You are on page 1of 10

Available online at www.sciencedirect.


Solar Energy Materials "Solar Cells te/solmat


Solar Energy Materials & Solar Cells 88 (2005) 1-10

Dye-sensitized Ti02 thin-film solar cell research at the National Renewable Energy Laboratory (NREL) *
Satyen K. Deb
National Renewable Energy Laboratory, Golden, CO 80401-3393, USA Received 30 October 2003; accepted 10 September 2004

Abstract The idea of dye-sensitization of inorganic materials has been around for a long time, and a vast amount of literature exists on this subject. The first studies of photo electrochemical effects in dye-sensitized Ti02 for solar energy conversion were carried out by Deb et al. (Unpublished Report on Project SECSC (Solar Energy Convertion and Storage cell) Optel Corporation, Princeton, NJ, 1975-76), in the mid-1970s. A breakthrough occurred in recent years when Graetzel (Nature 414 (200 I) 338) reported a photoelectrochemical solar cell in which a thin film based on nanoparticles of Ti02 was sensitized by a more efficient and stable dye system based on Ru(11)-complexes. Some of the key research issues that are currently being addressed at NREL include: device fabrication and characterization, role of structural properties of Ti02, electron transfer processes, novel ideas on dye-sensitization and light harvesting, and applications in optoelectronic devices. The current status and future direction of research and technology development are discussed. © 2004 Elsevier B.V. All rights reserved.
Keywords: Dye-sensitization; Ti02 solar cells; Electron transport; Dye-Ti02 interface; Photoelectrochromic device

*Paper presented at the ISES solar world congress, Gothenburg, Sweden. 14-19 June 2003. E"mail address: (S.K. Oeb)_ 0927-0248/$ - see front matter © 2004 Elsevier BY All rights reserved. doi: 10.1016/j.solmaL2004.09 .007

2 SK. The first use of a dye-sensitized TiOz particle and thin film in a PEC configuration (Fig. HQIQ. (ii) finding that the use of anatase instead of rutile structure of TiOl improved the conversion efficiency by 500%./°2. The sensitization of wide-bandgap semiconductors. Tsubomura eta!' in the 1970s achieved up to 1% conversion efficiency in dye-sensitized ZnOphotoelectrodes [4]. (vii) recognizing that the smaller the particle size of Ti021 the higher the surface area and Wavelength (om) Fig. SIS = in the electrolyte.5]. Significant progress was made in the performance of a TiOl PEC solar cell in several areas. by organic dyes was investigated by Gerischer and Tributsch in the late 1960s [2] and Hauffe et aJ. including: (i) establishing that the primary photoconversion process involved the creation or an electron-hole pair in TiOl (thin film/polycrystalline) by excitation with photon energy corresponding to the bandgap of Ti02. (vi) finding that tbe use of organic dyes such as N-methylphenazinium ion (Eastman Kodak) and other organic dyes extended the spectral response of TiOl from near UV to 500 om and thin-film CdS and Cd'Se extended the response up to 700 nm. OH. First dye-sensitized Ti02 PEe solar cell [4]. 1) was reported by Deb et al. such as ZnO. Fe4+ IFe3+. and use of small bandgap semiconductors to extend the spectral response characteristics of TiOz to longer wavelength. . and an extensive study has been made. Deb / Solar Enerqy Materials & Soiar Cells 88 (2005) 1-10 1. 1. doping with impurities. Introduction The use of dyes for the spectral sensitization of inorganic materials spans several decades. (v) investigating dye-sensitization. (iv) studying several redox couples such as 11/1-. in the early 1970s [3] for photoelectrochemical (PEe) processes. Fe2+ IFeH. (iii) finding that the use of platinized carbon electrode greatly improved the cell performance. in several US patents that were issued in 1978 [l. particularly on the dye-sensitization of AgBr for photographic applications.

