Optical Analysis of Blackbody Radiation, Absorption and Fluorescence

David R. Little and Michael Skocik Physics 457W, Pennsylvania State University (Dated: April 27, 2012)

One of the most important tenets of physics is that fact that matter is never isolated; in fact matter is constantly interacting with the environment through electromagnetic waves in processes such as blackbody radiation, optical absorption and fluorescence. A powerful and ubiquitous probe of such systems takes advantage of this fact, and derives its power from the systems dependence on wavelength or spectrum. With the advent of fiber optics, chargedcoupled device (CCD) radiation detectors, computer data acquisition, etc., spectrometry has become an even more effective and convenient measurement tool. This paper aims to verify the usefulness of these new tools by using them to carry out experiments on the three afore mentioned processes: blackbody radiation, optical absorption, and fluorescence. In blackbody radiation the Stefan-Boltzmann constant was measured, while with optical absorption and fluorescence the general trend was studied. After performing the blackbody experiment, the Stefan-Boltzmann constant measured at 1.1016E-81.7644E-13Wm-2K-4 was shown to be sufficiently close to the generally accepted value of 5.67E-8Wm-2K-4. However, the absorption and fluorescence experiments tended to have mixed results as the HITC absorption data did not exhibit any sort of trend and the ICG fluorescence trend was completely the opposite of what was expected. Overall though, these simplified spectroscopy methods taking advantage of new technology, still tended to prove sufficiently accurate.

One of the most powerful and ubiquitous probes of physical systems involves the interaction of the system with electromagnetic with radiation. The power of the probe lies in the dependence of the physical system on the wavelength of the radiation. Such a dependence on wavelength is referred to as a spectrum, and a crucial part of the probe is an instrument called a spectrometer. With the advent of fiber optics, charged-coupled device (CCD) radiation detectors, computer data acquisition, etc., spectrometry has become an ever more powerful and convenient experimental measurement tool. Spectroscopy is applied in a relatively large number of areas of physics, including blackbody radiation analysis of hot objects, optical absorption in liquids and solids, and fluorescence (the re-radiation of absorbed light) in optically active materials. In this paper, the power and convenience of a modern spectrometer is demonstrated in three representative and independent experimental measurements: blackbody radiation, optical absorption, and fluorescence.

Blackbody Radiation One of the most commonly discussed interactions between light and matter is known as blackbody radiation. Theoretically, a blackbody is a perfect absorber and a perfect emitter of electromagnetic radiation. A model for a blackbody was developed by Max Planck in 1901 as a large cavity with a small opening such that radiation could enter, but had a very low probability of leaving. Planck quantified this model with an equation known as the radiation density equation

(1)

where h, c and kB are known constants,

is the wavelength of the radiation and T is the

temperature of the blackbody. By integrating this equation over all wavelengths, Planck was able to derive another quantification

(2)

where Se is the radiated intensity and B is a constant known as the Stefan-Boltzmann constant. However, these equations assume an ideal blackbody and environment, so one must correct for factors such as the temperature difference between the blackbody and the environment, air convection, imperfections with the blackbody, and the power supplied to the blackbody. These factors were accounted for using the following equation ( ) ( ) ( )

(3)

where

is the temperature of the environment, P is the power supplied,

accounts for

convection in the air, ae is the average blackbody absorptivity, and A is the area of the blackbody, which in this case was a tungsten filament with an area of about 50.22E-6 m2 (calculated manually by examining a labled diagram). In this experiment, by taking advantage of the new, simpler methods for spectra data collection, it was possible to quickly obtain blackbody spectra. Using the data for the acquired spectra, it was possible to determine an experimental measurement for the value of B. Now that the physics governing blackbody radiation has been discussed, the apparatus for analyzing the blackbody spectrum may be described.

The physics described in the previous section was studied through the use of the apparatus shown in figure 1.

