- Email: [email protected]
Correlation of memory characteristics of polymer bistable memory devices with metal deposition process
Synthetic Metals 158 (2008) 861–864
Contents lists available at ScienceDirect
Synthetic Metals journal homepage: www.elsevier.com/locate/synmet
Correlation of memory characteristics of polymer bistable memory devices with metal deposition process Sung Hyun Kim a , Kyoung Soo Yook b , Jyongsik Jang a , Jun Yeob Lee b,∗ a b
School of Chemical and Biological Engineering, Seoul National University, Shinlim-dong, Kwanak-gu, Seoul 151-742, Republic of Korea Department of Polymer Science and Engineering, Dankook University, Jukjeon-dong, Suji-gu, Yongin-si, Kyeonggi-do 448-701, Republic of Korea
a r t i c l e
i n f o
Article history: Received 29 February 2008 Received in revised form 2 June 2008 Accepted 10 June 2008 Available online 18 July 2008 Keywords: Bistability Organic memory Metal deposition process
a b s t r a c t Origin of bistability in organic bistable memory devices (OBDs) was investigated by using two metal deposition processes of electron beam deposition and thermal deposition. Thermal deposition of Al was more effective than electron beam deposition to get high on/off ratio and stable operation of OBDs and metal nanoparticle formation during metal deposition was found to be critical to bistability of polymer OBDs. © 2008 Elsevier B.V. All rights reserved.
1. Introduction Organic bistable memory devices (OBDs) have gained considerable interest for the last decade due to their merits of simple fabrication process, high on/off ratio, design versatility, fast switching speed and so on. In particular, simple device structure and high packing density of OBDs are suitable for application in integrated non-volatile memory devices. There have been many studies to fabricate organic bistable memory devices. One approach is to use an organic/metal nanoparticle composite structure and it was effective to get high on/off ratio and long-term stability [1–7]. Yang’s group developed an OBD with a nano-composite of organic/Au nanoparticle and reported high on/off ratio and long-term durability [1–3]. Other than this, OBDs with nano-composite of Al and CdSe exhibited good memory characteristics [4–7]. Second approach for fabricating OBDs is to dope C60 [8], CNT [9] or low bandgap dopant materials [10] in organic semiconductor materials. Third method to make OBDs is to use pure organic materials in combination with metal electrodes [11–16]. This method is advantageous in that device structure and process is quite simple because it does not contain any metal nanoparticles. It was reported that metal diffusion after metal deposition induced doping effect at the interface between organic materials and electrodes, leading to bistability in OBDs even though no evi-
∗ Corresponding author. Tel.: +82 31 8005 3585; fax: +82 31 8005 3585. E-mail address: [email protected] (J.Y. Lee). 0379-6779/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2008.06.004
dence for the relationship between metal deposition and bistability was revealed. Native oxide formation during Al deposition was also proposed as the origin for bistability in Al based organic memory devices [17–18]. In this work, we investigated the effect of metal deposition process on memory performances of OBDs to clarify the origin of bistable behavior of polymer OBDs. High energy metal deposition processes of electron beam deposition was used instead of thermal evaporation process and memory characteristics of OBDs were compared. 2. Experimental Four different devices were fabricated in this work to study the origin of bistablity in polymer OBDs. Basic device configuration was indium tin oxide (ITO, 150 nm)/polyfluorene (PFO) or polyphenylenevinylene (PPV) (100 nm)/Al (200 nm). Two metal deposition processes of thermal deposition and electron beam deposition were used for Al evaporation and two different organic materials were applied in organic layer. Device configurations for OBDs fabricated in this work are shown in Fig. 1. PFO was supplied from Dow Chemical and it had the highest occupied molecular orbital (HOMO) of 5.6 eV and the lowest unoccupied molecular orbital (LUMO) of 2.6 eV. PPV was a superyellow® from Merck and it had the HOMO of 5.2 eV and LUMO of 2.8 eV. PFO and PPV were spin coated at a thickness of 100 nm from 1.0 wt.% toluene solution. Polymer thin film was baked at 150 ◦ C for 10 min after spin coating and it was transferred to vacuum chamber for Al deposition.
862
S.H. Kim et al. / Synthetic Metals 158 (2008) 861–864
Fig. 1. Device configurations for OBDs with different metal deposition processes.
