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The passivation layer formation in the cryo-etching plasma process
Microelectronic Engineering 84 (2007) 1128–1131 www.elsevier.com/locate/mee
The passivation layer formation in the cryo-etching plasma process R. Dussart
a,*
, X. Mellhaoui a, T. Tillocher a, P. Lefaucheux a, M. Boufnichel b, P. Ranson a
a
GREMI/Polytech’Orle´ans, Orle´ans 45067, France b STMicroelectronics, Tours 37071, France Available online 27 January 2007
Abstract The growth and destruction of the SiOxFy passivation layer is investigated in the so-called cryogenic process used for silicon etching. We show that etching products (SiF4) can play an important role in its formation. It can explain why overpassivating regime characterized by the appearance of black silicon is preferentially obtained in large structures. Test experiments clearly show that both SiFx and O radicals are necessary to create the passivation layer. By separating SiF4 plasma and O2 plasma, we could conclude that the reaction mainly occurred at the sidewalls of the structure. If we increase the power of the oxygen plasma, the passivation layer can be reinforced. Finally, we grew the passivation layer on a flat surface by using a system of electrostatic grids to get rid of ions and electrons in order to enhance the deposition on the surface. Ellipsometric analysis is reported during the growth of the passivation layer and its destruction, which occurs when the wafer is warmed back up to ambient temperature. Ó 2007 Elsevier B.V. All rights reserved. Keywords: Cryo-etching; Plasma process; Passivation layer
1. Introduction Cryogenic process in SF6/O2 plasma is commonly used for deep etching of silicon for the microfabrication of MEMS and power microelectronic components [1,2]. In this particular process, both oxygen and low temperature are necessary to create a passivation layer on the sidewalls of the etched structures. Ion bombardment is also necessary to avoid the formation of the passivation layer at the bottom of the structure [3]. High aspect ratio microstructures can be obtained with a quite high etch rate compared to other processes [4]. The main issue remains the passivation layer, which seems very fragile. As a consequence, the process is not as robust as other processes like the so-called Bosch process [5]. In another hand, the cryogenic process is reputed for its cleanness: it does not contaminate the reactor and the passivation layer desorbs during the wafer warm-up leaving the structure sidewalls without any other material than silicon [3].
*
Corresponding author. E-mail address: [email protected] (R. Dussart).
0167-9317/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.mee.2007.01.048
In a previous article [6], we have presented a first characterization of the passivation layer by mass spectrometry. We actually analyzed the residual gas coming from the layer desorption during the increase of the substrate temperature. We obtained a significant increase of the SiFþ 3 signal between 70 and 30 °C. SiFþ is the main 3 fragmentation product of SiF4. We concluded that etching products (SiF4) could play an important role on the passivation layer growth. Then, we successfully created a SiOxFy layer with a SiF4/O2 plasma in a cavity obtained by isotropic etching. This layer was able to resist to a 3 min additional isotropic etching process. With this experiment, we clearly showed that a strong passivation layer could be made with the SiF4/O2 plasma at low temperature [6]. Finally, two different mechanisms were proposed to explain the formation of the passivation layer in the cryo-etching process [6]. In this paper, we present some other test experiments carried out to better understand the passivation mechanism. Overpassivating regime characterized by black silicon appearance [7] can also be enhanced by SiFx redeposition in the etched structure. Finally, we present new ellipsometric measurements carried out in a new con-
R. Dussart et al. / Microelectronic Engineering 84 (2007) 1128–1131
figuration of the experiment. We have already presented a first study of the desorption of the passivation layer by spectroscopic ellipsometry analysis in [6]. A 19 nm thick layer had been obtained on a bare silicon wafer cooled down to 100 °C during a 10 min SiF4/O2 plasma. We could follow the desorption of this layer when the wafer was warmed back up to ambient temperature. In order to favour the growth regime during the SiF4/O2 plasma, we have installed electrostatic grids at the top of the wafer. The layer growth could be in situ monitored and its desorption could be detected after the process during the wafer warm-up. The results with this new configuration are presented in this article. 2. Experiment An Alcatel 601E ICP reactor is used for the experiments (see Fig. 1). It is composed of a plasma source and a diffusion chamber [4]. The chuck is independently biased. SF6,
1129
O2 and SiF4 are injected by mass flow controllers. SiO2 mask is used to selectively etch the (1 0 0) silicon wafers. The chuck is cooled by liquid nitrogen to a set point temperature between 110 °C and 80 °C. A Leica Cambridge Ltd., S360. Scanning electron microscope is used to characterize the etched profiles of the test experiments. A Uvisel/Jobin–Yvon–Horiba spectroscopic ellipsometer is used to characterize in situ the SiOxFy layer obtained in SiF4/O2 plasmas. Three biased grids have been installed just above the wafer to significantly decrease the ion bombardment on the wafer (Fig. 1). The transparency of each grid is 54%. The period of the mesh is 150 lm and the diameter of the wires is 40 lm. The upper grid is connected to the ground. The second grid is negatively biased to reject electrons. The lower grid is positively biased to reject ions to the plasma. 3. Results and discussion 3.1. SiOxFy layer
Fig. 1. Schematic of the ICP reactor used for the experiments.
