Cu2ZnGeS4 nanocrystals from air-stable precursors for sintered thin film alloys

Anthony S. R. Chesman, Joel van Embden, Enrico Della Gaspera, Noel W. Duffy, Nathan A. S. Webster, Jacek J. Jasieniak

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Abstract

The synthesis of an air and moisture stable germanium complex and its use in the synthesis of ternary and quaternary copper containing nanocrystals (NCs) is described. Through the use of 1H-/13C nuclear magnetic resonance and Fourier transform infrared spectroscopies, thermogravimetric analysis, and powder X-ray diffraction, the speciation and chemistry of this precursor is elucidated. This germanium source is employed in the gram scale, noninjection synthesis of Cu2ZnGeS4 (CZGeS) and Cu2GeS3 (CGeS) NCs using a binary sulfide precursor approach. To demonstrate the versatility of such NCs for fabricating thin films suitable for high-efficiency optoelectronic devices, they are blended with Cu2ZnSnS4 (CZTS) NCs and selenized to form homogeneously alloyed Cu2ZnSnxGe1-xSySe4-y (CZTGeSSe) thin films. The structural, optical, and electronic properties of such thin films are studied using X-ray di ffraction, scanning electron microscopy, UV-vis-NIR spectroscopy, and photoelectron spectroscopy in air. These measurements demonstrate collectively that incorporating Ge into micrometer-sized, tetragonal Cu2ZnSnSxSe4-x (CZTSSe) provides a facile manner in which the conduction band energy can be readily tuned. The strategy developed herein provides a pathway to controlled levels of Ge incorporation in a single step process, thus avoiding the need for intra-alloyed Cu2ZnSnxGe1-xS4 nanocrystals. (Chemical Equation Presented).
Original languageEnglish
Pages (from-to)5482-5491
Number of pages10
JournalChemistry of Materials
Volume26
Issue number19
DOIs
Publication statusPublished - Oct 2014
Externally publishedYes

Cite this

Chesman, A. S. R., van Embden, J., Della Gaspera, E., Duffy, N. W., Webster, N. A. S., & Jasieniak, J. J. (2014). Cu2ZnGeS4 nanocrystals from air-stable precursors for sintered thin film alloys. Chemistry of Materials, 26(19), 5482-5491. https://doi.org/10.1021/cm501393h
Chesman, Anthony S. R. ; van Embden, Joel ; Della Gaspera, Enrico ; Duffy, Noel W. ; Webster, Nathan A. S. ; Jasieniak, Jacek J. / Cu2ZnGeS4 nanocrystals from air-stable precursors for sintered thin film alloys. In: Chemistry of Materials. 2014 ; Vol. 26, No. 19. pp. 5482-5491.
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abstract = "The synthesis of an air and moisture stable germanium complex and its use in the synthesis of ternary and quaternary copper containing nanocrystals (NCs) is described. Through the use of 1H-/13C nuclear magnetic resonance and Fourier transform infrared spectroscopies, thermogravimetric analysis, and powder X-ray diffraction, the speciation and chemistry of this precursor is elucidated. This germanium source is employed in the gram scale, noninjection synthesis of Cu2ZnGeS4 (CZGeS) and Cu2GeS3 (CGeS) NCs using a binary sulfide precursor approach. To demonstrate the versatility of such NCs for fabricating thin films suitable for high-efficiency optoelectronic devices, they are blended with Cu2ZnSnS4 (CZTS) NCs and selenized to form homogeneously alloyed Cu2ZnSnxGe1-xSySe4-y (CZTGeSSe) thin films. The structural, optical, and electronic properties of such thin films are studied using X-ray di ffraction, scanning electron microscopy, UV-vis-NIR spectroscopy, and photoelectron spectroscopy in air. These measurements demonstrate collectively that incorporating Ge into micrometer-sized, tetragonal Cu2ZnSnSxSe4-x (CZTSSe) provides a facile manner in which the conduction band energy can be readily tuned. The strategy developed herein provides a pathway to controlled levels of Ge incorporation in a single step process, thus avoiding the need for intra-alloyed Cu2ZnSnxGe1-xS4 nanocrystals. (Chemical Equation Presented).",
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Chesman, ASR, van Embden, J, Della Gaspera, E, Duffy, NW, Webster, NAS & Jasieniak, JJ 2014, 'Cu2ZnGeS4 nanocrystals from air-stable precursors for sintered thin film alloys', Chemistry of Materials, vol. 26, no. 19, pp. 5482-5491. https://doi.org/10.1021/cm501393h

