Large-grained Cu<sub>2</sub>ZnSnS<sub>4</sub>layers sintered from Sn-rich solution-deposited precursors

Sutter‐Fella, Carolin M.; Uhl, Alexander R.; Romanyuk, Yaroslav E.; Tiwari, Ayodhya N.

doi:10.1002/pssa.201431147

Cited by 9 publications

(10 citation statements)

References 20 publications

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“…23 The large-grained and vertical-penetration CZTS film was only achieved by annealing in nitrogen without sulfur vapor. 23 If the sample was annealed in sulfur vapor, CZTS with only about 200 nm grain size was obtained. Calcining in nitrogen at a high temperature led to an amount of impurities and sulfur deficiencies in the films, which indicated poor performance.…”

Section: Resultsmentioning

confidence: 99%

“…During sulfuration at 580 °C, SnS 2 plays as a fluxing agent to promote CZTS grain growth, which were also observed in previous studies. 23,39,40 After sulfurization, we obtained vertical-penetration CZTS thin film with micron-scale grain sizes by aging precursor solution in a high-humidity air.…”

Section: Acs Applied Materials and Interfacesmentioning

confidence: 99%

“…18,19 Very recently, a large-grained and verticalpenetration CZTS film was obtained by a solution method, with excess Sn ratio in precursor solution. 23 However, in this solution method, large-grained and vertical-penetration CZTS film was only obtained by annealing in a closed reactor in nitrogen, not sulfur, which resulted in an amount of impurities and sulfur deficiencies. Therefore, it is still a key challenge to prepare large-grained and vertical-penetration CZTS with appropriate composition by a low-cost solution method.…”

Section: Introductionmentioning

confidence: 99%

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Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu₂ZnSnS₄ Films

Guan

Luo

et al. 2016

ACS Appl. Mater. Interfaces

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Earth-abundant Cu2ZnSnS4 (CZTS) is a promising material for thin film solar cells or solar water splitting cells. Generally, large grain size and vertical penetration are highly desirable microstructures to high-efficiency solar conversion devices. Up to date, some kinds of vacuum methods have been used to prepare large grain-sized CZTS, which are expensive and limit their applications on a large scale. It is still a key challenge to prepare large-grained and vertical-penetration CZTS by a low-cost solution method. In this study, we obtained vertical-penetration CZTS thin film with 1.3 μm grain sizes by a faclie solution method. Different from previous studies, precursor solution was aged in high-humidity air before it was used to prepare CZTS films. The grain size prepared with aging precursor solution was one of the largest among the samples prepared by a solution method after sulfurizing. Moreover, the large-grained CZTS films were used as photocathodes for solar water splitting, which exhibited a much higher photocurrent than those of the samples without aging. To the best of our knowledge, this is the first demonstration to promote grain growth in CZTS by aging precursor solution in high-humidity air. This aging method can offer a reference to prepare other high-performance films.

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Section: Resultsmentioning

confidence: 99%

Section: Acs Applied Materials and Interfacesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu₂ZnSnS₄ Films

Guan

Luo

et al. 2016

ACS Appl. Mater. Interfaces

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“…[ 73 ] Annealing in an inert atmosphere yields a large-grain CZTS material only if an excess of Sn is present in the precursor (Figure 4 b), whereas the annealing in Se results in a smaller grain material and a signifi cant loss of Sn (Figure 4 c). [ 74 ] The Sn loss can be partially reduced when sintering in closed systems providing a higher partial overpressure of chalcogen ( Figure 4 d and 4 e), which yields the sintered top layer with large crystals. Despite the observed bi-layer morphology (Figure 4 d) such an absorber can be processed into a solar cell with a conversion effi ciency of 8.3%, especially if Na dopant is present in the precursor solution.…”

Section: Cztsmentioning

confidence: 99%

All Solution‐Processed Chalcogenide Solar Cells – from Single Functional Layers Towards a 13.8% Efficient CIGS Device

