CHY3001 Advanced Physical Practical Reports

Nik Amelina Nik Adnan 073341288 Date 10 November 2009 Title Experiment I : Infrared Spectroscopy of Porous Silicon Abstract Experiment I was done in order to obtain infrared spectra of hydrogen-terminated silicon and to assign the bands corresponding to each type of them, to use infrared spectroscopy to observe the oxidation and the alkylation process of porous silicon, to determine the rate of oxidation of porous silicon under various conditions of pH and EtOH/H2O mole fractions. Introduction Infrared spectroscopy is one of the surface-sensitive instrument which can be used to obtain spectra of molecules adsorbed at an interface, but few enhancements of the signals were still required such as applying multiple reflections of IR beam from the interface or increasing specific surface area. Porous silicon provided has free valence on the surface which then being filled by forming bonds to hydrogen. The hydrogen-terminated surface of silicon will be 1xidized in water and react with unsaturated molecules to undergo hydrosilation. Theory Reaction scheme of porous silicon surface reactions with unsaturated molecules
R H Si H Si H Si Heat R Si H Si Si R

Reaction scheme of porous silicon surface oxidation Si-H + H2O Si-OH + H2 2Si-OH + 2H2O 2SiO2 + 6H2 Si-H + EtOH Si-OEt + H2 Si-OEt + H2O SiO2 + EtH

Pre-lab Questions Undecene : R22 Harmful if swallowed R36/37/38 Irritating to eyes, respiratory system and skin S37 Wear suitable gloves Toluene : R11 Highly flammable R38 Irritating to skin R48/20 Harmful : danger of serious damage to health by prolonged exposure through inhalation R63 Possible risk of harm to the unborn child R65 Harmful : may cause lung damage if swallowed R67 Vapours may cause drowsiness and dizziness S36/37 Wear suitable protective clothing and gloves S29 Do not empty into drains S46 If swallowed, seek medical advice immediately and show this container or label S62 If swallowed, do not induce vomiting, seek medical advice immediately and show this container or label NaOH : R35 Causes severe burns S26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice S37/39 Wear suitable gloves and eye/face protection S45 In case of accident or you feel unwell seek medical advice immediately

Experimental Procedures Software IR Spectrometer was entirely software controlled. Spectra was exported as ascii files and replotted in Excel Obtaining Spectra of Solid Samples A 1 x 1 cm piece of silicon wafer was attached to the steel plate using blu-tack and was ensured that it covers the hole. IR beam was passed through this hole to generate the spectrum and a clean 1 x 1 cm piece of non-porous silicon wafer as the background. Task 1 An IR spectrum of a sample of porous silicon was obtained. The reflux was set up to carry out the alkylation of this sample, and the solution used is 0.1M undecene in toluene. The chip was refluxed for 3 hours, allowed to cool, washed with toluene and blowed dry under nitrogen. Another spectrum of the sample was measured. This spectrum was compared with a spectrum of neat undecene by placing a drop on a non-porous Si chip. Task 2 An IR spectrum of a sample of porous silicon was obtained. The sample was then allowed to sit in a beaker of distilled water for 10, 20 and 30 minutes. After that, it was dried and its IR spectrum was re-measured. Dilute NaOH was added to the water, and effect on the oxidation of porous silicon was observed by FTIR.

Analysis of Results i. Porous Si

Plot of Absorbance versus Wavenumber for Porous Si

0.4 0.3 Absorbance 0.2 0.1 0 -0.1400 -0.2 Wavenumber (cm-1) 800 1200 1600 2000 2400 2800 3200 3600 4000

Peak Absorbance 0.29 0.05 -0.05 -0.10 Broad peak at 2118 cm-1 is due to Si-H stretch. Peak at 2365 cm-1 is due to CO2 presence in air.

Wavenumber (cm-1) 629 914 2118 2365

ii. Porous Si with undecene (refluxed)

Plot of Absorbance versus Wavenumber for Porous Si with Undecene (Refluxed)

0.3 0.2 Absorbance 0.1 0 -0.1400 -0.2 -0.3 Wavenumber (cm -1) 800 1200 1600 2000 2400 2800 3200 3600 4000

Peak Absorbance 0.17 -0.02

Wavenumber (cm-1) 1072 2928

After 3 hours refluxing with undecene, there is no more peak at the region ~2118 cm-1, showing that no Si-H bond present. Si-C stretch, however cannot be seen in the spectra. Both Si and C have about the same electronegativities, so Si-C bond is not strongly distorted, and hence, only give very weak absorbance, which cannot be seen in the spectrum. Peak at 2928 cm-1 is due to saturated C-H stretch on undecene carbon chain.

