailed bipyridine ancillary ligand, [Ru(H(2)dcbpy)(4,4'-bis(R(f)CH(2)OCH(2))-2,2'-bpy)(NCS)(2)] [where R(f) = HCF(2)CF(2) (CT4), C(3)F(7) (CT7), and HCF(2)CF(2)CF(2)CF(2) (CT8)], have been synthesized and fully characterized by UV/vis, visible emission, NMR, fast atom bombardment mass spectrometry, and cyclic voltammetric studies. Dye-sensitized solar cells (DSCs) based on these dyes exhibit efficiencies comparable with that of the standard cell based on N719. The conversion efficiency of a CT7- or CT8-based DSC is ~9% higher than that of Z907 with a nonfluorous bis-ponytailed bipyridine ancillary ligand. The fluorous chains were found to increase the dye density on TiO(2) and to help to suppress the dye desorption.     

长链双烷基次膦酸作为共吸附剂修饰TiO_2光阳极

对TiO2/染料/电解质界面进行修饰是提高染料敏化太阳电池(DSC)性能的有效手段,其中引入共吸附剂有机小分子和染料共同吸附在TiO2表面是一种简单有效提高DSC性能的方法.本文合成了长链的双正十二烷基次膦酸(DDdPA)作为染料的共吸附剂应用于染料敏化太阳电池.通过红外光谱(FT-IR)表征DDdPA在TiO2表面的吸附;借助电化学阻抗谱(EIS)及强度调制光电流谱(IMPS)/强度调制光电压谱(IMVS)等技术表征了电子的传输与复合动力学过程.研究发现,DDdPA可以很好地与染料共同吸附在TiO2表面;与二(3,3-二甲基丁基)次膦酸(DINHOP)相比,DDdPA的引入可以更好地抑制TiO2/染料/电解质界面处的电子复合;在优化浓度配比下,DDdPA的引入有效提高了器件的电子寿命,使TiO2导带边负移约30 mV,最终使器件的开路电压提高了47 mV,光电转换效率提升约10%.     

Long-wavelength sensitization of TiO2 by ruthenium diimine compounds with low-lying π* orbitals

The role of low-lying π* orbitals in dye-sensitized solar cells based on mesoporous thin films of anatase TiO(2) nanocrystallites remains unknown. Herein we report three ruthenium compounds, cis-Ru(dcbq)(2)(NCS)(2), cis-Ru(dcbq)(bpy)(NCS)(2), and cis-Ru(dcb)(bq)(NCS)(2), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO(2)H)(2)-2,2'-bipyridine, bq is 2,2'-biquinoline, and dcbq is 4,4'-(CO(2)H)(2)-2,2'-biquinoline, that were synthesized, characterized, and contrasted with the well-known N3 compound (i.e., cis-Ru(dcb)(2)(NCS)(2)) in dye-sensitized solar cells. These compounds maintain the same cis-Ru(NCS)(2) core with a systematic variation in the energy of the π* orbitals of the diimine ligand: bpy > dcb > bq > dcbq. The lowered π* orbitals resulted in enhanced red absorption relative to N3. With HCl pretreated TiO(2) in regenerative solar cells, sensitization from 400 to 900 nm was realized with cis-Ru(dcb)(bq)(NCS)(2) and global power conversion efficiencies as high as 6.5% were achieved under 1 sun of AM 1.5 irradiation. The energy conversion efficiency was found to be acutely sensitive to the presence of p-tert-butylpyridine (TBP) in a 0.5 M LiI/0.05 M I(2) acetonitrile electrolyte. Nanosecond transient absorption studies revealed that the addition of TBP decreased the excited-state injection yield for the compounds with biquinoline ligands. Spectro-electrochemical studies showed that the HCl pretreatment lowered the effective density of TiO(2) acceptor states and confirmed that the presence of TBP raised them toward the vacuum level. There was no spectroscopic data to support the hypothesis that the π* levels of the diimine ligand mediate back-electron transfer to the oxidized dye or the redox mediator was found.     