Figure 1. Blackbody Setup

The blackbody in this case was a bulb with a tungsten filament located inside a metal casing with a small hole which allowed light to escape. For this setup, a power supply was connected to the tungsten filament light source which, along with a pinhole and a fiber adaptor (CCD array), was placed inside a black box. This light passed through a pinhole and was incident upon a fiber, fixed in place with an adaptor. An optical fiber then connected the fiber adaptor to an HR2000+ spectrometer. From there the spectral data was delivered to the computer so the blackbody spectra could be analyzed. This setup was then used to measure the Stefan-Boltzmann constant using the procedure described in the next section.

Using the apparatus from the previous section, the procedure for data collection may now be described. By altering the current and voltage across the tungsten filament it was possible to determine different resistances for the filament, and thus obtain different values for the power dissipated. Then, by using the computer to analyze the blackbody spectra of the tungsten filament at several different voltages and resistances, it was possible to obtain multiple graphs of the of the blackbody spectrum. These graphs are recorded in figures 5 through 8 in the appendix. In order to obtain an experimental value for the Stefan-Boltzmann constant, it was necessary to first calculate the temperature of the black body. By picking two different points on each graph corresponding to two different wavelengths, it was then possible obtain two different forms of

equation 1, one for each wavelength. By dividing these equations one by the other and obtaining a ratio of the two intensities, it was possible to solve for the temperature of the blackbody. After obtaining the blackbody temperature, it was a simple matter of plugging the temperature into equation 3 with the known power and solving for B. The procedures described above were followed under a number of different conditions, and the particular conditions and the results obtained are presented in the next section.

Following the procedures for measurement and data analysis as discussed in the preceding section, using a of .024W/mK and an <ae> of .45 obtained from the literature [1]; the results of the experiment yielded an experimental value of 1.1016E-81.7644E-13Wm-2K-4. When compared to the generally accepted value of 5.67E-8Wm-2K-4, the experimentally calculated value was of the same order of magnitude and sufficiently close to what was expected. The calculated percent error between the accepted value and the experimental one turned out to be roughly 80 percent. While this seems to be a large number, for numbers of such a small scale the experiment proved to be relatively accurate. Additionally, when examining the uncertainty of the calculated measurement, it seemed to be quite small in comparison to the calculated value without the uncertainty, stressing that the experiment was quite precise as well. While the sources of error in this experiment were minimalized, certainly one of the issues was with the estimation of the tungsten filament surface area. While it was possible to obtain a close estimate for the value of the area, it would be nearly impossible to obtain a flawless measurement without breaking the bulb and measuring the filament personally. When repeating this experiment it would be useful to have a tungsten filament with a precalculated area. Finally, it may also be of some help to find a more efficient way to fix position of the pinhole and CCD array, as the tended to move ever so slightly when the top of the black box was moved into place. When dealing with things of such small scale, this can tend to be an issue.

Optical Absorption A second way that matter is capable of interacting with electromagnetic radiation is through a process known as optical absorption. This is in fact one of the reasons why

blackbodies are incapable of being completely efficient. This electromagnetic interaction was discovered by August Beer in 1852 and was quantified by an equation known as Beers Law
( ) ( )

( )

(3)

where OA is the optical absorbance, Absorptivity,

is the wavelength,

( ) is the Coefficient of Molar ( ) and ( ) are the radiation

is the path length, Cm is the concentration and

incident upon the sample and the radiation transmitted through the sample respectively. Equation 1 is governed by the factor ( ) which is different for every substance. Additionally, ( ).
( ) ( )

by rearranging equation 1, it is possible to solve for

( )

(4)

In this experiment, two different test samples, Indocyanine Green (ICG) and Hexamethyl Indotricarbocyanine Tetraflouroborate (HITC), were used in order to verify the effects of changing concentration and path length on the Coefficient of Molar Absorptivity. Now that the physics governing optical absorption has been discussed, the apparatus for analyzing the absorption data may be described.

The described in the previous section was studied through the use of the apparatus which is shown in figure 2.

