Electron beam technology for single nanometer fabrication

Implementation of extreme ultra violet lithography (EUVL) for printing features of dimensions around 32nm and below has faced multiple challenges that have been overcome mostly through tool and process engineering. Currently, the main concern for implementation of EUVL in high volume manufacturing is related to stochastic defects, such as line bridges or breaks, which may occur randomly and have an impact on device performance.1 Photon shot noise, in addition to the inherent process variability and material non-homogeneities can lead to defects on the final patterned structures. As the pitch and critical dimension (CD) approach 32nm pitch and below, the dependency of stochastics defects increases exponentially. This paper fits within imec’s EUV stochastics and defectivity program, which investigates the key parameters for the generation and mitigation of defects from both a theoretical and practical approach. Initially, a reference process has been established and a methodology has been developed to capture and characterize bridge-type defects after pattern transfer into relevant layers for metrology and applications. Optical inspection and scanning electron microscopy (SEM) review are used to collect information on the number and types of defects present over large patterned areas (in the order of cm2). With a well-defined inspection technique, experiments related to fundamentals as well as materials and processes are continuously run. In the past years, imec has been leading the fundamental work on stochastic defects.2,3 De Bisschop et al. identified the “defect cliff”, or the exponential dependency of defect density as a function of space CD for multiple parameters, such as resist formulation and exposure/imaging conditions. More recently, the focus has changed to the investigation of the “defect floor”, which as the name suggests, is a flat response of defects to CD. The defect floor suggests that defectivity cannot be further improved, making one of the most relevant problems to solve for implementation of EUV in high volume manufacturing (HVM). Our results show a decomposition of the potential contributors to explore the effect of processing conditions related to scanner, track and pattern transfer on final defect density for a chemically amplified resist and attempt a comparison to a metal-oxide resist. Goal is to understand the contributors to the defect floor and identify an effective route to avoid/minimize defect formation.

Extreme ultraviolet (EUV) lithography is crucial to enabling technology scaling in pitch and critical dimension (CD). Currently, one of the key challenges of introducing EUV lithography to high volume manufacturing (HVM) is throughput, which requires high source power and high sensitivity chemically amplified photoresists. Important limiters of high sensitivity chemically amplified resists (CAR) are the effects of photon shot noise and resist blur on the number of photons received and of photoacids generated per feature, especially at the pitches required for 7 nm and 5 nm advanced technology nodes. These stochastic effects are reflected in via structures as hole-to-hole CD variation or local CD uniformity (LCDU). Here, we demonstrate a synergy of film stack deposition, EUV lithography, and plasma etch techniques to improve LCDU, which allows the use of high sensitivity resists required for the introduction of EUV HVM. Thus, to improve LCDU to a level required by 5 nm node and beyond, film stack deposition, EUV lithography, and plasma etch processes were combined and co-optimized to enhance LCDU reduction from synergies. Test wafers were created by depositing a pattern transfer stack on a substrate representative of a 5 nm node target layer. The pattern transfer stack consisted of an atomically smooth adhesion layer and two hardmasks and was deposited using the Lam VECTOR PECVD product family. These layers were designed to mitigate hole roughness, absorb out-of-band radiation, and provide additional outlets for etch to improve LCDU and control hole CD. These wafers were then exposed through an ASML NXE3350B EUV scanner using a variety of advanced positive tone EUV CAR. They were finally etched to the target substrate using Lam Flex dielectric etch and Kiyo conductor etch systems. Metrology methodologies to assess dimensional metrics as well as chip performance and defectivity were investigated to enable repeatable patterning process development. Illumination conditions in EUV lithography were optimized to improve normalized image log slope (NILS), which is expected to reduce shot noise related effects. It can be seen that the EUV imaging contrast improvement can further reduce post-develop LCDU from 4.1 nm to 3.9 nm and from 2.8 nm to 2.6 nm. In parallel, etch processes were developed to further reduce LCDU, to control CD, and to transfer these improvements into the final target substrate. We also demonstrate that increasing post-develop CD through dose adjustment can enhance the LCDU reduction from etch. Similar trends were also observed in different pitches down to 40 nm. The solutions demonstrated here are critical to the introduction of EUV lithography in high volume manufacturing. It can be seen that through a synergistic deposition, lithography, and etch optimization, LCDU at a 40 nm pitch can be improved to 1.6 nm (3-sigma) in a target oxide layer and to 1.4 nm (3-sigma) at the photoresist layer.