Romanyuk

Hagendorfer

Stücheli

et al. 2014

Adv Funct Materials

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Solution processing of inorganic thin fi lms has become an important thrust in material research community because it offers low-cost and high-throughput deposition of various functional coatings and devices. Especially inorganic thin fi lm solar cells -macroelectronic devices that rely on consecutive deposition of layers on large-area rigid and fl exible substrates -could benefi t from solution approaches in order to realize their low-cost nature. This article critically reviews existing deposition approaches of functional layers for chalcogenide solar cells with an extension to other thin fi lm technologies. Only true solutions of readily available metal salts in appropriate solvents are considered without the need of pre-fabricated nanoparticles. By combining three promising approaches, an air-stable Cu(In,Ga)Se 2 thin fi lm solar cell with effi ciency of 13.8% is demonstrated where all constituent layers (except the metal back contact) are processed from solutions. Notably, water is employed as the solvent in all steps, highlighting the potential for safe manufacturing with high utilization rates. remarkable improvements in conversion effi ciency. [ 1 ] The highest effi ciency of 21.0% has been achieved for two thin fi lm technologies so far: Cu(In,Ga)Se 2 (CIGS) [ 2 ] and CdTe. [ 3 ] Remarkably, both CIGS and CdTe records are exceeding the highest value of 20.4% for the market leading polycrystalline silicon wafer technology. Kesterite Cu 2 ZnSn(S,Se) 4 (CZTSSe) solar cells are often considered as low-cost alternatives to CIGS and CdTe because they consist of only earth-abundant and nontoxic elements although the effi ciency is currently limited to 12.6% (12.7% not certifi ed). [ 4 ] Well-established dye-sensitized solar cell (DSSC) and amorphous silicon (a-Si) technology peak at 12.3% and 13.4%, respectively. [ 1 ] The most recent boom in TFPV -organometallic halide perovskite cells -has shown an incredible spurt by advancing effi ciency from below 5% to 17.9%(!) within just 3 years. [ 5 ] On the border to classical TFSC is the thin crystalline silicon technology that employs liftoff of 50-micrometer-thick Si wafers to yield up to 21.2%-efficient solar cells. [ 6 ] These massive research and development efforts in the fi eld of TFSC clearly refl ect their commercial value for manufacturing inexpensive effi cient solar modules -rigid or fl exible. Functional layers for the high effi ciency devices are deposited mostly in a batch-to-batch manner using vacuum-based methods such as evaporation, sputtering, or chemical vapor deposition. For example, Figure 1 exhibits a cross-section of a >20% effi cient CIGS solar cell in the so-called substrate confi guration, where 5 out of 6 functional layers are deposited by evaporation or sputtering. In this respect, non-vacuum deposition methods are often promoted as alternative approaches to reduce capital investment costs, offer fast roll-to-roll (R2R) processing and eventually reduce the PV module prices. Particularly desirable among non-vacuum approaches are solutionb...

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“…However, utilization of hydrazine has limited the popularization because of the toxicity and residual of organic solvents in the film [7]. As a result, alternative solution process route using just non-toxic solvents have been reported by several groups [8,9,10].…”

Section: Introductionmentioning

confidence: 99%

Fabrication of Cu2ZnSnS4 Thin Films from Ball-Milled Nanoparticle inks under Various Annealing Temperatures

Zhang

Zheng

et al. 2019

Nanomaterials

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Cu2ZnSnS4 (CZTS) has been recognized as a promising thin-film absorber material of chalcopyrite-related solar cells. A two-stage method for fabricating CZTS films using CZTS nanoparticles was developed. Nanocrystal inks fabricated by a ball-milling method was utilized to °C deposit CZTS precursors by spin-coating approach. The CZTS precursors were annealed in the sulfur atmosphere under different annealing temperatures ranging from 550 °C to 650 °C. Influences of annealing temperature on grain growth, composition, crystallinity, and photovoltaic properties of CZTS films were characterized. With the increase of annealing temperature, grain growth was enhanced, while the sulfur atomic ratio fist increased then decreased. The crystallinity of the films was significantly improved after the annealing, and the obvious peak of the secondary phase of ZnS, were observed from the X-ray diffraction results, when the annealing temperature increased to 625 °C. However, the secondary phase was not detected from the surface Raman spectrum. Through comparing the Raman spectrum of different areas of the CZTS film, secondary phases of ZnS and SnS were observed, indicating the decomposition of CZTS films, due to the high temperature. The highest conversion efficiency of 7.5% was obtained when the annealing temperature was 600 °C.

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Large-grained Cu₂ZnSnS₄layers sintered from Sn-rich solution-deposited precursors

Cited by 9 publications

References 20 publications

Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu₂ZnSnS₄ Films

Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu₂ZnSnS₄ Films

All Solution‐Processed Chalcogenide Solar Cells – from Single Functional Layers Towards a 13.8% Efficient CIGS Device

Fabrication of Cu2ZnSnS4 Thin Films from Ball-Milled Nanoparticle inks under Various Annealing Temperatures

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Large-grained Cu2ZnSnS4layers sintered from Sn-rich solution-deposited precursors

Cited by 9 publications

References 20 publications

Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu2ZnSnS4 Films

Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu2ZnSnS4 Films

All Solution‐Processed Chalcogenide Solar Cells – from Single Functional Layers Towards a 13.8% Efficient CIGS Device

Fabrication of Cu2ZnSnS4 Thin Films from Ball-Milled Nanoparticle inks under Various Annealing Temperatures

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Product

Resources

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Large-grained Cu₂ZnSnS₄layers sintered from Sn-rich solution-deposited precursors

Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu₂ZnSnS₄ Films

Aging Precursor Solution in High Humidity Remarkably Promoted Grain Growth in Cu₂ZnSnS₄ Films