Figure 2. Optical Absorption apparatus

For this experiment the entire apparatus except for the computer was enclosed in a large black box in order to isolate the system from ambient light. The light source, an infrared laser, was shown through a quartz lens of focal length 11cm, and was incident upon a fiber adaptor connected to an optical fiber. The optical fiber then emitted the same laser through a collimating lens and then through a cuvette containing the sample. At this point, the remaining, unabsorbed radiation passed through another lens and into another optical fiber connected to a spectrometer. After obtaining a spectrum for the sample, the data was transmitted to the computer in order to be analyzed. This setup was then used to measure the coefficient of optical absorbance for both HITC and ICG using the procedure described in the next section.

Using the apparatus from the previous section, the procedure for data collection may now be described. In order to obtain a controlled value for the intensity in this experiment, the first sample placed in the cuvette was pure isopropyl alcohol. This made it possible to gather an initial intensity for the laser as isopropyl alcohol only gets a baseline spectrum. After obtaining a value for the initial intensity of the laser, the cuvette containing the alcohol could be switched with one containing ICG or HITC. After obtaining the spectra for both HITC and ICG, it was then possible to obtain values for the coefficient of optical absorbance for both samples. By repeating this process with several different concentrations of ICG and HITC, it was possible to

evaluate the coefficient of optical absorption at different concentrations. The graphs of these different concentrations are recorded as figures 9 to 16 in the appendix. The procedures described above were followed under a number of different conditions, and the particular conditions and the results obtained are presented in the next section.

Following the procedures for measurement and data analysis as discussed in the preceding section, the spectral results for the different concentrations of HITC and ICG could be obtained.

Figure 3. Experimental results for Optical Absorption

When evaluating the results for the Absorption Coefficients of ICG and HITC, one can see that for ICG (figures 13 to 16 in the appendix), the absorptivity steadily increased as the concentration decreased, which follows the expected trend. However, when examining the results for HITC, they did not seem to follow any sort of trend because as the concentration was decreased, the Absorption Coefficient first rose and then fell. Overall, the data captured for the ICG seemed to be somewhat accurate while the data for the HITC seemed somewhat flakey and unreliable. In addition to this, the uncertainty values for the results tended to be relatively large,

but at the same time not large enough to justify the possibility of an uncertainty error being able to account for the HITC results. Thusly, this particular tended to gather somewhat accurate data, but was not nearly as reliable as expected. There are several sources for error in this experiment including imperfect dilution of the sample, inaccurate laser alignment, and possibly most important, the interaction between the laser light and the cuvette material. Since it is possible for the cuvette to absorb radiation itself as well as possibly deflect some of the laser, this is a very prominent source of error. Additionally, if the cuvette was not perfectly clean, it could have easily corrupted some of the data. When reproducing this experiment it would be beneficial to insure the cuvette is extremely clean and fingerprint free to help insure accurate results.

Fluorescence One final way that light and matter may interact is through a process known as fluorescence. In fluorescence, light at some frequency may be absorbed by some substance, causing electrons within the substance to be excited to higher energy states. Once this occurs, the energized electrons are capable of emitting electromagnetic waves of a completely different frequency in order to fall back down to a lower energy state, a process which usually takes around 10 nanoseconds to occur. Then, the substance will give off its own light and fluoresce. However this process will only occur for incoming light of specific frequencies. In addition to the frequency of the incoming light, the intensity of the emitted radiation is dependent upon the concentration of the substance which the light is incident upon. In simpler terms, the less concentrated a sample of a substance is, the less it will fluoresce. In this experiment, two different test samples, Indocyanine Green (ICG) and Hexamethyl Indotricarbocyanine Tetraflouroborate (HITC), were used in order to verify the effects of changing concentration on the intensity of the re-emitted radiation. Now that the physics governing fluorescence has been discussed, the apparatus for analyzing the intensity of the re-emitted radiation data may be described.

