Analysis of "Erratum: “History of atomic layer deposition and its relationship with the American Vacuum Society” [J. Vac. Sci. Technol. A 31, 050818 (2013)]"

A correction has been recently published related to a scientific review article on the history of atomic layer deposition (ALD). The correction is entitled "Erratum: “History of atomic layer deposition and its relationship with the American Vacuum Society” [J. Vac. Sci. Technol. A 31, 050818 (2013)]" and it is authored by G. N. Parsons, J. W. Elam,  S. M. George, S. Haukka,  H. Jeon,  W. M. M. Kessels,  M. Leskelä, P. Poodt, M. Ritala, and S. M. Rossnagel. It is published in Journal of Vacuum Science & Technology A 38 (2020) 037001; https://doi.org/10.1116/6.0000143. As the title indicates, the article corrects an article published earlier in the same journal, by the same authors: Journal of Vacuum Science & Technology A 31 (2013) 050818; https://doi.org/10.1116/1.4816548.

This blog post analyses, what exactly has changed.

Paragraph corrected describing the early days of the molecular layering origin of ALD

The publication (https://doi.org/10.1116/6.0000143) says that the first two and the last two sentences of the fourth paragraph of Section II, which describes molecular layering, are changed. 

The new, updated paragraph has not been recreated in full. To help the scientific ALD community, I have here attempted to recreate the corrected paragraph.
This involved replacing the first three (not two) and the last two sentences of the said paragraph.

Below, first, the paragraph is presented in the final corrected form, as I think the authors have intended. Two new references have been added, meaning that the reference list had to be recreated/renumbered and the numbering of references is not the same as in the original publication. Second, for clarity, a version is presented with corrected text underlined and the changed parts highlighted in blue and the removed text in grey, strikethrough and the changed text in red.

1. Corrected paragraph of the JVSTA 2013 review (changes not indicated), 
Journal of Vacuum Science & Technology A 31 (2013) 050818; https://doi.org/10.1116/1.4816548, Section II ("Early years of atomic layer processes"), fourth paragraph should read: 

"The ALD principle, where surface reactions follow a binary sequence of self-limiting half-reactions, was reported under the name ‘molecular layering’ in the 1960s by S. I. Kol’tsov from Leningrad Technological Institute [2-6]. These experiments were conducted under the scientific supervision of V. B. Aleskovskii. The ‘framework hypothesis,’ an antecedent to molecular layering, was proposed by V. B. Aleskovskii in 1952 [6]. Based on the early publications from Kol'tsov and Aleskovskii 
[4], the work was initially motivated by the desire to modify the surfaces of sorbents and catalysts. They were able to quantify the reaction between TiCl4 and Si–OH groups on silica gel by titration and colorimetry. The product stoichiometry indicated reaction of 3 Si–OH groups with TiCl4 producing (Si–O)3–Ti units and one Ti–Cl. They later showed [2] that the Ti–Cl group density scaled with the amount of Si–OH present in the initial gel, so that less Si–OH led to more Ti–Cl2 units. Further work published in 1969 described the sequential exposure of TiCl4 and water to form TiO2 [3]. The reaction scheme from that publication is reproduced here in Fig. 4 [3]. Earlier work on this topic may also be available [7]. In the 1969 article [3], the authors report that the initial reaction between TiCl4 and Si–OH tends to involve 3 Si–OH, forming one Ti–Cl, whereas after the first water step, the second TiCl4 exposure reacts with 2 Ti–OH, forming Ti–Cl2 groups. In the 1969 paper [3], a planar thin film was not produced or evaluated, although nanolayers were prepared by molecular layering at that time [6]." 

References:
[2] S. I. Kol’tsov and V. B. Aleskovskii, Russ. J. Phys. Chem. 42, 630 (1968). [3] S. I. Kol’tsov, Zh. Prikl. Khim. 42, 1023 (1969). [4] S. I. Kol’tsov and V. B. Aleskovskii, Zh. Prikl. Khim. 40, 907 (1967). [5] R. L. Puurunen, J. Appl. Phys. 97, 121301 (2005). [6] A. A. Malygin, “The molecular layering method: progress in science and practical works for creation of functional nanomaterials,” in Surface Chemistry in Biomedical and Environmental Science, edited by J. P. Blitz and V. M. GunKo (Springer, Berlin, 2006), Vol. 228, p. 35. [7] S. I. Kol'tsov, G. N. Kuznetsov, and V. B. Aleskovskii, Zh. Prikl. Khim. 40, 2774 (1967). 

