SPEKTROSKOPI ANALITIK

(UV, UV-VIS, IR, NMR) dan

PADATAN MICROSKOPI

Oleh : Mushlihah (1406 201 703)

Nur Komariyah (1406 201 705)
Amin Makmun (1406 201 710)
Edi Sutanto (1406 201 726)
PENDAHULUAN

Spektrofotometer adalah alat untuk mengukur transmitans atau
absorban suatu cuplikan sebagai fungsi dari panjang
gelombang, digunakan untuk pengukuran serapan pada sinar
UV/VIS

Dalam spektrum elektronik yang penting adalah intensitas
absorpsi atau emisi

Intensitas absorpsi pada panjang gelombang tertentu dapat
ditentukan dengan melewatkan berkas cahaya monokromatis
lewat cuplikan dengan tebal dan konsentrasi tertentu

Transmitansi dapat ditentukan pada bermacam-macam panjang
gelombang sehingga didapatkan suatu spektrum absorpsi

Lambert mengembangkan teori yang menghubungkan berkas
cahaya yang keluar dengan ketebalan medium homogen, Beer
mengembangkan rumus untuk pengaruh konsentrasi

Pada penyerapan sinar UV/VIS mengikuti hukum Lambert Beer
A =εbc
SPEKTROFOTOMETER

Peralatan spektrofotometer dibedakan

menjadi empat :

Spektrofotometer single Beam

Spektrofotometer Double Beam

Spektrofotometer Multichannel

Spektrofotometer flourometer
SPEKTROFOTOMETER
SPEKTROFOTOMETER
SPEKTROFOTOMETER
SPEKTROFOTOMETER
SPEKTROFOTOMETER
SPEKTROFOTOMETER
SPEKTROFOTOMETER
SPEKTROFOTOMETER
Komponen-komponen penting dalam
alat spektrofotometer

Sumber sinar,
menggunakan lampu
awa muatan hidrogen
atau deuterium
Komponen-komponen penting dalam
alat spektrofotometer

Pemilih panjang gelombang, , menggunakan
monokromator
Komponen-komponen penting dalam
alat spektrofotometer

Sel/kuvet

Detektor

recorder
 ABSORBSI MOLEKULAR

Spesi absorbing

UV/Vis

- Terkait dengan transisi elektron

- Karena besarnya jumlah bentuk vibrasi dan transisi maka spekra
muncul sebagai pita
- Dasar teorinya adalah teori orbital Molekul
- Orbital yang terlibat adalah orbital σ, σ*, π, π* dan n
Abrsobsi UV/Vis oleh senyawa organik terjadi bila energi
terabsorbsi yang menyebabkan lompatan elektron dari orbital
dasar (populated orbital) ke orbital yang lebih tinggi (unpopulated
orbital)
Tidak teramati pada UV/Vis normal

Maxima absorbsi pada < 150 nm

Energi terlalu besar

Tipe absorbsi ini terkait dengan

pemecahan ikatan C – C, C – H, C – O,
C – X, …
Senyawa harus mempunyai atom
dengan pasangan elektron bebas

Senyawa mengandung O, S, N dan

halogen bisa mengabsorb melalui
transisi tipe ini

Absorbsi pada area 150 – 250 nm dan

sangat tidak intensif
Untuk orbital π* harus ada ketidakjenuhan
dengan beberapa ikatan rangkap yang
terkonjugasi

Merupakan absorbsi yang cukup intensif pada

area 200 – 700 nm)

Tingkat ketidakjenuhan meningkat akan

mengakibatkan pergeseran ke λ yang lebih
tinggi
- Solvent yang dipergunakan dapat mempengaruhi hasil
spektrum dan bisa mengakibatkan pita melebar
- Solvent Polar menstabilkan transisi tingkat dasar π* ← n dan
menyebabkan pergeseran biru, untuk transisi π* ← π tingkat
tereksitasi yang distabilkan dan terjadi pergeseran merah

Tidak ada solvent

dan interaksi antar
molekul minimal
Absorbsi oleh anorganik
Sama seperti organik- khususnya nitrat
Dapat juga terlihat beberapa absorbansi
untuk spesi dengan orbital d yang terisi
sebagian

Banyak absorbsi dramatik yang teramati

untuk kompleks logam transisi. Merupakan
akibat interaksi ligan dengan orbital d dari
logam
Absorbsi oleh anorganik
Logam transisi pada umumnya
mengandung orbital d yang terisi sebagian

