Abstract
UV- and E-beam direct patterning processes using photosensitive precursor films are reviewed in this chapter. For the UV patterning process, discussed in the first part, reaction processes of precursors, such as metal alkoxides modified with β-diketones and metal complexes of carboxylic acids, with UV-irradiation are reported. The discussion of multi-component oxide film, as well as simple oxide film preparation, some applications of direct UV-patterning, and limitation of this process completes this section. The second part covers the progress made in the direct sub-10 nm electron beam patterning of metal oxides over the last 30 years, moving from physical deposition to chemical solution deposition of resists. Patterning of inorganic resists began with thermally evaporated metal halides. They were soon taken over by sputtered metal oxide films due to their excellent environmental stability. However, these inorganic materials, both halides and oxides, suffered from very steep electron dose requirement, thus rendering them useless for practical applications. This gave way to highly electron beam-sensitive chemical solution deposited stabilized metal alkoxides and metal naphthenates, with sensitively close to conventional electron beam resists such as poly(methylmethacrylate), PMMA, and calixarene. Furthermore, they show excellent line edge roughness characteristics at sub-10 nm scale, which is currently unmatched by any other electron beam resist. Recent applications of these resists such as etch mask and their suitability as gate oxides closes the chapter.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Tohge N, Shinmou K, Minami T (1994) Photolysis of organically modified gel films and its application to the fine-patterning of oxide thin films. In: Mackenzie JD (ed) Sol–gel optics III, Proc SPIE 2288, p 589
Shinmou K, Tohge N, Minami T (1994) Fine-patterning of ZrO2 thin films by the photolysis of chemically modified gel films. Jpn J Appl Phys 33:L1181
Tohge N, Shinmou K, Minami T (1994) Effects of UV-irradiation on the formation of oxide thin films from chemically modified metal-alkoxides. J Sol-Gel Sci Tech 2:581
Zhao G, Tohge N (1995) Fine patterning of Al2O3 thin films by the photolysis of gel films chemically modified with benzoylacetone. J Ceram Soc Jpn 103:1293 (in Japanese)
Zhao G, Tohge N (1998) Preparation of photosensitive gel films and fine patterning of amorphous Al2O3-SiO2 thin films. Mater Res Bull 33:21
Zhao G, Tohge N, Nishii J (1998) Fabrication and characterization of diffraction gratings using photosensitive Al2O3 gel films. Jpn J Appl Phys 37(part 1):1842
Tohge N, Takama Y (1999) Direct fine-patterning of PZT thin films using photosensitive gel films derived from chemically modified metal-alkoxides. J Mater Sci Mater Electron 10:273
Kawahara T, Ishida T, Tada H, Tohge N, Ito S (2002) Positive-type patterned ZnO films prepared by a chemically modified sol–gel method. J Mater Sci Lett 21:1423
Kawahara T, Ishida T, Tada H, Noma N, Tohge N, Ito S (2003) Photoreaction of a ZnO gel film chemically modified with beta-diketones. J Mater Sci 38:1703
Tohge N, Zhao G, Chiba F (1999) Photosensitive gel films prepared by the chemical modification and their application to surface-relief gratings. Thin Solid Films 351:85
Tohge N, Ueno R, Chiba F, Kintaka K, Nishii J (2000) Characteristics of diffraction gratings fabricated by the two-beam interference method using photosensitive hybrid gel films. J Sol-Gel Sci Technol 19:119
Nishii J, Kintaka K, Tohge N, Noma N, Hasegawa M, Mizutani A, Kikuta H (2002) Low-reflection microstructure formed by sol–gel process. Jpn J Appl Phys 41(part 1):5210
Tohge N, Hasegawa M, Noma N, Kintaka K, Nishii J (2003) Fabrication of two-dimensional gratings using photosensitive gel films and their characterization. J Sol-Gel Sci Technol 26:903
