In this study, we prepare pure WO3 inverse opal(IO) film with a thickness of approximately 3 μm by electrodeposition, and an ultra-thin TiO2 layer having a thickness of 2 nm is deposited on WO3 IO film by atomic layer deposition. Both sets of photoelectrochemical properties are evaluated after developing dye-sensitized solar cells(DSSCs). In addition, morphological, crystalline and optical properties of the developed films are evaluated through field-emission scanning electron microscopy(FE-SEM), High-resolution transmission electron microscopy(HR-TEM), X-ray diffraction(XRD) and UV/ visible/infrared spectrophotometry. In particular, pure WO3 IO based DSSCs show low VOC, JSC and fill factor of 0.25 V, 0.89 mA/cm2 and 18.9 %, achieving an efficiency of 0.04 %, whereas the TiO2/WO3 IO based DSSCs exhibit VOC, JSC and fill factor of 0.57 V, 1.18 mA/cm2 and 50.1 %, revealing an overall conversion efficiency of 0.34 %, probably attributable to the high dye adsorption and suppressed charge recombination reaction.

염료감응형 태양전지는 지속 가능한 에너지원으로서 많은 관심을 받고 있다. 염료감응형 태양전지의 효율과 장기 안정성은 전극 물질과 전해질에 의해 크게 영향을 받는데 본 총설에서는 전해질에 초점을 두어 서술하고자 한다. 고분자 전해질막은 염료감응형 태양전지에서 기존의 액체 전해질을 대체하기 위한 대안으로 제시되어 왔다. 기존의 액체 전해질은 높 은 효율을 나타낼 수 있지만 장기적인 안정성 문제와 누액 문제로 인해 고분자 전해질막에 관한 관심은 지속적으로 증가하고 있으며 매년 이와 관련된 논문들이 활발히 보고되고 있다. 본 총설은 염료감응형 태양전지를 위한 고분자 전해질막의 개념과 개발에 대한 간단한 설명을 다루고 있으며 고분자 매트릭스의 개질, 유-무기 가소제 및 이온성 액체와 같은 첨가제의 도입에 따른 염료감응형 태양전지의 효율과 전기화학적 특성에 대해서도 최근의 연구들이 정리되어 있다.

Flexible dye-sensitized solar cells using binder free TiO2 paste for low temperature sintering are developed. In this paste a small amount of titanium gel is added to a paste of TiO2 nanoparticle. Analysis of titanium gel paste prepared at 150 ℃ shows that it has a pure anatase phase in XRD and mesoporous structure in SEM. The formation of the titanium gel 1- 2 nm coated layer is confirmed by comparing the TEM image analysis of the titanium gel paste and the pristine paste. This coating layer improves the excited electron transfer and electrical contact between particles. The J-V curves of the organic binder DSSCs fabricated at 150℃ shows a current density of 0.12 mA/cm2 and an open-circuit voltage of 0.47 V, while the titanium gel DSSCs improves electrical characteristics to 5.04 mA/cm2 and 0.74 V. As a result, the photoelectric conversion efficiency of the organic binder DSSC prepared at low temperature is as low as 0.02 %, but the titanium gel paste DSSCs has a measured effciency of 2.76%.

Uniform TiO2 blocking layers (BLs) are fabricated using ultrasonic spray pyrolysis deposition (USPD) method. To improve the photovoltaic performance of dye-sensitized solar cells (DSSCs), the BL thickness is controlled by using USPD times of 0, 20, 60, and 100 min, creating TiO2 BLs of 0, 40, 70, and 100 nm, respectively, in average thickness on fluorine-doped tin oxide (FTO) glass. Compared to the other samples, the DSSC containing the uniform TiO2 BL of 70 nm in thickness shows a superior power conversion efficiency of 7.58±0.20% because of the suppression of electron recombination by the effect of the optimized thickness. The performance improvement is mainly attributed to the increased open-circuit voltage (0.77±0.02 V) achieved by the increased Fermi energy levels of the working electrodes and the improved short-circuit current density (15.67±0.43 mA/cm2) by efficient electron transfer pathways. Therefore, optimized TiO2 BLs fabricated by USPD may allow performance improvements in DSSCs.

Ni nanoparticles (NPs)-graphitic carbon nanofiber (GCNF) composites were fabricated using an electrospinning method. The amounts of Ni precursor used as catalyst for the catalytic graphitization were controlled at 0, 2, 5, and 8 wt% to improve the photovoltaic performances of the nanoparticles and make them suitable for use as counter electrodes for dyesensitized solar cells (DSSCs). As a result, Ni NPs-GCNF composites that were fabricated with 8 wt% Ni precursors showed a high circuit voltage (0.73 V), high photocurrent density (14.26 mA/cm2), and superb power-conversion efficiency (6.72 %) when compared to those characteristics of other samples. These performance improvements can be attributed to the reduced charge transport resistance that results from the synergetic effect of the superior catalytic activity of Ni NPs and the efficient charge transfer due to the formation of GCNF with high electrical conductivity. Thus, Ni NPs-GCNF composites may be used as promising counter electrodes in DSSCs.