the use of liquid electrolyte and long-term stability remained as barriers to further technology development. they achieved a major improvement in solar energy conversion efficiency of 11% in a dye-sensitized TiOz (anatase) thin-film solar cell [7]. sensitization by alternate dyes. dynamics of electron injection at the dye-Ti02 interface. 30-60% quantum efficiency. particle size. (ix) achieving up to I % power conversion efficiency. surface and interface states. Some of the key research issues addressed at NREL are the: role of morphology (porosity). the analog of metal-semiconductor Schottky-barrier devices. with support from the United States Department of Energy (US DOE). Si. GaAs. rutile). and major advances were made in improving the conversion efficiency. However. and (xi) using several inorganic semiconductors.g. and Ise up to 3--6mA.S. innovative ideas on all-solid-state devices. The Solar Energy Research Institute (SERI). and crystal structure (anatase vs. 2. effect of UV irradiation.the photosensitivity. dynamics of electron injection at the dye-Tifr. novel ideas on efficient light harvesting (photonic crystals). The current status ofDSSC technology has been documented in an excellent review by Arakawa and Hara [8]. and the PEC research program at SERI and elsewhere came to a grinding halt in preference to more promising thin-film photovoltaic (PV) solar cell research options.. The PEC approach to solar energy conversion. then shifted toward the use of narrow-bandgap semiconductors (e. NRELjDOE initiated a research program in DSSC and quickly achieved up to "-'9. (x) finding that the stability of dyes under optical irradiation caused a problem. CdSe) in conjunction with electrolytes. maintained a vigorous subcontracted PEC solar cell research program during the period of 1978-1982. with bandgaps lower than Ti02 as sensitizers (although the conversion efficiencies remained low) [5]. interface. The field of dye-sensitized solar cell (DSSC) research gained a renewed worldwide interest after Graetzel et al. and novel applications such as photoelectrochromic devices. effect of UV irradiation. novel ideas on charge transport and recombination kinetics. Ti02 thin film charge transport and recombination kinetics.2% conversion efficiency. osee project at NREL The DSSC project at NREL is a basic and applied research effort that is funded jointly by the US DOE Office of Science and Office of Energy Efficiency and . This remarkable accomplishment was demonstrated in a PEC device consisting of a nanocrystalline and mesoporous Ti02 (anatase) thin-film electrode sensitized by a stable Ru-terpyridine complex dye and an 1-/13 redox couple in non-aqueous solvent.K Deb / Solar Energy Materials & Solar Cells 88 (2005) 1-10 3 . at the Swiss Federal Institute of Technology (EPFL) reported the use of a Ru-based dye to achieve higher efficiency in a cell made of Ti02 nanoparticles [6]. predecessor of NREL. such as CdS and CdSe. Voe up to 900mV. Following this important development at EPFL. Recent results on some of these research topics will be highlighted briefly in this presentation. (viii) studying extensively a unique solar energy conversion and storage device involving Ti02 as the conversion electrode and thin film ofW03 as the storage electrode. Recently. surface and interface states.

Unthick film of nanocrystalline Ti02 particles (10-30 om in diameter) that contain a monolayer of adsorbed dye molecules.. The highest conversion efficiency of a DSSC achieved at NREL is 9. 2. there has to be sufficient interparticle connectivity so that Uquld ".2% (Jsc = 17.K Deb I Solar Energy Materials & Solar Cells 88 (2005) 1-10 Renewable Energy (EERE). PEC solar cell operational principle.899mAjcm2. The current status of DSSC efficiencies worldwide has been compiled by Arakawa and Hara [8}and is shown in Table 1. particle size.1. Even at such high levels of porosity. (b) Dye-sensitized uanoycrystalline TiO. the dye-coated particles are supported on a transparent conducting glass substrate (Sb or F-doped Sn02) [Fig./1-:. 2(b).. the excited dye molecules inject electrons efficiently into the Ti02 conduction band. DSSC device structure A typical photo electrode of a dye-sensitized PV cell consists of a 10-20-J. such as acetonitrile. The operational principle of a DSSC is shown in Fig. Morphology. redox couple in a non-aqueous electrolyte. to 1-. The injected electrons traverse the nanocrsytalline film with little loss and are collected at the conducting glass substrate.756V.2. (a) Dye-sensitized nanocrystalline TiD! PEC solar cell device structure. the electrons re-enter the cell at the counterelectrode and reduce 1-:. Upon photoexcitation of the cell. and FF=68%). A transparent counterelectrode is placed over the nanocrystalline Ti02. a brief overview of our research results is given. 2.1'IIIctro~yte Adsorb . and the edges of the cell are sealed. and crystal structure The TiOz thin film used in a typical DSSC consists of highly porous (50-65% porosity) interconnected particles of average diameter around 20 nm. In this section. After passing through the external circuit and delivering power to a load. The pores of the nanocrystalline Ti02 film are filled with a liquid electrolyte containing the 1. effecting charge separation. which then diffuses into the pores of the TiOz film to reduce the photooxidized dye back to its original state. 2. which compares favorably with the highest efficiency of ""II % reported by EPFL [7]. d dye rnolecUla& T~afu~pa~n~ co-un •• '" elQlctorQcJe {Teo} (a) Fig. A detailed procedure for the fabrication of the complete device structure has been discussed previously [9].4 S. . 2(a)]. Voc = 0.

