Polysiloxane Films and Methods of Making Polysiloxane Films

Abstract

A polysiloxane film comprises Si—O bonds and has a thickness of 0.3 to 1.5 microns. Adjacent electrodes coated with the polysiloxane film have a leakage current of at most 0.01 mA at 10 V after contact with water. An electrode coated with the polysiloxane film has a contact resistance of at least 0.01 ohms at 1.0 mm of pogo pin compression under a 1.0 N load. The polysiloxane film provides IPx7 protection from ingress of water.

Claims

1. A polysiloxane film comprising Si—O bonds and having a thickness of 0.3 to 1.5 microns, wherein the polysiloxane film passes the corrosion current test, and the polysiloxane film passes the contact resistance test.

2. The polysiloxane film of claim 1, wherein the polysiloxane film provides IPx7 protection from ingress of water.

3. The polysiloxane film of claim 1, wherein the polysiloxane film has a thickness of 0.5 to 1.1 microns.

4. The polysiloxane film of claim 1, wherein the polysiloxane film comprises fluorine.

5. The polysiloxane film of claim 1, wherein the polysiloxane film comprises carbon deposits.

6. The polysiloxane film of claim 1, wherein the polysiloxane film has a thickness of 0.5 to 1.1 microns, the polysiloxane film provides IPx7 protection from ingress of water, and the polysiloxane film comprises fluorine.

7. The polysiloxane film of claim 1, wherein the polysiloxane film comprises (SiO)(R1).sub.2 units, wherein each R1 is independently selected from the group consisting of amino, hydroxyl, mercapto, alkoxy, alkyl, cycloalkyl, aryl and heteroaryl.

8. The polysiloxane film of claim 7, wherein R1 is substituted with a substituent selected from the group consisting of alkyl, cycloalky, aryl, heteroaryl, amino, hydroxyl, mercapto, alkoxy, a carboxylic acid, phenethyl, a phosphonic acid, a sulfonic acid, a carboxylic ester, a carboxylic amide, a carboxylic anhydride, a saccharide, a halogen, and salts thereof.

9. A method of forming a polysiloxane film, comprising: polymerizing monomers comprising at least one siloxane monomer having the formula (X1).sub.nSi(R1).sub.4-n, wherein n is 1, 2 or 3; (X1)Si(R1).sub.2OSi(R1).sub.2(X1); (X1)(Si(R1).sub.2O).sub.2Si(R1).sub.2(X1); and [OSi(R1).sub.2].sub.m, wherein m is 3 or 4; wherein X1 is Cl or OR2, R2 is alkyl, each R1 is independently selected from the group consisting of amino, hydroxyl, mercapto, alkoxy, alkyl, cycloalkyl, aryl and heteroaryl, the polysiloxane film contains Si—O bonds, the polysiloxane film has a thickness of 0.3 to 1.5 microns, the polysiloxane film passes the corrosion current test, and the polysiloxane film passes the contact resistance test.

10. A method of forming a polysiloxane film in a reaction chamber, comprising: polymerizing monomers comprising at least one siloxane monomer having the formula (X1).sub.nSi(R1).sub.4-n, wherein n is 1, 2 or 3; (X1)Si(R1).sub.2OSi(R1).sub.2(X1); (X1)(Si(R1).sub.2O).sub.2Si(R1).sub.2(X1); and [OSi(R1).sub.2].sub.m, wherein m is 3 or 4; wherein the polymerization is catalyzed by a 30-60 W radio frequency plasma, the pressure in the reaction chamber during the polymerization is 100-400 mTorr, X1 is Cl or OR2, R2 is alkyl, each R1 is independently selected from the group consisting of amino, hydroxyl, mercapto, alkoxy, alkyl, cycloalkyl, aryl and heteroaryl, the polysiloxane film contains Si—O bonds, the polysiloxane film has a thickness of 0.3 to 1.5 microns.

11. The method of claim 10, wherein the residence time of the siloxane monomer in the reaction chamber is 5-120 minutes.

12. The method of claim 10, wherein the siloxane monomer is heated to 30-200° C. before entering the reaction chamber.

13. The method of claim 10, wherein the polymerization is carried out at a temperature of 30-100° C.

14. The method of claim 10, wherein the reaction chamber comprises an inert gas.

15. The method of claim 14, wherein the gas further comprises oxygen, wherein oxygen is present as oxygen (O.sub.2), ozone (O.sub.3), nitrous oxide (N.sub.2O), carbon dioxide (CO.sub.2), water (H.sub.2O), and mixtures thereof.

