Application noteSimultaneous determination of mineralacids, fluoride and silicate in etching bathsby ion chromatography wi...
APPLICATION NOTE                Figure 3: UV/vis chromatogram of a 10 mg/L silicic acid                                   ...
APPLICATION NOTE  H4SiO4 + 12 MoO42− + 24 H+ — H4[Si(Mo3O10)4] + 12 H2O                             >                     ...
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Ion Chromatography in determining mineral acids in Etching baths


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Metrohm Applications for Simultaneous determination of mineral acids, fluoride and silicate in etching baths by ion chromatography with dual detection

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Ion Chromatography in determining mineral acids in Etching baths

  1. 1. Application noteSimultaneous determination of mineralacids, fluoride and silicate in etching bathsby ion chromatography with dual detectionThe presented ion chromatographic method is used for the simultaneous determination of HF,HNO3, H2SO4 , short-chain organic acids and H2SiF6 in acidic texturing baths that are used in thewet chemical etching process of solar cell production. Fluoride, nitrate, sulphate and acetate aredetermined by conductivity detection after chemical suppression, while the silicon present in the formof hexafluorosilicate is detected spectrophotometrically as molybdosilicic acid after derivatization in thesame analysis. The analytical results are validated by titration.Introduction This article describes an ion chromatographic method thatEnergy production from renewable sources such as biomass, separates all relevant components in the bath on an anion-biogas, biofuels, water, wind and solar power is becoming exchange column and identifies them by dual detectionincreasingly important in our energy-hungry society. in a single run. After suppressed conductivity detection ofParticular interest is given to solar energy, which by human the acid anions, the undissociated silicic acid reacts in acriteria is inexhaustible. Solar cells used in photovoltaic units post-column reaction (PCR) to form molybdosilicic acid,convert the radiation energy in sunlight directly into electric which is determined spectrophotometrically at 410 The concentrations of fluoride and hexafluorosilicate are Solar cells are manufactured from ultrapure mono- or determined by way of a simple stoichiometric calculation thatpolycristalline silicon wafers whose surface is treated in is performed by the chromatography software.acid etching baths (also known as texturing baths) beforebeing spiked with foreign atoms (P, B). The etching solutions Instruments and Reagentsconsist of various acids, which act as an oxidizing agent a) Instrument setup(HNO3), complexing agent (HF), stabilizer and wetting agent • 850 Professional IC Anion – MCS with post-column reactor(CH 3 COOH), or buffers (H 3 PO4, CH 3 COOH) and determine • 858 Professional Sample Processorthe surface structure and thus the efficiency of the solar cells. • Lambda 1010 UV/VIS DetectorThe replenishment of components used up in the etching • 771 IC Compact Interfaceprocess extends the bath life and saves costs, though it • MagIC Net chromatography softwaredoes require knowledge of the exact composition of the bath, b) Reagents and eluentespecially the concentration of silicon and hexafluorosilicate. The standard solutions were prepared with CertiPURBy using titration and ion chromatography (IC), it is possible standards from Merck (SiO2 in NaOH; solutions of NaF andto determine the key components quickly and precisely. NaNO3 in ultrapure water) and the TraceCERT standard from Figure 2: Conductivity chromatogram of a simulated Figure 1: 850 Professional IC Anion – MCS and etching bath with 25 mg/L fluoride, 20 mg/L acetate and 858 Professional Sample Processor. 10 mg/L nitrate. The undissociated orthosilicic acid is not recorded in the conductivity detector. Separation column: Metrosep A Supp 15 - 250/4.0 fluoride Column temperature: 45 ˚C 12 Eluent: 3.5 mmol/L Na2CO3 3.0 mmol/L NaHCO3 11 Flow-rate: 0.7 mL/min Sample volume: 1.5 µL 10 Conductivity (µS/cm) 9 8 7 6 5 4 acetate 3 nitrate 2 1 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Time (min)THEAPPLICATIONSBOOK August 2011 37
