Structural characteristics

The structural characteristics of films are studied using X–Ray Diffraction (XRD). Figure 2 shows X–Ray Diffraction (XRD) of the produced films in various temperatures. The results obtained from X–Ray Diffraction (XRD) analysis shows that the produced films are polycrystalline and have a wurtzite structure. By increasing the temperature up to 500º C, a better crystalline structure with a certain preferred direction is obtained. At higher temperatures, the crystalline structure collapses and the intensity of (002) peak reduces. The crystallite size of Cadmium Oxide (CdO) can be calculated by Scherrer equation.

Figure 2 X–Ray Diffraction (XRD) of the produced films in various temperatures.

The variations of crystallite size as a function of substrate temperature is shown in Figure 3. Firstly, the crystallite size increases up to the maximum value of 63.7 (nm), at 500º C, with increase in temperature of substrate and then decreases. Increase in crystallite size with increase in temperature may be due to improve in process of reaction between sprayed drops as well as improve in mobility of atoms in the surface of substrate.

Figure 3 Variation of crystallite size against temperature.

Optical characteristics

Figure 4 shows the spectrum transmitted through Cadmium Oxide (CdO) films in a region with wavelength ranged between 400-1000 (nm) at the temperature between 450-600º C. Temperature variation is of a key role in transparency and optical characteristics of films. The diagrams obtained from spectrum transmitted through films are transparent in visible region and by increasing the temperature of substrates, transparency reduces. It can be concluded that increase in temperature makes devastating effects due to penetration of substrate compounds into films and hence, leads to reduce in transparency.

Figure 4 The spectrum transmitted through Cadmium Oxide (CdO) films produced at various temperatures.

Optical, Medicinal and Pharmaceutical Characteristics of Cadmium Oxide (CdO) Nanoparticles

Sample preparation: Cadmium Oxide (CdO) nanoparticles used in the current study are produced by gas evaporation technique. As the goal of the current study is using Cadmium Oxide (CdO) in bioapplications, 0.1 (gr) of the nanoparticles are solved in 55 (ml) of deionized water. All presented results are obtained in room temperature. Figure 1 is pointed out in abstract shows the results obtained from Scanning Electron Microscope (SEM) technique on Cadmium Oxide (CdO) nanoparticles with 50000x zoom. The size of these nanoparticles are about 250-400 nanometers.

Fluorescence: Fluorescence is a spontaneous emission induced by linear stimulation of photons. Fluorescence of semiconductors such as Cadmium Oxide (CdO) can be explained using energy levels. Using a photon with higher energy level than gap energy, it can be possible to stimulate electrons of conducting band and move them to conducting band and hence, only holes with positive charge remain on the valence band. This electron and hole is called exciton. Electrons on conducting band and before recombination can be non–optically transited (usually vibration transition type) between the available compressed levels in conducting band. In this state, the energy difference between electron and hole is lower than the initial state and hence, the produced photon from recombination of electron and hole is of longer wavelength than the initial stimulator photon. If the energy level of stimulator photon is higher than the gap energy of semiconductor, electron moves to higher levels of conducting band but if the energy level of photon is lower than the gap energy, there is no absorption and hence, there is no emission. The single photon fluorescence stimulation of these nanoparticles obtained from stimulation gap and 9 nanometers disclosure with wavelength of 430 and 470 nanometers are shown in Figure 5. As can be seen in this figure, the fluorescence emission of these nanoparticles has a peak in 380 nanometers wavelength (4.4 eV) which is related to gap edge exciton transition.

Figure 5 Fluorescence spectrum of Cadmium Oxide (CdO) nanoparticles.

The other peak, which is wider and is seen in green zone, is induced by surficial deficiencies such as impurities, Oxygen and or Cadmium vacuum. In these nanoparticles, such impurities and hence, the associated transitions were inevitable. However, the emissions induced by deficiencies are not always inappropriate; they can be used as efficient source of white light.

