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Thermal behaviour of precursors for CuInS2 thin films deposited by spray pyrolysis

Identifieur interne : 000327 ( Main/Repository ); précédent : 000326; suivant : 000328

Thermal behaviour of precursors for CuInS2 thin films deposited by spray pyrolysis

Auteurs : RBID : Pascal:13-0335181

Descripteurs français

English descriptors

Abstract

The thermal decomposition of precursors for copper indium disulphide (CuInS2) thin films obtained by drying aqueous solutions of copper chloride (CuCl2), indium chloride (InCl3) and thiourea (SC(NH2)2) at the Cu:In:S molar ratios of 1:1:3 (1) and 1:1:6 (2) was monitored by simultaneous thermogravimetry /differential thermal analysis/ evolved gas analysis-mass spectrometry (TG/DTA/EGA-MS) measurements in a dynamic 80 %Ar + 20 %O2 atmosphere. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to characterise the dried precursors and products of the thermal decomposition. The precursors 1 and 2 are mixtures of copper and indium chloride thiourea complex compounds, whilst 1 can also contain unreacted InCl3. The thermal degradation of 1 and 2 in the temperature range of 30-800 °C consists of six steps with a total mass loss of 71.5 and 89.8 %, respectively. According to XRD, CuInS2 is formed below 300 °C. Decomposition of 1 and 2 is completed at 620 and 600 °C, respectively. The final decomposition product of 1 at 800 °C consists of a mixture of In2O3 and CuO phases, whilst 2 consists of In2O3, CuO and Cu2In2O5 phases. EGA by MS revealed the release of CS2, NH3, H2NCN and HNCS, which upon their oxidation also yield COS, SO2, HCN and CO2.