Imano T, Horiuchi T, Noma N, Ito S (2006) Preparation of new photosensitive TiO2 gel films using chemical additives including nitrogen and their patterning. J Sol-Gel Sci Technol 39:119
Kowada Y, Noma N (2009) Electronic state and photosensitivity of metal alkoxides chemically modified with beta-diketones. J Solgel Sci Technol 52:166
Tadanaga K, Owan T, Morinaga J, Urbanek S, Minami T (2000) Fine patterning of transparent, conductive SnO2 thin films by UV-irradiation. J Sol-Gel Sci Technol 19:791
Avey AA, Hill RH (1996) Solid state photochemistry of Cu2(OH2)2(O2C(CH2)4CH3)4 in thin films: the photochemical formation of high-quality films of copper and copper(I) oxide. Demonstration of a novel lithographic technique for the patterning of copper. J Am Chem Soc 118:237
Ching CLW, Hill RH (1998) Photolithographic deposition of indium oxide from metalorganic films. J Vac Sci Technol A16:897
Gao M, Hill RH (1998) High efficiency photoresist-free lithography of UO3 patterns from amorphous films of uranyl complexes. J Mater Res 13:1379
Law WL, Hill RH (2000) Photolithographic deposition of insulating Al2O3 films from thin amorphous films of aluminum complexes on silicon surfaces. Thin Solid Films 375:42
Park HH, Yoon S, Park HH, Hill RH (2004) Electrical properties of PZT thin films by photochemical deposition. Thin Solid Films 447–448:669
Park HH, Kim WS, Yang JK, Park HH, Hill RH (2004) Characterization of PLZT thin film prepared by photochemical deposition using photosensitive metal-organic precursors. Microelectron Eng 71:215
Park HH, Park HH, Hill RH (2006) Direct-patterning of SnO2 thin film by photochemical metal-organic deposition. Sens Actuators A 132:429
Park HH, Lee HS, Park HH, Hill RH, Hwang YT (2009) Ferroelectric properties of direct-patternable La substituted Bi4Ti3O12 thin films formed by photochemical metal-organic deposition. J Ceram Soc Jpn 117:604
Kololuoma T, Karkkainen AHO, Tolonen A, Rantaral JT (2003) Lithographic patterning of benzoylacetone modified SnO2 and SnO2:Sb thin films. Thin Solid Films 440:184
Yogo T, Takeichi T, Kikuta K, Hirano S (1995) Ultraviolet patterning of alkoxy-derived lithium-niobate film. J Am Ceram Soc 78:1649
Kikuta K, Takagi K, Hirano S (1999) Photoreaction of titanium-based metal-organic compounds for ceramic fine patterning. J Am Ceram Soc 82:1569
Kikuta K, Suzumori K, Takagi K, Hirano S (1999) Patterning of tin oxide film from photoreactive precursor solutions prepared via the addition of N-phenyldiethanolamine. J Am Ceram Soc 82:2263
Martin CR, Aksay IA (2004) Submicrometer-scale patterning of ceramic thin films. J Electroceram 12:53
Yasin S, Hasko DG, Ahmed H (2001) Fabrication of <5 nm width lines in poly(methylmethacrylate) resist using a water:isopropyl alcohol developer and ultrasonically-assisted development. Appl Phys Lett 78:2760–2762
Broers AN, Cuomo J, Harper J, Molzen W, Laibowitz R, Promerantz M (1978) High resolution electron beam fabrication using STEM. In: Sturgess JM (ed) Proceedings of the 9th international congress on electron microscopy, vol 3, Imperial, ON, pp 343–354
Isaacson M, Muray A (1981) In situ vaporization of very low molecular weight resists using ½ nm diameter electron beams. J Vac Sci Technol 19:1117–1120
Mochel ME, Humphreys CJ, Eades JA, Mochel JM, Petford AM (1983) Electron beam writing on a 20 Å scale in metal β-aluminas. Appl Phys Lett 42:392–394
Devenish RW, Eaglesham DJ, Maher DM, Humphreys CJ (1989) Nanolithography using field emission and conventional thermionic electron sources. Ultramicroscopy 28:324–329
Salisbury IG, Timsit RS, Berger SD, Humphreys CJ (1984) Nanometer scale electron beam lithography in inorganic materials. Appl Phys Lett 45:1289–1291