In Fig. 2, we present a series of test experiments performed in order to check the efficiency of the passivation layer. We started with a 10 min process described in [6] which provides a kind of cavity due to isotropic etching. This profile is represented in dashed line for comparison on the other profiles. This first process is called ‘INI’. Then we alternated 5 or 10 times a 30 s plasma of SiF4 and a 30 s plasma of O2. The source power for the SiF4 plasma was 1000 W, whereas the source power for the O2 plasma was either 1000 W or 400 W. During this step, the wafer was biased to reduce the deposition on the bottom of the cavity. Then, a 3 min isotropic plasma (called ‘FIN’) with bias was added to check, if the passivation layer was created or not and if it can resist to this final etching step. If we alternate the two plasmas of SiF4 and O2 only 5 times for the 1000 W oxygen plasma, we can form a second cavity at the bottom of the first structure. In this case, we were able to create a passivation layer, which protected
Fig. 2. (Left) Profile obtained after a 10 min isotropic etching process called INI. (Right) Profiles obtained after inserting O2 and SiF4 30 s plasmas and a 3 min additional isotropic etching process called FIN. The results are given after 5 and 10 cycles and for 400 W and 1000 W plasma source power for the O2 plasma.
1130
R. Dussart et al. / Microelectronic Engineering 84 (2007) 1128–1131
the sidewalls of the first cavity. If we compare the obtained profile with the INI profile, we can see that the first cavity was protected except at the top of the first cavity. If we alternate the two plasmas 10 times instead of only 5 times, then the passivation layer is too efficient and the FIN step is not able to remove the passivation layer at the bottom of the cavity to form the second cavity. If the same experiment is made with 400 W oxygen plasmas, the passivation layer is not as strong as at 1000 W. A second cavity can be formed during the FIN step whereas the sidewalls of the first cavity remain protected. In this case, 5 cycles are not sufficient to efficiently protect the sidewalls. When the oxygen plasma power is increased, more oxygen radicals are produced. We have shown in [6] that oxygen radicals are responsible for the passivation layer formation by reaction with SiFx radicals of the sidewalls. By increasing their concentration, we could make the passivation layer stronger.
Fig. 4. Evolution of the SiOxFy layer thickness evaluated by ellipsometric analysis during the SiF4/O2 plasma and during the wafer warm-up.
3.3. Spectroscopic ellipsometry 3.2. Overpassivating regime In overpassivating regime (high oxygen content in the SF6/O2 plasma), columnar microstructures (CMS) can appear in large silicon patterns (>1 lm) [7]. An example is given in Fig. 3, a 50 lm diameter big hole and 10 lm diameter small holes are shown. CMS are obtained on both types of hole. However, their typical dimension is not the same. CMS are denser in the bigger hole indicating that the overpassivating regime was enhanced in this region. This behaviour could be explained by etching product redeposition. SiFx and O radicals could reach more easily the bottom of the structure in the 50 lm diameter hole, because the aspect ratio (depth/diameter) was smaller in this case. As a consequence, passivation mechanisms could be enhanced in the 50 lm diameter hole compared to the 10 lm diameter hole.
