IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS J. Phys. D: Appl. Phys. 40 (2007) 5588–5591 doi:10.1088/0022-3727/40/18/013 Temperature-dependent photoluminescence of undoped, N-doped and N-In codoped ZnO thin films H B Ye1 , J F Kong1 , W Z Shen1,3 , J L Zhao2 and X M Li2 1 Laboratory of Condensed Matter Spectroscopy and Opto-Electronic Physics, Department of Physics, Shanghai Jiao Tong University, 1954 Hua Shan Road, Shanghai 200030, People’s Republic of China 2 State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, People’s Republic of China E-mail: email@example.com Received 21 June 2007, in final form 3 August 2007 Published 30 August 2007 Online at stacks.iop.org/JPhysD/40/5588 Abstract Temperature-dependent photoluminescence properties of undoped, N-doped and N-In codoped p-type ZnO thin films have been investigated in detail. The yielded temperature dependences of ultraviolet peak energy, width and intensity for several resolved emissions exhibit the different carrier recombination processes associated with doping mechanisms. We have revealed the acceptor binding energy of 113 meV, 140 meV and 112 meV and donor one of 56 meV, 82 meV and 112 meV for undoped, N-doped and N-In codoped ZnO, respectively, together with the broadening of the acceptor levels in N-doped and N-In codoped ZnO. We have also clarified the origin of the ZnO deep-level visible emission. As a wide band gap (3.37 eV at room temperature) semiconductor with a large exciton binding energy (about 60 meV), ZnO has recently attracted much attention for optoelectronic devices, such as light-emitting diodes and laser diodes . Due to the asymmetric doping limitations in ZnO , a great deal of effort has been made to realize the p-type doping of ZnO. Many groups have reported the fabrication of p-type ZnO by intentionally undoping , single-doping with Li , N [5,6], P , As [8, 9] and Sb , as well as codoping techniques [11–13]. In contrast to the growth interest, the understanding of fundamental properties in p-type ZnO is still relatively incomplete, especially for the doping mechanisms and the acceptor and donor levels. It is essential to understand the carrier recombination processes and the role of defects in p-type ZnO to fabricate the optoelectronic devices. Photoluminescence (PL) properties have been studied for p-ZnO of undoped  and single-doped with N , P , As  and Sb . Recently, there is also a report on the compared PL study between P-doped and P-In codoped p-ZnO . However, owing to the lack of 3 Author to whom any correspondence should be addressed. 0022-3727/07/185588+04$30.00 © 2007 IOP Publishing Ltd effective methods to resolve the experimental emission spectra, the exact mechanisms of ultraviolet (UV) emission in ZnO and the corresponding carrier recombination processes are still subjects of considerable debates. Furthermore, compared with the interest in UV emission properties, the temperaturedependent behaviour of the visible emission in ZnO is rarely studied and the responsible defects remain controversial. In this paper, we have presented a comprehensive investigation of temperature-dependent PL properties of undoped, N-doped and N-In codoped p-type ZnO thin films grown by ultrasonic spray pyrolysis (USP). Through multiGaussian fittings to the experimental spectra, the temperature dependences of UV peak energy, width and intensity have been obtained and fitted to reveal the different carrier recombination processes and doping mechanisms. In addition, the mechanism of the deep-level visible emission in ZnO has also been discussed. The studied undoped, N-doped and N-In codoped ZnO thin films were deposited by USP at atmosphere . The Zn(CH3 COO)2 · 2H2 O (AR, 0.5 mol l−1 ), CH3 COONH4 (AR, 2.5 mol l−1 ) and In(NO3 )3 (AR, 0.5 mol l−1 ) were chosen as the sources of Zn, N and In, respectively. The atomic Printed in the UK 5588 Temperature-dependent photoluminescence of ZnO thin films N-doped Undoped 2.4 3.2 83 K 103 K 123 K 143 K 163 K 183 K 203 