Friday, June 24, 2022

Hydrogen Peroxide Gas on the road from R&D to HVM for superior HZO films

Device shrinkage, three-dimensional and High Aspect Ratio (HAR) structures, and lower thermal budgets drive the continued search for new materials. A by-product of this search is a need for better oxidants for atomic layer deposition (ALD) and other thin film deposition processes.

While metal usage is rapidly expanding across the periodic table, oxidant choices are few: water, O2, ozone, and oxygen plasma being the leading choices for thin-film processing.

Each oxidant has its strengths and weaknesses. Plasma has limitations with the line of sight and may damage underlying sensitive channel materials or metal interconnects. Ozone is too aggressive with most metals. Water and oxygen are not reactive enough for today’s lower thermal budgets and more demanding precursors. Therefore, new oxidants could help address low-temperature thermal applications and simplify precursor design and selection.

At RASIRC, the investigation began for alternative oxidants when water vapor proved too limited for many ALD applications. Interest in delivering gas generated from hydrogen peroxide liquid began in 2007, with the first commercial sales in 2011 and 2012.

While the perception of the semiconductor industry is one of rapid innovation, the adoption of new technology is a slow process. If successful, it can frequently exceed a decade to reach high volume manufacturing.

Recently, RASIRC presented (April 2022 CMC2022, AZ, USA) benchmarking hydrogen peroxide vs. water and ozone in ALD of ferroelectric hafnium zirconium oxide (HZO). HZO is one of the primary candidate materials for new non-volatile memory using a capacitor device; it can be integrated into both Logic devices and as a stand-alone memory chip similar to Flash memory.

RASIRC and UT Dallas fabricated capacitor structures (MIM) and deposited HZO using water, ozone, or hydrogen peroxide at comparable process conditions.

The first finding was that the growth rate per cycle (GPC, below left) was considerably higher in the hydrogen peroxide case, essentially lowering the overall process time and precursor consumption of rather expensive Hafnium and Zirconium precursors. The hydrogen peroxide HZO films also proved to have a higher density (XRR, below middle) and lower etch rate (wet etch rate below right).


Growth rate per cycles, density by X-ray Reflectivity (XRR) and wet etch rate determination of HZO films deposited by ALD using either hydrogen peroxide, water or ozone.

Higher density metal oxide films are a sure sign of better electrical performance regarding high-k dielectrics and ferroelectrics. First, the hydrogen peroxide films showed a comparably higher effective k-value, lower leakage current (Jg), and could withstand a higher breakdown voltage (VBD), as seen below right. Water results were inferior to both ozone and hydrogen peroxide are not shown for clarity.

Indicative for ferroelectric phase content is a peak at approx. 2T= 30.3 deg and 35.8 (below right). In X-ray diffractograms, when comparing hydrogen peroxide vs. ozone, it[JS1] was shown that the hydrogen peroxide films could show a higher orthorhombic (ferroelectric) phase content at a lower thermal budget, i.e., the onset temperature for crystallization. Even though the orthorhombic ferroelectric phase is metastable over preferred tetragonal and monoclinic HfO2 and ZrO2 most stable phases, this can be understood that the atoms in higher density and purer hydrogen peroxide films will find their optimum positions under given conditions in the lattice faster due to less disturbance from contamination species that has to diffuse out of the lattice before a ferroelectric phase content can crystalize quenching the HZO films into the metastable ferroelectric phase.


Leakage (Jg) vs breakdown voltage (VBD) and gracing incidence x-ray diffraction (GI-XRD) after post deposition anneals for hydrogen peroxide HZO films compared to ozone HZO films.

