Solution Chemistry to Control Boron-Containing Monolayers on Silicon: Reactions of Boric Acid and 4-Fluorophenylboronic Acid with H- and Cl-terminated Si(100)

Silva-Quinones, Dhamelyz; Butera, Robert E.; Wang, George T.; Teplyakov, Andrew V.

doi:10.1021/acs.langmuir.1c00763

Solution Chemistry to Control Boron-Containing Monolayers on Silicon: Reactions of Boric Acid and 4-Fluorophenylboronic Acid with H- and Cl-terminated Si(100)

Journal Article · Tue Jun 01 00:00:00 EDT 2021 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.1c00763· OSTI ID:1822251

Silva-Quinones, Dhamelyz ^[1]; ^[2]; ^[3]; ^[1]

Univ. of Delaware, Newark, DE (United States)
Univ. of Maryland, College Park, MD (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

In this work, the reactions of boric acid and 4-fluorophenylboronic acid with H- and Cl-terminated Si(100) surfaces in solution were investigated. X-ray photoelectron spectroscopy (XPS) studies reveal that both molecules react preferentially with Cl–Si(100) and not with H–Si(100) at identical conditions. On Cl–Si(100), the reactions introduce boron onto the surface, forming a Si–O–B structure. The quantification of boron surface coverage demonstrates that the 4-fluorophenylboronic acid leads to ~2.8 times higher boron coverage compared to that of boric acid on Cl–Si(100). Consistent with these observations, density functional theory studies show that the reaction of boric acid and 4-fluorophenylboronic acid is more favorable with the Cl- versus H-terminated surface and that on Cl–Si(100) the reaction with 4-fluorophenylboronic acid is ~55.3 kJ/mol more thermodynamically favorable than the reaction with boric acid. The computational studies were also used to demonstrate the propensity of the overall approach to form high-coverage monolayers on these surfaces, with implications for selective-area boron-based monolayer doping.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 1822251