16. An electronic device comprising electrical components coated with the polysiloxane film of claim 1.

17. An electronic device comprising electrical components coated with the polysiloxane film of claim 2.

18. The polysiloxane film of claim 1, further comprising a non-volatile diluent.

19. The method of claim 10, further comprising swelling the polysiloxane film with a non-volatile diluent.

20. A polysilxane film prepared by the method of claim 9.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The invention can be better understood with reference to the following drawings and description.

[0027] FIG. 1 illustrates a schematic of a plasma-enhanced chemical vapor deposition system.

[0028] FIG. 2 illustrates a method for applying a film to an electronic component on a substrate.

[0029] FIG. 3 illustrates the UV-visible spectra of a 40 W argon plasma.

[0030] FIG. 4 illustrates the UV-visible spectra of a 40 W argon/phenethyltrimethoxysilane (PETMS) gas mixture plasma.

[0031] FIG. 5 illustrates a scanning electron microscopy (SEM) micrograph of a component coated with a polysiloxane film.

[0032] FIG. 6 illustrates a printed circuit board (PCB) with substrate assemblies including copper circuit traces from leads to rectangular test pads.

[0033] FIG. 7 illustrates a corrosion current experiment.

[0034] FIG. 8 illustrates bubbles formed during a corrosion current experiment.

[0035] FIG. 9 illustrates a graph of contact resistance as a function of pogo pin load for untreated electrodes and electrodes coated with a fluorinated film. The left y-axis is the pogo pin load in N, and the right y-axis is measured electrical resistance of the film in ohms.

[0036] FIG. 10 illustrates a graph of contact resistance as a function of pogo pin load for electrodes coated with a polymer formed from phenethyltrimethoxysilane PETMS and perfluorododecyltriethoxysilane (PFDTES)—two measurements are shown.

[0037] FIG. 11 illustrates a graph of contact resistance as a function of pogo pin load for electrodes coated with a polymer formed from hexamethylcyclotrisiloxane (HMCTS) heated to 75° C., at a process pressure of approximately 301 mTorr and a plasma power of 40 W (Film D)—a very rough polymer surface was obtained.

[0038] FIG. 12 illustrates two SEM micrographs of an electrode coated with a polymer formed from phenethyltrimethoxysilane (PETMS) at two levels of magnification.

[0039] FIG. 13 illustrates two SEM micrographs of an electrode coated with a polymer formed from phenethyltrimethoxysilane (PETMS) at two levels of magnification.

[0040] FIG. 14 illustrates two SEM micrographs of an electrode coated with a polymer formed from phenethyltrimethoxysilane (PETMS) and perfluorododecyltriethoxysilane (PFDTES) at two levels of magnification.

[0041] FIG. 15 illustrates two SEM micrographs of an electrode coated with a polymer formed from hexamethylcyclotrisiloxane (HMCTS) at two levels of magnification.

[0042] FIG. 16 illustrates two SEM micrographs of an electrode coated with a polymer formed from hexamethylcyclotrisiloxane (HMCTS) at two levels of magnification.

[0043] FIG. 17 illustrates two SEM micrographs of an electrode coated with a polymer formed from hexamethylcyclotrisiloxane (HMCTS) at two levels of magnification.

[0044] FIG. 18 illustrates two SEM micrographs of an electrode coated with a polymer formed from hexamethylcyclotrisiloxane (HMCTS) at two levels of magnification.

DETAILED DESCRIPTION

[0045] An electronic device coated with a protective film should be able to be exposed to water, preferably submerged in water, while having voltage applied to all relevant circuits as if it were in use. The electronic device should be able to be exposed to an applied external charging voltage after exposure and still be functional until the device dries out completely. The electronic device should also show no visible signs of corrosion when inspected after exposure to water.

[0046] The present invention is a polysiloxane film that provides better water resistance than existing films to mechanically, electrically, and/or chemically protect electronic components attached to substrates in electronic devices. The polysiloxane film may contain fluorine, may completely cover the active electronic features on the surface being coated, and may prevent ion conduction. The film may be formed from monomers that are capable of wetting the surface to be coated and presenting reactive groups to form pendant grafts. The graft segments are rich in 7-electrons, which form an electron cloud that may prevent ion transport and may hinder corrosion while still allowing electrical contact between connector electrodes. The films may be pinhole free while retaining a degree of mechanical compliance. The monomers may be capable of diffusing into highly reticulated volumes found in substrate assemblies and wetting the electronic components on the substrate. The polysiloxane film may provide up to IPx7 protection from ingress of water.

