Cu-Doping Effects in CdI2Nanocrystals: The Role of Cu-Agglomerates
© to the authors 2008
Received: 12 September 2008
Accepted: 11 November 2008
Published: 22 November 2008
Cu-doping effects in CdI2nanocrystals are studied experimentally. We use the photostimulated second harmonic generation (PSSHG) as a tool to investigate the effects. It is found that the PSSHG increases with increasing Cu content up to 0.6% and then decreases due to the formation of the Cu-agglomerates. The PSSHG for the crystal with Cu content higher than 1% reduces to that for the undoped CdI2crystal. The results suggest that a crucial role of the Cu-metallic agglomerates is involved in the processes as responsible for the observed effects.
KeywordsNanocrystals Defects Surface properties Electron–phonon interaction
Nonlinear spectroscopy and photostimulated second harmonic generation (PSSHG) are the two important tools to investigate the higher-order nonlinear optical processes, in particular, in semiconductors . The PSSHG is prevented by symmetry in a centrosymmetric material process. So, in order to observe the PSSHG, one needs to have a noncentrosymmetric process. Fortunately, there are different ways to enhance the PSSHG. These include (1) the reduction of the size of the crystals to the nanometer scale, (2) lowering the crystal temperature and (3) insertion of suitable impurities into the crystal with an appropriate amount . The nanometer-sized crystals take into account the quantum-confined effect (quantum confinement dominates the material’s electronic and optical properties), where k-space bulk-like dispersion disappears and discrete excitonic-like nanolevels occur within the forbidden energy gap.
CdI2 single crystals are indirect and wide-bandgap semiconductors having layered structure, space group , with highly anisotropic chemical bonds. The band structure calculations of the CdI2 crystals have also shown [2–4] a large anisotropy in the space charge density distribution causing high anisotropy in the corresponding optical spectra. The anisotropic behaviour of the CdI2 crystals favours the local noncentrosymmetry, making them be able for the PSSHG investigations.
Experimental as well as theoretical investigations performed in pure CdI2 single crystals in the last few years using nonlinear spectroscopy have shown that CdI2 possesses higher-order optical nonlinearities [5–8]. An investigation for the magnetic field stimulated ferroelectricity in CdI2–Cu has also been reported . However, this measurement was preliminary performed a decade ago and the most recent report for this system is rare [10, 11].
Here we study Cu-doping effects in CdI2nanocrystals experimentally. We use the photostimulated second harmonic generation (PSSHG) as a tool to investigate the effects. It is found that the PSSHG increases with increasing Cu content up to 0.6% and then decreases due to the formation of the Cu-agglomerates, suggesting that a crucial role of the Cu-metallic agglomeration is involved in the processes. The PSSHG for the crystal with Cu content higher than 1% reduces to that for the undoped CdI2crystal.
where l is the length of the nonlinear medium, i.e. the crystal thickness, μ0 and ε0 are the magnetic and dielectric static (in vacuum) susceptibilities, respectively, A is the area of the pumping beam which processes Gaussian-like form, n(ω) and n(2ω) are, respectively, the refractive indices for the pumping and PSSHG doubled frequencies, χ ijk are the components of the second-order nonlinear optical susceptibility determined from different angle of the incident light and is phase matching wave vector factor defined by photostimulated birefringence. The light intensities of the time-dependent pumping I(ω,t) and frequency doubled PSSHG signals I(2ω,t − τ) were measured for different times (t) of pulse duration and for different delaying times (τ).
Results and Discussion
The PSSHG is found to be decreased for Cu density higher than 0.6%. This decrease of PSSHG with increasing Cu content is caused by agglomeration of the Cu impurities that is typical of such kinds of layered crystals. As demonstrated earlier , this can be understood in terms of the agglomerate chemistry. The creation of the Cu agglomerates favours a reduction in the active electron–phonon centres, effectively contributing to the noncentrosymmetry of the output charge density, as well as leads to the occurrence of metallic clusters which additionally scatter light, and consequently, suppresses the effect at higher Cu content through the limitation of the enhancement of the local hyperpolarizability for the Cu agglomerate as well as the corresponding nonlinear dielectric susceptibility. From the above analysis, one can conclude that a crucial role of the metallic agglomerates was involved in the processes and was responsible for the observed effects.
