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SAMs

Revised 11/22/10

SELF-ASSEMBLED MONOLAYERS (SAMs)


Theresa M. McIntire, Sergey A. Nizkordov, and Kimberly Edwards Department of Chemistry, University of California, Irvine, Irvine, CA 92697-2025

OBJECTIVE The goal of this laboratory experiment is to form models for the organic films present on surfaces in the environment (e.g. atmospheric aerosols, building materials, glass, vegetation, etc.) and measure the contact angle of these surfaces.

INTRODUCTION Water vapor is a vital component of the Earths atmosphere. The fraction of water molecules in the air rarely exceeds a few percent by weight, but water has a significant effect on the Earths climate and global air circulation. The presence of water is critical to life on Earth, and the physical state of water changes at various stages in the Earths water cycle. As a gas, atmospheric water acts as a major natural greenhouse gas, helping to warm the Earths surface. In contrast, liquid water in the form of aerosols, fogs, and clouds has an opposite effect on the climate as it scatters as much as 30% of incoming solar radiation back into space. In environmental and biological processes, water plays an essential role, yet, despite this importance, little is known about the fundamental molecular properties of water interacting with the organic films present on surfaces in the environment (e.g. atmospheric aerosols) or water interacting with organic surfaces in biosystems (e.g. membranes). Chemical and physical properties of many materials of interest to the environment are significantly affected by water in the air. Under normal ambient conditions, most surfaces in the environment have a very thin film of water adsorbed on them. As the relative humidity increases, the water film grows thicker, and water eventually condenses in droplets under the saturation conditions, i.e., when the relative humidity reaches 100%. The growth of cloud droplets occurs in a similar way with the exception that the growth takes place on tiny aerosol particles instead of surfaces. Materials strongly differ in their ability to adsorb water on their surfaces. Water films form easily on surfaces of hydrophilic materials such as glass or rust. Alternatively, hydrophobic materials such as Teflon or wax will inhibit water adsorption. One convenient way to classify materials by their ability to adsorb water is a measurement called the contact angle the angle a liquid droplet makes with the surface it is sitting on, as illustrated in Figure 1. Water droplets spread on hydrophilic surfaces resulting in a small contact angle, typically 10-30. Water minimizes its contact with a hydrophobic surface resulting in large contact angles, sometimes in excess of 90.

SAMs

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Figure 1. Left: A contact angle is the angle that the liquid/vapor interface makes with the solid surface. Hydrophilic surfaces have small contact angles, whereas hydrophobic surfaces have large ones. Right: Photographs of small water droplets on the surface of quartz (A) and quartz coated with a selfassembled monolayer (SAM) of hydrophobic organics (B).

The goal of this laboratory experiment is to measure contact angles formed by small water droplets on silicon surfaces. You will observe how chemical modification of these surfaces can dramatically affect the hygroscopicity of the material. Hygroscopicity is the property of adsorbing or attracting moisture from the air.

BACKGROUND The interface between water and organic materials is ubiquitous in nature and its importance in biological systems and atmospheric processes is broadly acknowledged. In general, surfaces play an important role in environmental chemistry. Urban surfaces, such as glass and concrete, are likely to be coated with films composed partially of organic compounds, such as organic surfactants5-7 or fatty acids of biological origin.7 Initially, the organic films formed on these surfaces are typically hydrophobic which inhibits water adsorption. However, as these organic films age, they react with atmospheric trace gases5,6,8-10 (such as OH, ozone, halogen atoms, and nitrogen trioxide) potentially leading to changes in their hygroscopic nature. 13-14 These surfaces can be used to better understand the chemistry of airborne particles called aerosols. Aerosols contain some of the same organic compounds that create the organic films mentioned above. Aging aerosols adsorb water resulting in surface reactivity changes. The result is a cloud condensation nuclei (CCN) which promotes cloud formation.1,2 This reactivity of organic aerosols has potential effects on atmospheric radiation, visibility, and human health.1,2 Hence, a large scientific interest exists in the reactivity of surface films. (See the Reading section Aerosols and Ozone for more information on aerosols.)
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SAMs