[0047] The present invention also includes a method of preparing a polysiloxane film.

[0048] The film may be formed by vapor phase polymerization in a plasma-enhanced chemical vapor deposition process. Plasmas that catalyze the surface-treatment reaction may be selected to create specific molecular fragments which further are film monomers. Heterogeneous plasma-polymerized film morphology may be controlled by the monomer mixture, the power of the applied plasma, the temperature of the gases used to form the plasma, and other operational parameters. The least stable bonds in the monomers are believed to be broken by energy pooling. Multi-layered and multi-compositional films are possible.

[0049] Polysiloxane films may be formed by polymerizing monomers comprising siloxane monomers, preferably linear or cyclic siloxane monomers. Especially preferred linear siloxane monomers may have the formula (X1).sub.nSi(R1).sub.4-n in which n is 1, 2 or 3, (preferably, n is 2 or 3); (X1)Si(R1).sub.2OSi(R1).sub.2(X1); or (X1)(Si(R1).sub.2O).sub.2Si(R1).sub.2(X1). Also especially preferred cyclic siloxane monomers may have the formula [OSi(R1).sub.2].sub.m, wherein m is 3 or 4. X1 may be a chemical leaving group comprised of chloro (CI) or OR2. The side chains may be hydrophilic and/or lipophilic, and are selected to impart specific protective properties to the polysiloxane film. The chloro or OR2 groups are hydrolyzable to form unstable silanol groups, which may condense to form a polysiloxane backbone, and may optionally be covalently bonded on or around a surface being coated.

[0050] Polysiloxane films prepared by polymerizing monomers comprising one or more of the especially preferred siloxane monomers may from films which pass the contact resistance test and the corrosion current test.

[0051] Each R1 may independently be selected from the group consisting of amino, hydroxyl, mercapto, alkoxy, alkyl, cycloalkyl, aryl and heteroaryl. If R1 is alkyl, cycloalkyl, or heteroaryl, it may be substituted or unsubstituted. Suitable substituents include alkyl, cycloalky, aryl, heteroaryl, amino, hydroxyl, mercapto, alkoxy, a carboxylic acid, phenethyl, a phosphonic acid, a sulfonic acid, a carboxylic ester, a carboxylic amide, a carboxylic anhydride, a saccharide, a halogen (such as F, Cl, and/or Br), or a salt of such groups that may be ionizable. A preferred substituent is fluorine (F). Each R1 may be the same, or may be different.

[0052] R2 may be an alkyl group. Preferably, R2 is an alkyl group containing 1-6 carbon atoms. Examples of especially preferred R2 groups are methyl and ethyl groups. Each R2 may be the same, or may be different.

[0053] Suitable monomers include phenethyltrimethoxysilane (PETMS), perfluorododecyltriethoxysilane (PFDTES), hexamethylcyclotrisiloxane (HMCTS), octamethylcyclotetrasiloxane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, phenyltrimethoxysilane, diphenyldimethoxysilane, octyltrimethoxysilane, diphenyldiethoxysilane, pentafluorophenylpropyltrimethoxysilane (PFPPTMS), and combinations thereof. Preferred monomers include phenethyltrimethoxysilane (PETMS), perfluorododecyltriethoxysilane (PFDTES), hexamethylcyclotrisiloxane (HMCTS), and combinations thereof.

[0054] It is believed that the polysiloxane film polymerizes through one or more trialkoxysilyl groups attached to the end of film chains. The trialkoxysilyl groups are likely displaced by a hydroxyl group on or around the electronic components being treated, forming silicon-to-oxygen bonds that mechanically anchor the film to the electrical component. The film does not need to be covalently bonded to the surface being coated. Bonding is likely achieved by reacting with di-functional coupling agents composed of hydrocarbon chains or polyoxyalkylene chain groups.

[0055] The polysiloxane films may optionally be swollen with non-volatile diluents. The addition of non-volatile diluents enables connectors to operate within the contact range dictated by the electronic device, yet be sufficiently mechanically robust to be attached and removed without disrupting the film properties. The non-volatile diluent also imparts a special flex to the connector. Suitable non-volatile diluents include alkyl and aryl hydrocarbons having 4-9 carbon atoms.

