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Metastable-atom-stimulated desorption from dodecanethiolate self-assembled monolayers
Applied Surface Science 241 (2005) 141–145 www.elsevier.com/locate/apsusc
Metastable-atom-stimulated desorption from dodecanethiolate self-assembled monolayers Y. Yamauchia,*, T. Norob, M. Kurahashia, T. Suzukia, X. Jua a
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-08910, Japan
b
Available online 19 November 2004
Abstract The potential curves for the dissociation of dodecane cation are calculated in order to discuss the indirect mechanism of metastable-atom-stimulated desorption of CHx+ from dodecanethiolate self-assembled monolayers. A single excitation configuration interaction method is used for drawing up the potential diagrams in two different reaction coordinates: C–H and C–C. The potential barrier height obtained for the ejection of CH3+ was smaller than that of H+, suggesting that CHx+ desorption can be triggered by the excitation of molecular orbitals even if a molecule is only locally stimulated. # 2004 Elsevier B.V. All rights reserved. PACS: 31.25; 79.20.L; 79.20.R; 85.40.H Keywords: CI; Potential curve; DIET; SAM; Metastable atom; Nanolithography
1. Introduction Self-assembled monolayers (SAMs) [1] have been investigated as alternative ultra-thin resists that improve the techniques for micropatterning of surfaces. Because of their ultimately small thickness, exposure methods should be extremely surfacesensitive. Metastable-atom beams at thermal energies possess such surface sensitivity resulting from their reflection above the topmost surface. According to the scenario of metastable-atom nanolithography [2], the * Corresponding author. Fax: +81 29 859 2801. E-mail address: [email protected] (Y. Yamauchi).
electron abstraction from a SAM molecule during the deexcitation of a metastable atom partially damages SAM, and the damaged portion of SAM is then oxidized in the air, where wet chemical etching is carried out. This partial oxidation changes the wettability from hydrophobic to hydrophilic, which controls the access of ions in the etchant to the underlying substrate and, thus, allows the selective etching of the substrate. However, this scenario is not fully understood. The damaging mechanism of SAM by metastable atoms, especially, is not obvious [3]. Metastable-atom-stimulated desorption (MSD) [4–7] provides direct evidence of damage to SAM, and, in addition, information on the damaging mechanism. In
0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2004.09.031
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Y. Yamauchi et al. / Applied Surface Science 241 (2005) 141–145
the present paper, after a brief description of our observation of the positive ion (H+, CHx+) desorption from dodecanethiolate (DDT)-SAM during helium metastable-atom (He*) beam irradiation, we discuss the mechanism of the indirect desorption of CHx+ on the basis of theoretical calculations, in which the indirect interaction, i.e., an electron-abstracted SAM molecule, is considered using a single excitation configuration interaction (SE-CI) method.
2. Molecular ion desorption MSD measurements were performed for DDTSAM/Au(1 1 1) mica samples [7]. Fig. 1 depicts the time-of-flight (TOF) spectra of positive ions and electrons ejected from DDT-SAM surfaces under helium metastable-atom (He*) beam irradiation [8]. While the TOF spectrum in the upper panel indicates that the desorbed ions, which have a kinetic energy of
4 eV, are mostly H+, the spectrum in the middle panel indicates that CHx+ ions are the major content of desorbed ions that have a kinetic energy of 1 eV. The latter molecular ion desorption was not observed in some of the previous studies [4–7], in which only H+ desorption for water and sodium coadsorbed surfaces and hydrogenated surfaces was observed. The metastable deexcitation spectra of DDT-SAM in the lower panel well reproduced the specific features reported earlier [9,10]. Electron emission mainly comes from s2p molecular orbitals of the methyl groups that are accessible to impinging metastable atoms rather than from those of the methylene groups. However, since slow He* atoms are reflected above the top surface, He* cannot interact directly with C–C bonding orbitals hidden under the methyl group. This local stimulation by slow He* is in marked contrast to the uniform stimulation by photons and electrons, which penetrate more than several atomic layers. CHx+ desorption cannot be explained within a direct C–C bond breaking because the local stimulation on the top end of the DDT molecule cannot abstract the electrons of the C–C bond. Instead, molecular orbitals, which distribute over the whole molecule, must be considered in order to discuss a possible channel of indirect C–C bond breaking.
