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Electron-beam lithography

Electron-beam lithography (often abbreviated as e-beam lithography, EBL) is the practice of scanning a focused beam of electrons to draw custom shapes on a surface covered with an electron-sensitive film called a resist (exposing).[1] The electron beam changes the solubility of the resist, enabling selective removal of either the exposed or non-exposed regions of the resist by immersing it in a solvent (developing). The purpose, as with photolithography, is to create very small structures in the resist that can subsequently be transferred to the substrate material, often by etching.

An example of Electron beam lithograph setup

The primary advantage of electron-beam lithography is that it can draw custom patterns (direct-write) with sub-10 nm resolution. This form of maskless lithography has high resolution but low throughput, limiting its usage to photomask fabrication, low-volume production of semiconductor devices, and research and development.

Systems edit

Electron-beam lithography systems used in commercial applications are dedicated e-beam writing systems that are very expensive (> US$1M). For research applications, it is very common to convert an electron microscope into an electron beam lithography system using relatively low cost accessories (< US$100K). Such converted systems have produced linewidths of ~20 nm since at least 1990, while current dedicated systems have produced linewidths on the order of 10 nm or smaller.

Electron-beam lithography systems can be classified according to both beam shape and beam deflection strategy. Older systems used Gaussian-shaped beams that scanned these beams in a raster fashion. Newer systems use shaped beams that can be deflected to various positions in the writing field (also known as vector scan).

Electron sources edit

Lower-resolution systems can use thermionic sources (cathode), which are usually formed from lanthanum hexaboride. However, systems with higher-resolution requirements need to use field electron emission sources, such as heated W/ZrO2 for lower energy spread and enhanced brightness. Thermal field emission sources are preferred over cold emission sources, in spite of the former's slightly larger beam size, because they offer better stability over typical writing times of several hours.

Lenses edit

Both electrostatic and magnetic lenses may be used. However, electrostatic lenses have more aberrations and so are not used for fine focusing. There is currently[when?] no mechanism to make achromatic electron beam lenses, so extremely narrow dispersions of the electron beam energy are needed for finest focusing.[citation needed][needs update]

Stage, stitching and alignment edit

 
Field stitching. Stitching is a concern for critical features crossing a field boundary (red dotted line).

Typically, for very small beam deflections, electrostatic deflection "lenses" are used; larger beam deflections require electromagnetic scanning. Because of the inaccuracy and because of the finite number of steps in the exposure grid, the writing field is of the order of 100 micrometre – 1 mm. Larger patterns require stage moves. An accurate stage is critical for stitching (tiling writing fields exactly against each other) and pattern overlay (aligning a pattern to a previously made one).

Electron beam write time edit

The minimum time to expose a given area for a given dose is given by the following formula:[2]

 

where   is the time to expose the object (can be divided into exposure time/step size),   is the beam current,   is the dose and   is the area exposed.

For example, assuming an exposure area of 1 cm2, a dose of 10−3 coulombs/cm2, and a beam current of 10−9 amperes, the resulting minimum write time would be 106 seconds (about 12 days). This minimum write time does not include time for the stage to move back and forth, as well as time for the beam to be blanked (blocked from the wafer during deflection), as well as time for other possible beam corrections and adjustments in the middle of writing. To cover the 700 cm2 surface area of a 300 mm silicon wafer, the minimum write time would extend to 7*108 seconds, about 22 years. This is a factor of about 10 million times slower than current optical lithography tools. It is clear that throughput is a serious limitation for electron beam lithography, especially when writing dense patterns over a large area.

E-beam lithography is not suitable for high-volume manufacturing because of its limited throughput. The smaller field of electron beam writing makes for very slow pattern generation compared with photolithography (the current standard) because more exposure fields must be scanned to form the final pattern area (≤mm2 for electron beam vs. ≥40 mm2 for an optical mask projection scanner). The stage moves in between field scans. The electron beam field is small enough that a rastering or serpentine stage motion is needed to pattern a 26 mm X 33 mm area for example, whereas in a photolithography scanner only a one-dimensional motion of a 26 mm X 2 mm slit field would be required.

Currently an optical maskless lithography tool[3] is much faster than an electron beam tool used at the same resolution for photomask patterning.

Shot noise edit

As features sizes shrink, the number of incident electrons at fixed dose also shrinks. As soon as the number reaches ~10000, shot noise effects become predominant, leading to substantial natural dose variation within a large feature population. With each successive process node, as the feature area is halved, the minimum dose must double to maintain the same noise level. Consequently, the tool throughput would be halved with each successive process node.

feature diameter (nm) minimum dose for one-in-a-million 5% dose error (μC/cm2)
40 127
28 260
20 509
14 1039
10 2037
7 4158

Note: 1 ppm of population is about 5 standard deviations away from the mean dose.

Ref.: SPIE Proc. 8683-36 (2013)

Shot noise is a significant consideration even for mask fabrication. For example, a commercial mask e-beam resist like FEP-171 would use doses less than 10 μC/cm2,[4][5] whereas this leads to noticeable shot noise for a target CD even on the order of ~200 nm on the mask.[6][7] CD variation can be on the order of 15-20% for sub-20 nm features.[8][9]

Defects in electron-beam lithography edit

Despite the high resolution of electron-beam lithography, the generation of defects during electron-beam lithography is often not considered by users. Defects may be classified into two categories: data-related defects, and physical defects.

