2.1.1.

Php o ph hp th Chiu mt chm tia sng n sc c cng I0 song song vo mt mi trng

vt cht c b dy l (cm) v nng C (mol/l), chm tia ny s b mi trng hp th v truyn qua. Cng I ca chm tia truyn qua mi trng ny b gim theo nh lut Lamber Beer: ln (I0/I) = Kn hay: Trong : ln (I0/I)= lC K- l h s hp th n- s mol cht nghin cu t trn ng i ca bc x i lng ln(I0/I) gi l mt quang (D) hay hp th (A), l h s hp th mol c gi tr bng mt quang ca dung dch khi nng cht hp th bng mt n v v dy cht hp th bng mt n v. H s hp th hay cn gi l h s tt ch ph thuc vo vt liu hp th v bc sng. truyn qua ca mi trng: T= I / I0. S hp th thng tp trung vo tng vng ph, cho nn thun li, ngi ta thng biu din v xem xt tng vng ph ring bit nh vng t ngoi, kh kin, hng ngoi. ng cong biu din s ph thuc ca h s hp th K vo tn s hoc bc sng gi l ng cong hp th (hay ph hp th). Mi cht u hp th lc la nhng tn s hay bc sng khc nhau. (2.2)

Hnh 2.9. S h o hp th quang UV-Vis

Nguyn tc o ph hp th:
Nu ta gi mt bc x n sc cng I0() ti mt mu ng th c di l, cng I() cn li li ra khi mu th nh hn I0(). Thng thng ta quan tm ti truyn qua T () = I()/ I0(). i khi ngi ta quan tm ti hp th A() = - log10 T(). Cc ph c v vi cc thit b truyn thng l vi "chm sng p" cho mt cch trc tip truyn qua T(). Vi k thut my tnh, hin nay ngi ta cng dng mt cch d dng c truyn qua v hp th. Cc my quang ph c dng, ging nh s b tr cc my tn sc, gm cc lng tr NaCl hoc tt hn l cc cch t vi cc knh lc giao thoa. H quang hc vi hai chm tia cho php nhn c trc tip t l I / I ref. gia cng I ca chm xuyn qua mu v cng I ca chm xuyn qua phn mu so snh. S so snh trc tip ny cho php bo m rng ph I () v I
ref.

() c

ghi trong cng mt iu kin. Cc php o ph hp th c tin hnh trn h my quang ph UV-visible-Nir Absorption Spectrophotometer (nhn hiu Cary 5000, Varian) c Vin Khoa hc v Cng ngh Vit nam. S h o hp th c trnh by trn hnh 2.9.

UV-VIS BASIC THEORY

Contact Info:

Josh Stapleton N050C MSC Bldg Email: Josh Stapleton Ph: 814-863-2224

Now in its new location:

N007 Millennium Science Complex (MSC)

UV-Vis Related Links Instrumentation Resource Links Ultraviolet (200-400 nm) and visible (400-800 nm) radiation are found towards the short wavelength, high frequency end of the electromagnetic spectrum. Figure 1 shows the portion of the electromagnetic spectrum where UV-Vis radiation exists.

Figure 1a: The Electromagnetic Spectrum. Short wavelength corresponds to high frequency and high energy. (click image above for larger version)

Figure 1b: The visible spectrum with respect to infrared and ultraviolet radiation. This energy range corresponds well with the energy range required to cause electronic excitations between molecular orbitals (??). ?? is defined as the energy difference between an occupied orbital (ground state) and an empty (excited state) orbital. The smaller the value of ??, the lower the frequency and also the longer the wavelength required to excite the electron. When the energy of the incoming photon matches ??, the photon is absorbed, and an electron from an occupied level "jumps" from its ground state to an empty level (also called an excited state). Note in Figure 2 that this transition could occur from various occupied to empty levels, but in reality, excitation only occurs between the two lowest energy transitions, the outer electron, ? -> ?* and the ? -> ?* levels for the energy range of 200800 nm associated with UV-Vis radiation. In general, this transition will occur between the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). When the photon is absorbed, a portion of the energy is absorbed as the electron is promoted to the excited state.