Untuk ion bebas, orbital2 d pada tingkat

energi yang sama. Namun orbitalnya tidak
identik

Interaksi antar ligan akan menyebabkan

pada beberapa orbital
Tipe dan tingkat splitting tergantung pada
ligan dan geometri kompleks yang
terbentuk
Splitting dari orbital d mengakibatkan
transisi d sampai >d yang berada pada
area UV/Vis
Charge transfer complexes
Kompleks terdiri dari spesi donor elektron
dan spesi akseptor elektron

Menghasilkan kompleks yang membentuk

struktur “resonansi-like” yang bisa
mengabsorbsi

Spesi ini cenderung memperlihatkan

absorbtifitas sangat besar (εmax > 10.000)
sehingga banyak metoda analitik yang
berdasarkan pada pembentukan komplek
tipe ini
Analisa kulitatif UV/Vis
Sangat tidak berguna

Spektra cenderung merupakan pita lebar

dengan struktur yang kecil

Spektra dengan gugus yang mempunyai daya

absorbsi sama denderung sama
Analisa kuantitatif UV/Vis
- Penggunaan umum untuk area spektra ini
- Aplikasi luas
- Metodanya ribuan
- Tipe yang umum untuk pengujian
- Sensitifitas tinggi
- batasan deteksi 10-4 – 10-6 M
- Selektif
- Akurasi baik : range 1 – 5 %
- Relatif mudah dan tidak mahal
 Langkah-langkah utama dalam analisa
dengan sinar UV/Vis

Pembentukan molekul yang dapat menyerap sinar UV/Vis

Harus dilakukan jika senyawa yang dianalisa tidak melakukan
penyerapan didaerah UV

Senyawa harus diubah menjadi bentuk lain yang dapat melakukan
penyerapan pada daerah yang dimaksud

Pemilihan panjang gelombang

Bila tidak ada zat lain yang mengganggu, maka panjang
gelombang yang digunakan biasanya adalah panjang gelombang
yang sesuai dengan absorbans maksimum

Pembuatan kurva kalibrasi

Untuk keperluan ini dibuat sejumlah larutan standart dengan
berbagai konsentrasi yang diketahui

Absorbans larutan standart ini diukur kemudian dibuat grafik A
terhadap C

Hukum Lambert Beer terpenuhi , jika grafik berbentuk garis lurus
yang melalui titik nol

Pengukuran absorbans cuplikan

Pembentukan warna pada cuplikan harus dilakukan pada kondisi
yang sama seperti pada pembentukan warna standart
Pendahuluan

Sinar IR ditemukan pertamakali oleh Sir William Herschel, tahun 1800

Daerah IR
 λ : 0,75-300 µm

Daerah serapan yang umum digunakan: 4000-667cm-1 (2,5-15µm)

Spektrum IR seny organik/anorganik

 mempunyai sifat yang khas

Spektrum IR suatu molekul

hasil transisi antara tingkat energi getaran (vibrasi) yg berlainan

Inti-inti atom yang terikat ikatan kovalen mengalami vibrasi

Bila molekul menyerap radiasi IR

 kenaikan dlm amplitudo getaran atom-atom yg terikat

MOLEKUL Vibrasi tereksitasi

Lanjutan Pendahuluan…

Vibrasi dari ikatan, perbedaan pada:
- Panjang gelombangidentifikasi gugus fungsi
- Banyaknya energi yang diserap krn perub momen dipol (µ≠0)
Misal : ikatan non polar (C-H atau C-C) : absorpsi lemah
ikatan polar (O-H, N-H dan C=O) : absorpsi kuat
- Dapat menyerap energi pada lebih dari satu panjang
gelombang
Misal: Ikatan O-H menyerap energi pada frekuensi
 3330 cm-1 : kenaikan vibrasi stretching
1250 cm-1 : kenaikan vibrasi bending

Tipe vibrasi yang berlainan  vibrasi fundamental

Penggunaan Secara Umum

Identifikasi senyawa organik maupun anorganik

Penentuan gugus fungsi senyawa organik

Penentuan komposisi molekul pada permukaan

Penentuan kuantitas senyawa dalam campuran

Metode  Nondestructive
Aplikasi

Identifikasi senyawa dengan menjodohkan spektrum dari senyawa

yang tidak diketahui dengan spektrum referensi (fingerprint)

Identifikasi gugus fungsi dalam zat yang belum diketahui

Identifikasi komponen-komponen reaksi dan untuk mempelajari kinetika

reaksi

Mendeteksi molecular impurities dalam jumlah 0,01- 0,1%

Samples

State: solid, liquid or gas  sampling accessories.

Amount: Solids 50 to 200 mg is desirable, but 10 µg ground with

transparent matrix (such as KBr); 1 µg in suitable solvent. Liquids 0.5
µL neat, less if pure. Gases 50 ppb.

KBr, suitable solvent (CCl4 and CS2).

Many types of sample holders and cells are available.