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In order to investigate these surfaces in the laboratory, we will be coating surfaces with long chain hydrocarbon molecules similar to organic compounds found in the films on urban surfaces. The hydrocarbons will spontaneously assembly into a complex chemical structure. This spontaneous molecular organization is called a self-assembled monolayer (SAM).15 As the name implies, a SAM consists of a single layer of organized organic molecules bound to a surface. In this lab, SAMs will be created by depositing (reacting) long chain hydrocarbon molecules on two different surfaces: silicon (which is chemically similar to glass in many ways) and gold. A monolayer of hydrocarbon molecules containing chlorosilane ends (silanes) will be deposited silicon as shown in Figure 2.16,17 A monolayer of hydrocarbon molecules containing sulfide ends (thiols) will be deposited a gold surface as shown in Figure 3. Silicon (or glass) is studied extensively because it more closely represents environmentally relevant surfaces such as dust particles upon which organics adsorb.18,19 However, silicon surfaces often have multilayers (layers stacked upon layers) which complicates the spectroscopic investigation of the surface. Gold, while not being a typical environmental surface, is also studied because it provides two major advantages over silicon: (1) Many more thiols with various numbers of carbons and various reactive atom arrangements (functional groups) are manufactured. (2) True monolayers always form on gold surfaces.

HCl

+ +
(H2O)
H O Si H O O Si O Si O Si O O

Cl

Si Cl

Cl

Figure 2. Formation of a SAM on a silica surface using trichlorosilane coupling chemistry.


thiol molecules + Au on glass organization SAM

Figure 3. Formation of a SAM on a gold surface via sulfide bridges.

SAMs

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In both cases, a relatively hydrophilic surface (gold or silicon) is coated with a densely organized layer of relatively hydrophobic organic molecules. Note: Cooking oils and candles, which are known to be very hydrophobic, contain long-chain saturated hydrocarbons similar to the ones in the SAMs that you will make. Therefore, we expect that depositing SAMs on each surface should make each surface more hydrophobic, increasing the value of the contact angle measured for this surface. The main goal of this lab is to verify this simple hypothesis. In addition, six different silanes and three different sulfides will be used to make the SAMs on the surfaces, so the importance of alkane chain length and the reactivity of the terminal chemical group on the contact angle can be determined. REFERENCES CITED
(1) Seinfeld, J. H.; Pandis, S. N. Atmospheric Chemistry and Physics: From Air Pollution to Climate Change.; Wiley-Interscience: New York, 1998, 1326 pp. (2) Finlayson-Pitts, B. J.; Pitts, J. N. Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications.; Academic Press: San Diego, 2000, 969 pp. (5) Gill, P. S.; Graedel, T. E.; Weschler, C. J. Organic Films on Atmospheric Aerosol-Particles, Fog Droplets, Cloud Droplets, Raindrops, and Snowflakes. Reviews of Geophysics 1983, 21, 903-920. (6) Ellison, G. B.; Tuck, A. F.; Vaida, V. Atmospheric Processing of Organic Aerosols. Journal of Geophysical Research-Atmospheres 1999, 104, 11633-11641. (7) Tervahattu, H.; Juhanoja, J.; Vaida, V.; Tuck, A. F.; Niemi, J. V.; Kupiainen, K.; Kulmala, M.; Vehkamaki, H. Fatty Acids on Continental Sulfate Aerosol Particles. Journal of Geophysical Research-Atmospheres 2005, 110, D06207, DOI: 10.1029/2004JD005400. (8) Bertram, A. K.; Ivanov, A. V.; Hunter, M.; Molina, L. T.; Molina, M. J. The Reaction Probability of OH on Organic Surfaces of Tropospheric Interest. Journal of Physical Chemistry A 2001, 105, 9415-9421. (9) Moise, T.; Rudich, Y. Uptake of Cl and Br By Organic Surfaces - A Perspective on Organic Aerosols Processing By Tropospheric Oxidants. Geophysical Research Letters 2001, 28, 4083-4086. (10) Moise, T.; Rudich, Y. Reactive Uptake of Ozone by Aerosol-Associated Unsaturated Fatty Acids: Kinetics, Mechanism, and Products. Journal of Physical Chemistry A 2002, 106, 6469-6476. (13) Sumner, A. L.; Menke, E. J.; Dubowski, Y.; Newberg, J. T.; Penner, R. M.; Hemminger, J. C.; Wingen, L. M.; Brauers, T.; Finlayson-Pitts, B. J. The Nature of Water on Surfaces of Laboratory Systems and Implications for Heterogeneous Chemistry in the Troposphere. Physical Chemistry Chemical Physics 2004, 6, 604-613. (14) Dubowski, Y.; Sumner, A. L.; Menke, E. J.; Gaspar, D. J.; Newberg, J. T.; Hoffman, R. C.; Penner, R. M.; Hemminger, J. C.; Finlayson-Pitts, B. J. Interactions of Gaseous Nitric Acid with Surfaces of Environmental Interest. Physical Chemistry Chemical Physics 2004, 6, 3879-3888. (15) Love, J. C.; Estroff, L. A.; Kriebel, J. K.; Nuzzo, R. G.; Whitesides, G. M. Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology. Chemical Reviews 2005, 105, 1103-1170. (16) Ulman, A. Self-Assembled Monolayers of Alkyltrichiorosilanes: Building Blocks for Future Organic Materials. Advanced Materials 1990, 2, 573-582. (17) Aswal, D. K.; Lenfant, S.; Guerin, D.; Yakhmi, J. V.; Vuillaume, D. Self Assembled Monolayers on Silicon for Molecular Electronics. Analytica Chimica Acta Molecular Electronics and Analytical Chemistry 2006, 568, 84-108. (18) Sagiv, J. Organized monolayers by adsorption. 1. Formation and structure of oleophobic mixed monolayers on solid surfaces. Journal of the American Chemical Society 1980, 102, 92-98.