Muray A, Isaacson M, Adesida I (1984) AlF3 – a new very high resolution electron beam resist. Appl Phys Lett 45:589–591
Kratschmer E, Isaacson M (1986) Nanostructure fabrication in metals, insulators, and semiconductors using self-developing metal organic resist. J Vac Sci Technol B 4:361–364
Kratschmer E, Isaacson M (1987) Progress in self-developing metal fluoride resists. J Vac Sci Technol B 5:369–373
Scherer A, Craighead HG (1987) Barium fluoride and strontium fluoride negative electron beam resists. J Vac Sci Technol B 5:374–378
Scherer A, Van de Gaag BP, Beebe ED, Lin PSD (1990) Fluoride etch masks for high-resolution pattern transfer. J Vac Sci Technol B 8:28–32
Mankiewich PM, Craighead HG, Harrison TR, Dayem AH (1984) High resolution electron beam lithography on CaF2. Appl Phys Lett 44:468–469
Zanetti R, Bleloch AL, Grimshaw M, Paterson JH, Jones GAC (1993) Inst Phys Conf Ser 138:67
Fujita J, Watanabe H, Ochiai Y, Manako S, Tsai JS, Matsui S (1995) Sub-10 nm lithography and development properties of inorganic resist by scanning electron beam. Appl Phys Lett 66:3065–3067
Fujita J, Watanabe H, Ochiai Y, Manako S, Tsai JS, Matsui S (1995) Sub-10 nm lithography and development properties of inorganic resist by scanning electron beams. J Vac Sci Technol B 13:2757–2761
Berger SD, Salisbury IG, Milne RH, Imeson D, Humphreys CJ (1987) Electron energy-loss spectroscopy studies of nanometer-scale structures in alumina produced by intense electron-beam irradiation. Philos Mag B 55:341–358
Mochel ME, Eades JA, Metzger M, Meyer JI, Mochel JM (1984) Electron beam cutting in amorphous alumina sheets. Appl Phys Lett 44:502–504
Hollenbech JL, Buchanan RC (1990) Oxide thin films for nanometer scale electron beam lithography. J Mater Res 5:1058–1072
Morgan CJ, Bailey SJ, Preston AR, Humphreys CJ (1991) Electron beam nanolithography of sputtered amorphous Al2O3 and the proximity effect. Inst Phys Conf Ser 119:503–506
Morgan CJ, Chen GS, Boothroyd CB, Bailey S, Humphreys CJ (1992) Ultimate limits of lithography. Phys World 5:28–32
Chen GS, Boothroyd CB, Humphreys CJ (1993) Novel fabrication method for nanometer-scale silicon dots and wires. Appl Phys Lett 62:1949–1951
Saifullah MSM, Boothroyd CB, Botton GA, Humphreys CJ (1998) Electron energy loss spectroscopy of silicon nanostructures in a scanning transmission electron microscope. In: Electron microscopy 96, vol 2. Committee of European Societies of Microscopy, Brussels
Fujita J, Maruno S, Watanabe H, Ichikawa M (1996) Nanostructure fabrication using the selective thermal desorption of SiO2 induced by electron beams. Appl Phys Lett 69:638–640
Turner PS, Bullough TJ, Devenish RW, Maher DM, Humphreys CJ (1990) Nanometre hole formation in MgO using electron beams. Philos Mag Lett 61:181–193
Devenish RW, Bullough TJ, Turner PS, Humphreys CJ (1990) Electron-beam machining of MgO and ZnO in the STEM. Inst Phys Conf Ser 98:215–218
Berger SD, Macaulay JM, Brown LM (1987) Radiation damage in TiOx at high current density. Philos Mag Lett 56:179–185
Saifullah MSM, Boothroyd CB, Botton GA, Humphreys CJ (1997) Electron beam damage in titanium dioxide films. Inst Phys Conf Ser 153:167–170
Pauza AJ, Barber Z, Campbell AM, Evetts JE, Somekh RE, Moore DF, Broers AN (1991) Direct writing of weak links in high Tc superconductors with electrons. In: Proceedings of the third international superconductive electronics conference, University of Strathclyde, Glasgow, Scotland, Meeting Makers, Glasgow
Saifullah MSM, Boothroyd CB, Botton GA, Humphreys CJ (1998) Irradiation damage of inorganic resists on a silicon substrate. In: Kirkland A, Brown PD (eds) The electron – proceedings of the international centennial symposium on the electron, IOM Communication Ltd, London