iii. Non-porous Si with undecene

Plot of Absorbance versus Wavenumber for Non-porous Si with Undecene

1.2 1 Absorbance 0.8 0.6 0.4 0.2 0 -0.2400 800 1200 1600 2000 2400 2800 3200 3600 4000 Wavenumber (cm-1)

Peak Absorbance 0.30 0.08 1.06 0.11

Wavenumber (cm-1) 910 1643 2926 3082

No peak at the region ~2118 cm-1 showing that no Si-H bond present. Peak at 1643 cm-1 is due to C=C presence in undecene Peak at 2926 cm-1 is due to C-H stretch (saturated) Peak at 3802 cm-1 is due to C-H stretch (unsaturated) Compared to the previous spectra of porous Si with undecene, we can see that porous Si, which is hydride-terminated was replaced by alkyl group to give alkyl-terminated Si. On the other hand, non-porous Si does not hydride-terminated, so C=C in undecene remains.

iv. Porous Si before addition of water

Plot of Absorbance versus Wavenumber for Porous Si before adding H 2O

0.4 0.3 Absorbance 0.2 0.1 0 -0.1400 -0.2 -0.3 Wavenumber (cm-1)

800 1200 1600 2000 2400 2800 3200 3600 4000

Peak Absorbance 0.29 0.05 -0.05 -0.10 Broad peak at 2118 cm-1 is due to Si-H stretch

Wavenumber (cm-1) 629 914 2118 2365

v. Porous Si after 10 minutes addition of water

Plot of Absorbance versus Wavenumber for Porous Si after 10 mins addition of H2O
0.4 0.3 Absorbance 0.2 0.1 0 -0.1400 -0.2 -0.3 Wavenumber (cm-1)

800 1200 1600 2000 2400 2800 3200 3600 4000

Peak Absorbance 0.29 0.05 -0.05 -0.10

Wavenumber (cm-1) 629 914 2118 2368

After 10 minutes sitting in water, there seems no changes appear to the spectra. Peak at 2118 cm-1 corresponding to Si-H stretch is still exist.

vi. Porous Si after 20 minutes addition of water

Plot of Absorbance versus Wavenumber for Porous Si after 20 mins addition of H2O
0.5 0.4 Absorbance 0.3 0.2 0.1 0 -0.1400 -0.2 800 1200 1600 2000 2400 2800 3200 3600 4000 Wavenumber (cm-1)

Peak Absorbance 0.38 0.09 -0.04 -0.03

Wavenumber (cm-1) 629 916 1101 2118

There is still no change in spectra for porous Si after 20 minutes sitting in water. Peak at 2118 cm-1 corresponding to Si-H stretch is still exist.

vii. Porous Si after 30 minutes addition of water

Plot of Absorbance versus Wavenumber for Porous Si after 30 mins addition of H2O
0.4 0.3 Absorbance 0.2 0.1 0 -0.1400 -0.2 -0.3 Wavenumber (cm-1)

800 1200 1600 2000 2400 2800 3200 3600 4000

Peak Absorbance 0.36 0.07 0.01 -0.05

Wavenumber (cm-1) 629 916 1101 2118

Observed that the same thing goes to porous Si after half an hour sitting in water. Peak at 2118 cm-1 for Si-H still exist.

viii. Porous Si after adding NaOH

Plot of Absorbance versus Wavenumber for Porous Si after addition of NaOH

0.2 Absorbance 0.1 0 400 -0.1 -0.2 -0.3 Wavenumber (cm-1) 800 1200 1600 2000 2400 2800 3200 3600 4000

Peak Absorbance 0.16 0.005 0.01 -0.13

Wavenumber (cm-1) 631 914 1088 2118

There is no significant changes in peak. Peak at 2118 cm-1 corresponding to Si-H is still exist, showing that progress of oxidation of porous Si with NaOH is also slow.

ix. Porous Si before treatment with EtOH/H2O

Plot of Absorbance versus Wavenumber for Porous Si before treatment with EtOH/H 2O
0.4 0.3 Absorbance 0.2 0.1 0 -0.1400 -0.2 -0.3 Wavenumber (cm-1)

800 1200 1600 2000 2400 2800 3200 3600 4000

Peak Absorbance 0.29 0.05 -0.05 -0.10 Peak at 2118 cm-1 corresponding to Si-H is existed.