Thermal deposition of Al was carried out at a deposition rate of ˚ ˚ 5 A/s, while electron beam deposition rate of Al was 2 A/s. Pixel size was 2 mm × 2 mm with a pixel of 4 mm2 . Current–voltage characteristics of memory devices were measured with Keithley 2400 source measurement unit. 3. Results and discussion Thermal and electron beam deposition has been widely used as methods for metal thin film formation and different film morphology was reported [19]. Island growth of metal particles was
observed in thermally deposited Al, while flat film is favored in electron beam deposited metal films. Considering that oxidized metal nanoparticle formation is important for bistability in polymer OBDs, it can be expected that different morphology of Al cathodes can affect the memory characteristics of pure polymer OBDs. Therefore, memory behavior of PPV and PFO devices was investigated according to metal deposition method. Fig. 2 compares current–voltage curves of PFO and PPV devices with different metal deposition processes. PPV OBD with thermally deposited Al showed clear bistability with high on/off ratio over 1000, while PPV OBD with electron beam deposited Al showed an on/off ratio of around 100. Similar curve shape was obtained in PPV device, but on/off ratio of OBDs at 2 V was decreased by one order when electron beam deposition process was used instead of thermal deposition. PPV has been known to exhibit memory behavior by deposition of Al on PPV [15]. Al nanocrystal formation during Al deposition was suggested as an origin for memory behavior in PPV OBDs. Al can penetrate inside PPV during thermal deposition process and it can play a role of nanocrystal for charge trapping and detrapping in common Al nanocrystal based OBDs. Similar mechanisms have been proposed in small molecule based OBDs [14]. Considering that uniform nanocrystal dispersion inside PPV is critical to memory performances, Al deposition process which can induce island structure of Al phase is expected to give better memory performances. It is already well known that island growth of Al is dominant in thermally deposited Al films, while continuous film growth is popular in electron beam deposited Al films [19]. To confirm the film morphology of Al films, surface morphology of Al was observed with scanning electron microscope (SEM). SEM images of e-beam deposited Al and thermally deposited Al are shown in Fig. 3. Smooth surface morphology
Fig. 2. Current density–voltage characteristics of OBDs with different metal deposition processes. (a) PPV OBD (Al thermal deposition), (b) PPV OBD (Al electron beam deposition) and (a) PFO OBD (Al thermal deposition), (b) PFO OBD (Al electron beam deposition).
S.H. Kim et al. / Synthetic Metals 158 (2008) 861–864
863
Fig. 3. Scanning electron microscopic images of e-beam deposited Al film (a) and thermally evaporated Al film (b).
can be clearly seen in e-beam evaporated Al film, while island-like rough surface morphology was obtained in thermally deposited film. Therefore, thermally deposited Al may be better than electron beam deposited Al and can improve bistable memory performances of PPV OBDs. This result also indicates that Al nanoparticle formation is important for stable memory performances in OBDs. Similar results were obtained in PFO OBDs. PFO OBDs with Al deposited by electron beam process showed poor bistability, while PFO OBDs with thermally deposited Al exhibited moderate bistable character. Bistability of PFO OBDs was greatly affected by metal deposition process, which indirectly implies that Al nanocrystal formation inside organic layer during deposition is critical to switching performances of PFO based OBDs. Fluorenone structure formation by oxidation of fluorine unit during synthesis and device fabrication was suggested as the origin of bistability in PFO based OBDs [16]. However, this result indicates that Al nanostructure formation inside organic layer is also responsible for memory characteristics of PFO OBDs. Therefore, it can be concluded that Al deposition process is important for bistable memory behavior in PPV and PFO based OBDs. To get more understanding of the memory mechanism in PPV and PFO devices, current-voltage curves were plotted in logarithmic scale. Fig. 4 shows log(current)–log(voltage) plots of PPV and PFO devices. Linear relationship between log(current)–log(voltage) was observed and this indicates that space charge limited conduction mechanism dominates charge transport in PPV and PFO OBDs. As proposed by Colle and co-workers [17] and Chen and Ma [10], oxidized nanoparticle formation during Al evaporation induces charge trapping at the interface, leading to space charge formation at the interface. These results agree with their results and oxidized nanoparticle formation at the interface may be responsible for bistable memory behavior and space charge limited conduction mechanism. Energy levels of organic materials may not be critical to memory performances as reported by Bozano et al. [5]. Considering the energy levels of PPV and PFO, PFO OBDs should have high on/off ratio due to large bandgap of PFO. However, high on/off ratio
Fig. 4. Log(current)–log(voltage) plots of PPV OBD with thermally deposited Al (a) and PFO OBD with thermally deposited Al (b).
