• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.02a
• /
• pp.434-436
• /
• 2013

Ga-doped ZnO (GZO) was substitutes of the SnO2:F films on soda lime glass substrate in the photovoltaic devices such as CIGS, CdTe and DSSC due to good properties and low cost. However, it was reported that the electrical resistivity of GZO is unstable above $300^{\circ}C$ in air atmosphere. To improve thermal stability of GZO thin films at high temperature above $300^{\circ}C$ an $TiO_2$ thin film was deposited on the top of GZO thin films as a barrier layer by Pulsed Laser Deposition (PLD) method. $TiO_2$ thin films were deposited at various thicknesses from 25 nm to 100 nm. Subsequently, these films were annealed at temperature of $300^{\circ}C$, $400^{\circ}C$, $500^{\circ}C$ in air atmosphere for 20 min. The XRD measurement results showed all the films had a preferentially oriented ( 0 0 2 ) peak, and the intensity of ( 0 0 2 ) peak nearly did not change both GZO (300 nm) single layer and $TiO_2$ (50 nm)/GZO (300 nm) double layer. The resistivity of GZO (300 nm) single layer increased from $7.6{\times}10^{-4}{\Omega}m$ (RT) to $7.7{\times}10^{-2}{\Omega}m$ ($500^{\circ}C$). However, in the case of the $TiO_2$ (50 nm)/GZO (300 nm) double layer, resistivity showed small change from $7.9{\times}10^{-4}{\Omega}m$ (RT) to $5.2{\times}10^{-3}{\Omega}m$ ($500^{\circ}C$). Meanwhile, the average transmittance of all the films exceeded 80% in the visible spectrum, which suggests that these films will be suitable for photovoltaic devices.

• Korean Journal of Materials Research
• /
• v.32 no.11
• /
• pp.481-488
• /
• 2022

The Cu₂ZnSn(S_xSe_1-x)₄ (CZTSSe) absorbers are promising thin film solar cells (TFSCs) materials, to replace existing Cu(In,Ga)Se₂ (CIGS) and CdTe photovoltaic technology. However, the best reported efficiency for a CZTSSe device, of 13.6 %, is still too low for commercial use. Recently, partially replacing the Zn²⁺ element with a Cd²⁺element has attracting attention as one of the promising strategies for improving the photovoltaic characteristics of the CZTSSe TFSCs. Cd²⁺ elements are known to improve the grain size of the CZTSSe absorber thin films and improve optoelectronic properties by suppressing potential defects, causing short-circuit current (J_sc) loss. In this study, the structural, compositional, and morphological characteristics of CZTSSe and CZCTSSe thin films were investigated using X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), and Field-emission scanning electron microscopy (FE-SEM), respectively. The FE-SEM images revealed that the grain size improved with increasing Cd²⁺ alloying in the CZTSSe thin films. Moreover, there was a slight decrease in small grain distribution as well as voids near the CZTSSe/Mo interface after Cd²⁺ alloying. The solar cells prepared using the most promising CZTSSe absorber thin films with Cd²⁺ alloying (8 min. 30 sec.) exhibited a power conversion efficiency (PCE) of 9.33 %, J_sc of 34.0 mA/cm², and fill factor (FF) of 62.7 %, respectively.

• Korean Journal of Metals and Materials
• /
• v.49 no.2
• /
• pp.187-191
• /
• 2011

In order to obtain a suitable back contacting electrode for $Cu(InGa)Se_2$-based photovoltaic devices, a molybdenum thin film was deposited using a chemical vapor transport (CVT) during the hydrogen reduction of $MoO_3$ powder. A $MoO_2$ thin film was successfully deposited on substrates by using the CVT of volatile $MoO_3(OH)_2$ at $550^{\circ}C$ for 60 min in a $H_2$ atmosphere. The Mo thin film was obtained by reduction of $MoO_2$ at $650^{\circ}C$ in a $H_2$ atmosphere. The Mo thin film on the substrate presented a low sheet resistance of approximately $1{\Omega}/sq$.

• Journal of Ceramic Processing Research
• /
• v.13 no.spc1
• /
• pp.140-144
• /
• 2012

Ga-doped ZnO (GZO) was a limit of application on the photovoltaic devices such as CIGS, CdTe and DSSC requiring high process temperature, because it's electrical resistivity is unstable above 300 ℃ at atmosphere. Therefore, ZTO (zinc tin oxide) was introduced in order to improve permeability and thermal stability of GZO film. The resistivity of GZO (300 nm) single layer increased remarkably from 1.8 × 10-3Ωcm to 5.5 × 10-1Ωcm, when GZO was post-annealed at 400 ℃ in air atmosphere. In the case of the ZTO (150 nm)/GZO (150 nm) double layer, resistivity showed relatively small change from 3.1 × 10-3Ωcm (RT) to 1.2 × 10-2Ωcm (400 ℃), which showed good agreement with change of carrier density. This result means that ZTO upper layer act as a barrier for oxygen at high temperature. Also ZTO (150 nm)/GZO (150 nm) double layer showed lower WVTR compared to GZO (300 nm) single layer. Because ZTO has lower WVTR compared to GZO, ZTO thin film acts as a barrier by preventing oxygen and water molecules to penetrate on top of GZO thin film.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2014.02a
• /
• pp.398.1-398.1
• /
• 2014