[0056] The polysiloxane film may have a thickness of 0.1 to 10.0 μm, including 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm, 5.0 μm, 5.5 μm, 6.0 μm, 7.0 μm, 7.5 μm, 8.0 μm, 9.0 μm and 9.5 μm. Preferably, the thickness is 0.3 to 1.5 μm. More preferably, the thickness is 0.5 to 1.1 μm. Under the conditions tested, films with thicknesses above 1.1 μm are typically soft and friable, and flake when subjected to mild levels of mechanical shear. However different conditions may produce dense films, which become thicker than 1.1 μm and are mechanically robust.

[0057] The polysiloxane film may be characterized by scanning electron microscopy (SEM). The resulting micrographs may show polysiloxane film appearances ranging from rough and highly textured, to smooth with even surfaces. Polysiloxane films with a smooth, even surface appear to be dense, and may indicate the electronic component is unable to make electrical contact with other electronic components. It is believed that rough areas of a polysiloxane film are less dense and provide areas, which may make electrical contact with other electronic components. Selecting monomers and/or processing conditions to tailor the density of the polysiloxane film also determines film surface roughness and controls the formation of deposits on the film, such as carbon deposits.

[0058] The polysiloxane film may form contoured regions on the surface being coated. The contoured regions may be visible under SEM, as in FIG. 5. The contoured regions may have a width from 0.1-3.0 μm. Preferably, the width of the contoured regions is 0.5-1.5 μm, including 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm and 1.4 μm. The contoured regions may have a length that is at least five times greater than their width. Preferably, the contoured regions may have a length that is at least six times greater than their width, at least seven times greater than their width, or at least 8 times greater than their width. For example, if the width is 1.3 μm, the length may be at least 6.5 μm, at least 7.8 μm, at least 9.1 μm, or at least 10.4 μm.

[0059] The polysiloxane film may be applied to a surface being coated using plasma-enhanced chemical vapor deposition (PECVD). FIG. 1 illustrates a schematic of a PECVD system. A typical vacuum plasma system has three modules: a rectangular reaction chamber, which may measure 12.5-in (W)×9.6-in (D)×10-in (H) and may be constructed of 6061 aluminum; a process controller module; and a solid-state radio frequency (RF) power generator. Preferably, the reaction chamber is grounded. The reaction chamber may be front-loaded and equipped with movable shelves for loading and unloading electrical components. The movable shelves may be powered so that they may be mechanically adjusted. Preferably, the shelves are supported by ceramic pieces to electrically isolate them from the reaction chamber. The reaction chamber may have an access door equipped with a viewing window for observing the UV-visible spectra of the plasma via an optical fiber. The process controller monitors and regulates the plasma process parameters, including chamber base pressure, RF power level, process duration, and gas flow rates. The RF generator may have a fixed frequency, such as 13.56 MHz, or may be adjustable. Impedance matching may be achieved by employing an inductive-capacitive tuning network to adjust the forward power to reflected power ratio during processing to achieve good power transfer to the plasma. The RF generator power level may be controlled and monitored by a technician using the device. Other suitable application methods include thermal vapor phase polymerization, plasma-assisted aerosol deposition and plasma-based ion implantation.

[0060] FIG. 2 illustrates a method 200 for applying a polysiloxane film to an electronic component on a substrate. First, the electronic component to be coated is loaded into a reaction chamber at 210. The reaction chamber is then sealed at 220. After the reaction chamber has been sealed, the pressure in the reaction chamber is reduced to a preset vacuum level at 230. Next, a gas that includes a monomer, or a plurality of monomers, is introduced into the reaction chamber at 240. Once the gas has been introduced to the chamber, RF energy is applied to the reaction chamber to create a plasma and initiate heterogeneous gas-phase polymerization at 250. Polymerization is stopped by ending the supply of RF energy to the reaction chamber at 260. Next, the flow of gas to the reaction chamber is stopped at 270. The chamber is then returned to atmospheric pressure at 280. The component with the polysiloxane film coating is then removed from the reaction chamber at 290. The polysiloxane film may optionally be swollen with a non-volatile diluent.