EPFL EPFL-NREL Uppsala University. X-ray diffraction.40 20.71 1/(%) Light source AM 1. Ltd.2 8. USA: ISC: Ishihara Sangyo Co.5 AM 1.50 0. The short-circuit photocurrent in a rutile- .13 0.37 0.5 21mWcm-2 AM 1. 3) are remarkably similar.x.0 Jac (mA/cm2) \8.s.31 0.50 0. The SCM studies of the particle shape and size show that the surface area of the rutile film is about 25% less than that of anatase film. Deb I Solar Energy Materials & Solar Cells 88 (2005) 1-10 5 Table I Performance of dye-sensitized TiO~ solar cells Institute. NREL conducted a comparative study of anatase and rutile-based Ti02 solar cells. and scanning electron microscopy (SCM) were used to characterize the morphology and structural properties of the film. [9].20 Vac(mV) 720 740 610 721 Fill factor 0.17 1. UppsalajEPFL" ISC Osaka University.2 7.73 0.90 14. Raman spectroscopy. The average coordination number of a particle decreases from about 6.6-2. The absorption spectra of the films show that the rutile film contains about 35% less adsorbed dyes than the anatase film. 570 756 698 780 9.20 3..0 EPFL: Swiss Federal Institute of Technology. NREL NIMC EPFL-NIMC INAP Cell size (cm2) 0.5 AM 1.71 0. electrons can readily percolate without a major impediment.5 AM 1. Germany. even though the most stable form of Ti02 is the rutile structure. A typical film with a porosity of 60% has a coordination number of 4.5 630 .60 30.1 9.5 AM 1.68 0.5 ELH lamp AM 1.50 15.0 6. van de Lagemaat et al.6 10. It is generally recognized that in DSSC the preferred crystal structure is anatase. The current-voltage characteristics of the rutile. to have a quantitative understanding of the relationship between the film porosity and the local three-dimensional structure of nanoparticles.74 0.21 144. therefore. and the results appear to be in excellent agreement with the film morphology [10].20 18.71 0. which has superior light-scattering properties that are beneficial for effective light harvesting.9 lOA 6.and anatase-based DSSC (Fig.50 14.67 0. Japan: NIMC: National Institute of Materials and Chemical Research. "Measured by NREL.90 17. Nanocrystalline Ti02 thin films (12-llm thick) of both crystalline modifications were used to fabricate the solar cell structure by a process described in detail by Park et al.8 when the porosity increases from 40% to 80%. made a simulation study based on random packing of spheres. It is important. Switzerland: NREL: National Renewable Energy Laboratory. This provides sufficient pathways for electrons to move through the mesophorous Ti02 films without being constrained spatially. They have shown that a strong relationship exists between film porosity and the coordination number of the nanoparticles.00 0. Japan (former name of PCRC/AISn: INAP: Instit fur Angewandte Photovoltaik Gmbh.5 AM 1.25 0.4 7. At NREL.73 0. which means that electrons can move to 4 adjoining particles.3 6.

3. the total trap density of the film is about 1017 cm".and anatase-films of the same thickness (I 1. Electron transport in Ti02 DSSC Once the electrons are injected from the photoexcited dye molecules to the conduction band of Ti02 nanoparticles. the electron transport in electrolyte-filled Ti02 mesoporous film is due to am bipolar diffusion [16].s: Deb I Solar Energy Materials & Solar Cells 88 (2005) ]-10 16 r------------------------.Anatase -0- g . It is also found that non-thermalized electron transport is important when .5 urn) at one-sun illumination. based device of identical film thickness is about 30% lower than the anatase-based device. the random-walk model describes the electron transport process very well. which means that the electron diffusion is coupled to the ionic motion. this has been the subject of considerable current interest from the point of view of device optimization. shallow traps contribute significantly to electron transport. 2. which corresponds roughly to one trap per particle.3. their transport dynamics determine the charge-collection efficiency. because the microscopic electric field across the film is negligible due to screening by the electrolyte. Several important conclusions emerged from these studies: the transport of photo-injected electrons to the collector (TCO) occurs by diffusion as proposed earlier [13-15]. This result is very striking. the results have been verified by transient photocurrent measurements [12]. Comparison of the J-V characteristics of dye-sensitized rutile.6 s.~ <II '0 C :s o ~ Fig. particularly in view of the early development phase of the rutile-based DSSC. electron transport through porous films is limited by electron trapping near the Fermi level. which was attributed to the difference in surface area. A random-walk approach using a Monte Carlo-type procedure has been developed at NREL to model the electron transport dynamics of Ti02 and DSSC by taking into account the multiple trapping phenomena first proposed by Schwarzburg and Willig in 1991 [11].§ ~ «: ~ ~ E 12 10 8 6 4 2 0 0 100 200 300 400 500 600 700 800 Voltage (mV) Rutile -<>.