Data-related defects may be classified further into two sub-categories. Blanking or deflection errors occur when the electron beam is not deflected properly when it is supposed to, while shaping errors occur in variable-shaped beam systems when the wrong shape is projected onto the sample. These errors can originate either from the electron optical control hardware or the input data that was taped out. As might be expected, larger data files are more susceptible to data-related defects.

Physical defects are more varied, and can include sample charging (either negative or positive), backscattering calculation errors, dose errors, fogging (long-range reflection of backscattered electrons), outgassing, contamination, beam drift and particles. Since the write time for electron beam lithography can easily exceed a day, "randomly occurring" defects are more likely to occur. Here again, larger data files can present more opportunities for defects.

Photomask defects largely originate during the electron beam lithography used for pattern definition.

Electron energy deposition in matter edit

 
Electron trajectories in resist: An incident electron (red) produces secondary electrons (blue). Sometimes, the incident electron may itself be backscattered as shown here and leave the surface of the resist (amber).

The primary electrons in the incident beam lose energy upon entering a material through inelastic scattering or collisions with other electrons. In such a collision the momentum transfer from the incident electron to an atomic electron can be expressed as [10]  , where b is the distance of closest approach between the electrons, and v is the incident electron velocity. The energy transferred by the collision is given by  , where m is the electron mass and E is the incident electron energy, given by  . By integrating over all values of T between the lowest binding energy, E0 and the incident energy, one obtains the result that the total cross section for collision is inversely proportional to the incident energy  , and proportional to 1/E0 – 1/E. Generally, E >> E0, so the result is essentially inversely proportional to the binding energy.

By using the same integration approach, but over the range 2E0 to E, one obtains by comparing cross-sections that half of the inelastic collisions of the incident electrons produce electrons with kinetic energy greater than E0. These secondary electrons are capable of breaking bonds (with binding energy E0) at some distance away from the original collision. Additionally, they can generate additional, lower energy electrons, resulting in an electron cascade. Hence, it is important to recognize the significant contribution of secondary electrons to the spread of the energy deposition.

In general, for a molecule AB:[11]

e + AB → AB → A + B

This reaction, also known as "electron attachment" or "dissociative electron attachment" is most likely to occur after the electron has essentially slowed to a halt, since it is easiest to capture at that point. The cross-section for electron attachment is inversely proportional to electron energy at high energies, but approaches a maximum limiting value at zero energy.[12] On the other hand, it is already known that the mean free path at the lowest energies (few to several eV or less, where dissociative attachment is significant) is well over 10 nm,[13][14] thus limiting the ability to consistently achieve resolution at this scale.

Resolution capability edit

 
Low energy electron migration. The distance (r) traveled by a low energy electron affects the resolution and can be at least several nanometers.

With today's electron optics, electron beam widths can routinely go down to a few nanometers. This is limited mainly by aberrations and space charge. However, the feature resolution limit is determined not by the beam size but by forward scattering (or effective beam broadening) in the resist, while the pitch resolution limit is determined by secondary electron travel in the resist.[15][16] This point was driven home by a 2007 demonstration of double patterning using electron beam lithography in the fabrication of 15 nm half-pitch zone plates.[17] Although a 15 nm feature was resolved, a 30 nm pitch was still difficult to do due to secondary electrons scattering from the adjacent feature. The use of double patterning allowed the spacing between features to be wide enough for the secondary electron scattering to be significantly reduced.

The forward scattering can be decreased by using higher energy electrons or thinner resist, but the generation of secondary electrons is inevitable. It is now recognized that for insulating materials like PMMA, low energy electrons can travel quite a far distance (several nm is possible). This is due to the fact that below the ionization potential the only energy loss mechanism is mainly through phonons and polarons. Although the latter is basically an ionic lattice effect,[18] polaron hopping can extend as far as 20 nm.[19] The travel distance of secondary electrons is not a fundamentally derived physical value, but a statistical parameter often determined from many experiments or Monte Carlo simulations down to < 1 eV. This is necessary since the energy distribution of secondary electrons peaks well below 10 eV.[20] Hence, the resolution limit is not usually cited as a well-fixed number as with an optical diffraction-limited system.[15] Repeatability and control at the practical resolution limit often require considerations not related to image formation, e.g., resist development and intermolecular forces.

A study by the College of Nanoscale Science and Engineering (CNSE) presented at the 2013 EUVL Workshop indicated that, as a measure of electron blur, 50-100 eV electrons easily penetrated beyond 10 nm of resist thickness in PMMA or a commercial resist. Furthermore dielectric breakdown discharge is possible.[21] More recent studies have indicated that 20 nm resist thickness could be penetrated by low energy electrons (of sufficient dose) and sub-20 nm half-pitch electron-beam lithography already required double patterning.[22][23]

As of 2022, a state-of-the-art electron multi-beam writer achieves about a 20 nm resolution.[24][25]

Scattering edit

In addition to producing secondary electrons, primary electrons from the incident beam with sufficient energy to penetrate the resist can be multiply scattered over large distances from underlying films and/or the substrate. This leads to exposure of areas at a significant distance from the desired exposure location. For thicker resists, as the primary electrons move forward, they have an increasing opportunity to scatter laterally from the beam-defined location. This scattering is called forward scattering. Sometimes the primary electrons are scattered at angles exceeding 90 degrees, i.e., they no longer advance further into the resist. These electrons are called backscattered electrons and have the same effect as long-range flare in optical projection systems. A large enough dose of backscattered electrons can lead to complete exposure of resist over an area much larger than defined by the beam spot.