The $Cu_2ZnSnSe_4$ (CZTSe) thin films solar cell is one of the next generation candidates for photovoltaic materials as the absorber of thin film solar cells because it has optimal bandgap (Eg=1.0eV) and high absorption coefficient of $10^4cm^{-1}$ in the visible length region. More importantly, CZTSe consists of abundant and non-toxic elements, so researches on CZTSe thin film solar cells have been increasing significantly in recent years. CZTSe thin film has very similar structure and properties with the CIGS thin film by substituting In with Zn and Ga with Sn. In this study, As-deposited CZTSe thin films have been deposited onto soda lime glass (SLG) substrates at different deposition condition using Pulsed Laser Deposition (PLD) technique without post-annealing process. The effects of deposition conditions (deposition time, deposition temperature) onto the structural, compositional and optical properties of CZTSe thin films have been investigated, without experiencing selenization process. The XRD pattern shows that quaternary CZTSe films with a stannite single phase. The existence of (112), (204), (312), (008), (316) peaks indicates all films grew and crystallized as a stannite-type structure, which is in a good agreement with the diffraction pattern of CZTSe single crystal. All the films were observed to be polycrystalline in nature with a high (112) predominant orientation at $2{\theta}{\sim}26.8^{\circ}$. The carrier concentration, mobility, resistivity and optical band gap of CZTSe thin films depending on the deposition conditions. Average energy band gap of the CZTSe thin films is about 1.3 eV.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2012.05a
• /
• pp.99.1-99.1
• /
• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.

• Korean Journal of Materials Research
• /
• v.31 no.11
• /
• pp.619-625
• /
• 2021

Cu₂ZnSn(S,Se)₄ (CZTSSe) based thin-film solar cells have attracted growing attention because of their earth-abundant and non-toxic elements. However, because of their large open-circuit voltage (V_oc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)₂ (CIGS) and CdTe based solar cells. One of the main causes of this large V_oc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 ℃ to 540 ℃ during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2012.05a
• /
• pp.65-65
• /
• 2012

Copper zinc tin sulfide ($Cu_2ZnSnS_4$, CZTS) is a very promising material as a low cost absorber alternative to other chalcopyrite-type semiconductors based on Ga or In because of the abundant and economical elements. In addition, CZTS has a band-gap energy of 1.4~1.5eV and large absorption coefficient over ${\sim}10^4cm^{-1}$, which is similar to those of $Cu(In,Ga)Se_2$(CIGS) regarded as one of the most successful absorber materials for high efficient solar cell. Most previous works on the fabrication of CZTS thin films were based on the vacuum deposition such as thermal evaporation and RF magnetron sputtering. Although the vacuum deposition has been widely adopted, it is quite expensive and complicated. In this regard, the solution processes such as sol-gel method, nanocrystal dispersion and hybrid slurry method have been developed for easy and cost-effective fabrication of CZTS film. Among these methods, the hybrid slurry method is favorable to make high crystalline and dense absorber layer. However, this method has the demerit using the toxic and explosive hydrazine solvent, which has severe limitation for common use. With these considerations, it is highly desirable to develop a robust, easily scalable and relatively safe solution-based process for the fabrication of a high quality CZTS absorber layer. Here, we demonstrate the fabrication of a high quality CZTS absorber layer with a thickness of 1.5~2.0 ${\mu}m$ and micrometer-scaled grains using two different non-vacuum approaches. The first solution-processing approach includes air-stable non-toxic solvent-based inks in which the commercially available precursor nanoparticles are dispersed in ethanol. Our readily achievable air-stable precursor ink, without the involvement of complex particle synthesis, high toxic solvents, or organic additives, facilitates a convenient method to fabricate a high quality CZTS absorber layer with uniform surface composition and across the film depth when annealed at $530^{\circ}C$. The conversion efficiency and fill factor for the non-toxic ink based solar cells are 5.14% and 52.8%, respectively. The other method is based on the nanocrystal dispersions that are a key ingredient in the deposition of thermally annealed absorber layers. We report a facile synthetic method to produce phase-pure CZTS nanocrystals capped with less toxic and more easily removable ligands. The resulting CZTS nanoparticle dispersion enables us to fabricate uniform, crack-free absorber layer onto Mo-coated soda-lime glass at $500^{\circ}C$, which exhibits a robust and reproducible photovoltaic response. Our simple and less-toxic approach for the fabrication of CZTS layer, reported here, will be the first step in realizing the low-cost solution-processed CZTS solar cell with high efficiency.