The promising results above for higher quality ferroelectric films were then proven by complete ferroelectric electric characterization sweeping the current and voltage across the capacitor structures accordingly. As seen below in the P-E hysteresis curves, a clearly defined hysteresis response curve could be verified for hydrogen peroxide HZO films at a lower RTA temperature than for ozone films, the onset of 325 vs. 350 deg C. It may seem like a slight difference, but please keep in mind that the overall thermal budget for device integration in copper interconnect layers is in the range 350 to 390 deg.C depending on layer and technology node, and it is critical to stay below this temperature and as can be seen below this study yielded beautiful ferroelectric hysteresis at 350 deg. C for hydrogen peroxide, whereas ozone films had to go up to the danger zone of 400 deg. To do the same.

P-E hysteresis curves for hydrogen peroxide (right) and ozone (left) ferroelectric HZO films for different RTA thermal budgets.

Finally, TEM analysis showed that films could be downscaled to 5 nm film thickness and most probably below, staying perfectly intact even though a high roughness metal bottom electrode was used. 


High-resolution transmission electron microscopy (HR-TEM) of ferroelectric HZO films deposited by ALD and using RASIRC hydrogen peroxide technology.

To conclude, HZO ferroelectric films showed many advantages when hydrogen peroxide was employed compared to water and ozone:

· Higher device yield as measured in the number of functional ferroelectric capacitors

· Higher density films with lower wet etch rate

· Higher effective k-value

· Faster growth (ALD GPC)

· Lower film thickness for yielding films in electrical testing

· Lower leakage current and higher breakdown voltage

· Crystallization onset for ferroelectric phase content for lower thermal budgets (RTA temperature)

Next you can meet RASIRC at the AVS 22nd International Conference on Atomic Layer Deposition (ALD 2022), will be a three-day meeting 26-29th of July in Ghent Belgium, dedicated to the science and technology of atomic layer-controlled deposition of thin films and now topics related to atomic layer etching. Jeff Spiegelman, CEO of RASIRC will be presenting “Higher Effective Dielectric Constant of Hafnium Oxide When Grown with Hydrogen Peroxide Compared to Water Vapor” in session AF-MoP18 on 27th of June.

About RASIRC

RASIRC transforms liquids into dynamic gases that power process innovation in semiconductor and adjacent markets. By commercializing molecules for lower temperature processes, RASIRC patented technology enables the manufacture of atomic-scale oxides, nitrides, and metals. Innovative products such as BRUTE Peroxide, BRUTE Hydrazine, the Peroxidizer®, and Rainmaker® Humidification Systems are being used to develop solutions for 5G, AI, IOT, and advanced automation.

What makes RASIRC a unique industry leader is our technical expertise and commitment to solving complex industry challenges for our customers. Our team of industry experts has a proven track record of being first to market by efficiently delivering state of the art technology that reduces cost, improves quality, and dramatically improves safety. With our customers at the forefront of all we do, we continue to research, develop, and design innovative products that purify and deliver ultra-pure gas from liquids for the semiconductor and related markets. Contact RASIRC to help solve your complex problems. P: 858-259-1220, email info@rasirc.om or visit http://www.rasirc.com

Wednesday, June 22, 2022

Solar Energy Research Institute of Singapore (SERIS) Opts for SALD

The Solar Energy Research Institute of Singapore (SERIS) gears up perovskite solar cells for industrial tandem cell production

Eindhoven/Netherlands, Singapore, 18 June 2022 - The Solar Energy Research Institute of Singapore (SERIS) at the National University of Singapore (NUS) announces that it will upgrade its "Spatial Atomic Layer Deposition" (SALD) equipment. SoLayTec and SERIS have been working closely together for over a decade in the field of silicon solar cells. Now, SERIS states that SoLayTec will upgrade its existing ALD system using the latest technology of SALD BV, a Dutch technology start-up, for development of scalable perovskite-silicon tandem solar cells.