[0061] Preferably, the polymerization is stopped by ending the supply of RF energy to the reaction chamber at a point just before the plasma is quenched. Quenching may be determined by monitoring the UV-visible spectrum of the plasma. A decrease in the UV-visible spectrum is an indication that the plasma is nearly quenched and that the polymerization should be stopped.

[0062] Suitable gases include inert gases such as argon, nitrogen, helium, and mixtures thereof. Preferably, the gas is argon.

[0063] The gas may optionally include substances that promote polymer cross-linking.

[0064] Examples of suitable substances include oxygen (O.sub.2 and O.sub.3), nitrous oxide (N.sub.2O), carbon dioxide (CO.sub.2), water, other oxygen-containing compounds, and mixtures thereof.

[0065] The amount of RF energy applied to the reaction chamber may be 30 to 60 W, including 35 W, 36 W, 37 W, 38 W, 39 W, 40 W, 41 W, 42 W, 43 W, 44 W, 45 W, 46 W, 47 W, 48 W, 49 W, 50 W, 51 W, 52 W, 53 W, 54 W and 55 W. Preferably, the RF energy is from 35 to 45 W. Varying the RF energy will remove or preserve OR2 groups in the monomer. For example, some alkoxy groups are retained at 30 W while most alkoxy groups are removed at 40 W. Use of lower amounts of RF energy may require an increase in reaction time to fully apply a polysiloxane film. Use of higher amounts of RF energy may result in the formation of unwanted side products.

[0066] The pressure in the reaction chamber may range from 100-400 mTorr, including 125 mTorr, 150 mTorr, 175 mTorr, 200 mTorr, 225 mTorr, 250 mTorr, 275 mTorr, 300 mTorr, 325 mTorr, 350 mTorr and 375 mTorr. Preferably, the pressure is 150-325 mTorr. More preferably, the pressure is 175-250 mTorr.

[0067] The monomer may be heated to 30-200° C., including 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C. and 190° C. Preferably, the monomer is heated to 40-170° C. More preferably, the monomer is heated to 75-140° C. Other temperatures may be selected based on the vapor pressure of the monomer and amount desired.

[0068] The polymerization may be carried out at a temperature of 30-100° C., including 35° C., 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., 90° C. and 95° C. Preferably, the temperature is 40-80° C.

[0069] The residence time of the monomer in the reaction chamber impacts the physical characteristics of the polysiloxane film. Decreasing the residence time in the reaction chamber produces a higher gas turnover rate, which increases the growth rate of the polysiloxane film. Increasing the residence time in the reaction chamber produces thinner, denser films. The residence time of the monomer in the reaction chamber may be 5-120 minutes, including 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes and 110 minutes. Preferably, the residence time of the monomer in the reaction chamber is 5-60 minutes.

[0070] Varying the parameters of the polymerization process allows for the characteristics of the polysiloxane film to be tailored to provide a desired protection. For example, polymerizing a hexamethylcyclotrisiloxane (HMCTS) monomer heated to 75° C. in argon at a pressure of 310 mTorr with 40 W RF energy creates a 1.4 μm thick polysiloxane film. Similarly, polymerizing a hexamethylcyclotrisiloxane (HMCTS) monomer heated to 120° C. in argon at a pressure of 310 mTorr with 30 W RF energy creates a 1.0 μm thick polysiloxane film with carbon-rich deposits.

[0071] The polysiloxane film may be applied to electronic components attached to a variety of substrates. For example, the substrate may be a ceramic substrate, a glass substrate, a silicone substrate, a polyimide substrate, a PCB or any other substrate used for attaching integrated circuits. External surfaces may also be coated by the film. The coated items may be used in portable electronic devices such as smart phones, media players, tablet computers, laptop computers and the like, including exterior surfaces and accessories for such devices.

[0072] The polysiloxane film may be applied to electronic devices in various stages of assembly. For example, individual electronic components of an electronic device may be coated with a film prior to being assembled. Alternatively, the electronic device may be partially-assembled before being coated with a film. A fully-assembled electronic device may also be coated with a film, but applying a film at this stage of assembly may limit access to some electronic components of the device.