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Pascal:13-0335181

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<title xml:lang="en" level="a">Thermal behaviour of precursors for CuInS
<sub>2</sub>
thin films deposited by spray pyrolysis</title>
<author>
<name sortKey="Oja Acik, I" uniqKey="Oja Acik I">I. Oja Acik</name>
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<s1>Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5</s1>
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<author>
<name sortKey="Otto, K" uniqKey="Otto K">K. Otto</name>
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<s1>Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5</s1>
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<name sortKey="Krunks, M" uniqKey="Krunks M">M. Krunks</name>
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<author>
<name sortKey="Mere, A" uniqKey="Mere A">A. Mere</name>
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<s1>Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5</s1>
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<date when="2013">2013</date>
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<idno type="ISSN">1388-6150</idno>
<title level="j" type="abbreviated">J. therm. anal. calorim.</title>
<title level="j" type="main">Journal of thermal analysis and calorimetry</title>
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<keywords scheme="KwdEn" xml:lang="en">
<term>Chalcopyrite structure</term>
<term>Characterization</term>
<term>Copper Chlorides</term>
<term>Copper Indium Sulfides</term>
<term>Copper Sulfides</term>
<term>Differential thermal analysis</term>
<term>Evolved gas analysis</term>
<term>Fourier transformation</term>
<term>Gas analysis</term>
<term>Gas release</term>
<term>Indium Chlorides</term>
<term>Indium Sulfides</term>
<term>Infrared spectroscopy</term>
<term>Mass spectroscopy</term>
<term>Precursor</term>
<term>Spray pyrolysis</term>
<term>Ternary compounds</term>
<term>Thermal analysis</term>
<term>Thermogravimetry</term>
<term>Thin films</term>
<term>Thiourea</term>
<term>XRD</term>
</keywords>
<keywords scheme="Pascal" xml:lang="fr">
<term>Analyse thermique</term>
<term>Précurseur</term>
<term>Couche mince</term>
<term>Thermogravimétrie</term>
<term>Analyse thermique différentielle</term>
<term>Spectrométrie masse</term>
<term>Cuivre Chlorure</term>
<term>Indium Chlorure</term>
<term>Caractérisation</term>
<term>Thiourée</term>
<term>Diffraction RX</term>
<term>Cuivre Indium Sulfure</term>
<term>Structure chalcopyrite</term>
<term>Composé ternaire</term>
<term>Cuivre Sulfure</term>
<term>Indium Sulfure</term>
<term>Analyse gaz</term>
<term>Dégagement gazeux</term>
<term>Spectrométrie IR</term>
<term>Transformation Fourier</term>
<term>CuInS2</term>
<term>FT IR</term>
<term>8190</term>
<term>Dépôt par pyrolyse d'aérosol</term>
<term>Analyse gaz dégagé</term>
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<front>
<div type="abstract" xml:lang="en">The thermal decomposition of precursors for copper indium disulphide (CuInS
<sub>2</sub>
) thin films obtained by drying aqueous solutions of copper chloride (CuCl
<sub>2</sub>
), indium chloride (InCl
<sub>3</sub>
) and thiourea (SC(NH
<sub>2</sub>
)
<sub>2</sub>
) at the Cu:In:S molar ratios of 1:1:3 (1) and 1:1:6 (2) was monitored by simultaneous thermogravimetry /differential thermal analysis/ evolved gas analysis-mass spectrometry (TG/DTA/EGA-MS) measurements in a dynamic 80 %Ar + 20 %O
<sub>2</sub>
atmosphere. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to characterise the dried precursors and products of the thermal decomposition. The precursors 1 and 2 are mixtures of copper and indium chloride thiourea complex compounds, whilst 1 can also contain unreacted InCl
<sub>3</sub>
. The thermal degradation of 1 and 2 in the temperature range of 30-800 °C consists of six steps with a total mass loss of 71.5 and 89.8 %, respectively. According to XRD, CuInS