Proximity effect edit

The smallest features produced by electron-beam lithography have generally been isolated features, as nested features exacerbate the proximity effect, whereby electrons from exposure of an adjacent region spill over into the exposure of the currently written feature, effectively enlarging its image, and reducing its contrast, i.e., difference between maximum and minimum intensity. Hence, nested feature resolution is harder to control. For most resists, it is difficult to go below 25 nm lines and spaces, and a limit of 20 nm lines and spaces has been found.[26] In actuality, though, the range of secondary electron scattering is quite far, sometimes exceeding 100 nm,[27] but becoming very significant below 30 nm.[28]

The proximity effect is also manifest by secondary electrons leaving the top surface of the resist and then returning some tens of nanometers distance away.[29]

Proximity effects (due to electron scattering) can be addressed by solving the inverse problem and calculating the exposure function E(x,y) that leads to a dose distribution as close as possible to the desired dose D(x,y) when convolved by the scattering distribution point spread function PSF(x,y). However, it must be remembered that an error in the applied dose (e.g., from shot noise) would cause the proximity effect correction to fail.

Charging edit

Since electrons are charged particles, they tend to charge the substrate negatively unless they can quickly gain access to a path to ground. For a high-energy beam incident on a silicon wafer, virtually all the electrons stop in the wafer where they can follow a path to ground. However, for a quartz substrate such as a photomask, the embedded electrons will take a much longer time to move to ground. Often the negative charge acquired by a substrate can be compensated or even exceeded by a positive charge on the surface due to secondary electron emission into the vacuum. The presence of a thin conducting layer above or below the resist is generally of limited use for high energy (50 keV or more) electron beams, since most electrons pass through the layer into the substrate. The charge dissipation layer is generally useful only around or below 10 keV, since the resist is thinner and most of the electrons either stop in the resist or close to the conducting layer. However, they are of limited use due to their high sheet resistance, which can lead to ineffective grounding.

The range of low-energy secondary electrons (the largest component of the free electron population in the resist-substrate system) which can contribute to charging is not a fixed number but can vary from 0 to as high as 50 nm (see section New frontiers and extreme ultraviolet lithography). Hence, resist-substrate charging is not repeatable and is difficult to compensate consistently. Negative charging deflects the electron beam away from the charged area while positive charging deflects the electron beam toward the charged area.

Electron-beam resist performance edit

Due to the scission efficiency generally being an order of magnitude higher than the crosslinking efficiency, most polymers used for positive-tone electron-beam lithography will also crosslink (and therefore become negative tone) at doses an order of magnitude higher than the doses used to cause scission in the polymer for positive tone exposure. In the case of PMMA, exposure of electrons at up to more than 1000 μC/cm², the gradation curve corresponds to the curve of a “normal” positive process. Above 2000 μC/cm², the recombinant crosslinking process prevails, and at about 7000 μC/cm² the layer is completely crosslinked which makes the layer more insoluble than the unexposed initial layer. If negative PMMA structures should be used, a stronger developer than for the positive process is required. [30] Such large dose increases may be required to avoid shot noise effects.[31][32][33]

A study performed at the Naval Research Laboratory [34] indicated that low-energy (10–50 eV) electrons were able to damage ~30 nm thick PMMA films. The damage was manifest as a loss of material.

  • For the popular electron-beam resist ZEP-520, a pitch resolution limit of 60 nm (30 nm lines and spaces), independent of thickness and beam energy, was found.[35]
  • A 20 nm resolution had also been demonstrated using a 3 nm 100 keV electron beam and PMMA resist.[36] 20 nm unexposed gaps between exposed lines showed inadvertent exposure by secondary electrons.
  • Hydrogen silsesquioxane (HSQ) is a negative tone resist that is capable of forming isolated 2-nm-wide lines and 10 nm periodic dot arrays (10 nm pitch) in very thin layers.[37] HSQ itself is similar to porous, hydrogenated SiO2. It may be used to etch silicon but not silicon dioxide or other similar dielectrics.

In 2018, a thiol-ene resist was developed that features native reactive surface groups, which allows the direct functionalization of the resist surface with biomolecules.[38]

New frontiers edit

To get around the secondary electron generation, it will be imperative to use low-energy electrons as the primary radiation to expose resist. Ideally, these electrons should have energies on the order of not much more than several eV in order to expose the resist without generating any secondary electrons, since they will not have sufficient excess energy. Such exposure has been demonstrated using a scanning tunneling microscope as the electron beam source.[39] The data suggest that electrons with energies as low as 12 eV can penetrate 50 nm thick polymer resist. The drawback to using low energy electrons is that it is hard to prevent spreading of the electron beam in the resist.[40] Low energy electron optical systems are also hard to design for high resolution.[41] Coulomb inter-electron repulsion always becomes more severe for lower electron energy.

 
Scanning probe lithography. A scanning probe can be used for low-energy electron beam lithography, offering sub-100 nm resolution, determined by the dose of low-energy electrons.

Another alternative in electron-beam lithography is to use extremely high electron energies (at least 100 keV) to essentially "drill" or sputter the material. This phenomenon has been observed frequently in transmission electron microscopy.[42] However, this is a very inefficient process, due to the inefficient transfer of momentum from the electron beam to the material. As a result, it is a slow process, requiring much longer exposure times than conventional electron beam lithography. Also high energy beams always bring up the concern of substrate damage.

Interference lithography using electron beams is another possible path for patterning arrays with nanometer-scale periods. A key advantage of using electrons over photons in interferometry is the much shorter wavelength for the same energy.