Morgan CJ, Humphreys CJ (1995) The proximity effect for electron beam lithography of aluminium oxide. Inst Phys Conf Ser 147:575–578
Hobbs LW (1987) Radiation effects in analysis by TEM. In: Hren JJ, Goldstein JI, Joy DC (eds) Introduction to analytical electron microscopy. Plenum, New York, pp 399–445
Pooley D (1966) F-centre production in alkali halides by electron–hole recombination and a subsequent [110] replacement sequence: a discussion of the electron–hole recombination. Proc Phys Soc (Lond) 87:245–256
Kabler MN, Williams RT (1978) Vacancy-interstitial pair production via electron–hole recombination in halide crystals. Phys Rev B 18:1948–1960
Knotek ML, Feibelman PJ (1978) Ion desorption by core-hole auger decay. Phys Rev Lett 40:964–967
Knotek ML, Feibelman PJ (1979) Stability of ionically bonded surfaces in ionizing environments. Surf Sci 90:78–90
Humphreys CJ, Bullough TJ, Devenish RW, Maher DM, Turner PS (1990) Electron beam nano-etching in oxides, fluorides, metals and semiconductors. Scanning Microsc Suppl 4:185–192
Kammlott GW, Sinclair WR (1974) Fe2O3 – an inorganic electron resist material. J Electrochem Soc 121:929–932
Baba M, Ikeda T (1981) A new inorganic electron resist using amorphous WO3 film. Jpn J Appl Phys 20:L149–L152
Carcenac F, Vieu C, Haghiri-Gosnet AM, Simon G, Mejias M, Launois H (1996) High voltage electron beam nanolithography on WO3. J Vac Sci Technol B 14:4283–4287
Saifullah MSM, Namatsu H, Yamaguchi T, Yamazaki K, Kurihara K (1999) Spin-coatable aluminum oxide resists in electron beam nanolithography. Proc SPIE 3678:633–642
Saifullah MSM, Namatsu H, Yamaguchi T, Yamazaki K, Kurihara K (1999) Effect of chelating agents on high resolution electron beam nanolithography of spin-coatable alumina gel films. Jpn J Appl Phys 38:7052–7058
Mitchell WJ, Hu EL (1999) Selective area chemical vapor deposition of titanium oxide films: characterization of Ti(OC3H7)4 as an electron beam resist. J Vac Sci Technol B 17:1622–1626
Mitchell WJ, Hu EL (1999) In situ electron-beam lithography on GaAs substrates using a metal alkoxide resist. Appl Phys Lett 74:1916–1918
Mitchell WJ, Hu EL (2002) High-resolution in situ electron beam patterning using Ti(OC3H7)4 as a negative-type resist. J Vac Sci Technol B 20:596–603
Yamazaki K, Saifullah MSM, Namatsu H, Kurihara K (2000) Sub-10 nm electron beam lithography with sub-10 nm overlay accuracy. Proc SPIE 3997:458–466
Saifullah MSM, Subramanian KRV, Tapley E, Kang DJ, Welland ME, Butler M (2003) Sub-10 nm electron beam nanolithography using spin-coatable TiO2 resists. Nano Lett 3:1587–1591
Subramanian KRV, Saifullah MSM, Tapley E, Kang DJ, Welland ME, Butler M (2004) Direct writing of ZrO2 on a sub-10 nm scale using an electron beam. Nanotechnology 15:158–162
Saifullah MSM, Khan MZR, Hasko D, Leong ESP, Neo XL, Goh ETL, Anderson D, Jones GAC, Welland ME (2010) Spin-coatable HfO2 resist for optical and electron beam lithographies. J Vac Sci Technol B 28:90–95
Liang LXY (2008) Synthesis and characterization of new oxide materials. Dissertation (BSc), National University of Singapore
Sim KS, Shahid M, Saifullah MSM, Subramanian KRV, Leong ESP, Sohn JI, Anderson D, Jones GAC, Welland ME, Kang DJ, unpublished work
Subramanian KRV (2006) Spin-coatable oxide resists for electron beam nanolithography, Dissertation (PhD), University of Cambridge
Chuang CM, Wu MC, Huang YC, Cheng KC, Lin CF, Chen YF, Su WF (2006) Nanolithography made from water-based spin-coatable LSMO resist. Nanotechnology 17:4399–4404
Wu MC, Chuang CM, Chen YF, Su WF (2008) Fabrication and optical properties of periodical structures based on a water-developable and tunable La0.7Sr0.3MnO3 resist. J Mater Chem 18:780–785