Effect of organic dye on the performance of dye-sensitized solar cell utilizing TiO2 nanostructure films synthesized via CTAB-assisted liquid phase deposition technique

This work is concerned with the growth of TiO₂ nanostructures as photovoltaic materials of dyesensitized solar cell (DSSC) via phase liquid deposition technique treated with CTAB surfactant. This work investigates the influence of organic dyes, N719, N3 and Z907 as photosensitizer on the photovoltaic parameters of TiO₂ nanostructures dye-sensitized solar cells (DSSCs). It also highlights the effect of the concentration of the best dye, N719 on the performance of the cell. The platinum films as counter electrode of the DSSC were prepared by sputtering platinum pellet on ITO substrate. The redox couple of the electrolyte utilized in the DSSC was iodide/triiodide. The cell sensitized with N719 dye demonstrated the best performance compared with the cell sensitized with another two dyes, N3 and Z907. This is due to N719 dye possess the highest optical absorption in visible region. The cell sensitized with 0.8 mM N719 dye performs the highest short-circuit current density, J _sc and power conversion efficiency, η since it posses the highest absorption in visible region. The DSSC utilizing 0.8 mM N719 dye demonstrated the highest J _sc and η of 6.48 mA cm^?2 and 1.69%, respectively.     

Composite Electrode SnO2／TiO2 for Dye-Sensitized Solar Cells

Composite nanoporous electrode SnO2/TiO2 was fabricated for the dye sensitized solar cell (DSSC) with N3 (Cis-Ru). After introducing of TiO2, the open-circuit photovoltage (Voc) was higher than that of the pure SnO2 electrode, while short-circuit photocurrent (Isc) was varied with the ratio of the TiO2. Appropriate content of the TiO2 can be beneficial to the efficiency of the solar cell, and it gives negative impact on the composite electrode when the content of TiO2 is higher.     

Cycloruthenated sensitizers: improving the dye-sensitized solar cell with classical inorganic chemistry principles

A divergence from the conventional approach to chromophore design has led to the establishment of many exciting new benchmarks for the dye-sensitized solar cell (DSSC), including the first documented power conversion efficiency in excess of 12% at 1 sun illumination [Yella et al., Science 2011, 334, 629]. Paramount to these advances is the deviation from polypyridyl ruthenium dyes bearing NCS(-) ligands, such as [Ru(dcbpy)(2)(NCS)(2)] (N3; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine). While metal-free and porphyrin dyes have demonstrated much promise, the discovery that the NCS(-) ligands of N3 can be replaced by anionic, chelating cyclometalating ligands without compromising device efficiencies has ushered in a new era of ruthenium dye development. A particularly appealing feature of this class of dyestuff is that they offer acute control of the frontier molecular orbitals to enable the precise attenuation of both the ground and excited state redox potentials through judicious chemical modification of the aryl ring. This Perspective summarizes very recent developments in the field, and demonstrates how the new and rapidly expanding class of Ru-based sensitizers provides a conduit for enhancing the performance (and potentially the stability) of the DSSC.     

Photophysical and (photo)electrochemical properties of a coumarin dye

A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface.     

Amphiphilic ruthenium dye as an ideal sensitizer in conversion of light to electricity using ionic liquid crystal electrolyte

The optimization of interfacial charge transfer between the dye and the electrolyte is crucial to the design of dye-sensitized solar cells. In this paper, we address the combined use of an ionic liquid crystal electrolyte and amphiphilic ruthenium dyes in dye-sensitized solar cells. The solar cell with an amphiphilic ruthenium dye [Ru(H₂dcbpy)(tdbpy)(NCS)2] (H₂dcbpy = 4,4′-dicarboxy-2,2′-bipyridine, tdbpy = 4,4′-tridecyl-2,2′-bipyridine), exhibited a short-circuit photocurrent density of 9.1 mA/cm², an open-circuit voltage of 665 mV and a fill factor of 0.58, corresponding to an overall conversion efficiency of 3.51%. We find that increasing dye alkyl chain length to octadecyl from tridecyl results in lower short-circuit photocurrent density and open-circuit voltage, and the suitable dyes for ionic liquid crystal electrolyte differed completely from those used in liquid and ionic liquid electrolyte cells.     