3. Potential curves
Fig. 1. Illustrative time-of-flight spectra, which show the number of detected positive ions (upper and middle panels) and electrons (lower panel) during the irradiation of a dodecanethiolate-SAM formed on an Au(1 1 1)/mica substrate with a pulsed metastable helium atom beam vs. their flight time from the discharge pulse of the pulsed metastable-atom source. Both desorbed positive ions and ejected electrons were energy-analyzed separately with a cylindrical mirror analyzer (CMA, PHI 590A) and detected by a channel electron multiplier (CEM). The effective flight distance between the sample and the CEM was 250 mm. The electron spectrum in the lower panel corresponds to the profile of a primary metastable-atom beam at the sample position because the flight time of electrons is negligibly short. The dotted vertical line indicates the mean arrival time of projectile atoms. The down arrows in the upper and middle panels indicate the arrivals of H+ and CH3+ delayed from the dotted line considering CMA pass energies of 4 and 1 eV, respectively.
The dodecane cation was chosen as a model of an electron-abstracted dodecanethiolate molecule in the DDT-SAM. Potential curves for dissociation of the stimulated dodecane cation were calculated within a SE-CI method using the program MOLCAS [11]. The minimal basis sets of (43/3) [12] for C and STO-3G [13] for H were used. Although SE-CI calculation does not fully account for the electron correlation, it provides a gross feature of the excited states expressed in the same orbitals, which makes it possible to compare the ground states. In order to discuss H+ and CH3+ desorption, two different reaction coordinates are considered: C–H of [CH3(CH2)10CH2–H]+ and C– C of [CH3(CH2)10–CH3]+, respectively. Fig. 2(a) and (b) shows several potential curves for excited states. According to the wavefunction analysis, the lower three curves in Fig. 2(a) correspond to the states dissociating into the neutral H atom, and the fourth
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Fig. 2. Potential curves for a dodecane cation taking reaction coordinates: (a) C–H of [CH3(CH2)10CH2–H]+ and (b) C–C of [CH3(CH2)10– CH3]+. The energy scale on the vertical axis and the distance scale on the horizontal axis are measured, respectively, from the minimum energy and from the equilibrium position of a neutral dodecane molecule in the ground state calculated by Hartree–Fock method. The energy minima at ˚ indicate a slight expansion of the ionized molecule due to abstraction of an electron. 0.1–0.3 A
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Y. Yamauchi et al. / Applied Surface Science 241 (2005) 141–145
curve from the bottom is the lowest state which can be connected to H+ ion dissociation. The discussion begins with the vertical ionization process, in which an electron is removed from a molecule in its ground state so rapidly that a cation is produced without changing the positions or momenta of the atoms. The resultant cation is often in an excited state. Thus, the unmixed solutions of states with the repulsive potential have relatively large energies at the vertical ionization and cross other unmixed solutions of states with the attractive potential, and then all solutions reach various dissociation limits. The crossing of potential curves of these unmixed solutions indicates a large interaction between unmixed solutions leading to mixing and to an adiabatic process in which the H atom or H+ ion dissociation proceeds along the potential curves after the vertical ionization. The adiabatically avoided crossings of potential curves, due to mixing, create potential barriers. One of them, found in the fourth curve from the bottom, gives a dissociation barrier of 17.73 eV for H+ ion dissociation. In Fig. 2(b), the lower two curves can be assigned to the states decomposing into a neutral CH3 molecule, and the third curve from the bottom is the lowest one connected to the CH3+ ion dissociation. As is shown by the third curve from the bottom, the potential barriers for CH3+ ion dissociation are estimated to be 15.61 eV. This potential barrier, that is 2 eV smaller than H+, should be passed over more easily than in the case of H+. The discussion provided here is qualitative and restricted to an SE-CI method. Reference data experimentally obtained is necessary for a qualitative discussion. In order to examine the calculation accuracy, the calculated ionization energy is compared with experimental data in an appearance potential database [14]. Our SE-CI calculation was then found to overestimate the ionization energy by 2 eV. Since the neutral dodecane molecule is calculated using Hartree–Fock and its cation is calculated using SE-CI, this deviation probably comes from insufficient consideration of the electron reconfiguration after ionization. Assuming the same deviation to other calculated values, we obtain potential barriers of 15.7 and 13.6 eV for H+ and CH3+ ion dissociations. The trends of these values fairly coincide with the roughly estimated ionization energies of 17.8 and 13.6 eV that are based on the experimental values for the
dissociation energies of ethane to hydrogen (4.2 eV) or to methyl (3.8 eV) and for the ionization energies of the hydrogen cation (13.6 eV) or the methyl cation (9.8 eV). Both our SE-CI calculation and the thermodynamic estimation from the current literature have shown that the barrier for the CH3+ ion ejection is lower than that for the H+ one and that CH3+ ion ejection should occur whenever H+ ion ejection takes place. The present calculation indicates that the local stimulation can induce CHx+ desorption through molecular orbitals even when certain bonding electrons are not stimulated directly.