Figure 2: Electronic excitation of electrons between molecular orbitals UV-Vis Absorption spectroscopy measures the percentage of radiation that is absorbed at each wavelength. Typically this is done by scanning the wavelength range and recording the absorbance. UV-Vis absorption spectroscopy is widely used in organic chemistry to investigate the extent of multiple bond or aromatic conjugation within molecules. Frequently, organic chemists have used liquid solutions, because solvents such as ethanol

and hexane do not absorb in the UV-Vis range and solutions can be easily prepared for many organic compounds. The technique can be expanded to gases and solids, and also beyond absorption to include measuring reflected rather than transmitted light. UV-Vis spectra tend to be broad in nature due to the fact that vibrational and rotational levels of the molecular orbitals are superimposed upon the electronic levels shown in Figure 2. This produces a combination of overlapping lines that appear as a continuous absorption band in the UV-Vis spectrum. Figure 3 illustrates the vibrational and rotational levels superimposed upon the electronic levels.

Figure 3: Vibrational and rotational levels are superimposed on the electronic levels. This broad nature makes their usefulness in identifying materials limited, but the technique is ideal for quantitative analysis of solutions.

Liquids / Solutions
For example, the concentration of an analyte in solution can be determined by measuring the absorbance (A) at a selected wavelength and applying the Beer-Lambert Law as follows:

A=?xbxc
where ? is the wavelength-dependent molar absorptivity coefficient, b is the path length, and c is the concentration. Note that the instrument is fixed at a constant wavelength as the absorption is recorded. Absorbance is measured as the maximum absorbance reading. If the absorptivity coefficient is not known, the unknown concentration can be determined by creating a calibration curve of absorbance versus concentration for a series of standards.

Solids
Materials researchers are often working not with liquids, but with solid materials. Some solid materials can be analyzed via UV-Vis spectroscopy by dissolving the solid in a solvent, but this process is labor intensive and can introduce many sources of error into the measurement. It is also a destructive technique so the sample can not be recovered for other measurements. These factors make dissolution methods for UV-Vis absorption spectroscopy generally undesirable for most solid materials. Fortunately, there is another option. Accessories are available that allow the analyst to take advantage of the reflection of the incoming beam rather than using the standard absorption configuration described previously. UV-Vis reflectance spectroscopy is ideal for characterizing optical and electronic properties of many different materials such as films,

filters, and pigments. Descriptions of the specific accessories available for the MCL instrument can be found on the MCL UV/Vis Instrument page. In our laboratory, researchers are primarily interested in characterizing thin films. Some of these films are transparent to UV-Vis radiation while others are not. For non-transparent highly scattering thin films, an integrating sphere accessory is needed to capture and then detect all the reflected light. This is known as a diffuse reflectance measurement. For transparent films that have a non-negligible reflectance, measurement of both the transmittance and reflectance is necessary for complete optical characterization.

Applications for Reflectance Accessories

1. Measurement of the electronic bandgap of semiconductor films. A classical semiconductor exhibits minimal optical absorption for photons with energies smaller than the bandgap and high absorption for photons with energies greater than the bandgap. As a result, there is a sharp increase in absorption at energies close to the bandgap that manifests itself as an absorption edge (or reflection threshold) in the UV-Vis absorbance spectrum. For TiO2 which has a bandgap between 3.0 and 3.2 eV, this absorption edge occurs at about 400 nm.

While the absorption edge is indicative of the location of the bandgap, accurate estimation of the bandgap requires use of the following formula:

For direct bandgap semiconductors :

where ? is the absorption coefficient, h? is the energy of incident photons and ?g is the electronic bandgap of the semiconductor. ?g is the intercept of the straight line obtained by plotting (? h?)2 vs h? For indirect bandgap semiconductors :

?g is the intercept of the straight line obtained by plotting the square root of (? h?) vs h?. 2. Calculation of the Optical Properties of Thin Films Transmission and reflection spectra give important information regarding the refractive indices of the film and the substrate which can be used to calculate the film thickness. For the simple case of high absorption and no interference,

where R is the reflection and nf is the refractive index of the film. When interference cannot be neglected, the calculation of refractive index is more complicated but is nevertheless possible. If the refractive index is known already and interference is present, the thickness of the film may be estimated by the wavelengths at which the peaks of the fringes occur for constructive and destructive interference. 3. Measurement of the Reflectance Loss in Photovoltaic Cells In any solar cell, the higher incident light intensity results in higher generated photocurrent. The reflection of light at the surface of the solar cell is a key parameter affecting the efficiency of these cells. Diffuse reflectance (DR) measurements can be used to quantify the amount of reflected light flux and hence the efficiency. When anti-reflection coatings are used to enhance the performance of the solar cells, DR can be used to measure the performance of the anti-reflection coating.