K 223 K 243 K 263 K 283 K 303 K N-In codoped 2.4 3.2 2.4 Photon Energy (eV) 2 3 Undoped T=83 K (c) 3.35 5 3.30 N-doped 2 4 1 3 N-In codoped 4 3 ratio of Zn/N was 1 : 3 for the N-doped film, and Zn/N/In was 1 : 3 : 0.05 for the N-In codoped film. The intrinsic Si (1 0 0) wafers (conductivity of 10−4 −1 cm−1 ) were used as the substrates, which were heated to 450 ◦ C. All films were controlled to be 300 nm thick. Room-temperature Hall measurements were taken in the Van der Pauw configuration at the magnetic field of 0.5 T, showing the p-type conductivity of 1.14 −1 cm−1 , 1.51 −1 cm−1 and 2.01 −1 cm−1 , hole density p of 6.60 × 1016 cm−3 , 1.26 × 1017 cm−3 and 2.46 × 1017 cm−3 and hole mobility µp of 108 cm2 V−1 s−1 , 75 cm2 V−1 s−1 and 51 cm2 V−1 s−1 for undoped, N-doped and N-In codoped ZnO, respectively. We have demonstrated the good agreement of p and µp between room-temperature Raman and Hall measurements in N-In codoped ZnO , while the effective N-In codoping and high hole mobility have also been confirmed in our previous work . Temperaturedependent PL measurements from 83 to 303 K were carried out on a Jobin Yvon LabRAM HR 800UV micro-Raman system with an Andor DU420 classic CCD detector and a Linkam THMS600 temperature stage under the excitation of a He–Cd laser (325 nm). Figures 1(a)–(c) show the experimental PL spectra of undoped, N-doped and N-In codoped ZnO measured from 83 to 303 K. Note that the intensity is displayed on a logarithmic scale. Generally, the PL spectrum of ZnO consists mainly of a near band edge (NBE) emission in the UV region and a deeplevel emission in the visible region due to structural defects and impurities . As shown in figure 1(a), the spectra of undoped ZnO clearly exhibit several resolved NBE emissions at low temperatures with a broad visible emission centred at about 2.5 eV. For the spectra of N-doped (figure 1(b)) and N-In codoped ZnO (figure 1(c)), an asymmetrical and combinational NBE emission is observed and becomes broader and broader compared with the undoped one, while the visible emissions become much weaker in N-doped film and are almost undetectable in codoped film. All the above luminescence behaviours indicate different carrier recombination processes associated with doping mechanisms. To better understand the nature of the NBE emission and different carrier recombination processes, we have performed the multi-Gaussian fittings to the experimental spectra throughout the measured temperature range. Figure 2(a) illustrates 83 K PL spectra (open circles) of undoped, N-doped (a) 3.36 1 3.1 3.2 3.3 3.4 Photon Energy (eV) N-doped 3.28 3.36 2 N-In codoped 3.28 3.2 Figure 1. Temperature-dependent PL spectra of (a) undoped, (b) N-doped and (c) N-In codoped ZnO measured from 83 to 303 K. The intensity is shown on a logarithmic scale. Undoped 1 4 Peak Energy (eV) (b) PL Intensity (arb. units) PL Intensity (arb. units) (a) (b) 100 200 300 Temperature (K) Figure 2. (a) NBE PL spectra at 83 K for undoped, N-doped and N-In codoped ZnO, where the solid curves show the Gaussian deconvolution of the experimental spectra (◦). (b) Temperature-dependent peak energies and the fitting curves for bands 1 ( ), 2 (•) and 3 ( ) in (a). Bands 1, 2 and 3 are assigned to FX, A0 X and eA0 , respectively. and N-In codoped ZnO with the multi-Gaussian fitting results (solid curves). Here, we use the least Gaussian bands to fit the PL spectra and the obtained self-consistent results testify to the reliability of the method. The best fitting result for undoped ZnO consists of five bands labelled as 1, 2, 3, 4 and 5, respectively. For N-doped and N-In codoped ZnO, the spectra are resolved into four individual bands labelled as 1, 2, 3 and 4, respectively. According to [3, 13], the resolved excitonic features in p-type ZnO are unlikely to be observed clearly from the PL spectra even at temperatures much lower than 83 K. The obtained temperature-dependent peak energies E(T ) of bands 1 (squares), 2 (circles) and 3 (triangles) for