4. Conclusions We have discussed the mechanism of metastableatom-stimulated desorption of CHx+, on the basis of theoretical calculations, taking into account the indirect interaction, i.e., the electron abstraction of the SAM molecule. The potential diagrams of the dodecane cation are calculated for two different reaction coordinates, C–H and C–C, within an SE-CI method. It is shown that the potential barrier for ejection of CH3+ can be smaller than that of H+. To proceed to a quantitative discussion on the different desorption intensities and kinetic energies for H+ and CH3+ ion desorption, we need to consider the branching ratio between H+ and CH3+ ion dissociation as well as more accurate potentials.
References [1] A. Ulman, Chem. Rev. 96 (1996) 1533. [2] K.K. Berggren, A.B. Bard, J.L. Wilbur, J.D. Gillaspy, A.G. Helg, J.J. McClelland, S.L. Rolston, W.D. Phillips, M. Pretiss, G.M. Whitesides, Science 269 (1995) 1255. [3] H. Yasufuku, K. Meguro, K. Okudaira, N. Ueno, Y. Harada, Jpn. J. Appl. Phys. 39 (2000) 4126. [4] M. Kurahashi, Y. Yamauchi, Phys. Rev. Lett. 84 (2000) 4725. [5] T. Suzuki, M. Kurahashi, Y. Yamauchi, T. Ishikawa, T. Noro, Phys. Rev. Lett. 86 (2001) 3654. [6] Y. Yamauchi, X. Ju, T. Suzuki, M. Kurahashi, Surf. Sci. 528 (2003) 91. [7] Y. Yamauchi, T. Suzuki, M. Kurahashi, X. Ju, J. Phys. Chem. B 107 (2003) 4107. [8] Y. Yamauchi, M. Kurahashi, N. Kishimoto, Meas. Sci. Technol. 9 (1998) 531. [9] B. Heinz, H. Morgner, Surf. Sci. 372 (1997) 100.
Y. Yamauchi et al. / Applied Surface Science 241 (2005) 141–145 [10] H. Morgner, Advances in Atomic, Molecular and Optical Physics, vol. 42, Academic Press, 2000 p. 387. [11] K. Andersson, M. Barysz, A. Bernhardsson, M.R.A. Blomberg, D.L. Cooper, T. Fleig, M.P. Fulscher, C. de Graaf, B.A. Hess, G. Karlstom, R. Lindh, P.A. Malmqvist, P. Neogrady, J. Olsen, B.O. Roos, A.J. Sadlej, M. Scutz, B. Schimmelpfennig, L. Seijo, L. Serrano-Andres, P.E.M. Siegbahn, J. Stalring, T.
145
Thorsteinsson, V. Veryazovf, P.O. Widmark, MOLCAS, Version 5, Lund University, Sweden, 2000. [12] H. Tatewaki, T. Koga, J. Chem. Phys. 10 (1996) 8493. [13] W.J. Hehre, R.F. Stewart, J.A. Pople, J. Chem. Phys. 6 (1969) 2657. [14] Gas phase ion energetics data, http://webbook.nist.gov/ chemistry/form-ser.html.