"Upgrading to the new SALD equipment brings us significant advantages," explains Dr. Shubham Duttagupta, Deputy Director of the Next-Generation Industrial Solar Cells & Modules Cluster at SERIS. The Dutch company SALD BV has developed a unique, patented technology for applying precise coatings on an industrial scale that can be as thin as a single atom. These so-called nanocoatings are promising to revolutionize numerous industrial manufacturing processes, and thus entire branches of industry. In the solar industry, SALD coatings are key for perovskite-silicon tandem solar cells, which can achieve efficiencies far above the theoretical limit of silicon-only solar cells, which are the most widely used solar cells today. It is precisely in this new area where SERIS aims to use the new SALD technology. Thanks to the SALD process, new solar cell materials can be used, including tin oxide and transparent conductive oxides, as well as novel passivation and tunnel recombination layers. The technologies developed by SERIS will be made available to industrial solar cell manufacturers through licensing agreements.



Perovskite solar cells are highly efficient, easy to process and inexpensive to produce, but still face technical challenges regarding their long-term stability. An atomically thin coating, as can be achieved with the SALD technology, makes the cells significantly more robust. SERIS wants to take the leap “from lab to fab”, i.e., from the laboratory environment to large-volume production with the new SALD machine. The potential for perovskite-silicon solar cells is great: According to forecasts, the global market is expected to exceed two billion dollars by 2027.

SALD BV has developed a unique worldwide patented technology for applying coatings that are as thin as a single atom on an industrial scale, termed "Spatial Atomic Layer Deposition" or SALD (www.spatialald.com). These atomically-thin coatings can bring revolutions to entire industries, such as the manufacturing of batteries for cars and smart devices, and the solar energy industry.

Further information: SALD BV, PO Box 520, 5600 AM Eindhoven, The Netherlands,
Web: www.spatialald.com, E-Mail: info@spatialald.com, Tel: +31 40 23 80 500,

contact: Lonneke van Wel, Tel. +31 40 238 05 00, E-mail: lonneke.vanwel@spatialald.com

PR-Agent: euromarcom public relations, Tel. +49611-973150, E-Mail: team@euromarcom.de, Internet: www.euromarcom.de, www.facebook.com/euromarcom (like if you like-:)

NCD supplied ALE and ASD equipment to Samsung Electronics Co., Ltd.

NCD has recently supplied ASD (Area Selective Deposition) equipment to Samsung Electronics Co., Ltd. Following ALE (Atomic Layer Etching).

This is the cluster system which consists of two process modules (PMs) and a wafer transfer module (TM) and applies a running program for process integration. In addition, it is equipped to process at high temperatures up to 500℃ and process with ozone and plasma for developing the next semiconductor devices.

ALE is able to etch a deposited layer by atomic scale as opposed to ALD and ASD can only deposit on the selective area not grow the whole area of substrates by ALD.

Today, lots of universities, institutes, and companies have actively been developing future high-tech and highly integrated devices using ALE and ASD processes.

NCD expects that the ALE/ASD system will contribute very much to the development of high-end semiconductor technology and is going to do all of the efforts to the best ALD equipment company with new challenges and continuous R&D.

<Lucida M200PL Series ALD System>



Thursday, June 16, 2022

Applied Materials Broadens its Technology Portfolio for Specialty Chips with Acquisition of Picosun

SANTA CLARA, Calif., June 16, 2022 – Applied Materials, Inc. today announced it has acquired Picosun Oy, a privately held semiconductor equipment company based in Espoo, Finland. Picosun is an innovator in atomic layer deposition (ALD) technology, primarily for specialty semiconductors.



As electronic products become smarter and more connected, they require greater numbers of specialty semiconductors built on non-leading-edge process nodes. Applied’s ICAPS (IoT, Communications, Automotive, Power and Sensors) group provides materials engineering solutions to customers in these growing markets. The addition of Picosun’s ALD technology broadens the Applied ICAPS product portfolio and customer engagements. Picosun also brings to Applied deep R&D capabilities, talented teams and strong relationships with leading research institutions and universities throughout the world.

“Picosun is a pioneer in ALD technology with products that serve fast-growing segments of the specialty foundry-logic market,” said Gary Dickerson, President and CEO of Applied Materials. “The addition of Picosun complements Applied Materials’ technology portfolio and expands our opportunities to accelerate our customers’ roadmaps.”