[0073] Multiple polysiloxane films may optionally be applied to an electronic component on a substrate. The same film may be applied multiple times to an electronic component, or different films may be applied to the electronic component. The films may be applied to the same location of the electronic component to provide a multi-layered film, or may be applied to different locations of the electronic component. The films may impart the same mechanical and chemical properties, or different mechanical and chemical properties. For example, a first polysiloxane film may be relatively hard, compliant, adhesion-promoting, or thermally conductive, and may be applied over one or more electronic components attached to a PCB. The second polysiloxane film may be relatively compliant, and may be applied between an electrical connector and the PCB to cover a plurality of leads which extend out of the connector and are electrically attached to bonding pads on the PCB.

Examples

Example 1—Deposition of Polymeric Films

[0074] The deposition of polymeric films onto substrate assemblies with argon plasmas at various process parameters was investigated. It was known that phenethyltrimethoxysilane (PETMS) and similar chemistries may react to form coatings via heterogeneous gas-phase polymerization with metal oxide surfaces at 125° C. to 200° C., depending on substrate chemistry, reaction environment, and catalyst. See, for example, U.S. Pat. No. 7,303,819 to Brotzman, Jr.; U.S. Pat. No. 7,182,938 to Andre et al.; U.S. Pat. No. 5,993,967 to Brotzman, Jr. et al., and U.S. Pat. No. 6,033,781 to Brotzman, Jr. et al.

[0075] In a first experiment, a substrate assembly was treated with an argon plasma that contained no monomers. The argon plasma was initiated and maintained by an RF generator at 40 W power at process temperature of 40° C. FIG. 3 illustrates the UV-visible spectra of the plasma (specific argon peaks are marked). No polysiloxane film was formed on the substrate assembly. This process was capable of cleaning the substrate assembly, if the plasma treatment time was sufficient.

[0076] In a second experiment, a substrate assembly was treated with argon gas containing phenethyltrimethoxysilane (PETMS) without plasma (0 W power) at a process temperature of 40° C. No polysiloxane film was formed on the substrate assembly. This process was not capable of cleaning the substrate assembly.

[0077] In a third experiment, a substrate assembly was treated with plasma of argon containing PETMS. The argon/PETMS plasma was initiated and maintained by an RF generator at 40 W power at a process temperature of 40° C. FIG. 4 illustrates the UV-visible spectra of the plasma (specific argon peaks are marked). A polysiloxane film was formed on the substrate assembly, as shown in the scanning electron microscopy (SEM) micrograph illustrated in FIG. 5. As visible in the image, the polysiloxane film contained contoured regions that were approximately 10.91 μm long and 1.29 μm wide.

[0078] These experiments demonstrate that an applied RF electric field of sufficient power is capable of exciting a gas containing a monomer and catalyzing the polymeric coating of a substrate assembly. It is believed that the polysiloxane film is formed by an energy pooling mechanism.

Example 2—Coating of PCBs

[0079] PCBs were coated with a polysiloxane film using the PECVD system described above and illustrated in FIG. 1. The PCBs had substrate assemblies including copper circuit traces from leads to rectangular test pads that were approximately 0.8 mm×4.5 mm, separated by 0.2 mm, as illustrated in FIG. 6. Argon was used as the gas. The monomer was heated to increase its vapor pressure and introduced into the argon flow. The reaction chamber had a pressure of approximately 350 mTorr to 50 mTorr against approximately a 10 mTorr vacuum. Plasma was initiated by RF electric field to catalyze a heterogeneous polymerization reaction to occur on or around the surface of the electrical components on the PCBs. The reaction products created a polysiloxane film on the electrical components attached to the PCB substrates.

Example 3—Corrosion Current Test (Comparative)

[0080] The corrosion current of electrodes coated with a commercially available fluorinated film was investigated. The PCB described in Example 2 was used as the substrate.

[0081] Corrosion current was measured by covering adjacent electrodes with a water drop as illustrated in FIG. 7. Bubbles rapidly evolved when corrosion occurred, as illustrated in FIG. 8. Adjacent electrodes may have an applied electrical potential from 0 to 10 V. An applied electrical potential of 10 V was selected to demonstrate the efficacy of applied films.

[0082] The results of the corrosion current experiment are shown in Table 1 below:

TABLE-US-00001 TABLE 1 Corrosion current of commercially-available fluorinated film Voltage Untreated PCB with 0.10 μm (dc) PCB (mA) thick film (mA) 2 V 0.005 0.001 4 V 0.233 0.058 6 V 0.522 0.263 8 V 0.679 0.473 10 V  0.758 0.652

[0083] The results show no significant difference between the current of the untreated PCB and the PCB with a 0.10 μm thick fluorinated film. The fluorinated film provided virtually no protection from water intrusion and ion mobility.

