Donor‐acceptor pair recombination luminescence from Cu<sub>2</sub>ZnSnS<sub>4</sub> bulk single crystals

Tanaka, Kunihiko; Miyamoto, Yusuke; Uchiki, Hisao; Nakazawa, Kentaro Ito; Araki, Hideki

doi:10.1002/pssa.200669545

Cited by 89 publications

(65 citation statements)

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“…Broadbands with similar shape and peak positions in the same energy range have been observed by other authors. [18][19][20][21] To the best of our knowledge, this is the first time this emission has been observed in CZTS thin films prepared by sulfurization of metallic precursors.…”

Section: Discussionmentioning

confidence: 64%

“…This technique probes the electronic structure of the semiconductor materials, revealing important information about the radiative and nonradiative recombination mechanisms. Recent works have shown PL characterization of different CZTS types of samples: bulk single crystals, 18,19 monograin powders, 20 and thin films prepared by sol-gel. 21 The optical transitions in chalcopyrite-and kesterite-type materials have been discussed regarding mainly the compositional dependencies and degree of doping.…”

Section: Introductionmentioning

confidence: 99%

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Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

et al. 2011

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In this work, we investigated structural, morphological, electrical, and optical properties from a set of Cu 2 ZnSnS 4 thin films grown by sulfurization of metallic precursors deposited on soda lime glass substrates coated with or without molybdenum. X-ray diffraction and Raman spectroscopy measurements revealed the formation of single-phase Cu 2 ZnSnS 4 thin films. A good crystallinity and grain compactness of the film was found by scanning electron microscopy. The grown films are poor in copper and rich in zinc, which is a composition close to that of the Cu 2 ZnSnS 4 solar cells with best reported efficiency. Electrical conductivity and Hall effect measurements showed a high doping level and a strong compensation. The temperature dependence of the free hole concentration showed that the films are nondegenerate. Photoluminescence spectroscopy showed an asymmetric broadband emission. The experimental behavior with increasing excitation power or temperature cannot be explained by donor-acceptor pair transitions. A model of radiative recombination of an electron with a hole bound to an acceptor level, broadened by potential fluctuations of the valence-band edge, was proposed. An ionization energy for the acceptor level in the range 29-40 meV was estimated, and a value of 172 ± 2 meV was obtained for the potential fluctuation in the valence-band edge.

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Section: Discussionmentioning

confidence: 64%

Section: Introductionmentioning

confidence: 99%

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

et al. 2011

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“…Some ambiguity exists regarding PL of CZTS as previous luminescence studies of CZTS single crystals have claimed that the observed luminescence is due to impurities giving rise to donor acceptor pair (DAP) emission. 18,19 More recent studies have proposed a model of fluctuating potentials 4,20 initially developed by Levanyuk and Osipov. 21 Hall measurements have shown that the CZTS system has high doping levels, around 2 Â 10 20 cm À3 , with high levels of compensation predominantly from native defects.…”

Section: Introductionmentioning

confidence: 99%

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Halliday

Claridge

Goodman

et al. 2013

Journal of Applied Physics

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The growth of Cu2ZnSnS4 (CZTS) polycrystals from solid state reaction over a range of compositions, including the regions which produce the highest efficiency photovoltaic devices, is reported. X-ray measurements confirm the growth of crystalline CZTS. Temperature and intensity dependent photoluminescence (PL) measurements show an increase in the energy of the main CZTS luminescence peak with both increasing laser power and increasing temperature. Analysis of the PL peak positions and intensity behavior demonstrates that the results are consistent with the model of fluctuating potentials. This confirms that the polycrystals are heavily doped with the presence of a large concentration of intrinsic defects. The behavior of the main luminescence feature is shown to be qualitatively similar over a broad range of compositions although the nature and amount of secondary phases vary significantly. The implications for thin-film photovoltaic devices are discussed.

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“…Very promising results have recently been obtained on photovoltaic devices based on related sulfoselenide compounds deposited with an ink-based approach [2,3], suggesting that this material might soon become competitive with Cu(In,Ga)(S,Se) 2 and CdTe for the production of commercial modules, due to the toxicity/availability issues affecting Cd, Te, Ga and In [4][5][6]. Although many studies are being performed on thin films of this material, some key questions can only be answered by studying single crystalline forms: crystal and electronic structures [7], phonon frequencies and line widths of Raman active modes and extension of the compositional homogeneity range [8]. It is therefore important to develop improved crystal growth methods.…”

Section: Introductionmentioning

confidence: 99%

Crystal growth of Cu2ZnSnS4 solar cell absorber by chemical vapor transport with I2

Colombara

Delsante

Borzone

et al. 2013

Journal of Crystal Growth

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Single crystals of Cu 2 ZnSnS 4 have been produced within sealed quartz ampoules via the chemical vapour transport technique using I 2 as the transporting agent. The effects of temperature gradient and I 2 load on the crystal habit and composition are considered. Crystals have been analysed with XRD, SEM, and TEM for compositional and structural uniformities at both microscopic and nanoscopic levels. The synthesized crystals have suitable (I 2 -load dependent) properties and are useful for further solar absorber structural and physical characterizations. A new chemical vapour transport method based on longitudinally isothermal treatments is attempted. Based on a proposed simplistic mechanism of crystal growth, conditions for crystal enlargement with the new method are envisaged.

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Donor‐acceptor pair recombination luminescence from Cu₂ZnSnS₄ bulk single crystals

Cited by 89 publications

References 10 publications

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Crystal growth of Cu2ZnSnS4 solar cell absorber by chemical vapor transport with I2

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Donor‐acceptor pair recombination luminescence from Cu2ZnSnS4 bulk single crystals

Cited by 89 publications

References 10 publications

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Crystal growth of Cu2ZnSnS4 solar cell absorber by chemical vapor transport with I2

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Donor‐acceptor pair recombination luminescence from Cu₂ZnSnS₄ bulk single crystals