Electron Beam Induced Deposition (EBID) allows deposition of three-dimensional micro- and nano-structures of conductive and insulating materials on a wide range of substrates. The process is based on the decomposition of molecules of a pre-selected precursor by a focused electron beam. In recent decades EBID of several metals, namely Au, W, Cu and Pt, from different families of precursors, has been achieved and the technique has found some application for small-scale production of laboratory devices and for repair of masks and micro-optoelectronic devices. The weak point of the technique is at present the low purity of the deposited material, caused by metal-organic precursors and by the lack of selectivity of the electron-induced decomposition process. This work is dedicated to EBID of Rh nanostructures from the precursor [RhCl(PF3)2]2. High metal content deposits are expected because the precursor does not contain C atoms and because Rh is one of the less reactive metals. [RhCl(PF3)2]2 as EBID precursor has been characterized by vapor pressure, mass spectrometry and surface residence time measurements. The vapor pressure of 7.5 Pa at room temperature reveals that the precursor is sufficiently volatile for room temperature EBID. The knowledge of the vapor pressure allows also to estimate the number of precursor molecules delivered to the reaction area per unit time. Mass spectrometry measurements allow to know the decomposition path of the precursor under electron impact in the gas phase. The measured spectrum indicates that the molecule decomposes by successive loss of PF3 groups, as confirmed by density functional theory calculations. This is compatible with a high metal content deposit. Residence time measurements show that [RhCl(PF3)2]2 does not decompose on stainless steel surfaces. The measured residence time of 2 ms allows to estimate that the activation energy for desorption of [RhCl(PF3)2]2 on stainless steel is about 0.6 eV and that precursor molecules can travel distances in the micrometer range before being desorbed. EBID structures obtained from [RhCl(PF3)2]2 have been characterized with a wide range of techniques for a better knowledge of the material properties and the deposition process. The deposit morphology has been studied by Transmisssion Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) to characterize the different steps of the deposition process. Crystallographic analysis is carried out by TEM in diffraction mode. Chemical analysis is carried out by Auger Electron Spectroscopy (AES) and Electron Energy Loss Spectroscopy (EELS). Morphological analysis of deposits carried out at different exposure times reveals that the first phase of the growth process, in close proximity to the substrate, is characterized by an increase of the deposit height and the deposit diameter. On the other hand the second phase of the growth process is characterized by increasing height and constant diameter. TEM contrast profiles of dots and Atomic Force Microscopy (AFM) sections of lines have clearly shown that the EBID rate is highest in the center of the beam and decreases in the peripheral regions. Deposition at variable distances from the precursor source allowed to obtain hollow structures, whose morphology reveals that the precursor reaches the reaction area mainly by direct gas phase transport. Structural analysis and TEM revealed that, independently of the deposition conditions, the deposited material is made up of Rh nanocrystals immersed in a lighter amorphous matrix. Chemical analysis by Auger Electron Spectroscopy revealed that, after removal of the C rich contamination layer by Ar ion sputtering, the average composition of the deposits is about: 60 at.% Rh, 20 at.% P, 5 at.% Cl, 7 at.% N, 8 at.% O. The absence of C and the presence of N and O in the deposit bulk have been confirmed by Electron Energy Loss Spectroscopy. This technique allowed also to prove that Rh is dominant also in deposits of sub-micrometer size (not analyzable with AES) and to determine the elemental distribution in the deposit with nanometer resolution. Comparison of the deposit composition and the positive ions detected by mass spectrometry revealed that EBID, compared to low pressure gas phase ionization, involves a higher number of events, i.e. multi-electron decomposition and rearrangements of partially decomposed species.

Presented here is the novel use of thermoplastic siloxane copolymers as nanoimprint lithography (NIL) resists for 60 nm features. Two of the most critical steps of NIL are mold release and pattern transfer through dry etching. These require that the NIL resist have low surface energy and excellent dry‐etching resistance. Homopolymers traditionally used in NIL, such as polystyrene (PS) or poly(methyl methacrylate) (PMMA), generally cannot satisfy all these requirements as they exhibit polymer fracture and delamination during mold release and have poor etch resistance. A number of siloxane copolymers have been investigated for use as NIL resists, including poly(dimethylsiloxane)‐block‐polystyrene (PDMS‐b‐PS), poly(dimethylsiloxane)‐graft‐poly(methyl acrylate)‐co‐poly(isobornyl acrylate) (PDMS‐g‐PMA‐co‐PIA), and PDMS‐g‐PMMA. The presence of PDMS imparts the materials with many properties that are favorable for NIL, including low surface energy for easy mold release and high silicon content for chemical‐etch resistance—in particular, extremely low etch rates (comparable to PDMS) in oxygen plasma, to which organic polymers are quite susceptible. These properties give improved NIL results.