Second harmonic generation

Since Cadmium Oxide (CdO) has a considerable non–linear coefficient, the other part of the current study is focused on investigating non–linear characteristics of Cadmium Oxide (CdO). High power pulse laser with high peak power should be used to observe non–linear characteristics. Tunable Titanium sapphire laser with pulselength of 185 femtoseconds was used to stimulate Cadmium Oxide (CdO) nanoparticles. Cadmium Oxide (CdO) nanoparticles sample solved in water was subjected to NIR emission in quartz cell. Laser light was focused on quartz cell using a lens with focal distance of 22 (cm) and second harmonic was generated. To detect the second harmonic signal, two lenses with wide mount and with degree of 180 from descending light were used. Before entering signal to detector, a NIR filter was installed on the mount of camera to remove the descending laser light. Figure 6 shows the results of second harmonic stimulation of Cadmium Oxide (CdO) nanoparticles in photon counting state and in wavelengths of 800, 825, 850, 875, 900, 925, 950, 975 and 1000 (nm). By distancing from 800 nanometers wavelength, laser power has a descending trend which causes to reduce in second harmonic peaks of these nanoparticles. Figure 6 shows normalized results.

Figure 6 Second harmonic spectrum of Cadmium Oxide (CdO) nanoparticles with various stimulated wavelength: (a) 800 (nm); (b) 825 (nm); (c) 850 (nm); (d) 875 (nm); (e) 900 (nm); (f) 925 (nm); (g) 950 (nm); (h) 975 (nm); (i) 1000 (nm).

Two photons absorption

When Cadmium Oxide (CdO) nanoparticles stimulate with a wavelength that the energy of descending photon (ex) satisfies 4ex>Eg and there is a considerable two photons absorption cross section, two photons absorption occurs. Therefore, if Cadmium Oxide (CdO) nanoparticles stimulate with wavelength ranged between 900–950 nanometers, two photons emissions occurs. In a narrow range (950-1000 nanometers), two photons absorption occurs in addition to second harmonic generation, simultaneously. Figure 7 shows this state for 4 different wavelengths schematically.

As can be seen, emission induced by two photons absorption is wider than second harmonic generation. In this narrow zone, shorter wavelength means that the contribution of two photons absorption is higher and by increasing wavelength, two photons emissions disappears. In Figure 7, Cadmium Oxide (CdO) nanoparticles are stimulated by wavelength between 900 and 930 nanometers and second harmonic generation and two photons emission are simultaneously appeared (in this case, arrangement is similar to second harmonic detection in counting photon case).

Figure 7 Simultaneous spectrums of two photons emission and second harmonic generation.

Applications of Cadmium Oxide (CdO) nanoparticles in medicine and pharmaceutics

Currently, nano–atto second pulse lasers are used to image from biosamples. Such systems are of very high power peak which is higher than the failure threshold of biosamples. However, average power of lasers is important for non–linear imaging of biosamples. It may be possible that pulse lasers have average power less than 1.5 (W) and peak power more than 1.5 (GW). Since relaxation time between pulses are adequate (repeat rate of about 105MHz), the average power of laser is lower than failure threshold of biosamples while their peak power is of required capability to non–linearly stimulate samples.

Second harmonic generation is only a frequency conversion process and no absorption occurs in this process, so it can be used to image from bioamples. Cadmium Oxide (CdO) is able to pass through cell wall and enters into the cell. In this manner, non–linear characteristics of Cadmium Oxide (CdO) nanoparticles were used for imaging and tracing of animal cells.

The current investigation shows that second harmonic signal of these nanoparticles can be used for stable and longtime imaging and tracing. Since two photons absorption is of more penetration depth and is accompanied by heat production, two photons imaging was always accompanied by heat and sample burning and can be used to eliminate cancer cells.

Figure 8 shows absorption spectrum of Cadmium Oxide (CdO) nanoparticles considering the absorption of distilled water as reference.

Figure 8 Absorption spectrum of Cadmium Oxide (CdO) nanoparticles in distilled water produced at (a) 784 nanometers wavelength, (b) 1046 nanometers wavelength.

The peak of UV absorption resulted from absorption of Cadmium Oxide (CdO) nanoparticles exciton is happened at 322–363 nanometers wavelength. The effect of size of nanoparticles on electronic structure of semiconductors explains by increase in band gap with decrease in size of particles which attributed to quantum surrounding effect. A blue shift in the edge of absorption was observed with increase in laser pulse energy which can be used to qualitatively describe the size distribution of particles. In smaller nanoparticles (in higher laser energies), a sharp peak of exciton is presented in the absorption spectrum which shows limited size distribution of nanoparticles in the sample and for larger particles, this is not observed in absorption spectrum (in lower laser energies). The reason is the fact that a number of exciton peaks in various energies are related to nanoparticles with various sizes which overlaps each other. Therefore, it can be expected that size distribution of nanoparticles extends. This assumption is confirmed using size distribution of nanoparticles resulted from Dynamic Light Scattering (DLS) analysis in various samples (Figure 9).