SAFETY Chemicals used in these experiments should not touch bare skin. Wear gloves, lab aprons, and goggles during the SAM preparation and throughout the entire lab. All work for the SAM preparations should be done in the hood to avoid inhalation of solvent vapors and release of irritating odors into the lab. No open flames solvents are flammable. If you have questions about the procedure ask your TA: do not improvise!
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SAMs EXPERIMENTAL PROCEDURE

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Work in pairs. Each pair will team up with another pair of students. In Part A, half the groups will prepare Group I and the other half will prepare Group II. Your TA will assign you to a group. By the end of lab, you will have 9 pictures of slides: 3 silica slides you prepared, 3 silica slides obtained from another group, and three gold slides you prepared. Utilization of time and equipment: Plan your time wisely for this experiment. You should start work on the next part before finishing the work on the first part. Preparation of the gold slides is very simple, but requires one hour to react. Whenever you have a wafer or slide prepared, immediately photograph the water droplet on it if you wait until the end of the laboratory you may not be able to photograph all of your slides. Note: The SLR camera provided in lab has a special macro lens to take the up close picture. Regular digital cameras will not focus on the small image well enough. Cleanliness is important for this experiment. Rinse all substances well and avoid fingerprints. Make sure the silicon wafers are always placed with the coated (mirror) side up and always try to avoid covering, touching, or scratching that side. Practice using the microliter pipette before beginning the experiment: make sure you know how to take up liquid and how to change the volume. Do NOT reuse pipette tips for any silane reagent (Part A). Hot plates should be used only in the hood!!! Part A. Preparation of SAM on Silicon 1. Your TA will assign you to either Group I or II. Use a diamond scribe to create three ~3/4 in.2 silicon wafer pieces. Using the scribe, label the corners of the wafer pieces. The labels should be as follows: Group I: C4, C8, C18 Group II: C=C, NC, FC Slides should be as small as possible and have an identifying mark specific to just you and your partner. 2. Silicon wafers require a thorough cleaning before a SAM can be deposited: a. In a 250 mL beaker, rinse and then boil the wafers with ethanol for 5 minutes. In another 250 mL beaker, rinse and then boil the wafers with isopropanol for another 5 minutes. b. Bring the silicon surfaces, shiny side up, to your TA. Your TA will place the slides in a plasma cleaner at low or medium frequency for 10 min. c. Upon removal from the plasma cleaner, rinse the clean wafers with nanopure water and then dry with a flow of UHP Ar (do not wipe or heat the wafer, as that will remove the surface hydroxyl group (-O-H)). 3. Crucibles in which SAM solutions are prepared need to be cleaned first with boiling ethanol and then boiling isopropanol (in order to avoid free OH on its walls that will attract the SAM). 4. SAM Preparation: Make three dilute solutions of the silane in n-hexadecane. Group I: Solution C4: Fill a small crucible (labeled C4) with 10.00 mL of n-hexadecane, and then add 3.3 L of the short-chained silane (n-butyltrichlorosilane, C4). Place the similarly
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SAMs