Panchromatic sensitization of nanocrystalline TiO2 with cis-Bis(4-carboxy-2-[2'-(4'-carboxypyridyl)]quinoline)bis(thiocyanato-N)ruthenium(II)

We compared the spectral (IR and Raman), electrochemical, and photoelectrochemical properties of nanocrystalline TiO(2) sensitized with the newly synthesized complex [NBu(4)](2)[cis-Ru(Hdcpq)(2)(NCS)(2)] (1; [NBu(4)](+) = tetrabutylammonium cation; H(2)dcpq = 4-carboxy-2-[2'-(4'-carboxypyridyl)]quinoline) with those of TiO(2) sensitized with [NBu(4)](2)[cis-Ru(Hdcbpy)(2)(NCS)(2)] (2; H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and [NBu(4)](2)[cis-Ru(Hdcbiq)(2)(NCS)(2)] (3; H(2)dcbiq = 4,4'-dicarboxy-2,2'-biquinoline). Complex 1 achieved efficient sensitization of nanocrystalline TiO(2) films over a wide visible and near-IR region, generating a large short-circuit photocurrent. The absorbed photon-to-current conversion efficiency decreased in the order 2 > 1 > 3 with the decrease in the free energy change (-Delta G(inj)) of the electron injection from the ruthenium complex to TiO(2). The open-circuit photovoltages (V(oc)'s) of dye-sensitized solar cells decreased in the order 2 > 1 > 3 with the increase in the dark current resulting from reverse electron transfer from TiO(2) to I(3)(-). The sensitizer-dependent V(oc) value can be interpreted as a result of reverse electron transfer through the sensitizing dye molecules.     

Effect of sensitizer adsorption temperature on the performance of dye-sensitized solar cells

Employing a mesoscopic titania photoanode whose bilayer structure was judiciously selected to fit the optoelectronic characteristics of the Ru-based heteroleptic complex Na-cis-Ru(4,4'-(5-hexyltiophen-2-yl)-2,2'-bipyridine)(4-carboxylic-acid-4'-carboxylate-2,2'-bipyridine)(thiocyanate)(2), coded as C101, we investigated the effect of temperature for dye adsorption on the photovoltaic performance of dye-sensitized solar cells (DSCs). We found a significant efficiency enhancement upon lowering the temperature applied during the sensitizer uptake from solution. When the dye adsorption was performed at 4 °C, the photovoltaic performance parameters measured under standard reporting conditions (AM1.5 G sunlight at 1000 W/m(2) intensity and 25 °C), i.e., the open circuit voltage (V(oc)), the short circuit photocurrent density (J(sc)), the fill factor (FF), and consequently the power conversion efficiency (PCE), improved in comparison to cells stained at 20 and 60 °C. Results from electrochemical impedance spectroscopy (EIS) and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) show that the self-assembled layer of C101 formed at lower temperature impairs the back-electron transfer from the TiO(2) conduction band to the triiodide ions in the electrolyte more strongly than the film produced at 60 °C. Profiting from the favorable influence that the low-temperature dye uptake exerts on photovoltaic performance, we have realized DSCs showing a power conversion efficiency of 11.5%.     

Effect of a coadsorbent on the performance of dye-sensitized TiO2 solar cells: shielding versus band-edge movement