this phenomenon is still very poorly understood.' Femtosecond pump-probe time-resolved spectroscopy has been used at NREL to study the electron injection kinetics at Ti02/Nrdye interfaces following photo excitation of the dye [17]. (3) completely reversible. in other words. UV irradiation effect on DSSC UV irradiation of a DSSe leads to a remarkable increase (l0-45-fold) in photoconversion efficiency [18]. such as those containing Nj-dye. (2) weak in more efficient cells. Alternative dyes A major effort has been directed toward finding an alternate dye that is based on both metal complexes and purely organic dyes for sensitizing Ti02 solar cells. Under approximately one-sun illumination (75mW/cm2. Some key features of this effect are that it is: (1) significant in non-Li + -ion-containing electrolyte.Ti02 interface has been the subject of considerable recent investigations. but can be regenerated by subsequent reassembling of the cell. The experimental results suggest that the bulk of this effect is related to the UV-induced generation of a large density of surface states. The ultrafast injection time is consistent with nearly 100% quantum efficiency of photon-to-electron conversion. and enhanced carrier transport. a short-circuit current of 0.5. 2. In principle. 2. the long wavelength peak at . interface One of the major factors that contribute to the high-energy conversion efficiency in DSSe is generally attributed to the ultra-fast electron injection from dye to the Ti02 conduction band and a much slower reverseprocess. (4) able to disappear on exposure to ambient conditions. At tbis time. A>400nm). particularly those based on perylene-based dye.K. which is the normal operating condition of Dsse. In an effort to replace the central Ru(ll) ion by another transition metal that could be potentially cheaper. 2. However. The measurement established an upper limit of electron injection time to "-"50fs.25mA/cm2 and a Voc = 360 mV were observed in a cell that has not been optimized. NREL researchers have examined Fe(ll)-bipyridyl complexes and observed substantial sensitization for the first time [19]. the Ru-complexes (Nj-dye) remain the most efficient dye. and (6) associated with mesoporous Ti02 and not with the dye or electrolyte. However.S.6. Deb / Solar Energy Materials & Solar Cells 88 (2005) 1-10 7 the light enters the cell from the collector side. the effect can be due to any of the following factors: increased photoinjection efficiency. the Fe-complex has intense visible absorption with peak positions at 430 and 635 nm and a shoulder at 550 nm. Analogous to Rufl I) bipyridyl complexes. The dynamics of electron injection at the dye. Electron injection of dye-TcO. decreased recombination. the response characteristic is band selective. The spectral response of photocurrent corresponds to the absorption spectra of the dye.4. (5) known that air and water are not involved in this effect. The effect is best observed in cells that are performing poorly.