Figure 9 Size distribution of nanoparticles resulted from Dynamic Light Scattering (DLS) analysis (1) sample 3, (2) sample 4, (3) sample 5 and (4) sample 6.

As can be seen in Figure 9, size of nanoparticles is decreased with increase in laser pulse energy. The average size of nanoparticles is listed in Table 2.

Considering the fact that Dynamic Light Scattering (DLS) analysis shows hydrodynamic size of particles, the results of this analysis is considerably higher than those resulted from Transmission Electron Microscope (TEM) images. It may be due to the forming of Hydrogen bond between carboxyl group on the next surface, which can lead to transversal connection between particles and hence, larger particles. Transmission Electron Microscope (TEM) images of Cadmium Oxide (CdO) nanoparticles, which are in the scale of about 250 nanometers, are shown in Figure 10. As can be seen, nanoparticles are approximately spherical and their sizes are reduced by increase in laser pulse energy.

Figure 10 Transmission Electron Microscope (TEM) images of Cadmium Oxide (CdO) nanoparticles with 35000x zoom

Variations of size distribution of nanoparticles by increase in laser pulse energy are similar to the results obtained from Dynamic Light Scattering (DLS) analysis. In other words, size distribution of nanoparticles is uniform. By increasing the laser pulse energy, larger nanoparticles can be simply broken into smaller parts due to interaction with intense laser pulse.

Figure 11 shows the fluorescence spectrum of Cadmium Oxide (CdO) nanoparticles which are stimulated by Xenon lamp in wavelength of 407 nanometers. Usually, emission band in UV and visible fields are observed in fluorescence spectrum of Cadmium Oxide (CdO) nanoparticles. UV peak, which is usually considered as an indication of Cadmium Oxide (CdO) emission, is called edge band emission or exciton transmission. However, emission bands in visible zone are induced by recombination of holes resulted from photon emission with charged, ionized state in inherent deficiencies such as Oxygen blank space, inter–lattice Cd and or impurities. First of all, if stimulation energy is considered considerably lower than gap energy and the second, if the intensity of visible light emission induced by increase in density of deficiencies is very high. In all samples of Cadmium Oxide (CdO) nanoparticles, the peak of UV in fluorescence spectrum is dominant and its intensity increases with increase in laser pulse energy while the intensity of the presented peaks in visible zone is decreased. In other words, severe exciton emission shows that the produced Cadmium Oxide (CdO) nanoparticles are of little deficiencies.

Figure 11 Fluorescence spectrum of Cadmium Oxide (CdO) nanoparticles produced at (a) 784 nanometers wavelength, (b) 1256 nanometers wavelength

General outline of energy level graph of Cadmium Oxide (CdO) nanoparticles is shown in Figure 12. Various deficiencies are considered in this model. The first principle shows that Cd_3d electron is severely interacted with O_2p electron of Cadmium Oxide (CdO). As can be seen in Figure 12, fluorescence in violet zone can be attributed to transmission from conducting band to deep holes tra pped in a level such as V_Cd. Blue emission can be considered as direct recombination of conducting electron in Cd_3d band and hole in O_2p valence band. The usual process for green emission is as following: transmission mechanism (a) from proximity of conducting band edge to deep level of receptor and (b) from deep level of donor to valence band. Recombination of surficial electron trapped in a deep hole trapped in center of V₀++ leads to visible emission.

Figure 12 General outline of energy level graph of Cadmium Oxide (CdO) nanoparticles

It should be noted that the effect of Cadmium Oxide (CdO) nanoparticles on DNA of human cancer cells is listed in Table 3. In addition, Figures 13 &14 demonstrate fluorescence and photoluminescence of Cadmium Oxide (CdO) nanoparticles in violet zone (a) from proximity of conducting band edge to deep level of receptor and (b) from deep level of donor to valence band, respectively. Moreover, as can be seen, Figures 15 & 16 display intensity dependence of fluorescence and photoluminescence of Cadmium Oxide (CdO) nanoparticles in different wavelengths. Furthermore, Scanning Electron Microscope (SEM) images and also Transmission Electron Microscope (TEM) images of Cadmium Oxide (CdO) nanoparticles (a) before interaction with DNA of cancer cells and (b) after interaction with DNA of cancer cells is shown in Figures 17 & 18, respectively. Also, as another novel achievement, simulation of Cadmium Oxide (CdO) nanoparticles before and after interaction with DNA of cancer cells is illustrated in Figure 19.

None.

None.

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