Water should be removed from sample if possible.

 For
Non transparent sample
Range Frekuensi IR
–1

13.000 sampai 10 cm , atau panjang gelombang dari 0,78 sampai
1000 µm.

IR dekat , IR sedang, IR jauh

Teori

Pada suhu absolut diatas nol, semua atom dalam molekul secara
kontinyu mengalami vibrasi. Frekuensi dari spesifik vibrasi sama
dengan frekuensi radiasi IR pada molekul molekul menyerap radiasi

Tipe utama dari vibrasi molekul adalah stretching dan bending

Perubahan dalam panjang ikatan stretching

Perubahan dalam sudut ikatan bending

Spektrum infrared (IR) umumnya diperoleh dengan melewatkan radiasi

infrared melalui sample dan menentukan apakah fraksi dari radiasi
terabsorb pada partikel
Lanj teori….

Energi pada puncak dalam spektrum absorbsi muncul sesuai dengan

frekwensi vibrasi dari molekul sample

Wavenumber (bilangan gelombang) cm-1

Peningkatan energipeningkatan wavenumber

Hukum Hooke’s

Suatu molekul dapat dianggap sebagai sistem massa yang tergabung
oleh ikatan bersifat spring like

Kekuatan ikatan lebih besar wavenumber lebih besar

m1 m2

Dua atom dihubungkan oleh ikatan kovalen ditunjukkan seperti 2 beban pada ujung-ujung pegas. Ketika beban dipindah dari
posisi diamnya dan dilepaskan,vibrasinya hanya pada frekwensi tertentu yang tergantung pada massa beban dan konstanta
berhubungan dengan kekakuan pegas.
Lanj Hukum Hooke‘s….

Penetapan Frekuensi regang hukum Hooke‘s

1/ 2
1  f 
ν=
2π c  (M x M y ) / M x + M y 
 
Dimana :
v = frekuensi vibrasi (cm-1)
c = kecepatan cahaya (cm/s)
f = konstanta kekuatan ikatan (dyne/cm)
 Faktor-faktor yang mempengaruhi frekuensi penyerapan

Massa dari atom-atom yang berikatan.

Massa meningkat bilangan gelombang menurun
C-H : 3000 cm-1 C-Cl : 750 cm-1
C-C : 1200 cm-1 C-Br : 600 cm-1
C-O : 1100 cm-1 C-I : 500 cm-1

Kekuatan ikatan kimia

Makin kuat ikatan bil.gelombang meningkat
CΞC : 2150 cm-1 C=C : 1650 cm-1 C-C : 1200 cm-1

Hibridisasi
Ikatan makin kuat dalam susunan SP>SP2>SP3
C-H (SP): 3300 cm-1 C-H (SP2): 3100 cm-1 C-H (SP3): 2900 cm-1

Resonansi
konjugasi mengurangi energi untuk vibrasi ikatan
keton terisolasi : 1715 cm-1 α,β keton tak jenuh : 1690 cm-1
α,β,γ keton tak jenuh : 1675 cm-1
Terjadinya Penyerapan Sinar IR

Bila molekul menyerap sinar IR dari daerah 0,75-25 µm terjadi
perubahan tingkat energi vibrasi & energi rotasi

Syarat molekul dpt menyerap energi sinar IRvibrasi&rotasi molekul

harus disertai perubahan momen dipol

Perubahan momen dipol besar pita serapan lebih kuat

Adanya perbedaan elektronegativitas antara karbon & oksigengugus

karbonil memberi serapan yang kuat
 Vibrasi Fundamental

Vibrasi ulur (stretching) terjadi perubahan kontinyu dari jarak antara dua
atom dalam suatu molekul

Ada 2 macam stretching : simetris & tak simetris

Vibrasi tekuk (bending) terjadi perubahan sudut antara dua ikatan kimia

Ada 4 macam bending,yaitu:

Scissoring
- Bending di dalam bidang
Rocking

Wagging
- Bending di luar bidang
Twisting
Peralatan

Spektrometer IR umumnya double-beam (berkas ganda)
Terdiri dari: sumber radiasi, daerah cuplikan fotometer, kisi difraksi
(monokromator), dan detektor

Sumber radiasi  pemijar Nerst (batang Sirkonium&Ytrium oksida)

atau Globar (batang Silikon karbida)

Monokromator terdiri dari :

celah masuk & keluar, alat pendispersi yang berupa kisi difraksi atau
prisma dan cermin untuk memantulkan & memfokuskan sinar

Detektor  menggunakan detektor panas

Characterization of Heterogeneous Catalysts
by Diffuse Reflectance Spectroscopy.
 Titanium silicalite (TS-
(TS-1)