Despite the various intricacies and subtleties of electron beam lithography at different energies, it remains the most practical way to concentrate the most energy into the smallest area.

There has been significant interest in the development of multiple electron beam approaches to lithography in order to increase throughput. This work has been supported by SEMATECH and start-up companies such as Multibeam Corporation,[43] Mapper[44] and IMS.[45] IMS Nanofabrication has commercialized the multibeam-maskwriter and started a rollout in 2016. [46]

See also edit

References edit

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  3. ^ Faster and lower cost for 65 nm and 45 nm photomask patterning[dead link]
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  34. ^ Bermudez, V. M. (1999). "Low-energy electron-beam effects on poly(methyl methacrylate) resist films". Journal of Vacuum Science and Technology B. 17 (6): 2512. Bibcode:1999JVSTB..17.2512B. doi:10.1116/1.591134.
  35. ^ H. Yang et al., Proceedings of the 1st IEEE Intl. Conf. on Nano/Micro Engineered and Molecular Systems, pp. 391–394 (2006).
  36. ^ Cumming, D. R. S.; Thoms, S.; Beaumont, S. P.; Weaver, J. M. R. (1996). "Fabrication of 3 nm wires using 100 keV electron beam lithography and poly(methyl methacrylate) resist". Applied Physics Letters. 68 (3, ) James Watt Nanofabrication Centre): 322. Bibcode:1996ApPhL..68..322C. doi:10.1063/1.116073. {{cite journal}}: External link in |issue= (help)
  37. ^ Manfrinato, Vitor R.; Zhang, Lihua; Su, Dong; Duan, Huigao; Hobbs, Richard G.; Stach, Eric A.; Berggren, Karl K. (2013). "Resolution limits of electron-beam lithography toward the atomic scale" (PDF). Nano Lett. 13 (4): 1555–1558. Bibcode:2013NanoL..13.1555M. doi:10.1021/nl304715p. hdl:1721.1/92829. PMID 23488936. S2CID 1060983.
  38. ^ Shafagh, Reza; Vastesson, Alexander; Guo, Weijin; van der Wijngaart, Wouter; Haraldsson, Tommy (2018). "E-Beam Nanostructuring and Direct Click Biofunctionalization of Thiol–Ene Resist". ACS Nano. 12 (10): 9940–9946. doi:10.1021/acsnano.8b03709. PMID 30212184. S2CID 52271550.
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  43. ^ Multibeam Corporation. Multibeamcorp.com (2011-03-04). Retrieved on 2011-08-27.
  44. ^ Mapper Lithography 2016-12-20 at the Wayback Machine. Mapper Lithography (2010-01-18). Retrieved on 2011-08-27.
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  46. ^ IMS Nanofabrications. IMS Nanofabrication(2011-12-07). Retrieved on 2019-02-28.