2. Corrected paragraph of the JVSTA 2013 review, with changes made indicated, 
Journal of Vacuum Science & Technology A 31 (2013) 050818; https://doi.org/10.1116/1.4816548, Section II ("Early years of atomic layer processes"), fourth paragraph should read: 

"The ALD principle, where surface reactions follow a binary sequence of self-limiting half-reactions, was reported under the name ‘molecular layering’ in the 1960s by S. I. Kol’tsov from Leningrad Technological Institute [2-6]. These experiments were conducted under the scientific supervision of V. B. Aleskovskii. The ‘framework hypothesis,’ an antecedent to molecular layering, was proposed by V. B. Aleskovskii in 1952 [6]. The ALD principle, where surface reactions follow a binary sequence of self-limiting half-reactions, was first published under name “molecular layering” in the early 1960s by Prof. S. I. Kol'tsov from Leningrad Technological Institute [2,3]. These experiments were conducted under the scientific supervision of Prof. V. B. Aleskovskii. The concept of molecular layering was first proposed by Prof. V. B. Aleskovskii in his Ph.D. thesis published in 1952. Based on the early publications from Kol'tsov and Aleskovskii [4], the work was initially motivated by the desire to modify the surfaces of sorbents and catalysts. They were able to quantify the reaction between TiCl4 and Si–OH groups on silica gel by titration and colorimetry. The product stoichiometry indicated reaction of 3 Si–OH groups with TiCl4 producing (Si–O)3–Ti units and one Ti–Cl. They later showed [2] that the Ti–Cl group density scaled with the amount of Si–OH present in the initial gel, so that less Si–OH led to more Ti–Cl2 units. Further work published in 1969 described the sequential exposure of TiCl4 and water to form TiO2 [3]. The reaction scheme from that publication is reproduced here in Fig. 4 [3]. Earlier work on this topic may also be available [7]. In the 1969 article [3], the authors report that the initial reaction between TiCl4 and Si–OH tends to involve 3 Si–OH, forming one Ti–Cl, whereas after the first water step, the second TiCl4 exposure reacts with 2 Ti–OH, forming Ti–Cl2 groups. In the 1969 paper [3], a planar thin film was not produced or evaluated, although nanolayers were prepared by molecular layering at that time [6]. In the 1969 article, the authors report that the initial reaction between TiCl4 and Si–OH tends to involve 3 Si–OH, forming one Ti–Cl, whereas after the first water step, the second TiCl4 exposure reacts with 2 Ti–OH, forming Ti–Cl2 groups. A planar thin film was not produced or evaluated." 

References:
[2] S. I. Kol’tsov and V. B. Aleskovskii, Russ. J. Phys. Chem. 42, 630 (1968). [3] S. I. Kol’tsov, Zh. Prikl. Khim. 42, 1023 (1969). [4] S. I. Kol’tsov and V. B. Aleskovskii, Zh. Prikl. Khim. 40, 907 (1967). [5] R. L. Puurunen, J. Appl. Phys. 97, 121301 (2005). [6] A. A. Malygin, “The molecular layering method: progress in science and practical works for creation of functional nanomaterials,” in Surface Chemistry in Biomedical and Environmental Science, edited by J. P. Blitz and V. M. GunKo (Springer, Berlin, 2006), Vol. 228, p. 35. [7] S. I. Kol'tsov, G. N. Kuznetsov, and V. B. Aleskovskii, Zh. Prikl. Khim. 40, 2774 (1967). 