Report Number(s):: SAND--2021-8833J; 700072

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 23 Vol. 37; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Boron Monolayer Doping: Role of Oxide Capping Layer, Molecular Fragmentation, and Doping Uniformity at the Nanoscale Tzaguy, Avra; Karadan, Prajith; Killi, Krushnamurty Advanced Materials Interfaces, Vol. 7, Issue 5 https://doi.org/10.1002/admi.201902198	journal	February 2020
Covalent Surface Modification of Oxide Surfaces Pujari, Sidharam P.; Scheres, Luc; Marcelis, Antonius T. M. Angewandte Chemie International Edition, Vol. 53, Issue 25 https://doi.org/10.1002/anie.201306709	journal	May 2014
Correlating the Surface Basicity of Metal Oxides with Photocatalytic Hydroxylation of Boronic Acids to Alcohols Leow, Wan Ru; Yu, Jiancan; Li, Bin Angewandte Chemie International Edition, Vol. 57, Issue 31 https://doi.org/10.1002/anie.201805395	journal	June 2018
A comprehensive study on the physicochemical and electrical properties of Si doped with the molecular doping method: On the physicochemical and electrical properties of doped Si Puglisi, Rosaria A.; Caccamo, Sebastiano; D'Urso, Luisa physica status solidi (a), Vol. 212, Issue 8 https://doi.org/10.1002/pssa.201532030	journal	June 2015
Quantitative analysis of an organic thin film by XPS, AFM and FT-IR: Analyzing organic thin films by XPS, AFM and FT-IR Park, Soon Mi; Yu, Hyunung; Park, Min Gyu Surface and Interface Analysis, Vol. 44, Issue 2 https://doi.org/10.1002/sia.3786	journal	May 2011
Characterization of the nitridation process of boric acid Gouin, X.; Grange, P.; Bois, L. Journal of Alloys and Compounds, Vol. 224, Issue 1 https://doi.org/10.1016/0925-8388(95)01532-9	journal	June 1995
Influence of B2H6/CH4 and B(CH3)3 as process gas on boron carbide coatings: an in situ photoelectron spectroscopy study Künzli, H.; Gantenbein, P.; Steiner, R. Journal of Nuclear Materials, Vol. 196-198 https://doi.org/10.1016/S0022-3115(06)80111-X	journal	December 1992
Organic functionalization of group IV semiconductor surfaces: principles, examples, applications, and prospects Bent, Stacey F. Surface Science, Vol. 500, Issue 1-3 https://doi.org/10.1016/S0039-6028(01)01553-9	journal	March 2002
Challenges and opportunities in chemical functionalization of semiconductor surfaces Gao, Fei; Teplyakov, Andrew V. Applied Surface Science, Vol. 399 https://doi.org/10.1016/j.apsusc.2016.12.083	journal	March 2017
Surface chemistry of thermal dry etching of cobalt thin films using hexafluoroacetylacetone (hfacH) Zhao, Jing; Konh, Mahsa; Teplyakov, Andrew Applied Surface Science, Vol. 455 https://doi.org/10.1016/j.apsusc.2018.05.182	journal	October 2018
Reaction of BCl3 with H- and Cl-terminated Si(1 0 0) as a pathway for selective, monolayer doping through wet chemistry Silva-Quinones, Dhamelyz; He, Chuan; Butera, Robert E. Applied Surface Science, Vol. 533 https://doi.org/10.1016/j.apsusc.2020.146907	journal	December 2020
Fluorine and sulfur co-doped amorphous carbon films to achieve ultra-low friction under high vacuum Wang, Fu; Wang, Liping; Xue, Qunji Carbon, Vol. 96 https://doi.org/10.1016/j.carbon.2015.09.084	journal	January 2016
Calibration of computationally predicted N 1s binding energies by comparison with X-ray photoelectron spectroscopy measurements Leftwich, Timothy R.; Teplyakov, Andrew V. Journal of Electron Spectroscopy and Related Phenomena, Vol. 175, Issue 1-3 https://doi.org/10.1016/j.elspec.2009.07.002	journal	December 2009
Metal-free silicon boride catalyst for oxidative dehydrogenation of light alkanes to olefins with high selectivity and stability Yan, Bing; Li, Wen-Cui; Lu, An-Hui Journal of Catalysis, Vol. 369 https://doi.org/10.1016/j.jcat.2018.11.014	journal	January 2019