whether organic or inorganic complexes. Deb / Solar Energy Materials & Solar Cells 88 (2005) 1-10 635 nm is much weaker than the 430-nm peaks. Therefore. One of the ideas that are currently being investigated at NREL is the use of inorganic semiconductor nanoparticles. significant enhancement of efficiency was observed on short-time U'V-irradiation. This implies that electrons are being transferred to the Ti02 nanoparticles before they thermalize to the band edge of the InP. The spectral response of the short-circuit photocurrent in a bilayer electrode was increased by 26% relative to the conventional DSSC structure in the wavelength range 540-750nm by adjusting the position of stopband maximum of photonic crystal layer to 610 nm. as reviewed by Arakawa and Hara [8]. A two-layer structure consisting of a photonic Ti02 crystal and the dyesensitized nanostructured TiOl film was fabricated by a process described in detail by Nishimura et al. such as quantum dots (QDs). Within the confines of quantum-size effect. 2. This work followed a prediction made by Usami [21]. Novel approach to sensitization The use of dyes. but the efficiency was poor. Recent studies on QD-Ti02 solar cells at NREL show photoresponse extending up to 900 om. as a sensitizer of Ti02. Japanese researchers have achieved up to 6% efficiency using conmarin dye with performance characteristics approaching that of cells based on Ru-cornplex dyes. it was possible to significantly enhance the light absorption in the dye at longer wavelength. however. Novel ideas on light harvesting A novel idea of coupling a photonic crystal with the conventional dye-sensitized nanocrystalline TiOl film to enhance the spectral response to the red end of the dye absorption band was pursued recently in a collaborative research effort involving NREL and Penn State University [20).7. These initial results are very exciting. The possibility also exists for efficient hot-carrier injection due to slow cooling of hot electrons in quantum dots and carrier multiplication by impact ionization. By tuning the position of the stopband maximum by controlling the filling fraction if TiOl in the inverse opal structure. Some preliminary experiments On transient absorption measurements at the band edge show that the addition of conoidal Ti02 nanoparticIes to the solution containing InP QDs decreases the magnitude of the IS absorption bleach at 658 nm.8 S. This asymmetric behavior is not clearly understood. can be modulated over a wide spectral range. in DSSC raises some concern with regard to the long-term photostability. its optical absorption. 2. (20). This points to a promising opportunity for using some of the photostable organic dyes as a sensitizer. the absorption strength and the photogenerated carrier lifetime can be enhanced significantly.8. K. Some work has been done on organic dyes like Perlene dyes. The electron transfer process appears to saturate once a certain concentration ratio of Ti02 and QDs is reached. hence. there is room for innovation in this area of research. Moreover. and a significant improvement of the two-layer structure is possible to further improve the cell efficiency. the bandgap of a semiconductor nanoparticJe and. .

we were able to combine just onehalf of a typical dye-sensitized solar cell with one-half of a typical electrochromic cell [23]. considerable research is under way to the develop an all solid-state DSSC. and Prof. Chen. 2.SK. therefore. expelling Li + from the W03 film and transferring electrons.A. Some of the avenues that should be pursued are: pushing the energy conversion efficiency to 15%. The work at NREL is . Deb I Solar Energy Materials & Solar Cells 88 (2005) 1-10 9 2.-G.J. Some of these concepts are currently under investigation at NREL. the photovoltage produced by the dye-sensitized electrode drives electrons and compensating Li + cations into the W03 film. the potential of the charged WO) film causes the coloration process to reverse.J. resulting in a colored electrochromic film. Ellingson. Because of the complementary nature of the two technologies.D. Future R &D directions Major advances have been made in recent years in this technology since the first DSSC devices based on Ti02 were fabricated in the mid-I 970s. When illumination ceases. A. Frank. S. B. pursuing radically new ideas such as use of QDs for spectral sensitization. E. Many opportunities and challenges exist for doing innovative research and technology development to bring this potentially low-cost device to commercial success. Solid-state DSSC One of the areas of concern about the large-scale commercialization of DSSC is _ use of liquid electrolyte. J. solving issues related to large-scale module fabrication. R. In this configuration. van de Lagemaat. N. back to the oxidized iodine species in solution. The 12 required in the electrolyte for high-power solar cells was eliminated in order to maximize the photovoltage. and a low concentration of a more transparent dye was employed as the sensitizer. Benkstein. Generally. S.11. The electrochromic film was deposited on the counterelectrode of a dyesensitized solar-cell and lithium ions were added to the electrolyte solution. A. developing all solid-state devices in preference to the liquid electrolyte that is currently used. Mallouk of Penn State University. and addressing long-term stability issues. and (2) use of a hole-conducting polymer. Some of them are: K. two approaches are being used: (1) the use of inorganic hole-conducting semiconductors such as CuI or CuSCN in a device configuration like Ti02/N3-dye/CuIJAu. 2. Acknowledgements The work presented here is largely due to contributions of many colleagues at NREL and their collaborators. Photoelectrochromic device A dye-sensitized solar cell electrode was recently combined with an electrochromic film to produce what we called a "photoelectrochromic" window [22].10. Gregg. via the external circuit. Ferrere. and. Nozik. T.9.A. Park.