In situ spectroscopic ellipsometry analysis was carried out during a SiF4/O2 plasma on a bare silicon wafer cooled down to 100 °C. The ellipsometric spectra were fitted using a Lorentz oscillator model for the dispersion law. As mentioned in part 2, a system of grids was installed to enhance the deposition mechanism. The middle grid was biased to 25 V, whereas the third grid was biased to +30 V. A planar probe was placed below the system to check their efficiency. The ionic current was reduced by more than two-orders of magnitude with this system. As a consequence, the deposited layer, which is quite fragile, was less submitted to ion bombardment and could grow with more efficiency than without grids. The results are presented in Fig. 4 for a process made at 100 °C. The film thickness is plotted as a function of time. During the first 1000 s, SiF4 and O2 are injected inside the reactor without plasma. We can observe a slight increase of the film thickness due to the physisorption of these molecules on the wafer. Then, the plasma is switched on during 10 min. The SiOxFy layer grows linearly as a function of time. At the end of the plasma, the layer was about 90 nm thick. Without grids, we obtained a thickness of 19 nm [6]. We clearly see the effect of the grids, which effectively favour the passivation regime. After the plasma deposition, we increased the temperature by steps of 10 °C and we took an ellipsometric spectrum for each temperature from 100 °C to +20 °C. The film thickness decreases when the wafer is warmed back up to ambient temperature. An 18 nm remaining layer is obtained at +20 °C. 4. Conclusion
Fig. 3. Micrograph of the top view of Columnar MicroStructures (CMS) obtained in overpassivating regime in SF6/O2 plasma on a cooled (85 °C) masked silicon wafer. CMS were observed in a 50 lm diameter hole and in 10 lm diameter holes.
This paper deals with new results concerning the passivation layer formation in the cryogenic process. In this particular process, etching products (mainly SiF4) can
R. Dussart et al. / Microelectronic Engineering 84 (2007) 1128–1131
participate to the layer growth on the sidewalls of the structure. Test experiments have been performed to deposit the passivation layer on a cavity obtained by isotropic etching. The deposition was made by alternating SiF4 plasmas and O2 plasmas. By separating the two plasmas, we showed that the reactions between SiFx radicals and O atoms occur at the cooled silicon sidewalls of the cavity and not in the plasma. The passivation layer efficiency could be enhanced by increasing the source power of the oxygen plasma. After 10 cycles, the passivation layer was so efficient that we could not remove it at the bottom of the cavity to form the second cavity during the FIN process. At higher power, oxygen atom concentration is larger, which contribute to create a thicker and more efficient SiOxFy layer. In overpassivating regime, larger patterns are covered by denser CMS than smaller patterns. This is due to the deposition of SiFx and oxygen, which is more efficient in bigger patterns. Finally, we could follow the film growth on a bare silicon by in situ ellipsometry experiments. A system of biased grids allowed us to significantly reduce the ion bombardment to simulate the conditions obtained on the side-
1131
walls. After a 10 min SiF4/O2 plasma, a 90 nm thick SiOxFy layer was grown on a cooled bare silicon, whereas a 19 nm thick layer had been obtained without grids in the same process conditions. A large part of this layer was desorbed during the wafer warm-up. References [1] M.A. Blauw, T. Zijlstra, R.A. Bakker, E. van der Drift, J. Vac. Sci. Technol. B 18 (2000) 3453. [2] M.J. de Boer, J.G.E. Gardeniers, H.V. Jansen, E. Smulders, M.-J. Gilde, G. Roelofs, J.N. Sasserath, M. Elwenspoek, J. Microelectron. Mech. Syst. 11 (2002) 4. [3] R. Dussart, M. Boufnichel, G. Marcos, P. Lefaucheux, A. Basillais, R. Benoit, T. Tillocher, X. Mellhaoui, H. Estrade-Szwarckopf, P. Ranson, J. Micromech. Microeng. 14 (2004) 190–196. [4] M. Boufnichel, S. Aachboun, P. Lefaucheux, P. Ranson, J. Vac. Sci. Technol. B 21 (1) (2003) 267–273. [5] F. La¨rmer and A. Schilp US patent no 5498312 (1996). [6] X. Mellhaoui, R. Dussart, T. Tillocher, P. Lefaucheux, P. Ranson, M. Boufnichel, L.J. Overzet, J. Appl. Phys. 98 (2005) 104901-1. [7] R. Dussart, X. Mellhaoui, T. Tillocher, P. Lefaucheux, M. Volatier, C. Socquet-Clerc, P. Brault, P. Ranson, J. Phys. D 38 (2005) 3395.