Self-assembled monolayers of partially fluorinated alcohols on Si(001): XPS and UV-photoemission study Szwajca, Anna; Krzywiecki, Maciej; Koroniak, Henryk Journal of Fluorine Chemistry, Vol. 180 https://doi.org/10.1016/j.jfluchem.2015.10.009	journal	December 2015
Interfacial modification via boronic acid functionalized self-assembled monolayers for efficient inverted polymer solar cells Kırbıyık, Çisem; Can, Mustafa; Kuş, Mahmut Materials Science in Semiconductor Processing, Vol. 107 https://doi.org/10.1016/j.mssp.2019.104860	journal	March 2020
c-Si solar cells formed from spin-on phosphoric acid and boric acid Yadav, Akash; Singh, Gajendra; Nekovei, Reza Renewable Energy, Vol. 80 https://doi.org/10.1016/j.renene.2015.01.055	journal	August 2015
Chemical manipulation of multifunctional hydrocarbons on silicon surfaces Leftwich, T.; Teplyakov, A. Surface Science Reports https://doi.org/10.1016/j.surfrep.2007.08.001	journal	November 2007
Monolayer Doping of Silicon through Grafting a Tailored Molecular Phosphorus Precursor onto Oxide-Passivated Silicon Surfaces Alphazan, Thibault; Mathey, Laurent; Schwarzwälder, Martin Chemistry of Materials, Vol. 28, Issue 11 https://doi.org/10.1021/acs.chemmater.5b04291	journal	May 2016
Spectroscopic Characterization of Fluorinated Benzylphosphonic Acid Monolayers on AlO _x /Al Surfaces Ford, William E.; Abraham, Ffion; Scholz, Frank The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.6b11089	journal	January 2017
Mechanism of Phosphorus Transport Through Silicon Oxide During Phosphonic Acid Monolayer Doping Longo, Roberto C.; Cho, Kyeongjae; Hohmann, Siegfried The Journal of Physical Chemistry C, Vol. 122, Issue 18 https://doi.org/10.1021/acs.jpcc.8b02545	journal	April 2018
Reaction of Hydrazine with Solution- and Vacuum-Prepared Selectively Terminated Si(100) Surfaces: Pathways to the Formation of Direct Si–N Bonds Silva-Quinones, Dhamelyz; He, Chuan; Dwyer, Kevin J. Langmuir, Vol. 36, Issue 43 https://doi.org/10.1021/acs.langmuir.0c02088	journal	October 2020
Boronic Acid-Functionalized Oxide-Free Silicon Surfaces for the Electrochemical Sensing of Dopamine Fabre, Bruno; Hauquier, Fanny Langmuir, Vol. 33, Issue 35 https://doi.org/10.1021/acs.langmuir.7b00699	journal	July 2017
Universal Calibration of Computationally Predicted N 1s Binding Energies for Interpretation of XPS Experimental Measurements Zhao, Jing; Gao, Fei; Pujari, Sidharam P. Langmuir, Vol. 33, Issue 41 https://doi.org/10.1021/acs.langmuir.7b02301	journal	October 2017
Full Activation of Boron in Silicon Doped by Self-Assembled Molecular Monolayers Gao, Xuejiao; Kolevatov, Ilia; Chen, Kaixiang ACS Applied Electronic Materials, Vol. 2, Issue 1 https://doi.org/10.1021/acsaelm.9b00748	journal	December 2019
Boric Acid as an Efficient Agent for the Control of Polydopamine Self-Assembly and Surface Properties Schneider, Anne; Hemmerlé, Joseph; Allais, Manon ACS Applied Materials & Interfaces, Vol. 10, Issue 9 https://doi.org/10.1021/acsami.7b08356	journal	September 2017
Boronic Acid Functionalized Au Nanoparticles for Selective MicroRNA Signal Amplification in Fiber-Optic Surface Plasmon Resonance Sensing System Qian, Siyu; Lin, Ming; Ji, Wei ACS Sensors, Vol. 3, Issue 5 https://doi.org/10.1021/acssensors.7b00871	journal	May 2018
Surface Modification Using Phosphonic Acids and Esters Queffélec, Clémence; Petit, Marc; Janvier, Pascal Chemical Reviews, Vol. 112, Issue 7 https://doi.org/10.1021/cr2004212	journal	April 2012