electron, beam, lithography, often, abbreviated, beam, lithography, practice, scanning, focused, beam, electrons, draw, custom, shapes, surface, covered, with, electron, sensitive, film, called, resist, exposing, electron, beam, changes, solubility, resist, en. Electron beam lithography often abbreviated as e beam lithography EBL is the practice of scanning a focused beam of electrons to draw custom shapes on a surface covered with an electron sensitive film called a resist exposing 1 The electron beam changes the solubility of the resist enabling selective removal of either the exposed or non exposed regions of the resist by immersing it in a solvent developing The purpose as with photolithography is to create very small structures in the resist that can subsequently be transferred to the substrate material often by etching An example of Electron beam lithograph setupThe primary advantage of electron beam lithography is that it can draw custom patterns direct write with sub 10 nm resolution This form of maskless lithography has high resolution but low throughput limiting its usage to photomask fabrication low volume production of semiconductor devices and research and development Contents 1 Systems 1 1 Electron sources 1 2 Lenses 1 3 Stage stitching and alignment 1 4 Electron beam write time 1 5 Shot noise 1 6 Defects in electron beam lithography 2 Electron energy deposition in matter 2 1 Resolution capability 2 2 Scattering 2 3 Proximity effect 3 Charging 4 Electron beam resist performance 5 New frontiers 6 See also 7 ReferencesSystems editElectron beam lithography systems used in commercial applications are dedicated e beam writing systems that are very expensive gt US 1M For research applications it is very common to convert an electron microscope into an electron beam lithography system using relatively low cost accessories lt US 100K Such converted systems have produced linewidths of 20 nm since at least 1990 while current dedicated systems have produced linewidths on the order of 10 nm or smaller Electron beam lithography systems can be classified according to both beam shape and beam deflection strategy Older systems used Gaussian shaped beams that scanned these beams in a raster fashion Newer systems use shaped beams that can be deflected to various positions in the writing field also known as vector scan Electron sources edit Lower resolution systems can use thermionic sources cathode which are usually formed from lanthanum hexaboride However systems with higher resolution requirements need to use field electron emission sources such as heated W ZrO2 for lower energy spread and enhanced brightness Thermal field emission sources are preferred over cold emission sources in spite of the former s slightly larger beam size because they offer better stability over typical writing times of several hours Lenses edit Both electrostatic and magnetic lenses may be used However electrostatic lenses have more aberrations and so are not used for fine focusing There is currently when no mechanism to make achromatic electron beam lenses so extremely narrow dispersions of the electron beam energy are needed for finest focusing citation needed needs update Stage stitching and alignment edit nbsp Field stitching Stitching is a concern for critical features crossing a field boundary red dotted line Typically for very small beam deflections electrostatic deflection lenses are used larger beam deflections require electromagnetic scanning Because of the inaccuracy and because of the finite number of steps in the exposure grid the writing field is of the order of 100 micrometre 1 mm Larger patterns require stage moves An accurate stage is critical for stitching tiling writing fields exactly against each other and pattern overlay aligning a pattern to a previously made one Electron beam write time edit The minimum time to expose a given area for a given dose is given by the following formula 2 D A T I displaystyle D cdot A T cdot I nbsp where T displaystyle T nbsp is the time to expose the object can be divided into exposure time step size I displaystyle I nbsp is the beam current D displaystyle D nbsp is the dose and A displaystyle A nbsp is the area exposed For example assuming an exposure area of 1 cm2 a dose of 10 3 coulombs cm2 and a beam current of 10 9 amperes the resulting minimum write time would be 106 seconds about 12 days This minimum write time does not include time for the stage to move back and forth as well as time for the beam to be blanked blocked from the wafer during deflection as well as time for other possible beam corrections and adjustments in the middle of writing To cover the 700 cm2 surface area of a 300 mm silicon wafer the minimum write time would extend to 7 108 seconds about 22 years This is a factor of about 10 million times slower than current optical lithography tools It is clear that throughput is a serious limitation for electron beam lithography especially when writing dense patterns over a large area E beam lithography is not suitable for high volume manufacturing because of its limited throughput The smaller field of electron beam writing makes for very slow pattern generation compared with photolithography the current standard because more exposure fields must be scanned to form the final pattern area mm2 for electron beam vs 40 mm2 for an optical mask projection scanner The stage moves in between field scans The electron beam field is small enough that a rastering or serpentine stage motion is needed to pattern a 26 mm X 33 mm area for example whereas in a photolithography scanner only a one dimensional motion of a 26 mm X 2 mm slit field would be required Currently an optical maskless lithography tool 3 is much faster than an electron beam tool used at the same resolution for photomask patterning Shot noise edit As features sizes shrink the number of incident electrons at fixed dose also shrinks As soon as the number reaches 10000 shot noise effects become predominant leading to substantial natural dose variation within a large feature population With each successive process node as the feature area is halved the minimum dose must double to maintain the same noise level Consequently the tool throughput would be halved with each successive process node feature diameter nm minimum dose for one in a million 5 dose error mC cm2 40 12728 26020 50914 103910 20377 4158Note 1 ppm of population is about 5 standard deviations away from the mean dose Ref SPIE Proc 8683 36 2013 Shot noise is a significant consideration even for mask fabrication For example a commercial mask e beam resist like FEP 171 would use doses less than 10 mC cm2 4 5 whereas this leads to noticeable shot noise for a target CD even on the order of 200 nm on the mask 6 7 CD variation can be on the order of 15 20 for sub 20 nm features 8 9 Defects in electron beam lithography edit Despite the high resolution of electron beam lithography the generation of defects during electron beam lithography is often not considered by users Defects may be