The passivation layer formation in the cryo-etching plasma process R. Dussart
a,*
, X. Mellhaoui a, T. Tillocher a, P. Lefaucheux a, M. Boufnichel b, P. Ranson a
a
GREMI/Polytech’Orle´ans, Orle´ans 45067, France b STMicroelectronics, Tours 37071, France Available online 27 January 2007
Abstract The growth and destruction of the SiOxFy passivation layer is investigated in the so-called cryogenic process used for silicon etching. We show that etching products (SiF4) can play an important role in its formation. It can explain why overpassivating regime characterized by the appearance of black silicon is preferentially obtained in large structures. Test experiments clearly show that both SiFx and O radicals are necessary to create the passivation layer. By separating SiF4 plasma and O2 plasma, we could conclude that the reaction mainly occurred at the sidewalls of the structure. If we increase the power of the oxygen plasma, the passivation layer can be reinforced. Finally, we grew the passivation layer on a flat surface by using a system of electrostatic grids to get rid of ions and electrons in order to enhance the deposition on the surface. Ellipsometric analysis is reported during the growth of the passivation layer and its destruction, which occurs when the wafer is warmed back up to ambient temperature. Ó 2007 Elsevier B.V. All rights reserved. Keywords: Cryo-etching; Plasma process; Passivation layer
1. Introduction Cryogenic process in SF6/O2 plasma is commonly used for deep etching of silicon for the microfabrication of MEMS and power microelectronic components [1,2]. In this particular process, both oxygen and low temperature are necessary to create a passivation layer on the sidewalls of the etched structures. Ion bombardment is also necessary to avoid the formation of the passivation layer at the bottom of the structure [3]. High aspect ratio microstructures can be obtained with a quite high etch rate compared to other processes [4]. The main issue remains the passivation layer, which seems very fragile. As a consequence, the process is not as robust as other processes like the so-called Bosch process [5]. In another hand, the cryogenic process is reputed for its cleanness: it does not contaminate the reactor and the passivation layer desorbs during the wafer warm-up leaving the structure sidewalls without any other material than silicon [3].
*
Corresponding author. E-mail address: [email protected] (R. Dussart).
0167-9317/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.mee.2007.01.048
In a previous article [6], we have presented a first characterization of the passivation layer by mass spectrometry. We actually analyzed the residual gas coming from the layer desorption during the increase of the substrate temperature. We obtained a significant increase of the SiFþ 3 signal between 70 and 30 °C. SiFþ is the main 3 fragmentation product of SiF4. We concluded that etching products (SiF4) could play an important role on the passivation layer growth. Then, we successfully created a SiOxFy layer with a SiF4/O2 plasma in a cavity obtained by isotropic etching. This layer was able to resist to a 3 min additional isotropic etching process. With this experiment, we clearly showed that a strong passivation layer could be made with the SiF4/O2 plasma at low temperature [6]. Finally, two different mechanisms were proposed to explain the formation of the passivation layer in the cryo-etching process [6]. In this paper, we present some other test experiments carried out to better understand the passivation mechanism. Overpassivating regime characterized by black silicon appearance [7] can also be enhanced by SiFx redeposition in the etched structure. Finally, we present new ellipsometric measurements carried out in a new con-
R. Dussart et al. / Microelectronic Engineering 84 (2007) 1128–1131
figuration of the experiment. We have already presented a first study of the desorption of the passivation layer by spectroscopic ellipsometry analysis in [6]. A 19 nm thick layer had been obtained on a bare silicon wafer cooled down to 100 °C during a 10 min SiF4/O2 plasma. We could follow the desorption of this layer when the wafer was warmed back up to ambient temperature. In order to favour the growth regime during the SiF4/O2 plasma, we have installed electrostatic grids at the top of the wafer. The layer growth could be in situ monitored and its desorption could be detected after the process during the wafer warm-up. The results with this new configuration are presented in this article. 2. Experiment An Alcatel 601E ICP reactor is used for the experiments (see Fig. 1). It is composed of a plasma source and a diffusion chamber [4]. The chuck is independently biased. SF6,
1129
O2 and SiF4 are injected by mass flow controllers. SiO2 mask is used to selectively etch the (1 0 0) silicon wafers. The chuck is cooled by liquid nitrogen to a set point temperature between 110 °C and 80 °C. A Leica Cambridge Ltd., S360. Scanning electron microscope is used to characterize the etched profiles of the test experiments. A Uvisel/Jobin–Yvon–Horiba spectroscopic ellipsometer is used to characterize in situ the SiOxFy layer obtained in SiF4/O2 plasmas. Three biased grids have been installed just above the wafer to significantly decrease the ion bombardment on the wafer (Fig. 1). The transparency of each grid is 54%. The period of the mesh is 150 lm and the diameter of the wires is 40 lm. The upper grid is connected to the ground. The second grid is negatively biased to reject electrons. The lower grid is positively biased to reject ions to the plasma. 3. Results and discussion 3.1. SiOxFy layer
Fig. 1. Schematic of the ICP reactor used for the experiments.