TS1--1
TS1

TS1--2
TS1
Ti - O - Si
970
TS1--3
TS1
TS1--3
TS1
TS1--4
TS1

TSIL
970
TSIL

800 SIL
550 SIL
1230 452

1105
TIO
TIO

1400 1200 1000 800 600 400

Wavenumber, cm-1
 TO4 Stretching, Si–O–Ti T-O Bending
Sample
Asymmetric Symmetric Asymmetric

TS-1 (1%) 1229 1105 799 978 548 453

TS-1 (2%) 1230 1105 804 971 549 452

TS-1 (3%) 1231 1102 803 971 548 452

TS-1 (4%) 1228 1107 799 968 549 544

SIL 1231 1106 799 - 551 452

Ti/SIL 1231 1109 799 - 551 452

ZSM-5 1227 1104 798 547 453

 Titanium MCM-
MCM-41 (Ti-
(Ti-MCM-
MCM-41)

TM4

TM3

TM2

SM

Ti - O - Si
H - O - Si

1400 1200 1000 800 600 400

Wavenumber, cm-1
 Bifunctional catalyst (Nb/TS1)

TS1

NTS1

NBA

NBO
Nb=O
Nb-O-Nb

1400 1200 1000 800 600 400

Wavenumber, cm-1
CaF2 window Cell
Tube Furnace

Sample holder Vacuum Pump

(Rotary and Diffusion)

Experimental setup for hydroxyl groups and acidity analysis

 3609
3 3
7 6
4 6
3 0

H-ZSM-5
3742

3733
3
5
2
8 SIL
3726 3
5
2 TS-1 (1%)
6

TS-1 (2%)
3730
3
5
2
6
TS-1 (3%)

TS-1 (4%)

3800 3600 3400 3200

Wavenumber, cm -1

Infrared spectra of the silicalite, ZSM-5 and TS-1 samples in the hydroxyl groups region, after
evacuation at 400oC in vacuum.
 3736

3526

TS-1

Absorbance, a.u.

SO42-/TS-1

SO42--Ti/TS-1

4000 3800 3600 3400 3200 3000

Wavenumber, cm-1

Figure 4.5: FTIR spectra of the TS-1, SO42-/TS-1 and SO42-Ti/TS-1 samples after
heated at 400oC for 4 h in vacuum.
 HZSM-5

SIL

TS-1 (1%)

Sample Brønsted, µmol/g Lewis, µmol/g

TS-1 (1%) - 30
TS-1 (2%) TS-1 (2%) - 52

TS-1 (3%) - 83

TS-1 (4%) - 48

SIL - 11
TS-1 (3%) HZSM-5 162 78

TS-1 (4%)

1700 1600 1500 1400

Wavenumber, cm-1

Infrared spectra of the silicalite, ZSM-5 and TS-1 samples after evacuation at 400oC under vacuum followed by pyridine
adsorption at room temperature and desorption at 150oC for one hour.
 0.8
0.8

ABS 3608.6 ABS

0.7 0.6

3742.6 3659.7
0.6
0.4

0.5

0.2
0.4

0.3 0.0

4000.0 3900.0 3800.0 3700.0 3600.0 3500.0 3400.0 3300.0 3200.0 3100.0 3000.0
Testscan Shimadzu FTIR 8000 series 1/cm
-0.2
1700.0 1675.0 1650.0 1625.0 1600.0 1575.0 1550.0 1525.0 1500.0 1475.0 1450.0 1425.0 1400.0
1/cm

0.6 3609.5 1.5

ABS 3664.5 ABS

0.55 1.25 1489.9

3744.5
0.5
1.0
1635.5
1624.0
0.45
0.75 1869.9 1545.8
1452.3
0.4

0.5
0.35

0.25
4000.0 3900.0 3800.0 3700.0 3600.0 3500.0 3400.0 3300.0 3200.0 3100.0 3000.0
Testscan Shimadzu FTIR 8000 series 1/cm 2000.0 1900.0 1800.0 1700.0 1600.0 1500.0 1400.0 1300.0
Testscan Shimadzu FTIR 8000 series 1/cm
 per 10
sample 1870 1545 1444 gr sample mg kB kL Luas
tzo 13.4928 2.88398 1.75824 13 0.00592 3.03 3.8 0.7857
tzht 11.50901 3.08807 1.39229 13 0.00592 3.03 3.8 0.7857
tzcu 8.429 1.169 7.7813 13 0.00592 3.03 3.8 0.7857
tbo 5.404 2.0926 2.904 13 0.00592 3.03 3.8 0.7857
tbcu 7.18748 0.0563 10.76245 13 0.00592 3.03 3.8 0.7857
t-zsm5 8.10955 2.2025 1.2672 13 0.00592 3.03 3.8 0.7857
tbea 6.09805 2.48797 2.2744 13 0.00592 3.03 3.8 0.7857
tzcuht 8.5891 1.4065 7.1721 13 0.00592 3.03 3.8 0.7857
sample 1870 1545 1444 1870 1545 1444
tzo 13.4928 2.88398 1.75824 13.4928 2.88398
tzht 11.50901 3.08807 1.39229 13.4928 3.620356
tzcu 8.429 1.169 7.7813 13.4928 1.871288
tbo 5.404 2.0926 2.904 13.4928 5.22484
tbcu 7.18748 0.0563 10.76245 13.4928 0.10569
t-zsm5 8.10955 2.2025 1.2672 13.4928 3.664555
tbea 6.09805 2.48797 2.2744 13.4928 5.504986
tzcuht 8.5891 1.4065 7.1721 13.4928 2.209501
 1390