Ni nanoparticles (NPs)-graphitic carbon nanofiber (GCNF) composites were fabricated using an electrospinning method. The amounts of Ni precursor used as catalyst for the catalytic graphitization were controlled at 0, 2, 5, and 8 wt% to improve the photovoltaic performances of the nanoparticles and make them suitable for use as counter electrodes for dyesensitized solar cells (DSSCs). As a result, Ni NPs-GCNF composites that were fabricated with 8 wt% Ni precursors showed a high circuit voltage (0.73 V), high photocurrent density (14.26 mA/cm2), and superb power-conversion efficiency (6.72 %) when compared to those characteristics of other samples. These performance improvements can be attributed to the reduced charge transport resistance that results from the synergetic effect of the superior catalytic activity of Ni NPs and the efficient charge transfer due to the formation of GCNF with high electrical conductivity. Thus, Ni NPs-GCNF composites may be used as promising counter electrodes in DSSCs.

Octahedral Co3O4/carbon nanofiber (CNF) composites are fabricated using electrospinning and hydrothermal methods. Their morphological characteristics, chemical bonding states, and electrochemical properties are used to demonstrate the improved photovoltaic properties of the samples. Octahedral Co3O4 grown on CNFs is based on metallic Co nanoparticles acting as seeds in the CNFs, which seeds are directly related to the high performance of DSSCs. The octahedral Co3O4/CNFs composites exhibit high photocurrent density (12.73 mA/m2), superb fill factor (62.1 %), and excellent power conversion efficiency (5.61 %) compared to those characteristics of commercial Co3O4, conventional CNFs, and metallic Co-seed/CNFs. These results can be described as stemmnig from the synergistic effect of the porous and graphitized matrix formed by catalytic graphitization using the metal cobalt catalyst on CNFs, which leads to an increase in the catalytic activity for the reduction of triiodide ions. Therefore, octahedral Co3O4/CNFs composites can be used as a counter electrode for Pt-free dye-sensitized solar cells.

Carbon nanofiber (CNF) composites coated with spindle-shaped Fe2O3 nanoparticles (NPs) are fabricated by a combination of an electrospinning method and a hydrothermal method, and their morphological, structural, and chemical properties are measured by field-emission scanning electron microscopy, transmission electron microscopy, Xray diffraction, and X-ray photoelectron spectroscopy. For comparison, CNFs and spindle-shaped Fe2O3 NPs are prepared by either an electrospinning method or a hydrothermal method, respectively. Dye-sensitized solar cells (DSSCs) fabricated with the composites exhibit enhanced open circuit voltage (0.70 V), short-circuit current density (12.82 mA/cm2), fill factor (61.30%), and power conversion efficiency (5.52%) compared to those of the CNFs (0.66 V, 11.61 mA/cm2, 51.96%, and 3.97%) and spindle-shaped Fe2O3 NPs (0.67 V, 11.45 mA/cm2, 50.17%, and 3.86%). This performance improvement can be attributed to a synergistic effect of a superb catalytic reaction of spindle-shaped Fe2O3 NPs and efficient charge transfer relative to the one-dimensional nanostructure of the CNFs. Therefore, spindle-shaped Fe2O3-NPcoated CNF composites may be proposed as a potential alternative material for low-cost counter electrodes in DSSCs.

We prepared polymethyl methacrylate (PMMA) beads with a particle size of 80 nm to improve the energy conversion efficiency (ECE) by increasing the effective surface area and the dye absorption ability of the working electrodes (WEs) in a dye sensitized solar cell (DSSC). We prepared the TiO2 layer with PMMA beads of 0.0~1.0 wt%; then, finally, a DSSC with 0.45 cm2 active area was obtained. Optical microscopy, transmission electron microscopy, field emission scanning electron microscopy, and atomic force microscopy were used to characterize the microstructure of the TiO2 layer with PMMA. UV-VIS-NIR was used to determine the optical absorbance of the WEs with PMMA. A solar simulator and a potentiostat were used to determine the photovoltaic properties of the PMMA-added DSSC. Analysis of the microstructure showed that pores of 200 nm were formed by the decomposition of PMMA. Also, root mean square values linearly increased as more PMMA was added. The absorbance in the visible light regime was found to increase as the degree of PMMA dispersion increased. The ECE increased from 4.91% to 5.35% when the amount of PMMA beads added was increased from 0.0 to 0.4 wt%. However, the ECE decreased when more than 0.6 wt% of PMMA was added. Thus, adding a proper amount of PMMA to the TiO2 layer was determined to be an effective method for improving the ECE of a DSSC.