  2. 2. APPLICATION NOTE Figure 3: UV/vis chromatogram of a 10 mg/L silicic acid Figure 4: (a) Conductivity and (b) UV/vis chromatograms standard. Silicic acid is derivatized to molybdosilicic acid of etching bath sample 1 with 1:2000 dilution. The which is then detected spectrophotometrically. chromatographic parameters are the same as those of the prior chromatograms. silicate Separation column: Metrosep A Supp 15 - 250/4.0 1.0 Column temperature: 45 ˚C (a) sulphate Eluent: 3.5 mmol/L Na2CO3 30 3.0 mmol/L NaHCO3 Flow-rate: 0.7 mL/min 0.5 Sample volume: 1.5 µL PCR reagent: 200 mmol/L HNO3 25 20 mmol/L Na2MoO4 Conductivity (µS/cm) Flow-ratePCR reagent: 0.25 mL/min 0.0 Wavelength: 410 nm Intensity (mV) 20 fluoride -0.5 15 -1.0 nitrate 10 -1.5 5 -2.0 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Time (min) Time (min) (b) Fluka (acetate solution). All the standard and eluent solutions -0.0 were prepared with ultrapure water with a specific resistance -0.2 silicate of more than 18 MΩ·cm. Etching bath samples were provided -0.4 by a solar cell manufacturer from Germany. -0.6 Intensity (mV) -0.8 Etching of Silicon -1.0 In the wet chemical etching of silicon surfaces, nitric acid is -1.2 used to oxidize silicon to form silicon dioxide which is further etched by hydrofluoric acid. -1.4 -1.6 3 Si + 4 HNO3 + 18 HF — 3 H2SiF6 + 4 NO + 8 H2O > -1.8 -2.0 During the etching process, the concentrations of HF and 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 HNO3 in the etching bath decrease and the concentrations of Time (min) water and hexafluorosilicate increase. To ensure a constant etching rate and surface properties, the etching bath can be regenerated a few times by subsequent replenishment and determined by conductivity detection (Figure 2). In of spent acids. The increasing concentration of H2SiF6, the alkaline eluent, the hexafluorosilicate is converted however, limits the number of possible recycling cycles. This into orthosilicic acid which is undissociated and therefore requires semi-continuous monitoring of the bath components, “invisible” in the conductivity detector. which can be achieved conveniently by automated ion chromatography. Na 2SiF6 + 4 NaOH — Si(OH)4 + 6 NaF > Dual Detection The undissociated orthosilicic acid is determined by way The acid anions present in the etching bath — mainly of post-column reaction with an acid molybdate solution and fluoride and nitrate, though sometimes also sulphate and subsequent UV/vis detection at 410 nm (Figure 3). acetate — are separated under alkaline elution conditions Table 1: Comparison of the concentrations of a few selected bath components determined by ion chromatography and titration. Etching bath sample 1c Etching bath sample 2 Etching bath sample 3 Etching bath sample 4 Si HF a HNO3 b Si HF a HNO3 b Si HF a HNO3 b Si HFa HNO3b IC (g/L) 3.3 22.4 216.6 34.8 47.2 248.4 17.6 98.9 504.4 19.3 94.8 516.8 Titration (g/L) 3.7 26.4 224.3 28.1 48.4 255.9 17.6 86.2 476.1 18.1 80.7 478.1 RSDIC (%) 2.2 1.2 0.3 1.8 5.6 0.6 2.0 2.0 0.4 2.2 3.1 0.7 RSDTitration (%) 1.2 3.3 0.3 0.5 2.4 1.1 0.4 1.3 0.6 0.2 1.8 1.1 a Calculated from fluoride and hexafluorosilicate concentrations. Determination via nitrate concentration. In etching bath sample 1, b c also 651 g/L sulphuric acid were detected.38 THEAPPLICATIONSBOOK August 2011
  3. 3. APPLICATION NOTE H4SiO4 + 12 MoO42− + 24 H+ — H4[Si(Mo3O10)4] + 12 H2O > Conclusion Ion chromatography with dual detection allows determining The injection of SiF 62− produces a fluoride peak in the the concentration of all relevant constituents of texturingconductivity detector and a silicate peak in the UV/vis baths for solar cell production in less than 30 minutes. Thedetector. The mass balance derived from the respective acids consumed in the texturing process can subsequentlypeak areas confirms that the concentration of SiF 62− results be replenished in a targeted way. This extends the life ofstoichiometrically from the determined fluoride and silicate the etching baths, guarantees clean and reproducible waferconcentrations, provided there are no other sources of surfaces, cuts costs and protects the environment.fluoride or silicate present. Thus the concentration of freeHF can be calculated as the difference between the total Referencesfluoride concentration and the fluoride concentration from 1. A. Henssge and J. Acker, Talanta, 73, 220–226 (2007).the hexafluorosilicate: 2. J. Acker and A. Henssge, Talanta, 72, 1540–1545 (2007). 3. M. Zimmer et al., 22nd European Photovoltaic Solar Energy Conference and Exhibition, Milan, Italy (2007). [HF] = [F−]total − [F−]hexafluorosilicate 4. G. Bogenschütz, C. Wilde and C. Hack, Pittcon 2009 (http://www., search for 8.000.6041EN).Analysis of the Texturing Baths and ValidationAfter being diluted at ratios between 1:1000 and 1:5000,four samples from different texturing baths are analysed fortheir constituents by using the above IC method with dualdetection. Figure 4 shows the chromatograms of etchingbath sample 1 obtained by conductivity (a) and UV/vis (b)detection. Table 1 provides an overview of the concentrationsof the relevant bath components determined by ionchromatography with dual detection. For comparison, the Metrohm International Headquartersconcentrations obtained by titration are also shown. The Ionenstrasse, CH-9101 Herisau, Switzerlandpotentiometric determination of acid concentrations and tel. +41 71 353 85 04H 2SiF 6 content was carried out using aqueous acid-base E-mail: aw@metrohm.comtitration with 1 mol/L NaOH solution. Website: www.metrohm.comTHEAPPLICATIONSBOOK August 2011 39