The experimental data for the measurements described in the previous section was obtained through the use of the apparatus which is shown in the figure 4 and will be described thereafter.

Figure 4. Schematic of the fluorescence setup.

In this experiment an infrared diode laser was shown through a collimating lens with the beam incident upon a cuvette. An alignment cage was placed next to the cuvette at a right angle to the beam such that only light due to fluorescence of the solution would be pass through light collecting lenses within the cage. The fluorescence light was then incident upon a fiber adaptor. An optical fiber then connected the fiber adaptor to an HR2000+ spectrometer. After analyzing the spectra of the samples, the data could be uploaded and analyzed by a computer in order to be evaluated. Every aspect of the apparatus except for the computer was contained within a large black box in order to isolate the experiment from ambient light. This setup was then used to measure the fluorescence of both HITC and ICG using the procedure described in the next section.

Using the apparatus from the previous section, the procedure for the fluorescence data collection may now be described. First, three different solutions of both ICG and HITC were obtained and placed in cuvettes, each at different concentrations. For each concentration of ICG and HITC, the cuvettes were placed in the sample holder in order to obtain a spectrum for each sample. For the samples of ICG, a 785nm laser was used to excite the sample, while a 635 nm laser was used for the excitation of HICG. By exciting each sample with the laser, it was possible to obtain a spectrum for each sample concentration. The graphs for these spectra are recorded in tables 17 to 22 in the appendix. By comparing the intensities of each peak, it was possible to evaluate the fluorescence intensity trend for both chemicals. The procedures described above were followed under a number of different conditions, and the particular conditions and the results obtained are presented in the next section.

Following the procedures for measurement and data analysis as discussed in the preceding section, the spectral results for the fluorescence of HITC and ICG could be analyzed. After examining the spectra of all the samples, it appeared that HITC followed the expected trend in the way that as the concentration of the sample decreased, the intensity of the fluorescence decreased as well. However, when examining the ICG samples it seemed that the data trend was opposite the expected trend, which is to say that as the concentration of the sample decreased, the intensity of the fluorescence actually went up. As of now, it is difficult to say why the later results were the reverse of what was expected for the experiment. It is difficult to determine the accuracy of these measurements and methods with the data in this section, because while the measurement worked quite well for the HITC, it was completely opposite the accepted trend for the ICG. When examining the sources of error for this experiment, it is certainly true to say that there could have been errors concerning the lucidity of the cuvette walls as well as the laser alignment. However, errors for both of these things could not account for a complete opposition to the expected trend. While repeating this experiment it is quite important to try and minimize those sources of error as much as possible, it is at this point impossible to determine the reason why the ICG data was completely flipped with relation to expectations.

APPENDIX

Figure 5. Blackbody Radiation at 3V

Figure 6. Blackbody radiation at 3.5V?

Figure 7. Blackbody Radiation at 4V

Figure 8. Blackbody Radiation at 5V

Figure 9. Optical Absorption baseline for HITC

Figure 10. Optical Absorption for HITC at 5E-5 molar concentration

Figure 11. Optical absorption for HITC at 5E-6 molar concentration

Figure 12. Optical absorption for HITC at 1E-6 molar concentration

Figure 13. Optical Absorption baseline for ICG

Figure 14. Optical Absorption for ICG at 1E-3 molar concentration

Figure 15. Optical Absorption for ICG at 1E-4 molar concentration

Figure 16. Optical Absorption for ICG at 1E-5 molar concentration

Figure 17. Fluorescence of HITC 5E-6 molar concentration

Figure 18. Fluorescence of HITC at 5E-7 molar concentration

Figure 19. Fluorescence of HICG at 1E-7 molar concentration

Figure 20. Fluorescence of ICG at 1E-3 molar concentration

Figure 21. Fluorescence of ICG at 1E-4 molar concentration

Figure 22. Fluorescence of ICG at 1E-5 molar concentration

REFERENCES

[1] Zhang, D., Optics (2005).