was obtained in PPV OBDs and the on/off ratio cannot be correlated with energy levels of organic materials. On/off stability of OBDs was measured using multicycle on/off test of OBDs and long-term stability results of PPV OBDs is shown in Fig. 5 representatively. Negative differential resistance behavior was observed in PPV OBDs as reported in previous work by Jabbour and co-workers [15] and on/off voltage could be set in positive bias region. Writing voltage to get high conductance state was set as the voltage at current peak (3 V), while erase voltage for low conductance state was 7 V which corresponds to valley of current–voltage curves. Reading voltage was 1 V. Average on/off ratio of PPV OBDs was about 500 even though some data were scattered. The on/off ratio could be maintained after multicycle test over 100 times and it was quite stable.
Fig. 5. Multicycle test results of PPV OBDs with thermally evaporated Al.
864
S.H. Kim et al. / Synthetic Metals 158 (2008) 861–864
4. Conclusions In summary, bistability of polymer OBDs was greatly affected by metal deposition process and it was found that metal nanocrystal formation during deposition process was critical to memory performances. Thermal deposition was better than electron beam deposition for high on/off ratio in polymer OBDs. Proper choice of metal deposition method was found to be important to get superior memory performances in OBDs. References [1] [2] [3] [4]
R.J. Tseng, J. Huang, J. Quyang, R.B. Kaner, Y. Yang, Nano Lett. 5 (2005) 1077. J. Quyang, C. Chu, D. Sieves, Y. Yang, Appl. Phys. Lett. 86 (2005) 123507. A. Prakash, J. Quyang, J. Lin, Y. Yang, J. Appl. Phys. 100 (2006) 054309. J. Quyang, C. Chu, C.R. Szmanda, L. Ma, Y. Yang, Nat. Mater. 3 (2003) 918.
[5] L.D. Bozano, B.W. Kean, M. Beinhoff, K.R. Carter, P.M. Rice, J.C. Scott, Adv. Funct. Mater. 15 (2005) 1933. [6] Y. Yang, J. Quyang, L. Ma, R.J. Tseng, C. Chu, Adv. Funct. Mater. 16 (2006) 1001. [7] F. Li, D. Son, J. Ham, B. Kim, J.H. Jung, T.W. Kim, Appl. Phys. Lett. 91 (2005) 162109. [8] A. Kanwal, M. Chhowalla, Appl. Phys. Lett. 89 (2006) 203103. [9] V. Meunier, S.V. Kalinin, B.G. Sumpter, Phys. Rev. Lett. 98 (2007) 056401. [10] J. Chen, D. Ma, J. Appl. Phys. 100 (2006) 034512. [11] J. Chen, D. Ma, Appl. Phys. Lett. 87 (2005) 023505. [12] Y. Lai, C. Tu, D. Kwong, J.S. Chen, Appl. Phys. Lett. 87 (2005) 122101. [13] M. Lauters, B. McCarthy, D. Sarid, G.E. Jabbour, Appl. Phys. Lett. 87 (2005) 231105. [14] J. Chen, L. Xu, J. Lin, Y. Geng, L. Wang, D. Ma, Appl. Phys. Lett. 89 (2006) 083514. [15] M. Lauters, B. McCarthy, D. Sarid, G.E. Jabbour, Appl. Phys. Lett. 89 (2006) 013507. [16] T. Ouisse, O. Stephan, Org. Electron. 5 (2004) 251. [17] F. Verbakel, S.C.J. Meskers, R.A.J. Janssen, H.L. Gomes, M. Colle, M. Buchel, D.M. De Leeuw, Appl. Phys. Lett. 91 (2007) 192103. [18] M. Colle, M. Buchel, D.M. De Leeuw, Org. Electron. 7 (2006) 305. [19] J. Klein, J. Schneider, M. Muske, S. Gall, W. Fuhs, Proc. Eur. Photovoltaic Sol. Energy Conf. 19 (2004) 1135.