In 2019, finally, extreme ultraviolet (EUV) lithography has been applied to high volume manufacturing (HVM) for preparing advanced semiconductor devices. That was very important year for EUV enthusiasts and semiconductor industry. Because it takes for a long time, more than 30 years, to study EUV lithography for realizing HVM. With recent rapid progress on the source power improvement, EUV lithography development including photoresist materials has been achieved HVM requirements. However, the performance of EUV resist materials are still not enough for the expected HVM requirements, even by using the latest qualifying EUV resist materials. One of the critical issues is the stochastic issues, which will be become ‘defectivity’, like a nano-bridge or a nano-pinching. The analyzing summary of the stochastic factors in EUV lithography, and their improvement status are described in this paper. 2 (two) major stochastic issues, which are photon stochastic and chemical stochastic, were observed in the lithography steps. And the improvement status of each stochastic issues including lithographic results are also described.

In this thesis, nanometer scale semiconductor lasers and micrometer scale polymer based dye lasers are our focus in bringing the miniaturized lasers to applications in data transmission; ultra-small chemical / biological sensors; and ultra-compact spectroscopic sources. Combining the advantage of electrically driven semiconductor lasers and the advantage of a broad emission spectrum of dye molecules would utilize the highly dense multi-functional lab-on-a-chip by integrating microfluidic PCR, microfluidic fluorescent detection system, and compact visible and NIR detectors which are commercially available. On the other hand, in the meantime of pushing the size limit of the laser cavities, new phenomena with the nanoscale lasers enable further exploration and understanding in fundamental physics. In the first part of this thesis, two sub-micron scale semiconductor lasers are presented. The smallest lasers utilizing the disk structures—with diameters of approximately 600 nm—were realized in the InGaP/InGaAlP quantum well material system at room temperature, featuring ultra-small mode volumes of approximately 0.03 cubic?microns, and exhibiting single-mode operation at low threshold powers. And the first visible photonic crystal ultra-small mode volume lasers, with cavity volumes of approximately 0.01 cubic?microns, are realized in the same material system. They are ideally suited for use as spectroscopic sources and both of them can be lithographically tuned from 650 – 690 nm. In the second part of this thesis, two sub-millimeter-scale polymer-based dye lasers—a poly(dimethylsiloxane) (PDMS)-based mechanically tunable DFB dye laser and a poly(methylmethacrylate) (PMMA)-based second-order circular grating distributed feedback dye laser—are presented. Both of them are compatible with microfluidic technology, which gives freedom in integrating the lasers with the microfluidic chips. Compared to the soft lithography used in the PDMS-based dye laser, the nanoimprint lithography used in the PMMA-based dye laser would be more useful for fabricating ultra-small dye lasers and enabling mass production in the near future. At the end of the thesis, a nano-linewidth metal grating mask pattern transferred transient grating (MPT-TG) technique is described as a potential technique using the ultra-small lasers for molecular-dynamics study in solutions.

Photomask used for optical lithography has been developed for purpose of fabrication a pattern along with finer designed rules and increase the productivity. With regard to pattern fabrication on mask, EB (Electron beam) mask writer has been used because it has high resolution beam. But in producing photomask, minimum pattern size on mask is hits a peak around 40nm by the resolution limit of ArF immersion systems. This value is easy to achieve by current EB writer. So, photomask process with EB writer has gotten attached to increase turnaround time. In next generation lithography such as EUV (Extreme ultraviolet) lithography and Nano-imprint lithography, it is enable to fabricate finer pattern beyond the resolution limit of ArF immersion systems. Thereby the pattern on a mask becomes finer rapidly. According to ITRS 2012, fabrication of finer patterns less than 20nm will be required on EUV mask and on NIL template. Especially in NIL template, less than 15nm pattern will be required half a decade later. But today’s development of EB writer is aiming to increase photomask’s productivity, so we will face a difficulty to fabricate finer pattern in near future. In this paper, we examined a potential of mask production process with EB writer from the view of finer pattern fabrication performances. We succeeded to fabricate hp (half-pitch) 17nm pattern on mask plate by using VSB (Variable Shaped Beam) type EB mask writer with CAR (Chemically Amplified Resist). This result suggests that the photomask fabrication process has the potential for sub-20nm generation mask production.