the three samples are displayed in figure 2(b). It can be observed that bands 1 and 2 systematically shift to lower energy with increasing temperature and their energy shifts can be well described by the Varshni equation E(T ) = E(0)−αT 2 /(T +β) , where E(0) is the transition energy at 0 K, α is related to the exciton-average phonon interaction and β is closely related to the Debye temperature. The energy shift of band 3 can be expressed as the Varshni equation plus kB T /2, where kB is the Boltzmann constant. The solid curves in figure 2(b) are leastsquares fits with the fitting parameters summarized in table 1 (we assumed β = 920 K according to ). The yielded α is close to the reported values . For clearness, we have also listed the differences between Eg (0) and E(0) in table 1, where Eg (0) = 3.437 eV is the ZnO band gap at 0 K. From the above analysis, we can assign the band 1 to free exciton (FX) emission and its binding energy is 58 meV, 62 meV and 58 meV for undoped, N-doped and N-In codoped ZnO, respectively. Band 2 corresponds to neutral-acceptorbound exciton (A0 X) emission and the band 3 is assigned to free-electron-to-neutral-acceptor transition (eA0 ). As the transition energy of eA0 can be written as EeA = Eg − EA + kB T /2 , the obtained acceptor binding energy EA is 113 meV, 140 meV and 112 meV for undoped, N-doped and N-In codoped ZnO, respectively. The emissions of band 4 at 3.271, 3.220 and 3.222 eV for the three samples shown in figure 2(a) should correspond to the donor– acceptor pair (DAP) transition. In this case, the donor 5589 H B Ye et al Table 1. Results of fitting peak energy and width for bands 1 (FX), 2 (A0 X) and 3 (eA0 ) in undoped, N-doped and N-In codoped ZnO. Here Eg (0) = 3.437 eV. Sample Band E(0) (eV) α (10−4 eV K−1 ) Eg (0) − E(0) (meV) Undoped ZnO 1 2 3 1 2 3 1 2 3 3.379 3.361 3.324 3.375 3.346 3.297 3.379 3.373 3.325 9.20 8.96 7.38 9.09 8.12 8.55 7.28 8.75 10.00 58 76 113 62 91 140 58 64 112 N-doped ZnO N-In codoped ZnO (b) (a) Undoped Peak Width (meV) 40 150 100 N-doped 50 180 N-In codoped 120 60 100 200 Integrated Intensity (arb. units) 80 300 100 Temperature (K) Undoped Ea=47 meV N-doped Ea=27 meV N-In codoped Ea=34 meV 200 300 Figure 3. (a) Temperature-dependent peak widths and the fitting curves for bands 1 ( ), 2 (•) and 3 ( ) in undoped, N-doped and N-In codoped ZnO. (b) Integrated PL intensity and the fitting curves for the band 2 (•) as a function of temperature. Bands 1, 2 and 3 are assigned to FX, A0 X and eA0 , respectively. binding energy ED can be estimated from the equation √ 1/3 ED = Eg − EA − EDAP + 3 4π/3(e2 /4πεε0 )NA,D , where NA,D is the majority impurity concentration, ε = 8.656 is the specific dielectric constant and ε0 is the dielectric constant in a vacuum. Making NA,D approximately equal to the hole density, we have ED of 56 meV, 82 meV and 112 meV for undoped, N-doped and N-In codoped ZnO, respectively. In addition, the weak emission of band 5 at 3.143 eV in undoped ZnO is attributed to the zinc vacancy (VZn )-related defect . Although the nature of shallow acceptor is difficult to identify in undoped ZnO, the obtained ED of 56 meV is in good agreement with the reported 56–58 meV . EA of 140 meV in N-doped film corresponds to NO acceptor while the smaller EA of 112 meV in N-In codoped ZnO is attributed to 2NO –InZn acceptor complex, which complies with the theoretical prediction of reduced acceptor transition energy due to the codoping technique . On the other hand, the N-doping and N-In codoping in ZnO result in the deeper and deeper donor level according to ED . Thus fewer and fewer free electrons can be activated to compensate holes. The enhanced hole density from Hall measurements in N-doped and N-In codoped ZnO is the best demonstration. Figure 3(a) displays the temperature dependence of peak width (T ) of bands 1 (squares), 2 (circles) and 3 (triangles) for undoped, N-doped and N-In codoped ZnO. The smaller peak width of bands 1 and 2 (FX and A0 X) than that of