Metastable-atom-stimulated desorption from dodecanethiolate self-assembled monolayers Y. Yamauchia,*, T. Norob, M. Kurahashia, T. Suzukia, X. Jua a
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-08910, Japan
b
Available online 19 November 2004
Abstract The potential curves for the dissociation of dodecane cation are calculated in order to discuss the indirect mechanism of metastable-atom-stimulated desorption of CHx+ from dodecanethiolate self-assembled monolayers. A single excitation configuration interaction method is used for drawing up the potential diagrams in two different reaction coordinates: C–H and C–C. The potential barrier height obtained for the ejection of CH3+ was smaller than that of H+, suggesting that CHx+ desorption can be triggered by the excitation of molecular orbitals even if a molecule is only locally stimulated. # 2004 Elsevier B.V. All rights reserved. PACS: 31.25; 79.20.L; 79.20.R; 85.40.H Keywords: CI; Potential curve; DIET; SAM; Metastable atom; Nanolithography
1. Introduction Self-assembled monolayers (SAMs) [1] have been investigated as alternative ultra-thin resists that improve the techniques for micropatterning of surfaces. Because of their ultimately small thickness, exposure methods should be extremely surfacesensitive. Metastable-atom beams at thermal energies possess such surface sensitivity resulting from their reflection above the topmost surface. According to the scenario of metastable-atom nanolithography [2], the * Corresponding author. Fax: +81 29 859 2801. E-mail address: [email protected] (Y. Yamauchi).
electron abstraction from a SAM molecule during the deexcitation of a metastable atom partially damages SAM, and the damaged portion of SAM is then oxidized in the air, where wet chemical etching is carried out. This partial oxidation changes the wettability from hydrophobic to hydrophilic, which controls the access of ions in the etchant to the underlying substrate and, thus, allows the selective etching of the substrate. However, this scenario is not fully understood. The damaging mechanism of SAM by metastable atoms, especially, is not obvious [3]. Metastable-atom-stimulated desorption (MSD) [4–7] provides direct evidence of damage to SAM, and, in addition, information on the damaging mechanism. In
0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2004.09.031
142
Y. Yamauchi et al. / Applied Surface Science 241 (2005) 141–145
the present paper, after a brief description of our observation of the positive ion (H+, CHx+) desorption from dodecanethiolate (DDT)-SAM during helium metastable-atom (He*) beam irradiation, we discuss the mechanism of the indirect desorption of CHx+ on the basis of theoretical calculations, in which the indirect interaction, i.e., an electron-abstracted SAM molecule, is considered using a single excitation configuration interaction (SE-CI) method.
2. Molecular ion desorption MSD measurements were performed for DDTSAM/Au(1 1 1) mica samples [7]. Fig. 1 depicts the time-of-flight (TOF) spectra of positive ions and electrons ejected from DDT-SAM surfaces under helium metastable-atom (He*) beam irradiation [8]. While the TOF spectrum in the upper panel indicates that the desorbed ions, which have a kinetic energy of
4 eV, are mostly H+, the spectrum in the middle panel indicates that CHx+ ions are the major content of desorbed ions that have a kinetic energy of 1 eV. The latter molecular ion desorption was not observed in some of the previous studies [4–7], in which only H+ desorption for water and sodium coadsorbed surfaces and hydrogenated surfaces was observed. The metastable deexcitation spectra of DDT-SAM in the lower panel well reproduced the specific features reported earlier [9,10]. Electron emission mainly comes from s2p molecular orbitals of the methyl groups that are accessible to impinging metastable atoms rather than from those of the methylene groups. However, since slow He* atoms are reflected above the top surface, He* cannot interact directly with C–C bonding orbitals hidden under the methyl group. This local stimulation by slow He* is in marked contrast to the uniform stimulation by photons and electrons, which penetrate more than several atomic layers. CHx+ desorption cannot be explained within a direct C–C bond breaking because the local stimulation on the top end of the DDT molecule cannot abstract the electrons of the C–C bond. Instead, molecular orbitals, which distribute over the whole molecule, must be considered in order to discuss a possible channel of indirect C–C bond breaking.