Contents lists available at ScienceDirect
Synthetic Metals journal homepage: www.elsevier.com/locate/synmet
Correlation of memory characteristics of polymer bistable memory devices with metal deposition process Sung Hyun Kim a , Kyoung Soo Yook b , Jyongsik Jang a , Jun Yeob Lee b,∗ a b
School of Chemical and Biological Engineering, Seoul National University, Shinlim-dong, Kwanak-gu, Seoul 151-742, Republic of Korea Department of Polymer Science and Engineering, Dankook University, Jukjeon-dong, Suji-gu, Yongin-si, Kyeonggi-do 448-701, Republic of Korea
a r t i c l e
i n f o
Article history: Received 29 February 2008 Received in revised form 2 June 2008 Accepted 10 June 2008 Available online 18 July 2008 Keywords: Bistability Organic memory Metal deposition process
a b s t r a c t Origin of bistability in organic bistable memory devices (OBDs) was investigated by using two metal deposition processes of electron beam deposition and thermal deposition. Thermal deposition of Al was more effective than electron beam deposition to get high on/off ratio and stable operation of OBDs and metal nanoparticle formation during metal deposition was found to be critical to bistability of polymer OBDs. © 2008 Elsevier B.V. All rights reserved.
1. Introduction Organic bistable memory devices (OBDs) have gained considerable interest for the last decade due to their merits of simple fabrication process, high on/off ratio, design versatility, fast switching speed and so on. In particular, simple device structure and high packing density of OBDs are suitable for application in integrated non-volatile memory devices. There have been many studies to fabricate organic bistable memory devices. One approach is to use an organic/metal nanoparticle composite structure and it was effective to get high on/off ratio and long-term stability [1–7]. Yang’s group developed an OBD with a nano-composite of organic/Au nanoparticle and reported high on/off ratio and long-term durability [1–3]. Other than this, OBDs with nano-composite of Al and CdSe exhibited good memory characteristics [4–7]. Second approach for fabricating OBDs is to dope C60 [8], CNT [9] or low bandgap dopant materials [10] in organic semiconductor materials. Third method to make OBDs is to use pure organic materials in combination with metal electrodes [11–16]. This method is advantageous in that device structure and process is quite simple because it does not contain any metal nanoparticles. It was reported that metal diffusion after metal deposition induced doping effect at the interface between organic materials and electrodes, leading to bistability in OBDs even though no evi-
∗ Corresponding author. Tel.: +82 31 8005 3585; fax: +82 31 8005 3585. E-mail address: [email protected] (J.Y. Lee). 0379-6779/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2008.06.004
dence for the relationship between metal deposition and bistability was revealed. Native oxide formation during Al deposition was also proposed as the origin for bistability in Al based organic memory devices [17–18]. In this work, we investigated the effect of metal deposition process on memory performances of OBDs to clarify the origin of bistable behavior of polymer OBDs. High energy metal deposition processes of electron beam deposition was used instead of thermal evaporation process and memory characteristics of OBDs were compared. 2. Experimental Four different devices were fabricated in this work to study the origin of bistablity in polymer OBDs. Basic device configuration was indium tin oxide (ITO, 150 nm)/polyfluorene (PFO) or polyphenylenevinylene (PPV) (100 nm)/Al (200 nm). Two metal deposition processes of thermal deposition and electron beam deposition were used for Al evaporation and two different organic materials were applied in organic layer. Device configurations for OBDs fabricated in this work are shown in Fig. 1. PFO was supplied from Dow Chemical and it had the highest occupied molecular orbital (HOMO) of 5.6 eV and the lowest unoccupied molecular orbital (LUMO) of 2.6 eV. PPV was a superyellow® from Merck and it had the HOMO of 5.2 eV and LUMO of 2.8 eV. PFO and PPV were spin coated at a thickness of 100 nm from 1.0 wt.% toluene solution. Polymer thin film was baked at 150 ◦ C for 10 min after spin coating and it was transferred to vacuum chamber for Al deposition.
862
S.H. Kim et al. / Synthetic Metals 158 (2008) 861–864
Fig. 1. Device configurations for OBDs with different metal deposition processes.