Saifullah MSM, Kang DJ, Subramanian KRV, Welland ME, Yamazaki K, Kurihara K (2004) Electron beam nanolithography of β-ketoester modified aluminium tri-sec-butoxide. J Sol-Gel Sci Technol 29:5–10
Ingold CK (1953) Structure and mechanism in organic chemistry. G. Bell & Sons Ltd, London
Gero A (1954) Studies on enol titration. II. Enol contents of some ketones and esters in the presence of methanol. J Org Chem 19:1960–1970
Liu BY, Ho ST (2008) Sub-100 nm nanolithography and pattern transfer on compound semiconductor using sol–gel-derived TiO2 resist. J Electrochem Soc 155:P57–P60
Liu BY, Huang YY, Xu GY, Ho ST (2008) Nanolithography using spin-coatable ZrO2 resist and its application to sub-10 nm direct pattern transfer on compound semiconductors. Nanotechnology 19:155303
Khan MZR, Hasko DG, Saifullah MSM, Welland ME (2008) Characterization of a sol–gel based high-k dielectric field effect transistor for cryogenic operation. J Vac Sci Technol B 26:1887–1891
Khan MZR, Hasko DG, Saifullah MSM, Welland ME (2009) Trapped charge dynamics in a sol–gel based TiO2 high-k gate dielectric silicon metal-oxide-semiconductor field effect transistor. J Phys Condens Matter 21:215902
Khan MZR, Hasko DG, Saifullah MSM, Welland ME (2008) Single shot measurement of the lifetime of a trapped electron in the gate dielectric of a high-k FET. Appl Phys Lett 93:193501
Alexe M, Harnagea C, Hesse D, Gösele U (1999) Patterning and switching of nano-size ferroelectric memory cells. Appl Phys Lett 75:1793–1795
Kakimi A, Okamura S, Yagi Y, Mori K, Tsukamoto T (1994) Fabrication of ferroelectric Bi4Ti3O12 thin films by dipping pyrolysis of metal naphthenates and micropatterns by an electron beam. Jpn J Appl Phys 33:5301–5304
Mori K, Okamura S (1992) Electron-beam-induced structuring of composite oxides by means of dipping pyrolysis of metal naphthenate films. Jpn J Appl Phys 31:L1143–L1145
Saifullah MSM, Subramanian KRV, Kang DJ, Anderson D, Huck WTS, Jones GAC, Welland ME (2005) Sub-10 nm high aspect ratio patterning of ZnO by an electron beam. Adv Mater 17:1757–1761
Saifullah MSM, Subramanian KRV, Anderson D, Kang DJ, Huck WTS, Jones GAC, Welland ME (2006) Sub-10 nm high aspect ratio patterning of ZnO in a 500 μm main field. J Vac Sci Technol B 24:1215–1218
Nedelcu M, Saifullah MSM, Hasko DG, Jang A, Anderson D, Kang DJ, Huck WTS, Jones GAC, Welland ME, Steiner U (2010) Fabrication of sub-10 nm metallic lines of low line-width roughness by hydrogen reduction of patterned metal-organic materials. Adv Funct Mater 20:2317–2323
Patole SP, Patole AS, Rhen DS, Shahid M, Min H, Kang DJ, Kim TH, Yoo JB (2009) Patterned carbon nanotube growth using an electron beam sensitive direct writable catalyst. Nanotechnology 20:315302
Okamura S, Yagi Y, Kakimi A, Ando S, Mori K, Tsukamoto T (1996) Crystallization of precursor micropatterns of ferroelectric Bi4Ti3O12 fabricated by electron beam scanning. Jpn J Appl Phys 35:5224–5228
Kiyohara S, Takamatsu H, Motoishi T, Mori K (2004) Nanopatterning of diamond films with composite oxide mask of metal octylates in electron beam lithography. J Mater Sci Mater Electron 15:99–102
Author information
Authors and Affiliations
Corresponding authors
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2013 Springer-Verlag Wien
About this chapter
Cite this chapter
Tadanaga, K., Saifullah, M.S.M. (2013). UV and E-Beam Direct Patterning of Photosensitive CSD Films. In: Schneller, T., Waser, R., Kosec, M., Payne, D. (eds) Chemical Solution Deposition of Functional Oxide Thin Films. Springer, Vienna. https://doi.org/10.1007/978-3-211-99311-8_20
Download citation
DOI: https://doi.org/10.1007/978-3-211-99311-8_20
Published:
Publisher Name: Springer, Vienna
Print ISBN: 978-3-211-99310-1
Online ISBN: 978-3-211-99311-8
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)