band 3 (eA0 ) 5590 0 16 11 35 25 36 74 28 42 98 (meV) γph (meV K−1 ) 0.033 0.017 0.022 0.101 0.171 0.128 0.066 0.287 0.212 LO (meV) 435 594 690 502 61 339 539 171 267 is due to the excitonic properties, which further supports the above assignments. The solid curves are least-square fits using the equation (T ) = 0 + γph T + LO /[exp(¯hωLO /kB T ) − 1] , where h ¯ ωLO = 72 meV is the energy of a longitudinal optical (LO) phonon, 0 is the intrinsic line width at 0 K, γph is the exciton-acoustic phonon coupling constant and ohlich) coupling LO represents the exciton-LO phonon (Fr¨ strength. The fitting parameters are also listed in table 1. Among them, the values of LO are much larger than those of γph , which is mainly owing to the high Fr¨ohlich constant and the LO energy. For the values of 0 , the ratios between N-doped and undoped ZnO are 1.56, 3.27 and 2.11 for FX, A0 X and eA0 , respectively, while the corresponding ratios are 1.75, 3.82 and 2.80 in codoped film. This broadening behaviour is attributed to the doping mechanisms. With the enhanced hole density by N-doping and N-In codoping, more temperatureindependent mechanisms including hole–hole interaction and impurity will be introduced to broaden 0 . On the other hand, the N-doping and N-In codoping will broaden the acceptor level in the band gap , which directly leads to the stronger broadening of A0 X and eA0 emissions than FX. Figure 3(b) shows the integrated intensity of A0 X (band 2) emission as a function of temperature for the three samples. The observed overall temperature-quenching behaviour can be well described by the equation I (T ) = I0 /[1 + A exp(−Ea /kB T )] , where I0 is the emission intensity at zero temperature, A is a parameter and Ea is the activation energy in the thermal quenching process. The good fits (solid curves) yielded Ea of 47 meV, 27 meV and 34 meV for undoped, N-doped and N-In codoped ZnO, respectively. In order to understand the thermal quenching process, the localization energy Eloc (FX-A0 X) of 18 meV, 29 meV and 6 meV for undoped, N-doped and N-In codoped ZnO, respectively, has been obtained to compare with Ea . We identify the dissociation process of A0 X to a FX and a neutral acceptor in N-doped ZnO because of the comparable values of the activation and localization energy. For undoped and codoped ZnO, the difference between Ea and Eloc is 29 and 28 meV. Considering the corresponding EA of 113 and 112 meV, we can deduce almost the same Haynes factor of 0.25. Therefore, the quenching processes include the thermal ionization of acceptor besides the above dissociation in undoped and N-In codoped films. The reported visible emission in ZnO was attributed to different types of electron transitions in various defects involving oxygen vacancy (VO ), VZn , zinc interstitial (Zni ) Temperature-dependent photoluminescence of ZnO thin films Acknowledgments Undoped ZnO This work was supported by the Natural Science Foundation of China (contract Nos 10674094, 60576067 and 90401010), National Major Basic Research Project of 2006CB921507, the Minister of Education of PCSIRT (contract No IRT0524), and the Shanghai Municipal Commission of Science and Technology Projects of 05QMH1411 and 06JC14039. E(0)=2.57 eV 2.50 2.45 Intensity (arb. units) Peak Energy (eV) 2.55 Ea=30 meV 100 2.40 100 200 300 Temperature (K) 200 Temperature (K) References 300 Figure 4. Temperature dependence of deep-level emission energy in undoped ZnO. The inset shows the integrated intensity as a function of temperature. The solid curves are the fitting results. and OZn . To clarify its origin, we have calculated the temperature-dependent peak energies of the deep-level emission in undoped ZnO (figure 4) from the good singleGaussian fittings of the experimental spectra. Since the deep-level emission follows the shrinkage of the band gap with increasing temperature (solid curve by Varshni fitting), we exclude the possibility of the transition within localized defects. The obtained E(0) of 