Identified list of changes made

The content-related changes made, as identified by the undersigned, are listed separately below. The same colour codes are used as above, and the order of appearance is the same. 
1. "first published" has been replaced with "reported". 
2. "in the early 1960s" has been replaced with "in the 1960s".  
3. Two new references have been added to the first sentence: Refs. 5 (Puurunen, 2005) and 6 (Malygin, 2006).
4. The Prof. titles have been left out from Aleskovskii and Koltsov.
5. It is no longer said that Aleskovskii first proposed the concept of molecular layering in 1952. Instead, it is said that Aleskovskii proposed the "framework hypothesis" in 1952, and that the framework hypothesis is an antedecent to molecular layering (ALD).
6. It is no longer suggested that Aleskovskii wrote his PhD thesis in 1952.
7. The reader is no longer guided to think that "planar thin film was not produced or evaluated (by molecular layering)". Instead, it is said that in that particular paper cited from 1969 (Ref. 3), a planar thin film was not produced or evaluated. Additionally, it is noted that nanolayers were prepared by molecular layering in 1969. 

Conclusion 

Earlier, in "(Invited) Learnings from an Open Science Effort: Virtual Project on the History of ALD", ECS Transactions 86 (3) (2018); https://doi.org/10.1149/08606.0003ecst (preprint https://ecsarxiv.org/exyv3/), I listed three items as "needing attention" in the JVSTA 2013 review. All three items have now been corrected. Great thank you to the authors for making the correction - this is important for the scientific ALD community.

I welcome anyone interested in the history of ALD to participate in the Virtual Project on the History of ALD (VPHA). In VPHA we read, write and share comments related to the early works in a co-creation file called ALD-history-evolving-file. Within the framework of VPHA, in addition to the mentioned invited ECS Transactions article, already two essays and one review article have been written (newest first), as listed below. More information in the VPHA website, http://vph-ald.com.

• Review article: “Recommended reading list of early publications on atomic layer deposition—Outcome of the “Virtual Project on the History of ALD””, Esko Ahvenniemi, Andrew R. Akbashev, Saima Ali, Mikhael Bechelany, Maria Berdova, Stefan Boyadjiev, David C. Cameron, Rong Chen, Mikhail Chubarov, Veronique Cremers, Anjana Devi, Viktor Drozd, Liliya Elnikova, Gloria Gottardi, Kestutis Grigoras, Dennis M. Hausmann, Cheol Seong Hwang, Shih-Hui Jen, Tanja Kallio, Jaana Kanervo, Ivan Khmelnitskiy, Do Han Kim, Lev Klibanov, Yury Koshtyal, A. Outi I. Krause, Jakob Kuhs, Irina Kärkkänen, Marja-Leena Kääriäinen, Tommi Kääriäinen, Luca Lamagna, Adam A. Łapicki, Markku Leskelä, Harri Lipsanen, Jussi Lyytinen, Anatoly Malkov, Anatoly Malygin, Abdelkader Mennad, Christian Militzer, Jyrki Molarius, Małgorzata Norek, Çağla Özgit-Akgün, Mikhail Panov, Henrik Pedersen, Fabien Piallat, Georgi Popov, Riikka L. Puurunen, Geert Rampelberg, Robin H. A. Ras, Erwan Rauwel, Fred Roozeboom, Timo Sajavaara, Hossein Salami, Hele Savin, Nathanaelle Schneider, Thomas E. Seidel, Jonas Sundqvist, Dmitry B. Suyatin, Tobias Törndahl, J. Ruud van Ommen, Claudia Wiemer, Oili M. E. Ylivaara, Oksana Yurkevich, Journal of Vacuum Science and Technology A 35 (2017) 010801 (13 pages). http://dx.doi.org/10.1116/1.4971389. Open access.
• Essay by A. A. Malygin, V. E. Drozd, A. A. Malkov, V. M. Smirnov, "From V. B. Aleskovskii’s "Framework" Hypothesis to the Method of Molecular Layering/Atomic Layer Deposition", Chemical Vapor Deposition 21 (2015) 216-240. DOI: 10.1002/cvde.201502013
• Essay by R. L. Puurunen, "A short history of Atomic Layer Deposition: Tuomo Suntola's Atomic Layer Epitaxy", Chemical Vapor Deposition 20 (2014) 332-344. DOI: 10.1002/cvde.201402012. Open Access. 

Espoo, Finland, 

June 9, 2020

Riikka Puurunen

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Virtual Project on the History of ALD (VPHA) - in atmosphere of Openness, Respect, and Trust