classified into two categories data related defects and physical defects Data related defects may be classified further into two sub categories Blanking or deflection errors occur when the electron beam is not deflected properly when it is supposed to while shaping errors occur in variable shaped beam systems when the wrong shape is projected onto the sample These errors can originate either from the electron optical control hardware or the input data that was taped out As might be expected larger data files are more susceptible to data related defects Physical defects are more varied and can include sample charging either negative or positive backscattering calculation errors dose errors fogging long range reflection of backscattered electrons outgassing contamination beam drift and particles Since the write time for electron beam lithography can easily exceed a day randomly occurring defects are more likely to occur Here again larger data files can present more opportunities for defects Photomask defects largely originate during the electron beam lithography used for pattern definition Electron energy deposition in matter edit nbsp Electron trajectories in resist An incident electron red produces secondary electrons blue Sometimes the incident electron may itself be backscattered as shown here and leave the surface of the resist amber The primary electrons in the incident beam lose energy upon entering a material through inelastic scattering or collisions with other electrons In such a collision the momentum transfer from the incident electron to an atomic electron can be expressed as 10 d p 2 e 2 b v displaystyle dp 2e 2 bv nbsp where b is the distance of closest approach between the electrons and v is the incident electron velocity The energy transferred by the collision is given by T d p 2 2 m e 4 E b 2 displaystyle T dp 2 2m e 4 Eb 2 nbsp where m is the electron mass and E is the incident electron energy given by E 1 2 m v 2 displaystyle E 1 2 mv 2 nbsp By integrating over all values of T between the lowest binding energy E0 and the incident energy one obtains the result that the total cross section for collision is inversely proportional to the incident energy E displaystyle E nbsp and proportional to 1 E0 1 E Generally E gt gt E0 so the result is essentially inversely proportional to the binding energy By using the same integration approach but over the range 2E0 to E one obtains by comparing cross sections that half of the inelastic collisions of the incident electrons produce electrons with kinetic energy greater than E0 These secondary electrons are capable of breaking bonds with binding energy E0 at some distance away from the original collision Additionally they can generate additional lower energy electrons resulting in an electron cascade Hence it is important to recognize the significant contribution of secondary electrons to the spread of the energy deposition In general for a molecule AB 11 e AB AB A B This reaction also known as electron attachment or dissociative electron attachment is most likely to occur after the electron has essentially slowed to a halt since it is easiest to capture at that point The cross section for electron attachment is inversely proportional to electron energy at high energies but approaches a maximum limiting value at zero energy 12 On the other hand it is already known that the mean free path at the lowest energies few to several eV or less where dissociative attachment is significant is well over 10 nm 13 14 thus limiting the ability to consistently achieve resolution at this scale Resolution capability edit nbsp Low energy electron migration The distance r traveled by a low energy electron affects the resolution and can be at least several nanometers With today s electron optics electron beam widths can routinely go down to a few nanometers This is limited mainly by aberrations and space charge However the feature resolution limit is determined not by the beam size but by forward scattering or effective beam broadening in the resist while the pitch resolution limit is determined by secondary electron travel in the resist 15 16 This point was driven home by a 2007 demonstration of double patterning using electron beam lithography in the fabrication of 15 nm half pitch zone plates 17 Although a 15 nm feature was resolved a 30 nm pitch was still difficult to do due to secondary electrons scattering from the adjacent feature The use of double patterning allowed the spacing between features to be wide enough for the secondary electron scattering to be significantly reduced The forward scattering can be decreased by using higher energy electrons or thinner resist but the generation of secondary electrons is inevitable It is now recognized that for insulating materials like PMMA low energy electrons can travel quite a far distance several nm is possible This is due to the fact that below the ionization potential the only energy loss mechanism is mainly through phonons and polarons Although the latter is basically an ionic lattice effect 18 polaron hopping can extend as far as 20 nm 19 The travel distance of secondary electrons is not a fundamentally derived physical value but a statistical parameter often determined from many experiments or Monte Carlo simulations down to lt 1 eV This is necessary since the energy distribution of secondary electrons peaks well below 10 eV 20 Hence the resolution limit is not usually cited as a well fixed number as with an optical diffraction limited system 15 Repeatability and control at the practical resolution limit often require considerations not related to image formation e g resist development and intermolecular forces A study by the College of Nanoscale Science and Engineering CNSE presented at the 2013 EUVL Workshop indicated that as a measure of electron blur 50 100 eV electrons easily penetrated beyond 10 nm of resist thickness in PMMA or a commercial resist Furthermore dielectric breakdown discharge is possible 21 More recent studies have indicated that 20 nm resist thickness could be penetrated by low energy electrons of sufficient dose and sub 20 nm half pitch electron beam lithography already required double patterning 22 23 As of 2022 a state of the art electron multi beam writer achieves about a 20 nm resolution 24 25 Scattering edit In addition to producing secondary electrons primary electrons from the incident beam with sufficient energy to penetrate the resist can be multiply scattered over large distances from underlying films and or the substrate This leads to exposure of areas at a significant distance from the desired exposure location For thicker resists as the primary electrons move forward they have an increasing opportunity to scatter laterally from the beam defined location This scattering is called forward scattering Sometimes the primary electrons are scattered at angles exceeding 90 degrees i e they no longer advance further into the resist These electrons are called backscattered electrons and have the same effect as long