1390

1357
SZ500

400oC 1446
Absorbance / a.u.

996
1074

Absorbance / a.u.
SZ600

13 1
73 3
300oC
1
5 1308

13
58

1 SZ700
2
7 150oC 1541
6

1400 1300 1200 1100 1000 900 1700 1600 1500 1400 1300 1200
Wavenumber, cm-1 Wavenumber, cm-1
NMR
nmr

Liquid - state

Solid - state
 Solid-State NMR

Impact of Structural Order on NMR Spectrum

• Factors that average to zero in solution due to
random motion are now factors in solid state NMR
• dipole-dipole interaction
• mutual spin flips occurring between pairs of spins
 Each nucleus is “fixed” in the crystal lattice
 Each nucleus produces a rotating magnetic field
as it precesses in the applied magnetic field 
lifetime of spin state is reduced
 Each spin has a static field component that
influences frequency of neighbors
- Spin directions vary randomly
- Range of frequencies that add to line-
line-width
 Chemical shift anisotropy
- Chemical shift varies with orientation relative to B0
- Contributes to line broadening
Static & dynamic disorder

Diffraction-based
methods are most suited
to “rigid solids”

Because NMR probes

local environment, it is
applicable to any system

But “inversion” to
structural information
may be non-trivial
Solid-State NMR

Solid-state B Solution-state
(ordered structure) o (random-orientation)
 Solid-State NMR

Broad Structureless Resonances

• Requires Different Approaches Compared to Solution
State NMR
• Contains Unique Information Relative to Solution
State NMR
 Peak width is caused by dipole-dipole interaction
which is distance related
- Solid state NMR spectrum can be used to obtain
internuclear distances
 Peak width can monitor motion within the crystal
lattice
- Slowly increase temperature
- Line--width transactions indicates introduction of
Line
motion
13C NMR of glycine
O

H2N
OH
glycine

solution-state solid-state

Angew. Chem. Int. Ed. 2002, 41, 3096-3129

 Solid-State NMR
Powder vs. Crystal
• Crystal – regular uniform and repeat lattice structure

• Powder – consists of very many crystals all with different orientations

 Solid-State NMR
Powder Pattern
• Dipolar coupling
 Interaction of nuclear magnetic moments of two different
nuclear spins (I & S)
 The local magnetic field at spin S will be affected by spin I
- Changes resonance frequency of spin S
 The degree by which spin I affects the magnetic field at
spin S is determined by the dipolar coupling constant (d):

( )
H IS = − d 3 cos 2 θ − 1 I z S z
 where θ is the angle between Bo and the internuclear
distance (r)
 The dipolar constant is dependant on the distance
between the nuclear spins and their gyromagnetic ratios z

 µo  hγ I γ S
d =  3 θ
r
 4π  rIS B0 1H

13C

• Through space interaction  structural information y

• In solution, random motion averages dipolar coupling to
zero
• In solids, orientations are static  defined by crystal
lattice
x
Angew. Chem. Int. Ed. 2002, 41, 3096-3129
 Solid-State NMR
Powder Pattern
• Dipolar coupling
 Contains structural information ( r, θ)

Dipolar coupling provides distance information

 µo  hγ I γ S
d =  3
 4π  rIS

Orientation relative to B0

( )
H IS = − d 3 cos 2 θ − 1 I z S z

Angew. Chem. Int. Ed. 2002, 41, 3096-3129

 Solid-State NMR
Powder Pattern
• Chemical Shift Anisotropy
 Chemical shift is dependent on orientation of nuclei in the solid
- Distribution of chemical shifts
- Averaged to zero for isotropic tumbling
- Leads to extensive line-
line-width broadening in solid-
solid-state NMR