“Rapid growth in the number of connected devices is driving a tremendous need for innovation in the chips used to bridge the analog and digital worlds,” said Sundar Ramamurthy, Group Vice President and General Manager of the ICAPS group at Applied Materials. “Bringing Picosun’s talented team to Applied Materials will strengthen our ability to help customers add more intelligence and functionality to a wide variety of edge computing devices.”

“Picosun has a strong history of innovation, with roots dating back to the invention of ALD technology nearly 50 years ago,” said Kustaa Poutiainen, Former Chairman of the Board of Picosun. “As we look ahead to our next phase of growth, we believe starting a new journey as part of Applied Materials – a company we have long admired – is the best path forward and will create exciting opportunities for our employees, customers and research partners.”

The Picosun team will continue to be based in Finland and will report into Applied’s ICAPS group.

The transaction has been approved by the Ministry of Economic Affairs and Employment of Finland; no other regulatory approvals were required. Financial terms of the transaction were not disclosed.

Goldman Sachs & Co. LLC served as financial advisor and Hogan Lovells US LLP served as legal counsel for Applied Materials.

About Applied Materials

Applied Materials, Inc. (Nasdaq: AMAT) is the leader in materials engineering solutions used to produce virtually every new chip and advanced display in the world. Our expertise in modifying materials at atomic levels and on an industrial scale enables customers to transform possibilities into reality. At Applied Materials, our innovations make possible a better future. Learn more at www.appliedmaterials.com.

About Picosun

Picosun provides the most advanced ALD (Atomic Layer Deposition) thin film coating solutions for global industries. Picosun’s ALD solutions enable a technological leap into the future, with turn-key production processes and unmatched, pioneering expertise in the field – dating back to the invention of the technology itself. Today, PICOSUN® ALD equipment are in daily manufacturing use in numerous leading industries around the world. Picosun is based in Finland, with subsidiaries in Germany, USA, Singapore, Japan, South Korea, China mainland and Taiwan, offices in India and France, and a world-wide sales and support network. Visit www.picosun.com.

Electronic Gases Markets – To Approach a US$9 Billion Market in 2022

New materials and increasing chip design complexity drives supply-chain problems for Specialty Gases, Rare Gases and Helium

San Diego, CA, June 15, 2022: TECHCET—the electronic materials advisory firm providing business and technology information— reports that the Electronic Gases market revenues hit US$6.3 billion in 2021 and is forecasted to grow to 8% in 2022. In its recently completed Electronic Gases Report , TECHCET forecasts the 2022 Electronic Gases market will reach almost US$6.8 billion—growth primarily attributed to Specialty Gases. As leading-logic and new generations of memory continue to ramp, Specialty Gases consumed in etching, deposition, chamber cleaning, and other applications remain in strong demand. This segment is forecasted to increase by 10% in 2022 with ~9% CAGR through to 2026, as indicated in TECHCET’s newly released 2022 Critical Materials Report™ on Electronic Gases, authored by Jonas Sundqvist, PhD.


In the near-term, there are supply issues for key industry gases, such as helium and neon; and in the longer term, the supply/demand balance for gases such as nitrogen trifluoride (NF3), tungsten hexafluoride (WF6), and others could tighten as industry demand grows.

Neon supply capacity is at risk due to the Russian invasion of Ukraine. Some gas supply from these sources may be at a permanent loss. Helium supply-chain disruptions stemming from lack of Russian supply availability are starting to have an impact on the semiconductor industry. Russia’s current export ban on helium and rare gases will prolong the supply-chain issues with Helium and rare gases like Neon. The war is only part of the helium supply issue – maintenance problems, delayed product availability, and production disruptions in other helium producing regions are all adding to the tightness in the supply chain.