range flare in optical projection systems A large enough dose of backscattered electrons can lead to complete exposure of resist over an area much larger than defined by the beam spot Proximity effect edit The smallest features produced by electron beam lithography have generally been isolated features as nested features exacerbate the proximity effect whereby electrons from exposure of an adjacent region spill over into the exposure of the currently written feature effectively enlarging its image and reducing its contrast i e difference between maximum and minimum intensity Hence nested feature resolution is harder to control For most resists it is difficult to go below 25 nm lines and spaces and a limit of 20 nm lines and spaces has been found 26 In actuality though the range of secondary electron scattering is quite far sometimes exceeding 100 nm 27 but becoming very significant below 30 nm 28 The proximity effect is also manifest by secondary electrons leaving the top surface of the resist and then returning some tens of nanometers distance away 29 Proximity effects due to electron scattering can be addressed by solving the inverse problem and calculating the exposure function E x y that leads to a dose distribution as close as possible to the desired dose D x y when convolved by the scattering distribution point spread function PSF x y However it must be remembered that an error in the applied dose e g from shot noise would cause the proximity effect correction to fail Charging editSince electrons are charged particles they tend to charge the substrate negatively unless they can quickly gain access to a path to ground For a high energy beam incident on a silicon wafer virtually all the electrons stop in the wafer where they can follow a path to ground However for a quartz substrate such as a photomask the embedded electrons will take a much longer time to move to ground Often the negative charge acquired by a substrate can be compensated or even exceeded by a positive charge on the surface due to secondary electron emission into the vacuum The presence of a thin conducting layer above or below the resist is generally of limited use for high energy 50 keV or more electron beams since most electrons pass through the layer into the substrate The charge dissipation layer is generally useful only around or below 10 keV since the resist is thinner and most of the electrons either stop in the resist or close to the conducting layer However they are of limited use due to their high sheet resistance which can lead to ineffective grounding The range of low energy secondary electrons the largest component of the free electron population in the resist substrate system which can contribute to charging is not a fixed number but can vary from 0 to as high as 50 nm see section New frontiers and extreme ultraviolet lithography Hence resist substrate charging is not repeatable and is difficult to compensate consistently Negative charging deflects the electron beam away from the charged area while positive charging deflects the electron beam toward the charged area Electron beam resist performance editDue to the scission efficiency generally being an order of magnitude higher than the crosslinking efficiency most polymers used for positive tone electron beam lithography will also crosslink and therefore become negative tone at doses an order of magnitude higher than the doses used to cause scission in the polymer for positive tone exposure In the case of PMMA exposure of electrons at up to more than 1000 mC cm the gradation curve corresponds to the curve of a normal positive process Above 2000 mC cm the recombinant crosslinking process prevails and at about 7000 mC cm the layer is completely crosslinked which makes the layer more insoluble than the unexposed initial layer If negative PMMA structures should be used a stronger developer than for the positive process is required 30 Such large dose increases may be required to avoid shot noise effects 31 32 33 A study performed at the Naval Research Laboratory 34 indicated that low energy 10 50 eV electrons were able to damage 30 nm thick PMMA films The damage was manifest as a loss of material For the popular electron beam resist ZEP 520 a pitch resolution limit of 60 nm 30 nm lines and spaces independent of thickness and beam energy was found 35 A 20 nm resolution had also been demonstrated using a 3 nm 100 keV electron beam and PMMA resist 36 20 nm unexposed gaps between exposed lines showed inadvertent exposure by secondary electrons Hydrogen silsesquioxane HSQ is a negative tone resist that is capable of forming isolated 2 nm wide lines and 10 nm periodic dot arrays 10 nm pitch in very thin layers 37 HSQ itself is similar to porous hydrogenated SiO2 It may be used to etch silicon but not silicon dioxide or other similar dielectrics In 2018 a thiol ene resist was developed that features native reactive surface groups which allows the direct functionalization of the resist surface with biomolecules 38 New frontiers editTo get around the secondary electron generation it will be imperative to use low energy electrons as the primary radiation to expose resist Ideally these electrons should have energies on the order of not much more than several eV in order to expose the resist without generating any secondary electrons since they will not have sufficient excess energy Such exposure has been demonstrated using a scanning tunneling microscope as the electron beam source 39 The data suggest that electrons with energies as low as 12 eV can penetrate 50 nm thick polymer resist The drawback to using low energy electrons is that it is hard to prevent spreading of the electron beam in the resist 40 Low energy electron optical systems are also hard to design for high resolution 41 Coulomb inter electron repulsion always becomes more severe for lower electron energy nbsp Scanning probe lithography A scanning probe can be used for low energy electron beam lithography offering sub 100 nm resolution determined by the dose of low energy electrons Another alternative in electron beam lithography is to use extremely high electron energies at least 100 keV to essentially drill or sputter the material This phenomenon has been observed frequently in transmission electron microscopy 42 However this is a very inefficient process due to the inefficient transfer of momentum from the electron beam to the material As a result it is a slow process requiring much longer exposure times than conventional electron beam lithography Also high energy beams always bring up the concern of substrate damage Interference lithography using electron beams is another possible path for patterning arrays with nanometer scale periods A key advantage of using electrons over photons in interferometry is the much shorter wavelength for the same energy Despite the various intricacies and subtleties of electron beam lithography at different energies it remains the most practical way to concentrate the most energy into the smallest area There has