Co-embedded graphitic porous carbon nanofibers(Co-GPCNFs) are synthesized by using an electrospinning method. Their morphological, structural, electrochemical, and photovoltaic properties are investigated. To obtain the optimum condition of Co-GPCNFs for dye-sensitized solar cells(DSSCs), the amount of cobalt precursor in an electrospinning solutuion are controlled to be 0 wt%(conventional CNFs), 1 wt%(sample A), and 3 wt%(sample B). Among them, sample B exhibited a high degree of graphitization and porous structure compared to conventional CNFs and sample A, which result in the performance improvement of DSSCs. Therefore, sample B showed a high current density(JSC, 12.88 mA/cm2) and excellent power conversion efficiency(PCE, 5.33 %) than those of conventional CNFs(12.00 mA/cm2, 3.78 %). This result can be explained by combined effects of the increased contact area between the electrode and elecytolyte caused by improved porosity and the increased conductivity caused by the formation of a high degree of graphitization. Thus, the Co-GPCNFs may be used as a promising alternative of Pt-free counter electrode in DSSCs.

Nitrogen-doped ZnO nanoparticle-carbon nanofiber composites were prepared using electrospinning. As the relative amounts of N-doped ZnO nanoparticles in the composites were controlled to levels of 3.4, 9.6, and 13.8 wt%, the morphological, structural, and chemical properties of the composites were characterized by means of field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). In particular, the carbon nanofiber composites containing 13.8 wt% N-doped ZnO nanoparticles exhibited superior catalytic properties, making them suitable for use as counter electrodes in dye-sensitized solar cells (DSSCs). This result can be attributed to the enhanced surface roughness of the composites, which offers sites for I3- ion reductions and the formation of Zn3N2 phases that facilitate electron transfer. Therefore, DSSCs fabricated with 13.8 wt% N-doped ZnO nanoparticle-carbon nanofiber composites showed high current density (16.3mA/cm2), high fill factor (57.8%), and excellent power-conversion efficiency (6.69%); at the same time, these DSSCs displayed power-conversion efficiency almost identical to that of DSSCs fabricated with a pure Pt counter electrode (6.57%).

염료감응형 태양전지를 위한 겔 고분자 전해질막을 제조하였다. 고분자물질로는 Poly(ethylene oxide) (PEO)를 사용하였으며, 가소제로서 poly(ethylene glycol) (PEG)을 첨가하였고, 전해질염 및 I-/I3-의 공급원으로서 KI 및 I2를 첨가하여 고분자 전해질막을 제조하였으며, 이와 같은 고분자 전해질막을 바탕으로 염료감응형 태양전지를 제조하였다. 고분자 전해질 내의 가소제로서의 PEG는 95%의 함량으로 주입되었으며, 전해질 내의 EO 1 mole 당 KI mole 수([KI]/[EO] 비)가 0.022, 0.044, 0.066 및 0.088이 되도록 KI가 주입되었다. 이러한 방식으로 제조된 겔 전해질막은 상온에서 왁스(wax) 형태를 보였다. 낮은 KI 함량의 영역에서는 KI 함량이 증가하면서 전해질막을 통한 이온전도도가 증가하였으며, [KI]/[EO]비가 0.066인 때에 이온전도도는 최대값을 보인 후 0.088로 증가하면서 이온전도도는 감소하였다. 염료감응형 태양전지에 있어서는 고분자 전해질막 내의 KI 함량이 증가하면서 VOC는 지속적으로 감소하였다. 반면, JSC의 경우 낮은 KI 함량의 범위에서는 KI 함량이 증가하면서 JSC는 증가하였으며 [KI]/[EO]비가 0.044인 때에 JSC가 최대값을 보인 후 그 이상의 높은 범위에서는 KI함량의 증가에 따라 JSC는 감소하였다.

원자전달 라디칼 중합(ATRP)에 의해 poly(vinyl chloride) (PVC) 주사슬과 poly(styrene sulfonic acid) (PSSA) 곁사슬로 되어있는 양쪽성 PVC-g-PSSA 가지형 공중합체를 합성하였다. PVC-g-PSSA 가지형 공중합체 고분자를 템플레이트로 사용하고 졸겔법을 적용하여, 결정성 아타네제상의 미세기공 이산화티타튬 필름을 제조하였다. TiO2 전구체인 TTIP를 친수성인 PSSA 영역과 선택적으로 작용시켜 TiO2 메조기공 필름을 성장하였으며, 이를 주사전자 현미경 (SEM)과 엑스레이회절 (XRD)분석을 통해 분석하였다. 스핀코팅 횟수와 P25 도입에 따른 염료감응 태양전지 성능을 체계적으로 분석하였다. 그 결과 준고체 고분자 전해질을 이용하였을 때, 100 mW/㎠ 조건에서 에너지 변환 효율이 2.7%에 이르렀다.