In Fig. 2, we present a series of test experiments performed in order to check the efficiency of the passivation layer. We started with a 10 min process described in [6] which provides a kind of cavity due to isotropic etching. This profile is represented in dashed line for comparison on the other profiles. This first process is called ‘INI’. Then we alternated 5 or 10 times a 30 s plasma of SiF4 and a 30 s plasma of O2. The source power for the SiF4 plasma was 1000 W, whereas the source power for the O2 plasma was either 1000 W or 400 W. During this step, the wafer was biased to reduce the deposition on the bottom of the cavity. Then, a 3 min isotropic plasma (called ‘FIN’) with bias was added to check, if the passivation layer was created or not and if it can resist to this final etching step. If we alternate the two plasmas of SiF4 and O2 only 5 times for the 1000 W oxygen plasma, we can form a second cavity at the bottom of the first structure. In this case, we were able to create a passivation layer, which protected
Fig. 2. (Left) Profile obtained after a 10 min isotropic etching process called INI. (Right) Profiles obtained after inserting O2 and SiF4 30 s plasmas and a 3 min additional isotropic etching process called FIN. The results are given after 5 and 10 cycles and for 400 W and 1000 W plasma source power for the O2 plasma.
1130
R. Dussart et al. / Microelectronic Engineering 84 (2007) 1128–1131
the sidewalls of the first cavity. If we compare the obtained profile with the INI profile, we can see that the first cavity was protected except at the top of the first cavity. If we alternate the two plasmas 10 times instead of only 5 times, then the passivation layer is too efficient and the FIN step is not able to remove the passivation layer at the bottom of the cavity to form the second cavity. If the same experiment is made with 400 W oxygen plasmas, the passivation layer is not as strong as at 1000 W. A second cavity can be formed during the FIN step whereas the sidewalls of the first cavity remain protected. In this case, 5 cycles are not sufficient to efficiently protect the sidewalls. When the oxygen plasma power is increased, more oxygen radicals are produced. We have shown in [6] that oxygen radicals are responsible for the passivation layer formation by reaction with SiFx radicals of the sidewalls. By increasing their concentration, we could make the passivation layer stronger.
Fig. 4. Evolution of the SiOxFy layer thickness evaluated by ellipsometric analysis during the SiF4/O2 plasma and during the wafer warm-up.
3.3. Spectroscopic ellipsometry 3.2. Overpassivating regime In overpassivating regime (high oxygen content in the SF6/O2 plasma), columnar microstructures (CMS) can appear in large silicon patterns (>1 lm) [7]. An example is given in Fig. 3, a 50 lm diameter big hole and 10 lm diameter small holes are shown. CMS are obtained on both types of hole. However, their typical dimension is not the same. CMS are denser in the bigger hole indicating that the overpassivating regime was enhanced in this region. This behaviour could be explained by etching product redeposition. SiFx and O radicals could reach more easily the bottom of the structure in the 50 lm diameter hole, because the aspect ratio (depth/diameter) was smaller in this case. As a consequence, passivation mechanisms could be enhanced in the 50 lm diameter hole compared to the 10 lm diameter hole.