<sub>2</sub>
is formed below 300 °C. Decomposition of 1 and 2 is completed at 620 and 600 °C, respectively. The final decomposition product of 1 at 800 °C consists of a mixture of In
<sub>2</sub>
O
<sub>3</sub>
and CuO phases, whilst 2 consists of In
<sub>2</sub>
O
<sub>3</sub>
, CuO and Cu
<sub>2</sub>
In
<sub>2</sub>
O
<sub>5</sub>
phases. EGA by MS revealed the release of CS
<sub>2</sub>
, NH
<sub>3</sub>
, H
<sub>2</sub>
NCN and HNCS, which upon their oxidation also yield COS, SO
<sub>2</sub>
, HCN and CO
<sub>2</sub>
.</div>
</front>
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<s1>Thermal behaviour of precursors for CuInS
<sub>2</sub>
thin films deposited by spray pyrolysis</s1>
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<s1>OTTO (K.)</s1>
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<s1>MERE (A.)</s1>
</fA11>
<fA12 i1="01" i2="1">
<s1>KIMURA (Takayoshi)</s1>
<s9>ed.</s9>
</fA12>
<fA14 i1="01">
<s1>Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5</s1>
<s2>19086 Tallinn</s2>
<s3>EST</s3>
<sZ>1 aut.</sZ>
<sZ>2 aut.</sZ>
<sZ>3 aut.</sZ>
<sZ>5 aut.</sZ>
</fA14>
<fA14 i1="02">
<s1>Laboratory of Inorganic Materials, Tallinn University of Technology, Ehitajate tee 5</s1>
<s2>19086 Tallinn</s2>
<s3>EST</s3>
<sZ>4 aut.</sZ>
</fA14>
<fA15 i1="01">
<s1>Department of Chemistry, Kinki University, Higashi-Osaka</s1>
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<s0>NLD</s0>
</fA66>
<fC01 i1="01" l="ENG">
<s0>The thermal decomposition of precursors for copper indium disulphide (CuInS
<sub>2</sub>
) thin films obtained by drying aqueous solutions of copper chloride (CuCl
<sub>2</sub>
), indium chloride (InCl
<sub>3</sub>
) and thiourea (SC(NH
<sub>2</sub>
)
<sub>2</sub>
) at the Cu:In:S molar ratios of 1:1:3 (1) and 1:1:6 (2) was monitored by simultaneous thermogravimetry /differential thermal analysis/ evolved gas analysis-mass spectrometry (TG/DTA/EGA-MS) measurements in a dynamic 80 %Ar + 20 %O
<sub>2</sub>
atmosphere. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to characterise the dried precursors and products of the thermal decomposition. The precursors 1 and 2 are mixtures of copper and indium chloride thiourea complex compounds, whilst 1 can also contain unreacted InCl
<sub>3</sub>
. The thermal degradation of 1 and 2 in the temperature range of 30-800 °C consists of six steps with a total mass loss of 71.5 and 89.8 %, respectively. According to XRD, CuInS
<sub>2</sub>
is formed below 300 °C. Decomposition of 1 and 2 is completed at 620 and 600 °C, respectively. The final decomposition product of 1 at 800 °C consists of a mixture of In
<sub>2</sub>
O
<sub>3</sub>
and CuO phases, whilst 2 consists of In
<sub>2</sub>
O
<sub>3</sub>
, CuO and Cu
<sub>2</sub>
In
<sub>2</sub>
O
<sub>5</sub>
phases. EGA by MS revealed the release of CS
<sub>2</sub>
, NH
<sub>3</sub>
, H
<sub>2</sub>
NCN and HNCS, which upon their oxidation also yield COS, SO
<sub>2</sub>
, HCN and CO
<sub>2</sub>
.</s0>
</fC01>
<fC02 i1="01" i2="3">
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<s0>Analyse thermique</s0>
<s5>01</s5>
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<fC03 i1="01" i2="3" l="ENG">
<s0>Thermal analysis</s0>
<s5>01</s5>
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<s0>Précurseur</s0>
<s5>02</s5>
</fC03>
<fC03 i1="02" i2="3" l="ENG">
<s0>Precursor</s0>
<s5>02</s5>
</fC03>
<fC03 i1="03" i2="3" l="FRE">
<s0>Couche mince</s0>
<s5>03</s5>
</fC03>
<fC03 i1="03" i2="3" l="ENG">
<s0>Thin films</s0>
<s5>03</s5>
</fC03>
<fC03 i1="04" i2="3" l="FRE">
<s0>Thermogravimétrie</s0>
<s5>04</s5>
</fC03>
<fC03 i1="04" i2="3" l="ENG">
<s0>Thermogravimetry</s0>
<s5>04</s5>
</fC03>
<fC03 i1="05" i2="3" l="FRE">
<s0>Analyse thermique différentielle</s0>
<s5>05</s5>
</fC03>
<fC03 i1="05" i2="3" l="ENG">
<s0>Differential thermal analysis</s0>
<s5>05</s5>
</fC03>
<fC03 i1="06" i2="3" l="FRE">
<s0>Spectrométrie masse</s0>
<s5>06</s5>
</fC03>
<fC03 i1="06" i2="3" l="ENG">