The mechanism by which the adsorbent chenodeoxycholate, cografted with a sensitizer onto TiO2 nanocrystals, alters the open-circuit photovoltage and short-circuit current of dye-sensitized solar cells was investigated. The influence of tetrabutylammonium chenodeoxycholate on dye loading was studied under a variety of conditions in which the TiO2 films were exposed to the sensitizing dye and coadsorbent. Photocurrent--voltage measurements combined with desorption studies revealed that adding chenodeoxycholate reduces the dye loading by as much as 60% while having a relatively small effect on the short-circuit photocurrent. Calculations along with measurements showed that even at low loading, enough dye is present to absorb a significant fraction of the incident light in the visible spectrum. In concurrence with the observations of others, we find evidence for weakly and strongly adsorbed forms of the dye resulting from either different binding conformations or aggregates. The most strongly adsorbed dyes are less susceptible to displacement by chenodeoxycholate than those that are weakly adsorbed. While having no observable effect on dye coverage, multiple exposures of a TiO2 film to a dye solution substantially increased the fraction of strongly adsorbed dye as judged by the resistance of the adsorbed dye to displacement by chenodeoxycholate. Measurements of the open-circuit voltage as a function of the photocharge density, determined by infrared transmittance, showed that chenodeoxycholate not only shifts the conduction band edge to negative potentials, but also significantly increases the rate of recombination. The net effect of adding chenodeoxycholate is, however, to improve the photovoltage.     

Combined experimental and DFT-TDDFT computational study of photoelectrochemical cell ruthenium sensitizers

We report a combined experimental and computational study of several ruthenium(II) sensitizers originated from the [Ru(dcbpyH(2))(2)(NCS)(2)], N3, and [Ru(dcbpyH(2))(tdbpy)(NCS)(2)], N621, (dcbpyH(2) = 4,4'-dicarboxy-2,2'-bipyridine, tdbpy = 4,4'-tridecyl-2,2'-bipyridine) complexes. A purification procedure was developed to obtain pure N-bonded isomers of both types of sensitizers. The photovoltaic data of the purified N3 and N621 sensitizers adsorbed on TiO(2) films in their monoprotonated and diprotonated state, exhibited remarkable power conversion efficiency at 1 sun, 11.18 and 9.57%, respectively. An extensive Density Functional Theory (DFT)-Time Dependent DFT study of these sensitizers in solution was performed, investigating the effect of protonation of the terminal carboxylic groups and of the counterions on the electronic structure and optical properties of the dyes. The calculated absorption spectra are in good agreement with the experiment, thus allowing a detailed assignment of the UV-vis spectral features of the two types of dyes. The computed alignments of the molecular orbitals of the different complexes with the band edges of a model TiO(2) nanoparticle provide additional insights into the electronic factors governing the efficiency of dye-sensitized solar cell devices.     

Electronic optimization of heteroleptic Ru(II) bipyridine complexes by remote substituents: synthesis, characterization, and application to dye-sensitized solar cells

We prepared a series of new heteroleptic ruthenium(II) complexes, Ru(NCS)(2)LL' (3a-3e), where L is 4,4'-di(hydroxycarbonyl)-2,2'-bipyridine and L' is 4,4'-di(p-X-phenyl)-2,2'-pyridine (X = CN (a), F (b), H (c), OMe (d), and NMe(2) (e)), in an attempt to explore the structure-activity relationships in their photophysical and electrochemical behavior and in their performance in dye-sensitized solar cells (DSSCs). When substituent X is changed from electron-donating NMe(2) to electron-withdrawing CN, the absorption and emission maxima reveal systematic bathochromic shifts. The redox potentials of these dyes are also significantly influenced by X. The electronic properties of the dyes were theoretically analyzed using density functional theory calculations; the results show good correlations with the experimental results. The solar-cell performance of DSSCs based on dye-grafted nanocrystalline TiO(2) using 3a-3e and standard N3 (bis[(4,4'-carboxy-2,2'-bipyridine)(thiocyanato)]ruthenium(II)) were compared, revealing substantial dependences on the dye structures, particularly on the remote substituent X. The 3d-based device showed the best performance: η = 8.30%, J(SC) = 16.0 mA·cm(-2), V(OC) = 717 mV, and ff = 0.72. These values are better than N3-based device.     