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labeled slide in the SAM solution with the shiny side up. Cover the solution with a watch glass. Discard pipette tip. Solution C8: Fill a small crucible (labeled C8) with 10.00 mL of n-hexadecane, and then add 4.6 L of the silane (n-octyltrichlorosilane, C8). Place the similarly labeled slide in the SAM solution with the shiny side up. Cover the solution with a watch glass. Discard pipette tip. Solution C18: Fill a small crucible (labeled C18) with 10.00 mL of n-hexadecane, and 7.9 L of the long-chained silane (octadecyltrichlorosilane, C18). Place the similarly labeled slide in the SAM solution with the shiny side up. Cover the solution with a watch glass. Discard pipette tip. Group II: Solution C=C: Fill a small crucible (labeled C=C) with 10.00 mL of n-hexadecane, and then add 2.9 L of the silane (allyltrichlorosilane, C=C). Place the similarly labeled slide in the SAM solution with the shiny side up. Cover the solution with a watch glass. Discard pipette tip. Solution CC: Fill a small crucible (labeled NC) with 10.00 mL of n-hexadecane, and then add 3.2 L of the silane ((3-cyanopropyl)trichlorosilane, NC). Place the similarly labeled slide in the SAM solution with the shiny side up. Cover the solution with a watch glass. Discard pipette tip. Solution FC: Fill a small crucible (labeled FC) with 10.00 mL of n-hexadecane, and 7.4 L of the silane ((tridecafluro-1,1,2,2,-tetrahydrooctyl)trichlorosilane, FC). Place the similarly labeled slide in the SAM solution with the shiny side up. Cover the solution with a watch glass. Discard pipette tip. 5. After 30 minutes remove the wafers from solution and rinse each with isopropanol. Boil the slides in isopropanol to remove any reagent not chemically bound to the surface. Use three beakers . (Again, make sure the slides remain face up.) 6. Obtain one sheet of laboratory lens paper from your TA. Rip into 3 pieces and use to wipe each of the silicon wafers with laboratory lens paper (to remove unbound silane or solvent residue). Place the wafers, SAM-coated side up in a covered dish, keeping them free of fingerprints and dust. (Keep slides covered until pictures taken in Part C.) 7. Pour solutions in crucibles into the waste bottles in the fume hood. Rinse crucibles with acetone until clean. Place acetone rinsings into the same waste bottle in the hood. Part B. Preparation of SAM on Gold 1. Use a diamond scribe to cut a gold coated microscope slide into 2 pieces. Using the scribe, label the corners of the slide pieces. Label the slides C12, OH, and COOH. Also, both slides should have an identifying mark in the corner specific to just you and your partner. These labels should be as small as possible. Rinse the pieces with nanopure water and then ethanol. 2. SAM Preparation: Make three dilute solutions of the thiol in ethanol. Solution C12: Fill a small crucible (labeled C12) with 20.00 mL of ethanol, and then add 4.8 L of the thiol (1-dodecanethiol, C12). Place the similarly labeled slide in the SAM solution with the gold-coated side up. Cover the solution with a watch glass. Solution OH: An ethanol solution containing 0.0010 M 11-mercaptoundecanol has been prepared for you by the stockroom. Fill a small crucible (labeled OH) with 20.00 mL of

SAMs

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the solution. Place the similarly labeled slide in the SAM solution with the gold-coated side up. Cover the solution with a watch glass. Solution COOH: An ethanol solution containing 0.0010 M 12-mercaptododecanoic acid has been prepared for you by the stockroom. Fill a small crucible (labeled OH) with 20.00 mL of the solution. Place the similarly labeled slide in the SAM solution with the gold-coated side up. Cover the solution with a watch glass. 3. In the hood, gently heat (~35 C usually a setting of 1 or 2 on the hotplate) the solution for 1 hour to give enough time for the SAM to assemble. Rinse with ethanol. (Keep slides covered until pictures taken in Part C.) 4. Pour solutions in crucibles into the waste bottles in the fume hood. Part C. Measurement of Contact Angles 1. A digital camera is set up for measuring the contact angle. You should take pictures as you complete each slide if you wait until the end, you will not finish. Your instructor will help you with the camera and take photos for you. Use the lab jacks to position the camera to obtain a picture of your slide with the perspective shown in Figure 1. 2. Place the slide on end of the stage, as close to the camera as possible. Using the microliter pipette, place a 2 L water droplet onto a surface near the surface edge. Make sure the camera is pointed directly at the slide (not at a downward or upward angle). Use the white piece of cardboard for the background. Focus on the water droplet in the middle of the view finder. On the computer log sheet set up by the TA, record the file number of your picture and the slide type (C4, C8, C18, C=C, NC, FC, C12, OH, COOH). 3. Repeat this process with for all slides created in this experiment. 4. Your TA will upload all picture files and the log sheet into EEE's DropBox. Part D. Physical Behavior of the Water Droplet on Surfaces 1. For all slides: Dry off the existing water droplet with a lens paper and add a 2 L droplet. 2. Tip the slide from side to side (so that the slide is no longer flat) and record any observations. 3. Dispose of slides in the broken glass container.