been significant interest in the development of multiple electron beam approaches to lithography in order to increase throughput This work has been supported by SEMATECH and start up companies such as Multibeam Corporation 43 Mapper 44 and IMS 45 IMS Nanofabrication has commercialized the multibeam maskwriter and started a rollout in 2016 46 See also editElectron beam technology Ion beam lithography Maskless lithography PhotolithographyReferences edit McCord M A M J Rooks 2000 2 SPIE Handbook of Microlithography Micromachining and Microfabrication Parker N W et al 2000 Dobisz Elizabeth A ed High throughput NGL electron beam direct write lithography system Proc SPIE Emerging Lithographic Technologies IV 3997 713 Bibcode 2000SPIE 3997 713P doi 10 1117 12 390042 S2CID 109415718 Faster and lower cost for 65 nm and 45 nm photomask patterning dead link M L Kempsell et al J Microlith Nanolith MEMS MOEMS vol 8 043001 2009 H Sunaoshi et al Prof SPIE vol 6283 628306 2006 K Ugajin et al Proc SPIE vol 6607 66070A 2007 F T Chen et al Proc SPIE vol 8683 868311 2013 The Significance of Point Spread Functions with Stochastic Behavior in Electron Beam Lithography K Ichimura et al Proc SPIE 12293 122930Q 2022 L Feldman J Mayer 1986 Fundamentals of Surface and Thin Film Analysis Vol 54 North Holland pp 130 133 ISBN 978 0 444 00989 0 Mason Nigel J Dujardin G Gerber G Gianturco F Maerk T D January 2008 EURONanochem Chemical Control at the Nanoscale Slovenian Research Agency European Space Foundation Archived from the original on 2011 07 20 Stoffels E Stoffels W W Kroesen G M W 2001 Plasma chemistry and surface processes of negative ions Plasma Sources Science and Technology 10 2 311 Bibcode 2001PSST 10 311S CiteSeerX 10 1 1 195 9811 doi 10 1088 0963 0252 10 2 321 S2CID 250916447 Seah M P Dench W A 1979 Quantitative electron spectroscopy of surfaces A standard data base for electron inelastic mean free paths in solids Surface and Interface Analysis 1 2 doi 10 1002 sia 740010103 Tanuma S Powell C J Penn D R 1994 Calculations of electron inelastic mean free paths V Data for 14 organic compounds over the 50 2000 eV range Surface and Interface Analysis 21 3 165 doi 10 1002 sia 740210302 a b Broers A N et al 1996 Electron beam lithography Resolution limits Microelectronic Engineering 32 1 4 131 142 doi 10 1016 0167 9317 95 00368 1 K W Lee 2009 Secondary electron generation in electron beam irradiated solids resolution limits to nanolithography J Korean Phys Soc 55 4 1720 Bibcode 2009JKPS 55 1720L doi 10 3938 jkps 55 1720 Archived from the original on 2011 07 22 SPIE Newsroom Double exposure makes dense high resolution diffractive optics Spie org 2009 11 03 Retrieved on 2011 08 27 Dapor M et al 2010 Monte Carlo modeling in the low energy domain of the secondary electron emission of polymethylmethacrylate for critical dimension scanning electron microscopy J Micro Nanolith MEMS MOEMS 9 2 023001 doi 10 1117 1 3373517 P T Henderson et al 1999 Long distance charge transport in duplex DNA The phonon assisted polaron like hopping mechanism Proc Natl Acad Sci U S A 96 15 8353 8358 Bibcode 1999PNAS 96 8353H doi 10 1073 pnas 96 15 8353 PMC 17521 PMID 10411879 H Seiler 1983 Secondary electron emission in the scanning electron microscope J Appl Phys 54 11 R1 R18 Bibcode 1983JAP 54R 1S doi 10 1063 1 332840 G Denbeaux et al 2013 International Workshop on EUV Lithography Complexities of the Resolution Limits of Advanced Lithography Resolution Limits Electron Blur Impact on Electron Beam and EUV Lithography M Chandramouli et al Proc SPIE 12293 122930O 2022 J A Liddle et al 2003 Resist Requirements and Limitations for Nanoscale Electron Beam Patterning Mater Res Soc Symp Proc 739 19 19 30 Ivin V 2002 The inclusion of secondary electrons and Bremsstrahlung X rays in an electron beam resist model Microelectronic Engineering 61 62 343 doi 10 1016 S0167 9317 02 00531 2 Yamazaki Kenji Kurihara Kenji Yamaguchi Toru Namatsu Hideo Nagase Masao 1997 Novel Proximity Effect Including Pattern Dependent Resist Development in Electron Beam Nanolithography Japanese Journal of Applied Physics 36 12B 7552 Bibcode 1997JaJAP 36 7552Y doi 10 1143 JJAP 36 7552 S2CID 250783039 Renoud R Attard C Ganachaud J P Bartholome S Dubus A 1998 Influence on the secondary electron yield of the space charge induced in an insulating target by an electron beam Journal of Physics Condensed Matter 10 26 5821 Bibcode 1998JPCM 10 5821R doi 10 1088 0953 8984 10 26 010 S2CID 250739239 J N Helbert et al Macromolecules vol 11 1104 1978 M J Wieland et al Proc SPIE vol 7271 72710O 2009 F T Chen et al Proc SPIE vol 8326 83262L 2012 P Kruit et al J Vac Sci Tech B 22 2948 2004 Bermudez V M 1999 Low energy electron beam effects on poly methyl methacrylate resist films Journal of Vacuum Science and Technology B 17 6 2512 Bibcode 1999JVSTB 17 2512B doi 10 1116 1 591134 H Yang et al Proceedings of the 1st IEEE Intl Conf on Nano Micro Engineered and Molecular Systems pp 391 394 2006 Cumming D R S Thoms S Beaumont S P Weaver J M R 1996 Fabrication of 3 nm wires using 100 keV electron beam lithography and poly methyl methacrylate resist Applied Physics Letters 68 3 James Watt Nanofabrication Centre 322 Bibcode 1996ApPhL 68 322C doi 10 1063 1 116073 a href Template Cite journal html title Template Cite journal cite journal a External link in code class cs1 code issue code help Manfrinato Vitor R Zhang Lihua Su Dong Duan Huigao Hobbs Richard G Stach Eric A Berggren Karl K 2013 Resolution limits of electron beam lithography toward the atomic scale PDF Nano Lett 13 4 1555 1558 Bibcode 2013NanoL 13 1555M doi 10 1021 nl304715p hdl 1721 1 92829 PMID 23488936 S2CID 1060983 Shafagh Reza Vastesson Alexander Guo Weijin van der Wijngaart Wouter Haraldsson Tommy 2018 E Beam Nanostructuring and Direct Click Biofunctionalization of Thiol Ene Resist ACS Nano 12 10 9940 9946 doi 10 1021 acsnano 8b03709 PMID 30212184 S2CID 52271550 C R K Marrian 1992 Electron beam lithography with the scanning tunneling microscope Journal of Vacuum Science and Technology 10 B 2877 2881 Bibcode 1992JVSTB 10 2877M doi 10 1116 1 585978 T M Mayer et al 1996 Field emission characteristics of the scanning tunneling microscope for nanolithography Journal of Vacuum Science and Technology 14 B 2438 2444 Bibcode 1996JVSTB 14 2438M doi 10 1116 1 588751 L S Hordon et al 1993 Limits of low energy electron optics Journal of Vacuum Science and Technology 11 B 2299 2303 Bibcode 1993JVSTB 11 2299H doi 10 1116 1 586894 Egerton R F et al 2004 Radiation damage in the TEM and SEM Micron 35 6 399 409 doi 10 1016 j micron 2004 02 003 PMID 15120123 Multibeam Corporation Multibeamcorp com 2011 03 04 Retrieved on 2011 08 27 Mapper Lithography Archived 2016 12 20 at the Wayback Machine Mapper Lithography 2010 01 18 Retrieved on 2011 08 27 IMS Nanofabrications IMS Nanofabrication 2011 12 07 Retrieved on 2019 02 28 IMS Nanofabrications IMS Nanofabrication 2011 12 07 Retrieved on 2019 02 28 Retrieved from https en wikipedia org w index php 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