Wavenumber (cm-1) 629 914 2118 2365

x. Porous Si with 10% (v/v) EtOH/H2O

Plot of Absorbance versus Wavenumber for Porous Si in 10% (v/v) EtOH/H2O

0.2 0.15 Absorbance 0.1 0.05 0 -0.05400 800 120 160 200 240 280 320 360 400 0 0 0 0 0 0 0 0 -0.1 -0.15 Wavenumber (cm )
10% (v/v) EtOH/H2O contains 3 cm3 of ethanol in 25 cm3 EtOH/H2O mixture Peak at 2118 cm-1 is still exist, but this time we can see the peak is not as intense as before. Oxidation is quite observable where we can detect bubbling in the reaction beaker, proving that colourless gas (hydrogen) is released.
-1

xi. Porous Si with 15% (v/v) EtOH/H2O

15% (v/v) EtOH/H2O contains 4.5 cm3 of ethanol in 25 cm3 EtOH/H2O mixture Now we can see clearer changes of peaks after using higher mole fraction of EtOH/H2O. Peak at 2118 cm-1 corresponding to Si-H bond is no longer exist after we ran the oxidation with 15% (v/v) EtOH/H2O. New peak has formed, which is around 2900 cm-1 corresponding to saturated C-H stretch. This proves that Si is no longer hyride-terminated. Bubbling is more vigorous in this part compared to the previous one. Rate of formation of hydrogen gas might be increases due to higher mole fraction of ethanol. We also can observed that, mole fraction of EtOH/H2O affects the rate of oxidation. Porous Si was immersed in both mole fraction, successively, for 15 minutes for each of the mole fraction. When using 10% (v/v) EtOH/H2O mixture, effect of oxidation is not so significant in the spectra, but when using the more concentrated one, we can see clearly that porous Si is now being oxidised.

Questions

Question 1 To describe this question in terms of energy level, we can illustrate it as below : hv E

According to equation Nu/Ng = e-E/RT For NMR, E << RT so Nu will be equal to Ng. Energy separation between various spin states where the nuclei have been distributed is very small, and hence, the nuclei were promoted to higher energy spin state by energy from thermal collisions. Boltzmann distribution describes numbers of nuclei in each spin state, Nu and Ng. NMR has very small energy gap of the spin states, so highly concentration of species are needed. Surfaces of materials only have tiny volume of the materials volume, and this will result in signals coming from bulk materials will drown out signals from the surfaces. Question 2 Other surface-sensitive spectroscopic technique is called Surface Enhanced Raman Spectroscopy (SERS). This technique will result in enhancement of Raman scattering by molecules adsorbed on rough metal surface, where the enhancement factor can be as big as 1014-1015 which allows the technique to be sensitive enough to detect single molecules. Question 3 Si-H stretch is around ~2100 cm-1

Conclusion

From all of reactions that were done in this experiment, we can see that hydride-terminated Si will react with undecene which contains C=C to form Si-C bond, where Si now is alkylterminated, and this reaction is called hydrosilation. Si=H was added across C=C bond in undecene. Presence of peak at 2117 cm-1 for Si-H is the main guideline to check that the porous Si has undergone this reaction. Due to hydrophobic character of porous Si, its oxidation with water is very slow, and same things happened when NaOH was added into. Peak at 2117 cm-1 is still observed showing that nothing is changing on the surface of porous Si. Oxidation, however, was ran even faster when using mixture of ethanol and water with certain determined mole fractions. Spectra shows significant changes for the peaks, especially when using higher concentration of ethanol in water. References CHY3001 Physical Practical Manual Dudley H William, Ian Fleming (1995) Spectrocopic Methods in Organic Chemistry, 5th edition, Berkshire, McGraw-Hill Buriak, J. M. Chem. Commun. 1999, 1051 Buriak, J. M. Chem. Rev. 2002, 102, 1272 Sailor, M. J; Lee, E. J. Adv. Mater. 1997, 9, 783

Appendix

Mass of undecene used in task 1 : Volume of solvent (toluene) = 25 cm3 Concentration of undecene = 0.1 M No. of moles of undecene used = 0.025 L x 0.1 mol L-1 = 2.5 x 10-3 mol Molecular mass of undecene = 154.30 g mol-1 Mass of undecene used = 2.5 x 10-3 mol x 154.30 g mol-1 = 0.386 g # Concentration of NaOH used in task 2 : Mass of solid NaOH used = 0.4482 g No. of moles of NaOH used = 0.4482/40 = 0.011 mol Volume of solution made up to = 100 cm3 n = MV/1000 M = 1000n/V = 1000(0.01)/100 = 0.1 M#