2.57 eV clearly indicates that this deep-level emission is caused by the electron transition from the VO donor level to the valence band . The inset of figure 4 presents the corresponding integrated intensity as a function of temperature. The yielded Ea through fitting to the thermal quenching equation (solid curve) is 30 meV, which is close to the reported value  and may attribute to the process VOx → VO• + e. Furthermore, as interpreted above, fewer and fewer free electrons can be thermally activated in N-doped and N-In codoped ZnO, i.e. weaker and weaker deep-level emissions in figure 1, confirming again the electron transition for the ZnO deep-level emission. In summary, we have performed the multi-Gaussian fittings to the experimental NBE spectra of undoped, N-doped and N-In codoped p-type ZnO in the temperature range from 83 to 303 K. With the assignments of FX, A0 X and eA0 transitions, the temperature dependences of UV peak energy, width and intensity have been analysed in detail. The obtained EA of 113 meV, 140 meV and 112 meV with ED of 56 meV, 82 meV and 112 meV for undoped, N-doped and N-In codoped ZnO, respectively, exhibits good correlations with the different carrier recombination processes. The broadening of acceptor levels has been observed in N-doped and N-In codoped ZnO. In addition, we have confirmed that the deep-level visible emission in ZnO originates from the electron transition from the VO donor level to the valance band. ¨ ur U, ¨ Alivov Ya I, Liu C, Teke A, Reshchikov M A,  Ozg¨ Do˘gan S, Avrutin V, Cho S-J and Morkoc H 2005 J. Appl. Phys. 98 041301  Yamamoto T and Yoshida H K 2001 Physica B 302–303 155  Zeng Y J, Ye Z Z, Xu W Z, Lu J G, He H P, Zhu L P, Zhao B H, Che Y and Zhang S B 2006 Appl. Phys. Lett. 88 262103  Zeng Y J, Ye Z Z, Xu W Z, Li D Y, Lu J G, Zhu L P and Zhao B H 2006 Appl. Phys. Lett. 88 062107  Wang L and Giles N C 2004 Appl. Phys. Lett. 84 3049  Look D C, Reynolds D C, Litton C W, Jones R L, Eason D B and Cantwell G 2002 Appl. Phys. Lett. 81 1830  Xiu F X, Yang Z, Mandalapu L J, Liu J L and Beyermann W P 2006 Appl. Phys. Lett. 88 052106  Ryu Y R, Lee T S and White H W 2003 Appl. Phys. Lett. 83 87  Look D C, Renlund G M, Burgener R H II and Sizelove J R 2004 Appl. Phys. Lett. 85 5269  Xiu F X, Yang Z, Mandalapu L J, Zhao D T and Liu J L 2005 Appl. Phys. Lett. 87 252102  Bian J M, Li X M, Gao X D, Yu W D and Chen L D 2004 Appl. Phys. Lett. 84 541  Lu J G, Ye Z Z, Zhuge F, Zeng Y J, Zhao B H and Zhu L P 2004 Appl. Phys. Lett. 85 3134  Ye J D, Gu S L, Li F, Zhu S M, Zhang R, Shi Y, Zheng Y D, Sun X W, Lo G Q and Kwong D L 2007 Appl. Phys. Lett. 90 152108  Kong J F, Chen H, Ye H B, Shen W Z, Zhao J L and Li X M 2007 Appl. Phys. Lett. 90 041907  Ye H B, Kong J F, Shen W Z, Zhao J L and Li X M 2007 Appl. Phys. Lett. 90 102115  Varshni Y P 1967 Physica 34 149  Hutson A R 1959 J. Phys. Chem. Solids 8 467  Ko H J, Chen Y F, Zhu Z, Yao T, Kobayashi I and Uchiki H 2000 Appl. Phys. Lett. 76 1905  Reynolds D C, Look D C, Jogai B, Litton C W, Collins T C, Harsch W C and Cantwell G 1998 Phys. Rev. B 57 12151  Yamamoto T 2003 Japan. J. Appl. Phys. Part 2 42 L514  Makino T, Chia C H, Tuan N T, Segawa Y, Kawasaki M, Ohtomo A, Tamura K and Koinuma H 2000 Appl. Phys. Lett. 76 3549  Shen W Z and Shen S C 1996 J. Appl. Phys. 80 5941  Kang H S, Kang J S, Kim J W and Lee S Y 2004 J. Appl. Phys. 95 1246  Liu Z S, Jing X P, Wang L X and Li Y 2006 J. Electrochem. Soc. 153 G1035 5591
1426147072_0c724902d6 jphysd7_18_013. Temperature-dependent photoluminescence of undoped... http://cmsoep.physics.sjtu.edu.cn/doc/2007/JPHYSD7_18_013.pdf 2015-03-12 08:57:52 http://Doczine.Com/406472.html#jphysd7_18_013. http://Doczine.Com/1426147072_0c724902d6.html#jphysd7_18_013. http://Doczine.Com/cracker/1426147072_0c724902d6/jphysd7_18_013.pdf http://Doczine.Com/cracker/1426147072_0c724902d6/jphysd7_18_013.txt
Link or Click Back
Here will be a configuration form
The Name Archives
Consider donating to the demonian archive to keep us ad free.