Thermal deposition of Al was carried out at a deposition rate of ˚ ˚ 5 A/s, while electron beam deposition rate of Al was 2 A/s. Pixel size was 2 mm × 2 mm with a pixel of 4 mm2 . Current–voltage characteristics of memory devices were measured with Keithley 2400 source measurement unit. 3. Results and discussion Thermal and electron beam deposition has been widely used as methods for metal thin film formation and different film morphology was reported [19]. Island growth of metal particles was
observed in thermally deposited Al, while flat film is favored in electron beam deposited metal films. Considering that oxidized metal nanoparticle formation is important for bistability in polymer OBDs, it can be expected that different morphology of Al cathodes can affect the memory characteristics of pure polymer OBDs. Therefore, memory behavior of PPV and PFO devices was investigated according to metal deposition method. Fig. 2 compares current–voltage curves of PFO and PPV devices with different metal deposition processes. PPV OBD with thermally deposited Al showed clear bistability with high on/off ratio over 1000, while PPV OBD with electron beam deposited Al showed an on/off ratio of around 100. Similar curve shape was obtained in PPV device, but on/off ratio of OBDs at 2 V was decreased by one order when electron beam deposition process was used instead of thermal deposition. PPV has been known to exhibit memory behavior by deposition of Al on PPV [15]. Al nanocrystal formation during Al deposition was suggested as an origin for memory behavior in PPV OBDs. Al can penetrate inside PPV during thermal deposition process and it can play a role of nanocrystal for charge trapping and detrapping in common Al nanocrystal based OBDs. Similar mechanisms have been proposed in small molecule based OBDs [14]. Considering that uniform nanocrystal dispersion inside PPV is critical to memory performances, Al deposition process which can induce island structure of Al phase is expected to give better memory performances. It is already well known that island growth of Al is dominant in thermally deposited Al films, while continuous film growth is popular in electron beam deposited Al films [19]. To confirm the film morphology of Al films, surface morphology of Al was observed with scanning electron microscope (SEM). SEM images of e-beam deposited Al and thermally deposited Al are shown in Fig. 3. Smooth surface morphology
Fig. 2. Current density–voltage characteristics of OBDs with different metal deposition processes. (a) PPV OBD (Al thermal deposition), (b) PPV OBD (Al electron beam deposition) and (a) PFO OBD (Al thermal deposition), (b) PFO OBD (Al electron beam deposition).
S.H. Kim et al. / Synthetic Metals 158 (2008) 861–864
863
Fig. 3. Scanning electron microscopic images of e-beam deposited Al film (a) and thermally evaporated Al film (b).
can be clearly seen in e-beam evaporated Al film, while island-like rough surface morphology was obtained in thermally deposited film. Therefore, thermally deposited Al may be better than electron beam deposited Al and can improve bistable memory performances of PPV OBDs. This result also indicates that Al nanoparticle formation is important for stable memory performances in OBDs. Similar results were obtained in PFO OBDs. PFO OBDs with Al deposited by electron beam process showed poor bistability, while PFO OBDs with thermally deposited Al exhibited moderate bistable character. Bistability of PFO OBDs was greatly affected by metal deposition process, which indirectly implies that Al nanocrystal formation inside organic layer during deposition is critical to switching performances of PFO based OBDs. Fluorenone structure formation by oxidation of fluorine unit during synthesis and device fabrication was suggested as the origin of bistability in PFO based OBDs [16]. However, this result indicates that Al nanostructure formation inside organic layer is also responsible for memory characteristics of PFO OBDs. Therefore, it can be concluded that Al deposition process is important for bistable memory behavior in PPV and PFO based OBDs. To get more understanding of the memory mechanism in PPV and PFO devices, current-voltage curves were plotted in logarithmic scale. Fig. 4 shows log(current)–log(voltage) plots of PPV and PFO devices. Linear relationship between log(current)–log(voltage) was observed and this indicates that space charge limited conduction mechanism dominates charge transport in PPV and PFO OBDs. As proposed by Colle and co-workers [17] and Chen and Ma [10], oxidized nanoparticle formation during Al evaporation induces charge trapping at the interface, leading to space charge formation at the interface. These results agree with their results and oxidized nanoparticle formation at the interface may be responsible for bistable memory behavior and space charge limited conduction mechanism. Energy levels of organic materials may not be critical to memory performances as reported by Bozano et al. [5]. Considering the energy levels of PPV and PFO, PFO OBDs should have high on/off ratio due to large bandgap of PFO. However, high on/off ratio
Fig. 4. Log(current)–log(voltage) plots of PPV OBD with thermally deposited Al (a) and PFO OBD with thermally deposited Al (b).
