Prinsip dasar analisis serapan dan

celah pita
Uyi Sulaeman, Ph.D

Referensi:
https://www.sciencedirect.com/topics/medicine-and-dentistry/diffus
e-reflectance-spectroscopy
A. Prinsip spektroskopi reflektan (reflectance
spectroscopy)
Ketika cahaya datang pada sample (elemen), maka akan
terbentuk refleksi specular dan difus.
Refleksi specular didefinisikan sebagai refleksi dari permukaan
elemen, di mana sudut datang sama dengan sudut reflektansi.

Refleksi difus, yang timbul dari interaksi cahaya dengan

berbagai faktor kimia dan fisik dalam isi elemen yang
merupakan komponen utama pengukuran. Interaksi ini
diantaranya: penyerapan, transmisi, dan hamburan.
 B. Hubungan konsentrasi dan reflektan
Reprinted with permission from Churchill-Livingstone, Inc., from V. Marks and
K.G.M.M.Alberit (Eds), “Clinical Biochemistry Nearer the Patient” (1985).Copyright
© 1985
Intensitas cahaya difus yang dipantulkan oleh lapisan elemen
dibandingkan dengan standar referensi dinyatakan sebagai
persen pantulan (reflektansi) (% R).

Is adalah cahaya yang dipantulkan dari sampel,

Ir adalah cahaya yang dipantulkan dari reflektor standar,
Rr adalah persen pemantulan/reflektansi standar.

Pengukuran reflektansi sebanding dengan pengukuran

transmitansi dalam spektroskopi absorpsi.

Pengukuran ini tidak memiliki hubungan linier dengan

konsentrasi, tetapi ada algoritma yang dikembangkan untuk
linierisasi hubungan antara % R dan konsentrasi analit:
Yaitu: persamaan Kubelka-Munk
Linierisasi reflektansi dengan konsentrasi:
 Aplikasi: analisis serapan, reflektan dan celah pita

Serapan E(eV)=1239.8/λ(nm)

=1239.8/400=3.10 eV

2.9 eV

UV-LED photocatalytic oxidation of carbon monoxide over TiO2 supported with

noble metal nanoparticles, The Chemical Engineering Journal 314:600 - 611
 Total and partial density of states of
anatase TiO2.
The electronic band structure of
anatase TiO2 projected on the
high symmetry lines of the
primitive tetragonal structure in
PW91 approximation

First principles study of hydrogen doping in anatase TiO2 (DOI: 10.1051/epjap/2014130582)

Reflektan

Morphological and Structural Properties of the TiO2 - SiO2 -Ag Porous Structures
Based System, Materials 8(3):1059-1073 (2015)
 Tipe Bandgap Semikonduktor

In direct bandgap semiconductor the electron “rising” from valence band to

the conduction band will only change it’s potential (energy).
In indirect bandgap semiconductor the electron “rising” from valence band
to the conduction band will change it’s potential (energy) and momentum
• Energy vs. crystal momentum for a
semiconductor with a direct band gap, showing
that an electron can shift from the highest-
energy state in the valence band (red) to the
lowest-energy state in the conduction band
(green) without a change momentum. Depicted
is a transition in which a photon excites an
electron from the valence band to the
conduction band.
• Energy vs. crystal momentum for a
semiconductor with an indirect band gap,
showing that an electron cannot shift from the
highest-energy state in the valence band (red) to
the lowest-energy state in the conduction band
(green) without a change in momentum. Here,
almost all of the energy comes from
a photon (vertical arrow), while almost all of the
momentum comes from a phonon(horizontal
arrow).
Direct semiconductors, the minimum energy of the conduction band occurs at the same
momentum as the maximum energy of the valence band.

Indirect semiconductors the maxima and minima do not coincide. This means that for an
electron to be promoted to the conduction band, a phonon must also be created to
conserve momentum.
Penentuan celah pita
The equation for photon energy is

E= hc/λ
Where E is photon energy, h is the Planck constant, c is the
speed of light in vacuum and λ is the photon's wavelength.
As h and c are both constants, photon energy E changes in
inverse relation to wavelength λ.

To find the photon energy in electronvolts, using the wavelength

in micrometres, the equation is approximately

E(eV)=1239.8/λ(nm)
Tauc’s Plot
 Tauc’s Plot

Y. Gao, Y. Masuda, and K. Koumoto, Band Gap Energy of SrTiO3 Thin film prepared
by the liquid phase deposition method, J. Korean Ceram. Soc. 40 (2003) 213-218.
The plot of (αhv)2 vs hv for
direct transition

The plot of (αhv)1/2 vs hv for

indirect transition
 direct band gap

UV−vis DRS spectra of

Cs2 O, Bi2O3 , and
ZnO and the Tauc's
indirect band gap plot of (b) Cs2O and
ZnO, and (c) Bi2O3 .

Direct Z‑Scheme Cs2O−Bi2O3−ZnO Heterostructures as Efficient

Sunlight-Driven Photocatalysts, ACS Omega 2018, 3, 12260−12269
Spektrum serapan Ag3PO4 yang disintesis dengan metode ion-
exchange, diukur dengan ultraviolet-visible diffuse reflectance
spectroscopy (a), plot (αhv)2 vs hv untuk direct transition (b) dan
plot (αhv)1/2 vs hv untuk indirect transition (c).
The Highly Active Photocatalyst of Silver Orthophosphate under Visible Light Irradiation for
Phenol Oxidation, Advanced Materials Research Vol. 896 (2014) pp 141-144