Cu2ZnGeS4 nanocrystals from air-stable precursors for sintered thin film alloys. / Chesman, Anthony S. R.; van Embden, Joel; Della Gaspera, Enrico; Duffy, Noel W.; Webster, Nathan A. S.; Jasieniak, Jacek J.

In: Chemistry of Materials, Vol. 26, No. 19, 10.2014, p. 5482-5491.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Cu2ZnGeS4 nanocrystals from air-stable precursors for sintered thin film alloys

AU - Chesman, Anthony S. R.

AU - van Embden, Joel

AU - Della Gaspera, Enrico

AU - Duffy, Noel W.

AU - Webster, Nathan A. S.

AU - Jasieniak, Jacek J.

PY - 2014/10

Y1 - 2014/10

N2 - The synthesis of an air and moisture stable germanium complex and its use in the synthesis of ternary and quaternary copper containing nanocrystals (NCs) is described. Through the use of 1H-/13C nuclear magnetic resonance and Fourier transform infrared spectroscopies, thermogravimetric analysis, and powder X-ray diffraction, the speciation and chemistry of this precursor is elucidated. This germanium source is employed in the gram scale, noninjection synthesis of Cu2ZnGeS4 (CZGeS) and Cu2GeS3 (CGeS) NCs using a binary sulfide precursor approach. To demonstrate the versatility of such NCs for fabricating thin films suitable for high-efficiency optoelectronic devices, they are blended with Cu2ZnSnS4 (CZTS) NCs and selenized to form homogeneously alloyed Cu2ZnSnxGe1-xSySe4-y (CZTGeSSe) thin films. The structural, optical, and electronic properties of such thin films are studied using X-ray di ffraction, scanning electron microscopy, UV-vis-NIR spectroscopy, and photoelectron spectroscopy in air. These measurements demonstrate collectively that incorporating Ge into micrometer-sized, tetragonal Cu2ZnSnSxSe4-x (CZTSSe) provides a facile manner in which the conduction band energy can be readily tuned. The strategy developed herein provides a pathway to controlled levels of Ge incorporation in a single step process, thus avoiding the need for intra-alloyed Cu2ZnSnxGe1-xS4 nanocrystals. (Chemical Equation Presented).

AB - The synthesis of an air and moisture stable germanium complex and its use in the synthesis of ternary and quaternary copper containing nanocrystals (NCs) is described. Through the use of 1H-/13C nuclear magnetic resonance and Fourier transform infrared spectroscopies, thermogravimetric analysis, and powder X-ray diffraction, the speciation and chemistry of this precursor is elucidated. This germanium source is employed in the gram scale, noninjection synthesis of Cu2ZnGeS4 (CZGeS) and Cu2GeS3 (CGeS) NCs using a binary sulfide precursor approach. To demonstrate the versatility of such NCs for fabricating thin films suitable for high-efficiency optoelectronic devices, they are blended with Cu2ZnSnS4 (CZTS) NCs and selenized to form homogeneously alloyed Cu2ZnSnxGe1-xSySe4-y (CZTGeSSe) thin films. The structural, optical, and electronic properties of such thin films are studied using X-ray di ffraction, scanning electron microscopy, UV-vis-NIR spectroscopy, and photoelectron spectroscopy in air. These measurements demonstrate collectively that incorporating Ge into micrometer-sized, tetragonal Cu2ZnSnSxSe4-x (CZTSSe) provides a facile manner in which the conduction band energy can be readily tuned. The strategy developed herein provides a pathway to controlled levels of Ge incorporation in a single step process, thus avoiding the need for intra-alloyed Cu2ZnSnxGe1-xS4 nanocrystals. (Chemical Equation Presented).

U2 - 10.1021/cm501393h

DO - 10.1021/cm501393h

M3 - Article

VL - 26

SP - 5482

EP - 5491

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 19

ER -