3. Potential curves
Fig. 1. Illustrative time-of-flight spectra, which show the number of detected positive ions (upper and middle panels) and electrons (lower panel) during the irradiation of a dodecanethiolate-SAM formed on an Au(1 1 1)/mica substrate with a pulsed metastable helium atom beam vs. their flight time from the discharge pulse of the pulsed metastable-atom source. Both desorbed positive ions and ejected electrons were energy-analyzed separately with a cylindrical mirror analyzer (CMA, PHI 590A) and detected by a channel electron multiplier (CEM). The effective flight distance between the sample and the CEM was 250 mm. The electron spectrum in the lower panel corresponds to the profile of a primary metastable-atom beam at the sample position because the flight time of electrons is negligibly short. The dotted vertical line indicates the mean arrival time of projectile atoms. The down arrows in the upper and middle panels indicate the arrivals of H+ and CH3+ delayed from the dotted line considering CMA pass energies of 4 and 1 eV, respectively.
The dodecane cation was chosen as a model of an electron-abstracted dodecanethiolate molecule in the DDT-SAM. Potential curves for dissociation of the stimulated dodecane cation were calculated within a SE-CI method using the program MOLCAS [11]. The minimal basis sets of (43/3) [12] for C and STO-3G [13] for H were used. Although SE-CI calculation does not fully account for the electron correlation, it provides a gross feature of the excited states expressed in the same orbitals, which makes it possible to compare the ground states. In order to discuss H+ and CH3+ desorption, two different reaction coordinates are considered: C–H of [CH3(CH2)10CH2–H]+ and C– C of [CH3(CH2)10–CH3]+, respectively. Fig. 2(a) and (b) shows several potential curves for excited states. According to the wavefunction analysis, the lower three curves in Fig. 2(a) correspond to the states dissociating into the neutral H atom, and the fourth
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Fig. 2. Potential curves for a dodecane cation taking reaction coordinates: (a) C–H of [CH3(CH2)10CH2–H]+ and (b) C–C of [CH3(CH2)10– CH3]+. The energy scale on the vertical axis and the distance scale on the horizontal axis are measured, respectively, from the minimum energy and from the equilibrium position of a neutral dodecane molecule in the ground state calculated by Hartree–Fock method. The energy minima at ˚ indicate a slight expansion of the ionized molecule due to abstraction of an electron. 0.1–0.3 A
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Y. Yamauchi et al. / Applied Surface Science 241 (2005) 141–145
curve from the bottom is the lowest state which can be connected to H+ ion dissociation. The discussion begins with the vertical ionization process, in which an electron is removed from a molecule in its ground state so rapidly that a cation is produced without changing the positions or momenta of the atoms. The resultant cation is often in an excited state. Thus, the unmixed solutions of states with the repulsive potential have relatively large energies at the vertical ionization and cross other unmixed solutions of states with the attractive potential, and then all solutions reach various dissociation limits. The crossing of potential curves of these unmixed solutions indicates a large interaction between unmixed solutions leading to mixing and to an adiabatic process in which the H atom or H+ ion dissociation proceeds along the potential curves after the vertical ionization. The adiabatically avoided crossings of potential curves, due to mixing, create potential barriers. One of them, found in the fourth curve from the bottom, gives a dissociation barrier of 17.73 eV for H+ ion dissociation. In Fig. 2(b), the lower two curves can be assigned to the states decomposing into a neutral CH3 molecule, and the third curve from the bottom is the lowest one connected to the CH3+ ion dissociation. As is shown by the third curve from the bottom, the potential barriers for CH3+ ion dissociation are estimated to be 15.61 eV. This potential barrier, that is 2 eV smaller than H+, should be passed over more easily than in the case of H+. The discussion provided here is qualitative and restricted to an SE-CI method. Reference data experimentally obtained is necessary for a qualitative discussion. In order to examine the calculation accuracy, the calculated ionization energy is compared with experimental data in an appearance potential database [14]. Our SE-CI calculation was then found to overestimate the ionization energy by 2 eV. Since the neutral dodecane molecule is calculated using Hartree–Fock and its cation is calculated using SE-CI, this deviation probably comes from insufficient consideration of the electron reconfiguration after ionization. Assuming the same deviation to other calculated values, we obtain potential barriers of 15.7 and 13.6 eV for H+ and CH3+ ion dissociations. The trends of these values fairly coincide with the roughly estimated ionization energies of 17.8 and 13.6 eV that are based on the experimental values for the
dissociation energies of ethane to hydrogen (4.2 eV) or to methyl (3.8 eV) and for the ionization energies of the hydrogen cation (13.6 eV) or the methyl cation (9.8 eV). Both our SE-CI calculation and the thermodynamic estimation from the current literature have shown that the barrier for the CH3+ ion ejection is lower than that for the H+ one and that CH3+ ion ejection should occur whenever H+ ion ejection takes place. The present calculation indicates that the local stimulation can induce CHx+ desorption through molecular orbitals even when certain bonding electrons are not stimulated directly.