In this paper the bias table models for the wafer scale SmartNIL™ technology are addressed and validated using complete Scanning Electron Microscopy (SEM) characterizations and polynomial interpolation functions. Like the other nanoimprint lithography (NIL) technics, this replication technology is known to induce Critical Dimension (CD) variations between the master and the imprint, due to polymer shrinkage, soft stamp deformation or thermal expansion. The bias between the former and final object follows peculiar rules which are specific to this process. To emphasis these singularities, Critical Dimension (CD) uniformity analyses were analyzed onto 200 mm wafers imprinted with the HERCULES® NIL equipment platform. Dedicated masters were manufactured to capture the process signatures: horizontal and vertical line arrays, local densities ranging from 0.1 to 0.9 and minimum CD of 250 nm. The silicon masters were manufactured with 248 optical lithography and dry etching and treated with an anti-sticking layer from Arkema. CD measurements were made for the master and the replicates on 48 well selected features to build interpolations. The bias table, modelled by polynomial functions with a degree of 5 for the density and a degree of 3 for the CD, are compared between horizontal and vertical features, and between the center and the edge of the wafers. Finally the focus is made on the validation of the interpolations by comparing the computed bias and the experimental data.

Semiconductor scaling is slowing down because of difficulties of device manufacturing below logic 7nm node generation. Various lithography candidates which include ArF immersion with resolution enhancement technology (like Inversed Lithography technology), Extreme Ultra Violet lithography and Nano Imprint lithography are being developed to address the situation. In such advanced lithography, shot counts of mask patterns are estimated to increase explosively in critical layers, and then it is hoped that multi beam mask writer (MBMW) is released to handle them within realistic write time. However, ArF immersion technology with multiple patterning will continue to be a mainstream lithography solution for most of the layers. Then, the shot counts in less critical layers are estimated to be stable because of the limitation of resolution in ArF immersion technology. Therefore, single beam mask writer (SBMW) can play an important role for mask production still, relative to MBMW. Also the demand of SBMW seems actually strong for the logic 7nm node. To realize this, we have developed a new SBMW, EBM-9500 for mask fabrication in this generation. A newly introduced electron beam source enables higher current density of 1200A/cm2. Heating effect correction function has also been newly introduced to satisfy the requirements for both pattern accuracy and throughput. In this paper, we will report the configuration and performance of EBM-9500.

Nanoimprint lithography (NIL), as a non-conventional pattern transfer technique, presents unique competitiveness in the fabrication of semiconductor structures for medium-to-low resolution, cost-sensitive, and high-volume applications, owing to its advantages in high resolution, high throughput, low cost, and scalability. Compared with conventional lithography, NIL achieves high-precision pattern transfer beyond the optical diffraction limitation by directly imprinting and transferring patterns through mechanical contact, without relying on complex optical systems, thereby significantly reducing equipment and operational costs. This article systematically reviews the fundamental principles of NIL and its major process types, including thermal nanoimprint lithography (T-NIL), ultraviolet nanoimprint lithography (UV-NIL), and roller nanoimprint lithography (R-NIL), elaborating on the characteristics and applicable scenarios of each in terms of resolution, process conditions, substrate compatibility, throughput, and cost. Furthermore, a multi-dimensional comparison is conducted to analyze NILs competitive positioning within the current universal lithography technology landscape, while potential future development directions are outlined. Although NIL still faces challenges such as limited mold lifetime and pattern flexibility, advancements in material engineering, process optimization, and technology integration are expected to broaden its industrialization prospects.