<s0>Mass spectroscopy</s0>
<s5>06</s5>
</fC03>
<fC03 i1="07" i2="3" l="FRE">
<s0>Cuivre Chlorure</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>07</s5>
</fC03>
<fC03 i1="07" i2="3" l="ENG">
<s0>Copper Chlorides</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>07</s5>
</fC03>
<fC03 i1="08" i2="3" l="FRE">
<s0>Indium Chlorure</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>08</s5>
</fC03>
<fC03 i1="08" i2="3" l="ENG">
<s0>Indium Chlorides</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>08</s5>
</fC03>
<fC03 i1="09" i2="X" l="FRE">
<s0>Caractérisation</s0>
<s5>09</s5>
</fC03>
<fC03 i1="09" i2="X" l="ENG">
<s0>Characterization</s0>
<s5>09</s5>
</fC03>
<fC03 i1="09" i2="X" l="SPA">
<s0>Caracterización</s0>
<s5>09</s5>
</fC03>
<fC03 i1="10" i2="3" l="FRE">
<s0>Thiourée</s0>
<s2>NK</s2>
<s5>10</s5>
</fC03>
<fC03 i1="10" i2="3" l="ENG">
<s0>Thiourea</s0>
<s2>NK</s2>
<s5>10</s5>
</fC03>
<fC03 i1="11" i2="3" l="FRE">
<s0>Diffraction RX</s0>
<s5>11</s5>
</fC03>
<fC03 i1="11" i2="3" l="ENG">
<s0>XRD</s0>
<s5>11</s5>
</fC03>
<fC03 i1="12" i2="3" l="FRE">
<s0>Cuivre Indium Sulfure</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>32</s5>
</fC03>
<fC03 i1="12" i2="3" l="ENG">
<s0>Copper Indium Sulfides</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>32</s5>
</fC03>
<fC03 i1="13" i2="X" l="FRE">
<s0>Structure chalcopyrite</s0>
<s5>33</s5>
</fC03>
<fC03 i1="13" i2="X" l="ENG">
<s0>Chalcopyrite structure</s0>
<s5>33</s5>
</fC03>
<fC03 i1="13" i2="X" l="SPA">
<s0>Estructura calcopirita</s0>
<s5>33</s5>
</fC03>
<fC03 i1="14" i2="3" l="FRE">
<s0>Composé ternaire</s0>
<s5>34</s5>
</fC03>
<fC03 i1="14" i2="3" l="ENG">
<s0>Ternary compounds</s0>
<s5>34</s5>
</fC03>
<fC03 i1="15" i2="3" l="FRE">
<s0>Cuivre Sulfure</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>35</s5>
</fC03>
<fC03 i1="15" i2="3" l="ENG">
<s0>Copper Sulfides</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>35</s5>
</fC03>
<fC03 i1="16" i2="3" l="FRE">
<s0>Indium Sulfure</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>36</s5>
</fC03>
<fC03 i1="16" i2="3" l="ENG">
<s0>Indium Sulfides</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>36</s5>
</fC03>
<fC03 i1="17" i2="3" l="FRE">
<s0>Analyse gaz</s0>
<s5>37</s5>
</fC03>
<fC03 i1="17" i2="3" l="ENG">
<s0>Gas analysis</s0>
<s5>37</s5>
</fC03>
<fC03 i1="18" i2="X" l="FRE">
<s0>Dégagement gazeux</s0>
<s5>38</s5>
</fC03>
<fC03 i1="18" i2="X" l="ENG">
<s0>Gas release</s0>
<s5>38</s5>
</fC03>
<fC03 i1="18" i2="X" l="SPA">
<s0>Desprendimiento gaseoso</s0>
<s5>38</s5>
</fC03>
<fC03 i1="19" i2="3" l="FRE">
<s0>Spectrométrie IR</s0>
<s5>39</s5>
</fC03>
<fC03 i1="19" i2="3" l="ENG">
<s0>Infrared spectroscopy</s0>
<s5>39</s5>
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<fC03 i1="20" i2="3" l="FRE">
<s0>Transformation Fourier</s0>
<s5>40</s5>
</fC03>
<fC03 i1="20" i2="3" l="ENG">
<s0>Fourier transformation</s0>
<s5>40</s5>
</fC03>
<fC03 i1="21" i2="3" l="FRE">
<s0>CuInS2</s0>
<s4>INC</s4>
<s5>76</s5>
</fC03>
<fC03 i1="22" i2="3" l="FRE">
<s0>FT IR</s0>
<s4>INC</s4>
<s5>77</s5>
</fC03>
<fC03 i1="23" i2="3" l="FRE">
<s0>8190</s0>
<s2>PAC</s2>
<s4>INC</s4>
<s5>78</s5>
</fC03>
<fC03 i1="24" i2="3" l="FRE">
<s0>Dépôt par pyrolyse d'aérosol</s0>
<s4>CD</s4>
<s5>96</s5>
</fC03>
<fC03 i1="24" i2="3" l="ENG">
<s0>Spray pyrolysis</s0>
<s4>CD</s4>
<s5>96</s5>
</fC03>
<fC03 i1="25" i2="3" l="FRE">
<s0>Analyse gaz dégagé</s0>
<s4>CD</s4>
<s5>97</s5>
</fC03>
<fC03 i1="25" i2="3" l="ENG">
<s0>Evolved gas analysis</s0>
<s4>CD</s4>
<s5>97</s5>
</fC03>
<fC07 i1="01" i2="3" l="FRE">
<s0>Métal transition</s0>
<s5>53</s5>
</fC07>
<fC07 i1="01" i2="3" l="ENG">
<s0>Transition elements</s0>
<s5>53</s5>
</fC07>
<fN21>
<s1>315</s1>
</fN21>
</pA>
<pR>
<fA30 i1="01" i2="1" l="ENG">
<s1>ICTAC15 International Congress of Thermal Analysis and Calorimetry</s1>
<s2>15</s2>
<s3>Higashi-Osaka JPN</s3>
<s4>2012-08-20</s4>
</fA30>
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