Progress in Nuclear Magnetic Resonance Spectroscopy 6 46 (2005) 1–

1–21
 Solid-State NMR
Temperature Dependence
• Crystal Lattice Mobility Changes with Temperature
 Changes in bond rotations
 Large changes in line-shape depending on mobility in lattice

Rotation about C-
C-N bond

Rotation of NMe3
Whole molecule rotates
and diffuse within crystal
 Solid-State NMR
Magic Angle Spinning (MAS)
• Nucleus with magnetic moment (µ) will create a field at a second nucleus at a
distance r away
 Magnetic field will have a z component (Bz) in direction of Bo direction
- Influences the frequency of the second nucleus
- Couples the two spins
 Magnitude of Bz will depend on the angle of the magnetic moment relative
to B0

Kµ
(
BZ = 3 3 cos 2 θ − 1
r
)
z

r
B0 θ 1H

13C

x
 Solid-State NMR
Magic Angle Spinning (MAS)
• Zero z component (Bz) if the angle (θ) relative to B0 is 54.44o
 All dipolar interactions disappear at this angle
 All chemical shift anisotropy disappear at this angle
 Quadrupole broadening is also reduced

Bz = 0

 Simulate a uniform distribution of magnetic moments in a powder by

spinning the sample very fast at 54.44o
 Solid-State NMR
Magic Angle Spinning (MAS)
• Spin Samples at 54.44o to reduce line-width
 Spinning speed must be greater than static line-width to be studied
(powder pattern width)
- Normal speed limit is 35 kHz

rotor at MAS

Sample holder rotor

Sample holder at MAS MAS probe

 Solid-State NMR
Magic Angle Spinning (MAS)
• Impact of Spinning Speeds at MAS

13C NMR of glycine powder

O
Similar to Solution Spectrum
H2N
OH
glycine
Increasing Spinning Speed

Number of lines are reduced

with increase in spinning speed
as it approaches static line-width

Lines are separated by

spinning speed

Powder Pattern

Angew. Chem. Int. Ed. 2002, 41, 3096-3129

 Solid-State NMR
Spin ½ Nuclei with Low Magnetogyric ratios (13C, 15N, 29Si, 31P, 113Cd)
• Combine MAS with high power 1H decoupling
 Double resonance technique
 High power is required because of very large 1H line-widths
- Long T1 requires slow pulse rates to avoid saturation of signal
- Low sensitivity of nuclei requires long acquisition times

MAS reduces linewidth

from 5000 Hz to 200 Hz

MAS & high power decoupling

reduces linewidth from 5000
Increase in sensitivity
(NOE, spin-
spin-splitting) Hz to 2 Hz

High power decoupling Similar to liquid state sample

reduces linewidth from
5000 Hz to 450 Hz
NMR spectra
Si

◇ External reference:
SiO2 Tetramethysilane (TMS)
◇ Spinning rate: 7kHz
◇ Pulse length: 5 µs
SiO ◇ Delay time: 10 s

0 -20 -40 -60 -80 -100 -120 -140 -160 -180 -200
Chemical Shift (ppm)

29Si MAS NMR spectra for Si, SiO2 and SiO powders.
NMR spectra
pristine

0.21 V on charge

0.14 V on charge

0.0 V on charge

2.0 V on discharge

50 0 -50 -100 -150 -200

Chemical Shift (ppm)

29Si MAS NMR spectra for the SiO electrodes

Contributions from the silicon
nuclei show Gaussian peaks
at approximately -109 ppm
(Q4), -101 ppm (Q3), -92 ppm
(Q2), -84 ppm (Q1). The
relative contributions of these
structural sites were
calculated from deconvoluted,
integrated areas. The NMR
data show that with the K/Mo
molar ratio the nature of the
silica surface changes. The
change in the silica surface
arises from the increasing
interaction of MoOx with the
surface hydroxyl groups.
 Solid-State NMR
Cross-polarization combined with MAS (CP-MAS)
• Exchange polarization from 1H to 13C
 Similar in concept to INEPT experiment

• 1H 90o pulse generates xy magnetization (B1H)

• Spin
Spin--lock pulse keeps magnetization in xy plane
at:
precessing at:
γHB1H/2π Hz
/2π
13
• C pulse generates xy magnetization that precesses
at:
2 ms 50 ms γCB1C/2π Hz
/2π
• Polarization transfer occurs if:
γHB1H/2π Hz = γCB1C/2 π Hz
/2π
Hartmann Hahn matching condition
Polarization transfer
1Ηβ β
13Cβ

γHB1H/2π γCB1C/2
π
1Ηα
α
13Cα

∆E = γ h Bo / 2π
π
 -101.4

-109.4
I I I I
0 -50 -100 -150

δ ppm

29Si CP MAS NMR (solid state) spectrum of

material X3-SH
 Solid-State NMR
Cross-polarization combined with MAS (CP-MAS)
• Simultaneously pulse 1H to 13C
 Use RF energy to equilibrate energy states