Phys. van de Lagemaat. B 105 (2001) 11194-11205. B. [6J R O'Regan. Nature 353 (1991) 737-740. M. Phys.e. Optel Corporation. Sodergren. Phys. Phys. [21] A Usami. G. Shaw. H. A. B 107 (2003) 2019-3029. K. Chern. 58 (1991) 2520.4080488. J. Frank. Rammurthy (Eds. Z. Graetzel. [18) B.A Schiff.-G. Nomuray. TE. A. Am. 1978. [15] F. Asbury.J. Phys.D. Oskarn. Phys. Lett. K. 2003. and photophysics. T. [16] N. Ferrere. Photoelectrochernical Cells. Hagfeldt.A. Dloczik. Am. Chern. E. van de Lagemaat. New experiments on the sensitization of zinc oxide by means of the electrochemical cell technique. Chern. Nozik. Olsson.K Deb / Solar Energy Materials & Solar Cells 88 (2005) 1-10 supported by the US DOE/Office of Basic Energy Sciences and the US DOE/Office of Energy Efficiency and Renewable Energy under contract #DE-AC-36-99G01033. [19] S. O. Nishimura.J. BIOI (1997) 10281. S. Ellingson. J. 212 (1999) 77-84.J. Chern.10 S.I. 1995. [Il] K. in: K. Schwarzburg. A. 98 (1994) 5552. Meyer. B 104 (2000) 3930. 72 (1968) 437-445. L. Danzmann. H. Chern. J. Redmond.2'-bipyridine-4. Park.J. [22] B. Chen. Soc. [8] H. IJ4] L. 1. B 105 (2001) 12433-12436. Matsumara.J. AJ. .x.B. Witzke. Chern. Gregg. and 4118247. Soc. Bd S. Range. [9] N.-G. Marcel Dekker. Nonthermalized electron transport in dye-sensitized nanocrystalline TiOl films. [4J H. S. Princeton. Phys. A. S. J. S. 277 (1997) 105. Current status of dye-sensitized solar cells. Unpublished report on project SECSAC (Solar Energy Conversion and Storage Ceil). J.D. Ferrere. Frank. 1975-76. vol. Cao. References [1] S. N.). K. Tsubomura. [10] 1. Chern. J. [17) R. Deb. Sub-picosecond injection of electrons from excited [Ru-complex dye] into Ti02 using transient mid-infrared spectroscopy. [5] S. B 104 (2000) 8989-8994. [2] H. M. Chen. Benkstein.J. Kopidakis. Pusch. S. F. Chern. Soc. 117 (1970) 993-999. L. Relation between particle coordination number and porosity in nanoparticle films: implications to dye-sensitized solar cells. B. Appl. AN. Gregg. 10. Chern. [12] 1. Elecrochemische Untersuchungen zur spectra leu sensibilisierung von ZnO-Einkristalien. J. N. Photosensitization of Ti02 by [Fell(2. (2003). J. Mallouk. J. 1.. New York. P. J. Phys. Uhlendorf.J. Peter. Phys. Lauermann. [20J S. J.A. Phys. Phys. Gerischer. Frank. Graetzel. Comparison of dye-sensitized rutile and anatase-based Ti02 solar cells.A Lewis. O. 1. B 100 (1996) 17021. H. Bee Bunsenges. Park. Abrams. high efficiency solar cell based on dye-sensitized colloidal Ti02 films.M. Amsterdam. 123-171. Benkstein. Standing wave enhancement of red absorbance and photocurrent in dyesensitized Ti02 photoelectrodes coupled to photonic crystals. Endeavour 21 (1997) 52-55. Phys. [13] S. A. Electrochem. Searson.A. van de Lagemaat. Ham. G. Halaoui. Ponomarev. H. 1. Elsevier.4'-dicarboxylic acidMCNMCN)2]: band selective electron injection from ultra-short-Jived excited states. Chern. Lindquist. US Patents 4117510. Chern. van de Lagemaat.N. Frank. Volz. A.I. Nature 414 (2001) 338-344.4118246. pp. Chen. [23] e. Granqvist. Chern. Ileperuma.-E. 1. Ghosh. Nature 261 (1976) 402. Enhanced dye-sensitized pbotoconversion efficiency via reversible production of UV-induced surface states in nanoporous Ti02. Frank. Ferrere. Handbook of Inorganic Electrochromic Materials. semiconductor photochemistry. T Lian. [7] M.G. [3) K. Deb. 120 (1998) 843-844. Tributsch. J. E. van de Lagernaat. Schanze. Photoelectrochromic cells and their applications. A low-cost. N.J. Chern. Hauffe. H. Gregg. NJ.A. Amamiya.K. Witzke.-G. Willig. Arakawa. r. 1. s. V. Lett.