The hybrid structured photo-electrode for dye-sensitized solar cells was fabricated based on the composites of nanoparticles and nanowires. Three samples with different hybrid structures were prepared with 17 vol%, 43 vol%, and 100 vol% nanowires. The energy conversion efficiency was enhanced from 5.54% for pure nanoparticle cells to 6.01% for the hybrid structure with 17 vol% nanowires. For the hybrid structured layers with high nanowires concentration (43 vol% and 100 vol%), the efficiency decreased with the nanowire concentration, because of the decrease of specific surface area, and of thus decreased current density. The random orientations of nanowires can be preserved by the doctor blade process, resulted in the enhanced efficiency. The hybrid structured layer can possess the advantages of the high surface area of nanoparticles and the rapid electron transport rate and the light scattering effect of nanowires.

To fabricate TiO2 nanoparticle-based dye sensitized solar cells (DSSCs) at a low-temperature, DSSCs were fabricated using hydropolymer and ZnO nanoparticles composites for the electron transport layer around a low-temperature (200˚C). ZnO nanoparticle with 20 nm and 60 nm diameter were used and Pt was deposited as a counter electrode on ITO/glass using an RF magnetron sputtering. We investigate the effect of ZnO nanoparticle concentration in hydropolymer and ZnO nanoparticle solution on the photoconversion performance of the low temperature fabricated (200˚C) DSSCs. Using cis-bis(isothiocyanato)bis(2,20 bipyridy1-4,40 dicarboxylato) ruthenium (II) bis-tetrabutylammonium (N719) dye as a sensitizer, the corresponding device performance and photo-physical characteristics are investigated through conventional physical characterization techniques. The effect of thickness of the ZnO photoelectrode and the morphology of the ZnO nanoparticles with the variations of hydropolymer to ZnO ratio on the photoconversion performance are also investigated. The morphology of the ZnO layer after sintering was examined using a field emission scanning electron microscope (FE-SEM). 60 nm ZnO nanoparticle DSSCs showed an incident photon-to-current conversion efficiency (IPCE) value of about 7% higher than that of 20 nm ZnO nanoparticle DSSCs. The maximum parameters of the short circuit current density (Jsc), the open circuit potential (Voc), fill factor (ff), and efficiency (η) in the 60 nm ZnO nanoparticle-based DSSC devices were 4.93 mA/cm2, 0.56V, 0.40, and 1.12%, respectively.

염료감응형 태양전지를 위한 고분자 전해질막을 제조하였다. 고분자물질로는 Poly(ethylene oxide) (PEO)를 사용하였으며, 가소제로서 poly(ethylene glycol) (PEG)를 첨가하였고, 전해질염 및 I - /I3 - ,의 공급원으로서 KI 및 I2를 첨가하여 고분자 전해질막을 제조하였으며, 이와 같은 고분자 전해질막을 바탕으로 염료감응형 태양전지를 제조하였다. 고분자 전해질 내의 가소제로서의 PEG 함량은 0%에서 85%의 범위로 변화하였다. 이러한 PEG 함량 전 구간에서 고분자 전해질막은 그 형태를 자체적으로 유지하는(self supporting) 완벽한 고체 전해질막의 형태로 제조되었다. PEG 함량이 증가하면서 전해질막을 통한 이온전도도와 I3- 이온의 확산도계수는 증가하였다. 염료감응형 태양전지에 있어서는 고분자 전해질막 내의 PEG 함량이 증가하면서 그 효율이 증가함을 볼 수 있었다.

In the fabrication of dye-sensitized solar cells (DSSCs), carbon counter electrode has been tested for replacing the platinum counter electrode which has two drawbacks: limited surface area and high material cost. Poor mechanical stability of carbon layer due to weak bonding strength to electrically conductive TCO (transparent conducting oxide) glass substrate is a crucial barrier for practical application of carbon counter electrode. In the present study a carbon counter electrode with high conversion efficiency, comparable to Pt counter electrode, could be fabricated by adaption of a bonding layer between particulate carbon material and TCO substrate.

Dye-sensitized solar cells(DSSCs) have been under investigation for the past decade due to their attractive features such as high energy conversion efficiency and low production costs. The basis for energy conversion in the injection of electrons from a photoexcited stateof a dye sensitizer into the conduction band of the nanocrystalline semiconductor upon absorption of light. It is believed that the DSSC is one of the most promising technologies to solve the significant energy problems. In this article, the development trends and perspective of DSSCs were reviewed.