In situ spectroscopic ellipsometry analysis was carried out during a SiF4/O2 plasma on a bare silicon wafer cooled down to 100 °C. The ellipsometric spectra were fitted using a Lorentz oscillator model for the dispersion law. As mentioned in part 2, a system of grids was installed to enhance the deposition mechanism. The middle grid was biased to 25 V, whereas the third grid was biased to +30 V. A planar probe was placed below the system to check their efficiency. The ionic current was reduced by more than two-orders of magnitude with this system. As a consequence, the deposited layer, which is quite fragile, was less submitted to ion bombardment and could grow with more efficiency than without grids. The results are presented in Fig. 4 for a process made at 100 °C. The film thickness is plotted as a function of time. During the first 1000 s, SiF4 and O2 are injected inside the reactor without plasma. We can observe a slight increase of the film thickness due to the physisorption of these molecules on the wafer. Then, the plasma is switched on during 10 min. The SiOxFy layer grows linearly as a function of time. At the end of the plasma, the layer was about 90 nm thick. Without grids, we obtained a thickness of 19 nm [6]. We clearly see the effect of the grids, which effectively favour the passivation regime. After the plasma deposition, we increased the temperature by steps of 10 °C and we took an ellipsometric spectrum for each temperature from 100 °C to +20 °C. The film thickness decreases when the wafer is warmed back up to ambient temperature. An 18 nm remaining layer is obtained at +20 °C. 4. Conclusion
Fig. 3. Micrograph of the top view of Columnar MicroStructures (CMS) obtained in overpassivating regime in SF6/O2 plasma on a cooled (85 °C) masked silicon wafer. CMS were observed in a 50 lm diameter hole and in 10 lm diameter holes.
This paper deals with new results concerning the passivation layer formation in the cryogenic process. In this particular process, etching products (mainly SiF4) can
R. Dussart et al. / Microelectronic Engineering 84 (2007) 1128–1131
participate to the layer growth on the sidewalls of the structure. Test experiments have been performed to deposit the passivation layer on a cavity obtained by isotropic etching. The deposition was made by alternating SiF4 plasmas and O2 plasmas. By separating the two plasmas, we showed that the reactions between SiFx radicals and O atoms occur at the cooled silicon sidewalls of the cavity and not in the plasma. The passivation layer efficiency could be enhanced by increasing the source power of the oxygen plasma. After 10 cycles, the passivation layer was so efficient that we could not remove it at the bottom of the cavity to form the second cavity during the FIN process. At higher power, oxygen atom concentration is larger, which contribute to create a thicker and more efficient SiOxFy layer. In overpassivating regime, larger patterns are covered by denser CMS than smaller patterns. This is due to the deposition of SiFx and oxygen, which is more efficient in bigger patterns. Finally, we could follow the film growth on a bare silicon by in situ ellipsometry experiments. A system of biased grids allowed us to significantly reduce the ion bombardment to simulate the conditions obtained on the side-
1131
walls. After a 10 min SiF4/O2 plasma, a 90 nm thick SiOxFy layer was grown on a cooled bare silicon, whereas a 19 nm thick layer had been obtained without grids in the same process conditions. A large part of this layer was desorbed during the wafer warm-up. References [1] M.A. Blauw, T. Zijlstra, R.A. Bakker, E. van der Drift, J. Vac. Sci. Technol. B 18 (2000) 3453. [2] M.J. de Boer, J.G.E. Gardeniers, H.V. Jansen, E. Smulders, M.-J. Gilde, G. Roelofs, J.N. Sasserath, M. Elwenspoek, J. Microelectron. Mech. Syst. 11 (2002) 4. [3] R. Dussart, M. Boufnichel, G. Marcos, P. Lefaucheux, A. Basillais, R. Benoit, T. Tillocher, X. Mellhaoui, H. Estrade-Szwarckopf, P. Ranson, J. Micromech. Microeng. 14 (2004) 190–196. [4] M. Boufnichel, S. Aachboun, P. Lefaucheux, P. Ranson, J. Vac. Sci. Technol. B 21 (1) (2003) 267–273. [5] F. La¨rmer and A. Schilp US patent no 5498312 (1996). [6] X. Mellhaoui, R. Dussart, T. Tillocher, P. Lefaucheux, P. Ranson, M. Boufnichel, L.J. Overzet, J. Appl. Phys. 98 (2005) 104901-1. [7] R. Dussart, X. Mellhaoui, T. Tillocher, P. Lefaucheux, M. Volatier, C. Socquet-Clerc, P. Brault, P. Ranson, J. Phys. D 38 (2005) 3395.