γHB1H/2π Hz = γCB1C/2
/2ππ Hz

 The increase in the 13C signal depends on the strength of the dipolar
interaction and the duration of the mixing or contact time

 Maximum enhancement is γH/γC

 Solid-State NMR
Cross-polarization combined with MAS (CP-MAS)
• Example of CP-MAS 13C spectrum
 Cross-polarization increases the 13C population difference by the factor γH/γC
 Increases signal sensitivity
 Solid-State NMR
Spin ½ Nuclei with High Magnetogyric ratios (1H, 19F)
• Homonuclear interactions are very strong
 Difficult to remove by MAS
 Highest field strength and spinning rates can reduce a 10 kHz line-width to
1500 Hz
• Static line-widths are very large and chemical shifts are small
 Obtaining resolution is challenging
• Simulate MAS spinning by a series of RF pulses (MREV-8)

 Shift magnetization quickly between the three orhogonal axes

 Hop around magic angle and reduce dipole-dipole interaction
 Does not affect CSA or heteronuclear interactions
• MAS can be used to remove CSA
• CRAMPS – combines MAS with MREV-8
 Solid-State NMR
Spin ½ Nuclei with High Magnetogyric ratios (1H, 19F)
• Example of CRAMPS
 Resolution on the order of 180 Hz is possible

1H NMR of aspartic acid powder

O
CRAMPS
OH
HO

NH2 O
aspartic acid

MAS with increasing

spinning rates

Static Spectrum with

Broad Line-
Line-widths
Surface morphology

(Microscopy)
 Scanning Electron Microscope
SEM
is an incredible tool for seeing the unseen worlds of microspace.
Conventional light microscopes use a series of glass
lenses to bend light waves and create a magnified image.
 The Scanning Electron Microscope creates the
magnified images by using electrons instead of
light waves.
 The SEM shows very detailed 3-dimensional images at much higher
magnifications than is possible with a light microscope. The images created
without light waves are rendered black and white.
Samples have to be prepared carefully to withstand the vacuum
inside the microscope.
 Biological specimens are dried in a special way that prevents
them from shriveling. Because the SEM illuminates them with
electrons, they also have to be made to conduct electricity.
How do you make a mosquito conductive? Our SEM samples are coated
with a very thin layer of gold by a machine called a sputter coater.
Now the prepared specimen is ready.
The sample is placed inside the microscope's vacuum column
through an air-tight door.
 After the air is pumped out of the column, an electron gun [at the top] emits a
beam of high energy electrons. This beam travels downward through a series of
magnetic lenses designed to focus the electrons to a very fine spot.
Near the bottom, a set of scanning coils moves the focused beam
back and forth across the specimen, row by row.
As the electron beam hits each spot on the sample, secondary electrons are
knocked loose from its surface. A detector counts these electrons and sends
the signals to an amplifier.
The final image is built up from the number of electrons emitted from
each spot on the sample.
The Scanning Electron Microscope is revealing new levels of detail
and complexity in the amazing world of micro-organisms and
miniature structures.
Here is a small picture of the whole system
 Field Emission
Scanning Electron Microscopy (FESEM)

Principle of Operation
A field-emission cathode in the electron gun of a scanning electron microscope
provides narrower probing beams at low as well as high electron energy, resulting
in both improved spatial resolution and minimized sample charging and
damage.

For applications which demand the highest magnification

possible

Applications include
•Semiconductor device cross section analyses for gate widths, gate oxides, film
thicknesses, and construction details
•Advanced coating thickness and structure uniformity determination
•Small contamination feature geometry and elemental composition measurement
Why Field Emission SEM?
FESEM produces clearer, less electrostatically distorted images
with spatial resolution down to 1 1/2 nm. That's 3 to 6 times
better than conventional SEM.
Smaller-area contamination spots can be examined at electron
accelerating voltages compatible with Energy Dispersive X-ray
Spectroscopy.
Reduced penetration of low kinetic energy electrons probes
closer to the immediate material surface.
High quality, low voltage images are obtained with negligible
electrical charging of samples. (Accelerating voltages range
from 0.5 to 30 kV.)
Need for placing conducting coatings on insulating materials is
virtually eliminated.