Dehydrative Cyclocondensation Reactions on Hydrogen-Terminated Si(100) and Si(111): An ex Situ Tool for the Modification of Semiconductor Surfaces Leftwich, Timothy R.; Madachik, Mark R.; Teplyakov, Andrew V. Journal of the American Chemical Society, Vol. 130, Issue 48 https://doi.org/10.1021/ja802645t	journal	December 2008
Spectroscopic Studies of the Modification of Crystalline Si(111) Surfaces with Covalently-Attached Alkyl Chains Using a Chlorination/Alkylation Method Bansal, Ashish; Li, Xiuling; Yi, Sang I. The Journal of Physical Chemistry B, Vol. 105, Issue 42 https://doi.org/10.1021/jp010284p	journal	October 2001
Infrared and X-ray Photoelectron Spectroscopic Studies of the Reactions of Hydrogen-Terminated Crystalline Si(111) and Si(100) Surfaces with Br ₂ , I ₂ , and Ferrocenium in Alcohol Solvents Haber, Joel A.; Lewis, Nathan S. The Journal of Physical Chemistry B, Vol. 106, Issue 14 https://doi.org/10.1021/jp0102872	journal	March 2002
Chemical and Electrical Passivation of Single-Crystal Silicon(100) Surfaces through a Two-Step Chlorination/Alkylation Process Nemanick, E. Joseph; Hurley, Patrick T.; Webb, Lauren J. The Journal of Physical Chemistry B, Vol. 110, Issue 30 https://doi.org/10.1021/jp056773x	journal	August 2006
Nitroxidation of H-Terminated Si(111) Surfaces with Nitrobenzene and Nitrosobenzene Tian, Fangyuan; Cui, Yuexing; Teplyakov, Andrew V. The Journal of Physical Chemistry C, Vol. 118, Issue 1 https://doi.org/10.1021/jp4102702	journal	December 2013
Building Organic Monolayers Based on Fluorinated Amines on the Si(111) Surface Cui, Yuexing; Tian, Fangyuan; Gao, Fei The Journal of Physical Chemistry C, Vol. 118, Issue 46 https://doi.org/10.1021/jp507158x	journal	November 2014
Aqueous Etching Produces Si(100) Surfaces of Near-Atomic Flatness: Strain Minimization Does Not Predict Surface Morphology Clark, Ian T.; Aldinger, Brandon S.; Gupta, Ankush The Journal of Physical Chemistry C, Vol. 114, Issue 1 https://doi.org/10.1021/jp908527e	journal	December 2009
Switching from a [2 + 2] Cycloaddition-Like to an Ene-Like Reaction in Covalent Attachment of Halogenated Acetonitrile on Si(100)-2×1: Effect of Halogen Substituent Shao, Yan Xia; Dong, Dong; Cai, Ying Hui The Journal of Physical Chemistry C, Vol. 114, Issue 6 https://doi.org/10.1021/jp910314p	journal	January 2010
Surface-Initiated Atom Transfer Radical Polymerization from Halogen-Terminated Si(111) (Si−X, X = Cl, Br) Surfaces for the Preparation of Well-Defined Polymer−Si Hybrids Xu, F. J.; Cai, Q. J.; Kang, E. T. Langmuir, Vol. 21, Issue 8 https://doi.org/10.1021/la0473714	journal	March 2005
Simulation of XPS C1s Spectra of Organic Monolayers by Quantum Chemical Methods Giesbers, Marcel; Marcelis, Antonius T. M.; Zuilhof, Han Langmuir, Vol. 29, Issue 15 https://doi.org/10.1021/la400445s	journal	April 2013
Surface Modification of Silicon Oxide with Trialkoxysilanes toward Close-Packed Monolayer Formation Tanaka, Mutsuo; Sawaguchi, Takahiro; Kuwahara, Masashi Langmuir, Vol. 29, Issue 21 https://doi.org/10.1021/la4009834	journal	May 2013
Palladium-Catalyzed Coupling Reactions for the Functionalization of Si Surfaces: Superior Stability of Alkenyl Monolayers Collins, Gillian; O’Dwyer, Colm; Morris, Michael Langmuir, Vol. 29, Issue 38 https://doi.org/10.1021/la402480f	journal	September 2013
Interfacial Recognition of Sugars by Boronic Acid-Carrying Self-Assembled Monolayer Kanayama, Naoki; Kitano, Hiromi Langmuir, Vol. 16, Issue 2 https://doi.org/10.1021/la990182e	journal	November 1999
Controlled nanoscale doping of semiconductors via molecular monolayers Ho, Johnny C.; Yerushalmi, Roie; Jacobson, Zachery A. Nature Materials, Vol. 7, Issue 1 https://doi.org/10.1038/nmat2058	journal	November 2007
Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers Guan, Bin; Siampour, Hamidreza; Fan, Zhao Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep12641	journal	July 2015
Wet chemical routes to the assembly of organic monolayers on silicon surfaces via the formation of Si–C bonds: surface preparation, passivation and functionalization Ciampi, Simone; Harper, Jason B.; Gooding, J. Justin Chemical Society Reviews, Vol. 39, Issue 6 https://doi.org/10.1039/b923890p	journal	January 2010
Doping and characterization of boron atoms in nanocrystalline silicon particles Sato, Keisuke; Fukata, Naoki; Hirakuri, Kenji Applied Physics Letters, Vol. 94, Issue 16 https://doi.org/10.1063/1.3120768	journal	April 2009
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions Krishnan, R.; Binkley, J. S.; Seeger, R. The Journal of Chemical Physics, Vol. 72, Issue 1 https://doi.org/10.1063/1.438955	journal	January 1980
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 McLean, A. D.; Chandler, G. S. The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648 https://doi.org/10.1063/1.438980	journal	May 1980
In situ XPS study of low temperature atomic layer deposition of B ₂ O ₃ films on Si using BCl ₃ and H ₂ O precursors Pilli, Aparna; Jones, Jessica; Lee, Veronica Journal of Vacuum Science & Technology A, Vol. 36, Issue 6 https://doi.org/10.1116/1.5044396	journal	November 2018
Atomic layer deposition of BN as a novel capping barrier for B ₂ O ₃ Pilli, Aparna; Jones, Jessica; Chugh, Natasha Journal of Vacuum Science & Technology A, Vol. 37, Issue 4 https://doi.org/10.1116/1.5092806	journal	July 2019
Selective Removal of Native SiO2 Using XeF2 Hinckley, A.; Mancheno-Posso, P.; Lai, C. S. ECS Transactions, Vol. 69, Issue 7 https://doi.org/10.1149/06907.0225ecst	journal	September 2015
The Evolution of Silicon Wafer Cleaning Technology Kern, Werner Journal of The Electrochemical Society, Vol. 137, Issue 6 https://doi.org/10.1149/1.2086825	journal	January 1990
Boron Diffusion with Boric Acid for High Efficiency Silicon Solar Cells Das, A.; Kim, D. S.; Nakayashiki, K. Journal of The Electrochemical Society, Vol. 157, Issue 6 https://doi.org/10.1149/1.3392364	journal	January 2010
Effect of the fluorination technique on the surface-fluorination patterning of double-walled carbon nanotubes Bulusheva, Lyubov G.; Fedoseeva, Yuliya V.; Flahaut, Emmanuel Beilstein Journal of Nanotechnology, Vol. 8 https://doi.org/10.3762/bjnano.8.169	journal	January 2017
Inductively Coupled BCl3/O2 Plasma Etching of Germanium Shim, Kyu-Hwan Journal of the Korean Physical Society, Vol. 55, Issue 5(1) https://doi.org/10.3938/jkps.55.1799	journal	November 2009

Similar Records

Formation of a Boron-Oxide Termination for the (100) Diamond Surface

Journal Article · Wed May 29 20:00:00 EDT 2024 · Advanced Materials Interfaces · OSTI ID:2377001

Reaction of BCl₃ with H- and Cl-terminated Si(100) as a pathway for selective, monolayer doping through wet chemistry

Journal Article · Wed Jun 03 20:00:00 EDT 2020 · Applied Surface Science · OSTI ID:1639068

Tribological properties of boric acid and boric-acid-forming surfaces: Part 2, Formation and self-lubrication mechanisms of boric acid films on boron- and boric-oxide-containing surfaces

Conference · Sun Dec 31 23:00:00 EST 1989 · OSTI ID:7257960

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Boron
Chemical reactions
Molecules
Silicon
X-ray photoelectron spectroscopy

Solution Chemistry to Control Boron-Containing Monolayers on Silicon: Reactions of Boric Acid and 4-Fluorophenylboronic Acid with H- and Cl-terminated Si(100)

Citation Formats

References (55)

Similar Records

Related Subjects