As new semiconductor device fabs come online globally over the next several years, supply constraints may appear for other gases (B2H6, WF6, NF3, CF-gases) since demand increases are expected to outpace supply. With semiconductor manufacturers increasing fab production capacity, the demand for diborane (B2H6) material is rapidly increasing as it is critical in many device applications such as in doped carbon hard masks.

As more CVD/ALD deposition process passes are added for multi-patterning and EUV-lithography, cleaning demand is increasing, thus we anticipate huge growth in NF3 (used for chamber cleaning). With the current projections, demand may outrun supply causing tightness in NF3 availability come 2025-2026. Similarly, TECHCET estimates there may be supply issues with WF6 around 2025-2026. However, the possibility of molybdenum (Mo) replacing tungsten (W) for memory applications could circumvent any WF6 shortage. WF6 demand is primarily driven by vertical scaling in 3DNAND to higher layer counts, though new interconnect materials could lessen any future supply/demand imbalance.

Among the sources of electronic gases highlighted in TECHCET’s CMR are Air Products, Air Liquide, EMD / Merck, Linde, Matheson Gas, SK Materials, Gazprom, Huate Gas, Peric, and many others. For more details on the Electronic Gases market segments and growth trajectory go to: https://techcet.com/product/gases/

ABOUT TECHCET: TECHCET CA LLC is an advisory services firm focused on process materials supply-chains, electronic materials business, and materials market analysis for the semiconductor, display, solar/PV, and LED industries. Since 2000, the company has been responsible for producing the Critical Material Reports™, covering silicon wafers, semiconductor gases, wet chemicals, CMP consumables, Photoresists, and ALD/CVD Precursors. The Critical Materials Council (CMC) of semiconductor fabricators is a business service offered by TECHCET, and includes materials supplier Associate Members. For additional information about reports, market briefings, CMC membership, or custom consulting please contact info@cmcfabs.org, +1-480-332-8336, or go to www.techcet.com.

Friday, June 10, 2022

Atomic Layer Deposition Expected to Grow to Meet Demand for More-than-Moore Devices and Applications

(Interview by SEMI) Atomic Layer Deposition (ALD) players are poised to seize a new growth opportunity after the chip shortage pushed manufacturers to announce fab capacity expansions worldwide. Geared toward 200mm market needs, 300mm ALD platforms have recently advanced to meet the demand of More-than-Moore (MtM) devices and applications for MEMS, sensors, power and RF devices, photonics. Driven by the wafer production volume increase, ALD solutions are now expected to grow and enter the MtM devices market.



SEMI spoke with Dr. Patrick Rabinzohn, Strategic Development Executive of Semiconductor ALD at Beneq, about the benefits of ALD and shared how Beneq is building a comprehensive ALD product portfolio – from Beneq Transform® to ProdigyTM – covering different device applications and wafer sizes. We also talked about Beneq solutions to customer challenges, thanks to its vision and future trends for MtM devices for ALD.

SEMI: Beneq is already a familiar name in the ALD equipment business. For those new to the brand, please introduce the company.

Rabinzohn: Beneq is the home of atomic layer deposition and has ALD in its DNA. In fact, the very first industrial application of ALD was done in 1984 here on electroluminescent displays – the same location where Beneq still is headquartered today! Beneq was formed in 1984 and today we are a leading provider of ALD solutions for More-than-Moore semiconductor device fabrication with the Beneq Transform®.

Beneq’s state of art applications lab enables proof-of-concept and customer adoption for new ALD processes. Our team of engineers and experts is dedicated to making ALD tools accessible to our customers and partners.

SEMI: Beneq introduced the first Beneq Transform® in late 2019. How has adoption been so far?

Rabinzohn: The Beneq Transform® has revolutionized ALD cluster tools for More-than-Moore semiconductor markets in the EU, the U.S. and Asia since its launch in 2019. As of November 2021, Beneq has seen higher than expected demand for both the Transform and Transform Lite product configurations across key customer regions such as Europe, Japan, China, Taiwan and the U.S. We are super excited to see more customers adopting ALD in their More-than-Moore applications.