Nanoelectrodes for Molecular Devices: A Controllable Fabrication

Pattern transfer by deep anisotropic etch is a well-established technique for fabrication of nanoscale devices and structures. For this technique to be effective, the resist material plays a key role and must have a high resolution, reasonable sensitivity, and high etch selectivity against the conventional silicon substrate or underlayer film. In this work, the lithographic performance of two high etch resistance materials was evaluated: ZEP520A (Nippon Zeon Co.) and mr-PosEBR (micro resist technology GmbH). Both materials are positive tone, polymer-based, and nonchemically amplified resists. Two exposure techniques were used: electron beam lithography (EBL) and extreme ultraviolet (EUV) lithography. These resists were originally designed for EBL patterning, where high quality patterning at sub-100 nm resolution was previously demonstrated. In the scope of this work, the authors also aim to validate their extendibility to EUV for high resolution and large area patterning. For this purpose, the same EBL process conditions were employed at EUV. The figures of merit, i.e., dose to clear, dose to size, and resolution, were obtained, and these results are discussed systematically. It was found that both materials are very fast at EUV (dose to clear lower than 12 mJ/cm2) and are capable of resolving dense lines/space arrays with a resolution of 25 nm half-pitch. The quality of patterns was also very good, and the sidewall roughness was below 6 nm. Interestingly, the general-purpose process used for EBL can be extended straightforwardly to EUV lithography with comparably high quality and yield. Our findings open new possibilities for lithographers who wish to devise novel fabrication schemes exploiting EUV for fabrication of nanostructures by deep etch pattern transfer.

Deep-learning-based SEM image denoiser Dorin Cerbu1, Sandip Halder1, Philippe Leray1 1IMEC, Kapeldreef 75, B-3001 Leuven, Belgium We report the development of a new method to denoise SEM images with the help of artificial neural networks. Upon using a preprocessing and training scheme tailored for SEM images of structures, most often encountered in semiconductor manufacturing, we can efficiently denoise images affected with varying degrees of noise severity and origin. In the figure below, we show an example of how we can use this filter efficiently to treat noisy images and improve the image quality. This can help in acquisition of more stable and better metrology data. Fig1(a) original image (b) Image which has been denoised using deep-learning based algorithms This development is of utmost importance for the case of post-litho processing step where resist nanostructures when SEM inspected are usually impacted by the electron beam and shrink, hence skewing critical dimension measurements. This is especially true as we push towards sub N-10 nm nodes. Application of our deep-learning processing scheme allows efficient noise reduction on SEM inspection images and helps us discern minor details previously shadowed by noise. This is extremely important as we move towards using EUV in high volume manufacturing. Small details can be crucial to understand the root-cause of stochastic and process defects. In previous work, we have already shown different approaches to understand stochastic defects [1-2]. The goal of this work is to enhance the image quality as much as possible to gain further fundamental understanding on nano-defects. [1] S. Halder et. al., ‘Using machine learning techniques to understand EUV stochastics, SPIE Photomask Technology + Extreme Ultraviolet Lithography, 2018 [2] K. Sah et.al., ‘EUV stochastic defect monitoring with advanced Broadband optical wafer inspection and e-Beam review systems’, SPIE Photomask Technology + Extreme Ultraviolet Lithography, 2018

Electron beam induced deposition (EBID) is a promising technique for fabricating nanometre-sized structures in a position-controlled manner. In this technique, organometallic precursors are decomposed by focused electron beams. Then, the non-volatile part of the decomposed precursor deposits on the substrate. As electron beams can be focused to a subnanometre scale in modern electron microscopes, the resolution of EBID is now reaching down to subnanometres. However, the deposits generally contain a large amount of amorphous carbon. This carbon contamination may be the most serious drawback and is preventing practical uses of EBID in nanodevice technology. In this study, nanostructures, such as nanowires, were fabricated by EBID using methyl cyclopenta dienyl platinum trimethyl (MeCpPtMe3) and iron pentacarbonyl (Fe(CO)5) precursors in a scanning electron microscope with a custom-made gas introduction system. After the deposition, nanostructures were heated at 400°C in air for 30 min. to remove contaminated carbon. Then, the nanostructures were observed using a transmission electron microscope (TEM). TEM observation revealed that a post-deposition heat-treatment in air resulted in the removal of carbon. The nanostructures made from MeCpPtMe3 and Fe(CO)5 became pure Pt and a mixture of hematite and maghemite iron oxides, respectively.

The following topics are dealt with: low-power electronics; Internet of Things; integrated circuit design; video coding; integrated circuit manufacture; CMOS integrated circuits; field programmable gate arrays; magnetic sensors; calibration; power consumption.