4. Conclusions We have discussed the mechanism of metastableatom-stimulated desorption of CHx+, on the basis of theoretical calculations, taking into account the indirect interaction, i.e., the electron abstraction of the SAM molecule. The potential diagrams of the dodecane cation are calculated for two different reaction coordinates, C–H and C–C, within an SE-CI method. It is shown that the potential barrier for ejection of CH3+ can be smaller than that of H+. To proceed to a quantitative discussion on the different desorption intensities and kinetic energies for H+ and CH3+ ion desorption, we need to consider the branching ratio between H+ and CH3+ ion dissociation as well as more accurate potentials.
References [1] A. Ulman, Chem. Rev. 96 (1996) 1533. [2] K.K. Berggren, A.B. Bard, J.L. Wilbur, J.D. Gillaspy, A.G. Helg, J.J. McClelland, S.L. Rolston, W.D. Phillips, M. Pretiss, G.M. Whitesides, Science 269 (1995) 1255. [3] H. Yasufuku, K. Meguro, K. Okudaira, N. Ueno, Y. Harada, Jpn. J. Appl. Phys. 39 (2000) 4126. [4] M. Kurahashi, Y. Yamauchi, Phys. Rev. Lett. 84 (2000) 4725. [5] T. Suzuki, M. Kurahashi, Y. Yamauchi, T. Ishikawa, T. Noro, Phys. Rev. Lett. 86 (2001) 3654. [6] Y. Yamauchi, X. Ju, T. Suzuki, M. Kurahashi, Surf. Sci. 528 (2003) 91. [7] Y. Yamauchi, T. Suzuki, M. Kurahashi, X. Ju, J. Phys. Chem. B 107 (2003) 4107. [8] Y. Yamauchi, M. Kurahashi, N. Kishimoto, Meas. Sci. Technol. 9 (1998) 531. [9] B. Heinz, H. Morgner, Surf. Sci. 372 (1997) 100.
Y. Yamauchi et al. / Applied Surface Science 241 (2005) 141–145 [10] H. Morgner, Advances in Atomic, Molecular and Optical Physics, vol. 42, Academic Press, 2000 p. 387. [11] K. Andersson, M. Barysz, A. Bernhardsson, M.R.A. Blomberg, D.L. Cooper, T. Fleig, M.P. Fulscher, C. de Graaf, B.A. Hess, G. Karlstom, R. Lindh, P.A. Malmqvist, P. Neogrady, J. Olsen, B.O. Roos, A.J. Sadlej, M. Scutz, B. Schimmelpfennig, L. Seijo, L. Serrano-Andres, P.E.M. Siegbahn, J. Stalring, T.
145
Thorsteinsson, V. Veryazovf, P.O. Widmark, MOLCAS, Version 5, Lund University, Sweden, 2000. [12] H. Tatewaki, T. Koga, J. Chem. Phys. 10 (1996) 8493. [13] W.J. Hehre, R.F. Stewart, J.A. Pople, J. Chem. Phys. 6 (1969) 2657. [14] Gas phase ion energetics data, http://webbook.nist.gov/ chemistry/form-ser.html.