Before coming to lab prepare your duplicate page notebook as demonstrated in previous labs: Your name, ID#, TA name, and date should appear in the upper right-hand corner or in the space provided for this information on each page. The experiment title and reference source should appear at the top of the first page, followed by a brief statement of objectives. Chemical tables should contain molecular formulae and weight, densities and Spartan images demonstrating structure. Make sure the equipment table contains information about the microliter pipettes, et cetera. The tables should be followed by procedures and observations. Data should be reported in concise table(s). Finally, the answers to the results and discussion section should be answered clearly and concisely.

SAMs DATA

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1. Different reagents were used to create different self assembled monolayers in this experiment. Calculate the concentrations (in mM) of those reagents in the solutions created in Part A & B. Show one sample calculation and report all the concentrations in a table. a. n-butyltrichlorosilane (C4) b. n-octyltrichlorosilane (C8) c. octadecyltrichlorosilane (C18) d. allyltrichlorosilane (C=C) e. (3-cyanopropyl)trichlorosilane (NC) f. (tridecafluro-1,1,2,2,-tetrahydrooctyl)trichlorosilane (FC) g. 1-dodecanethiol (C12) h. 11-mercaptoundecanol (OH) concentration given in procedures i. 12-mercaptododecanoic acid (COOH) concentration given in procedures 2. The stockroom prepared the solutions for the last two reagents used. How much of each reagent (in grams) is needed to create 1L of each solution? What piece of glassware should be used to make the solution? 3. On the computer screen, use a protractor to roughly determine contact angles. Then create 3 tables for the photos (one for each silicon group and one for gold) and order the photos by increasing contact angle magnitude. The photos of water droplets on untreated silica and plasma cleaned silica (available on the course website) should be included in both silicon tables. Photos should be the size of the those shown in Figure 1. Using a protractor, measure and clearly indicate the contact angle and its magnitude on all photos (you may printout the tables and do this part by hand if you wish). For each SAM type, calculate the average contact angle and the relative average deviation. A Q-test should be performed on the smallest and largest angle measured for each SAM. Throw out any values that are greater than the 90% confidence level.

RESULTS AND DISCUSSION 1. Explain how each of the following is related to the magnitude of the contact angle: a. surface hydrophobicity b. cohesion between water molecules c. adhesion between water molecules and the surface 2. Explain the nature of the relationship between the chain length of the molecules in Group I and contact angle.

SAMs

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3. Below are drawings of the silane reagents used in Group II. a. Based on your observations, rank these molecules in order of polarity. b. What is the relationship between polarity of the molecules bound to the surface and contact angle? c. Explain the order of molecular polarity based on the structures drawn below?
H 2C CH CH2 SiCl3 C=C N C CH 2 CH2 CH2 SiCl3 NC F3C (CF2 )5 CH 2 CH2 SiCl3 FC

4. Below are drawings of the thiol reagents used to form the gold SAMs. a. Using the data you obtained, rank these molecules in order of polarity. b. Explain the order of polarity based on the structures drawn. (you might want to consider using dipole arrows and drawing in your explanation)
O HO C (CH2)9 CH2 SH COOH H3C (CH2)10 CH2 SH C12 HO CH2 (CH2)9 CH2 SH OH

5. The surface images below were taken with an atomic force microscope (AFM).20 As seen to the right, AFM uses a cantilever (a beam supported at one end) with a very sharp silicon tip to image (feel) a samples surface. As the tip is brought close to a surface, the interaction with the surface atoms deflects the cantilever according to Hooke's law (F = -kx). A laser beam is reflected from the backside of the cantilever tip into a photodiode to create a topographical image of the surface showing rough terrain, peaks, and valleys.

Match the images below with the slides given: a. uncoated plasma cleaned silicon wafer b. SAM-coated silicon wafer 1) 2)

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500 nm 500 nm

SAMs Match the images below with the slides given: a. uncoated cleaned gold slide b. SAM-coated gold slide 1) 2)

Revised 11/22/10

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