was obtained in PPV OBDs and the on/off ratio cannot be correlated with energy levels of organic materials. On/off stability of OBDs was measured using multicycle on/off test of OBDs and long-term stability results of PPV OBDs is shown in Fig. 5 representatively. Negative differential resistance behavior was observed in PPV OBDs as reported in previous work by Jabbour and co-workers [15] and on/off voltage could be set in positive bias region. Writing voltage to get high conductance state was set as the voltage at current peak (3 V), while erase voltage for low conductance state was 7 V which corresponds to valley of current–voltage curves. Reading voltage was 1 V. Average on/off ratio of PPV OBDs was about 500 even though some data were scattered. The on/off ratio could be maintained after multicycle test over 100 times and it was quite stable.
Fig. 5. Multicycle test results of PPV OBDs with thermally evaporated Al.
864
S.H. Kim et al. / Synthetic Metals 158 (2008) 861–864
4. Conclusions In summary, bistability of polymer OBDs was greatly affected by metal deposition process and it was found that metal nanocrystal formation during deposition process was critical to memory performances. Thermal deposition was better than electron beam deposition for high on/off ratio in polymer OBDs. Proper choice of metal deposition method was found to be important to get superior memory performances in OBDs. References [1] [2] [3] [4]
R.J. Tseng, J. Huang, J. Quyang, R.B. Kaner, Y. Yang, Nano Lett. 5 (2005) 1077. J. Quyang, C. Chu, D. Sieves, Y. Yang, Appl. Phys. Lett. 86 (2005) 123507. A. Prakash, J. Quyang, J. Lin, Y. Yang, J. Appl. Phys. 100 (2006) 054309. J. Quyang, C. Chu, C.R. Szmanda, L. Ma, Y. Yang, Nat. Mater. 3 (2003) 918.
[5] L.D. Bozano, B.W. Kean, M. Beinhoff, K.R. Carter, P.M. Rice, J.C. Scott, Adv. Funct. Mater. 15 (2005) 1933. [6] Y. Yang, J. Quyang, L. Ma, R.J. Tseng, C. Chu, Adv. Funct. Mater. 16 (2006) 1001. [7] F. Li, D. Son, J. Ham, B. Kim, J.H. Jung, T.W. Kim, Appl. Phys. Lett. 91 (2005) 162109. [8] A. Kanwal, M. Chhowalla, Appl. Phys. Lett. 89 (2006) 203103. [9] V. Meunier, S.V. Kalinin, B.G. Sumpter, Phys. Rev. Lett. 98 (2007) 056401. [10] J. Chen, D. Ma, J. Appl. Phys. 100 (2006) 034512. [11] J. Chen, D. Ma, Appl. Phys. Lett. 87 (2005) 023505. [12] Y. Lai, C. Tu, D. Kwong, J.S. Chen, Appl. Phys. Lett. 87 (2005) 122101. [13] M. Lauters, B. McCarthy, D. Sarid, G.E. Jabbour, Appl. Phys. Lett. 87 (2005) 231105. [14] J. Chen, L. Xu, J. Lin, Y. Geng, L. Wang, D. Ma, Appl. Phys. Lett. 89 (2006) 083514. [15] M. Lauters, B. McCarthy, D. Sarid, G.E. Jabbour, Appl. Phys. Lett. 89 (2006) 013507. [16] T. Ouisse, O. Stephan, Org. Electron. 5 (2004) 251. [17] F. Verbakel, S.C.J. Meskers, R.A.J. Janssen, H.L. Gomes, M. Colle, M. Buchel, D.M. De Leeuw, Appl. Phys. Lett. 91 (2007) 192103. [18] M. Colle, M. Buchel, D.M. De Leeuw, Org. Electron. 7 (2006) 305. [19] J. Klein, J. Schneider, M. Muske, S. Gall, W. Fuhs, Proc. Eur. Photovoltaic Sol. Energy Conf. 19 (2004) 1135.