Photovoltage improvements and recombination suppression by montmorillonite addition to PEO gel electrolyte for dye-sensitized solar cells

Montmorillonite (MMT) added to electrolytes has been reported in the literature to facilitate the transport of I(-)/I(3)(-), and improve the ionic conductivity and consequent photocurrent of dye-sensitized solar cells (DSCs). This paper firstly observes, investigates and reports that MMT addition to a poly(ethylene oxide) (PEO)-based gel electrolyte not only improves the ionic conductivity of the gel electrolyte, but also increases the photovoltage and decreases the dark current. From the results of electrochemical impedance spectroscopy (EIS) and transient photovoltage spectra, we evidence that MMT in the polymer gel electrolyte can efficiently retard the charge recombination that occurs at the TiO(2)/dye/electrolyte interfaces.     

Phenomenally high molar extinction coefficient sensitizer with "donor-acceptor" ligands for dye-sensitized solar cell applications

A phenomenally high molar extinction coefficient heteroleptic ruthenium(II) complex [Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-(4-{4-methyl-2,5-bis[3-methylbutoxy]styryl}-2,5-bis[3-methylbutoxy]-2,2'-bipyridine)(NCS) 2] ( DCSC13) was synthesized by incorporating donor-acceptor ligands. The absorption spectrum of the DCSC13 sensitizer is dominated by metal-to-ligand charge-transfer transitions (MLCT) in the visible region, with absorption maxima appearing at 442 and 554 nm. The lowest MLCT absorption bands are red-shifted, and the molar extinction coefficients of these bands are significantly higher at 72,100 and 30,600 M(-1) cm(-1), respectively, when compared to those of the analogous [Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-dimethyl-2,2'-bipyridine)(NCS)2] (N820) sensitizer. The DCSC13 complex, when anchored on nanocrystalline TiO 2 films, exhibited increased short-circuit photocurrent and consequent power-conversion efficiency when compared with the N820 sensitizer.     

Effect of chenodeoxycholic acid (CDCA) additive on phenothiazine dyes sensitized photovoltaic performance

The effects of chenodeoxycholic acid (CDCA) in a dye solution as a co-adsorbent on the photovoltaic performance of dye-sensitized solar cells (DSSCs) based on two organic dyes containing phenothiazine and triarylamine segments (P1 and P2) were investigated.It was found that the coadsorption of CDCA can hinder the formation of dye aggregates and improve electron injection yield and thus Jsc.This has also led to a rise in photovoltage,which is attributed to the decrease of charge recombination.The DSSC based ...     

The importance of dye chemistry and TiCl(4) surface treatment in the behavior of Al(2)O(3) recombination barrier layers deposited by atomic layer deposition in solid-state dye-sensitized solar cells

Atomic layer deposition (ALD) was used to fabricate Al(2)O(3) recombination barriers in solid-state dye-sensitized solar cells (ss-DSSCs) employing an organic hole transport material (HTM) for the first time. Al(2)O(3) recombination barriers of varying thickness were incorporated into efficient ss-DSSCs utilizing the Z907 dye adsorbed onto a 2 μm-thick nanoporous TiO(2) active layer and the HTM spiro-OMeTAD. The impact of Al(2)O(3) barriers was also studied in devices employing different dyes, with increased active layer thicknesses, and with substrates that did not undergo the TiCl(4) surface treatment. In all instances, electron lifetimes (as determined by transient photovoltage measurements) increased and dark current was suppressed after Al(2)O(3) deposition. However, only when the TiCl(4) treatment was eliminated did device efficiency increase; in all other instances efficiency decreased due to a drop in short-circuit current. These results are attributed in the former case to the similar effects of Al(2)O(3) ALD and the TiCl(4) surface treatment whereas the insulating properties of Al(2)O(3) hinder charge injection and lead to current loss in TiCl(4)-treated devices. The impact of Al(2)O(3) barrier layers was unaffected by doubling the active layer thickness or using an alternative ruthenium dye, but a metal-free donor-π-acceptor dye exhibited a much smaller decrease in current due to its higher excited state energy. We develop a model employing prior research on Al(2)O(3) growth and dye kinetics that successfully predicts the reduction in device current as a function of ALD cycles and is extendable to different dye-barrier systems.