Cu-doping effects in CdI2nanocrystals were studied experimentally using the PSSHG and the chemistry responsible for the effects discovered. It was found that the PSSHG increases with increasing Cu content up to 0.6% and then decreases due to the formation of the Cu-agglomerates, suggesting that a crucial role of the metallic agglomerates was involved in the processes. The PSSHG for the crystal with Cu content higher than 1% was found to be reduced to that for the undoped CdI2crystal.
- Born WE (Ed): Ultrashort Processes in Condensed Matter. Plenum Press, New York; 1993.
- Bordas J, Robertson J, Jakobsson A: J. Phys. C. 1978, 11: 2607. COI number [1:CAS:528:DyaE1MXnvVGrug%3D%3D]; Bibcode number [1978JPhC...11.2607B] 10.1088/0022-3719/11/12/021View Article
- Robertson J: J. Phys. C. 1979, 12: 4753. COI number [1:CAS:528:DyaL3cXhtFKkt74%3D]; Bibcode number [1979JPhC...12.4753R] 10.1088/0022-3719/12/22/017View Article
- Dovgii YaO, Kityk IV, Aleksandrov YuM, Kolobanov VN, Machov VN, Michailin VV: J. Appl. Spectrosc.. 1985, 43: 1168. Bibcode number [1985JApSp..43.1168D] Bibcode number [1985JApSp..43.1168D] 10.1007/BF00662338View Article
- Adducci F, Catalano IM, Cingolani A, Minafra A: Phys. Rev. B. 1977, 15: 926. Bibcode number [1977PhRvB..15..926A] Bibcode number [1977PhRvB..15..926A] 10.1103/PhysRevB.15.926View Article
- Catalano IM, Cingolani A, Ferrara R, Lepore M: Helv. Phys. Acta. 1985, 58: 329. COI number [1:CAS:528:DyaL2MXksVGntbo%3D]
- Miah MI: Opt. Mater.. 2001, 18: 231. COI number [1:CAS:528:DC%2BD3MXnsFOhur4%3D]; Bibcode number [2001OptMa..18..231M] 10.1016/S0925-3467(01)00168-9View Article
- Miah MI: Opt. Mater.. 2004, 25: 353. COI number [1:CAS:528:DC%2BD2cXivFKksL4%3D]; Bibcode number [2004OptMa..25..353M] 10.1016/j.optmat.2003.08.007View Article
- Kityk IV, Pyroha SA, Mydlarz T, Kasperczyk J, Czerwinski M: Ferroelectrics. 1998, 205: 107. COI number [1:CAS:528:DyaK1cXjtFGntLg%3D] 10.1080/00150199808228391View Article
- Bondar V: Mater. Sci. Eng. B. 2000, 71: 258. 10.1016/S0921-5107(99)00386-4View Article
- Ollafsson H, Stenberg F: Opt. Mater.. 2004, 25: 341. COI number [1:CAS:528:DC%2BD2cXhsVKgsbk%3D]; Bibcode number [2004OptMa..25..341O] 10.1016/j.optmat.2003.08.010View Article
- Kityk IV, Prikl Z: Spektrosck. 1985, 42: 487. COI number [1:CAS:528:DyaL2MXitFWqsro%3D]
- Devis CC: Laser and Electro-Optics, Fundamentals and Engineering. Cambridge University Press, New York; 1985.
- Pyroha SA, Metry S, Olekseyuk ID, Kityk IV: Funct. Mater.. 2000, 7: 209.
- McCanny JV, Williams RH, Murray RB, Kemeny PC: J. Phys. C: Solid State Phys.. 1977, 10: 4255. COI number [1:CAS:528:DyaE1cXht1Kmtrg%3D]; Bibcode number [1977JPhC...10.4255M] 10.1088/0022-3719/10/21/014View Article