Cross-section of a laser window showing multiple thin layers at

50,000x. (in the original photo)
Energy Dispersive X-Ray Spectroscopy (EDS)

EDS identifies the elemental composition of materials imaged

in a Scanning Electron Microscope (SEM) for all elements with
an atomic number greater than boron. Most elements are
detected at concentrations of order 0.1%.
Applications include

•Materials evaluation and identification

•Contaminants
•Elemental diffusion profiles
•Glassivation phosphorus content
•Multiple spot analysis of areas from 1 micron to 10 cm in diameter
•Failure analysis
•Contamination identification
•Unknowns identification
•Stringer location and identification
•Quality control screening
•Material verification
•Plating specification and certification
Principle of Operation
As the electron beam of the SEM is scanned across the sample
surface, it generates X-ray fluorescence from the atoms in its path.
The energy of each X-ray photon is characteristic of the element
which produced it. The EDS microanalysis system collects the X-
rays, sorts and plots them by energy, and automatically identifies and
labels the elements responsible for the peaks in this energy
distribution.
The EDS data are typically compared with either known or computer-
generated standards to produce a full quantitative analysis showing
the sample composition.
Data output is either this element analysis, the original spectrum
showing the number of X-rays collected at each energy, or maps of
distributions of elements over areas of interest.
Wavelength Dispersive X-Ray Spectrometry (WDS)

WDS identifies the elemental composition of materials

imaged in the SEM with an order of magnitude better
spectral resolution, sensitivity and ability to determine
concentratins of light elements than is achievable with
EDS. Most elements are detected below 0.1% and some as
low as a few ppm.
Applications include
spectrally overlapped elements, such as
•Identification of
•S in the presence of Pb or Mo
•W or Ta in Si, or N in Ti
•Br in Al, common in semiconductor device failure
•Detection of low concentration species (down to 100 or even 10 ppm)
•P or S in metals
•Contaminants in precious metal catalysts
•Trace heavy metal contamination
•Performance-degrading impurities in high temperature solder alloys
•Analysis of low atomic number elements
•Composition of advanced ceramics and composites
•B in BPSG films (sensitivity to 2000 ppm)
•Oxidation and corrosion of metals
•Characterization of biomedical and organically modified materials
Principle of Operation
The characteristic X-ray photons excited by the electron beam are
sorted using a diffracting crystal, whose angular placement relative to
the sample and photodetector is a unique measure of their wavelengths.
As with EDS, the resulting spectral distribution is automatically
compared with those from actual standards or synthetic X-ray
fluorescence spectra of material formulations.

WDS vs. EDS

X-ray microanalysis in the scanning electron microscope is
accomplished using EDS and/or WDS. EDS is more commonly applied
due to its simplicity and speed, while WDS offers an important and often
critical refinement of EDS data by providing
Analysis for light elements with at least an order of magnitude higher
sensitivity than available (ultrathin X-ray window) EDS instruments
Resolution of severely overlapped spectrum peaks for improved element
specificity
Lowered detection limits over the entire periodic table
More accurate quantitative analyses.
Atomic Force Microscope/Scanning Probe Microscopy

Atomic Force Microscopy and Scanning Probe Microscopy

(AFM/SPM) provide topographic information down to the
Angstrom level. Additional properties of the sample, such as
thermal and electrical conductivity, magnetic and electric field
strength, and sample compliance can simultaneously be
obtained using a specialty probe. Many applications require
little or no sample preparation.
Applications include

Materials Evaluation:
Surface roughness on implanted silicon wafers
Thermal properties such as thermal conductivity, glass transition
temperature (Tg), and melting temperature of various phases of a
blended polymer measured down to the nanometer scale
Surface profiles and magnetic field mapping of recording media or
reading heads
Nanomechanical testing

Failure Analysis
Rapid hot-spot analysis of powered electronic devices
Defect analysis of compact disk stampers

Quality Control
Surface profiles of thin film and coatings
Metrology of semiconductor devices and compact disks
Surface finish of substrates for thin film deposition
Principle of Operation
The Atomic Force Microcope uses a physical probe raster scanning
across the sample using piezoelectric ceramics. A feedback loop is used
to maintain a constant interaction between the probe and the sample.
The position of the probe and the feedback signal are electronically
recorded to produce a three dimensional map of the surface or other
information depending on the specialty probe used.
Data Output is either a three dimensional image of the surface or a line
profile with height measurements. The surface roughness parameters of
Ra or RMS are also available with either of the above outputs.
Other types of feature analysis include Partical Grain Size Analysis,
Bearing Ratio, Fractal Dimension, Power Spectrum, and Fast Fourier
Transform.
Atomic Force Microscope/Scanning Probe Microscopy
Scanning Auger Microanalysis (SAM)

SAM provides elemental and chemical composition for all elements

with an atomic number greater than helium. Its sampling depth of 2-3
nm allows films as thin as a few monolayers to be analyzed. Auger
also produces images of the distributions of elements along the
surface and produces profiles of composition vs. depth from 1 to 2000
nm.