Example 4—Contact Resistance (Comparative)

[0084] The contact resistance of electrodes coated with a commercially available fluorinated film was investigated. The PCB described in Example 2 was used as the substrate.

[0085] Contact resistance, as a function of pin load, was measured by compression of a film by a pogo pin. The pogo pin was 900 microns in diameter and had a contact area of approximately 100 microns diameter. The pogo pin was attached to the vertical translator of an MTS INSIGHT electromechanical instrument. Compression of the film by the pogo pin, normal force load, and electrical resistance of the film were measured to determine resistance of the film to electrical contact at room-temperature conditions. Untreated electrodes and electrodes coated with a fluorinated film were tested for contact resistance.

[0086] FIG. 9 illustrates a graph of contact resistance as a function of pogo pin load for untreated electrodes and electrodes coated with a fluorinated film. The light gray line shows the load as a function of pogo pin compression for the untreated electrodes. The diamond-shaped data points represent the contact resistance for the untreated electrode. The dark gray line shows the load as a function of pogo pin compression for the coated electrodes. The square-shaped data points represent the contact resistance for the coated electrodes. The graph shows no difference in contact resistance between the coated and uncoated electrodes. The fluorinated film provided virtually no protection from damage due to physical contact.

Example 5—Analysis of Polysiloxane Films

[0087] Seven polysiloxane films were prepared as follows:

[0088] Film A—The polysiloxane film included a first polymer layer formed from PETMS and a second polymer layer formed from a mixture of PETMS and perfluorododecyltriethoxysilane (PFDTES). This film was hydrophobic. The film layers were applied using process pressures of approximately 176 mTorr and 232 mTorr, respectively. The PETMS monomer was heated to 130° C., while the PFDTES monomer was headed to 140° C. The plasma power was 40 W and the total time of reaction was approximately 45 minutes. The composite PETMS/PFDTES film was 1.4 microns thick. FIG. 14 illustrates two SEM micrographs of the polymer formed from PETMS and PFDTES at two levels of magnification and shows the roughness of the film.

[0089] Film B—The polysiloxane film was formed from PETMS. This film was lipophilic. The film was applied at a process pressure of approximately 217 mTorr. The PETMS monomer was heated to 130° C. The plasma power was 40 W and the time of reaction was approximately 40 minutes. The PETMS film was 1.4 microns thick. FIG. 12 illustrates two SEM micrographs of the polymer formed from PETMS at two levels of magnification and shows the roughness of the film.

[0090] Film C—The polysiloxane film was formed from PETMS. This film was lipophilic. The film was applied using a process pressure of 311 mTorr. The PETMS monomer was heated to 130° C. The plasma power was 40 W. The PETMS film was 1.1 microns thick. FIG. 13 illustrates two SEM micrographs of the polymer formed from HMCTS at two levels of magnification and shows the roughness of the film.

[0091] Film D—The polysiloxane film was formed from hexamethylcyclotrisiloxane (HMCTS). This film was applied using a process pressure of approximately 301 mTorr. The HMCTS monomer was heated to 75° C. The plasma power was 40 W. The HMCTS film was 1.4 microns thick. FIG. 15 illustrates two SEM micrographs of the polymer formed from HMCTS at two levels of magnification and shows the high degree of roughness of the film.

[0092] Film E—The polysiloxane film was formed from HMCTS. This film was applied using argon gas at a process pressure of approximately 308 mTorr. The HMCTS monomer was heated to 120° C. The plasma power was 30 W. The HMCTS film was 1.0 micron thick. Film E contained substantially more carbon than other HMCTS films. The carbon was dispersed throughout the film in carbon-rich regions. FIG. 16 illustrates two SEM micrographs of the polymer formed from HMCTS at two levels of magnification and shows the carbon deposits as black dots.

[0093] Film F—The polysiloxane film was formed from HMCTS. This film was applied using a process pressure of approximately 318 mTorr. The HMCTS monomer was heated to 120° C. The plasma power was 40 W. The HMCTS film was 0.9 microns thick. FIG. 17 illustrates two SEM micrographs of the polymer formed from HMCTS at two levels of magnification and shows the roughness of the film.

[0094] Film G—The polysiloxane film was formed from HMCTS. This film was applied using argon gas containing oxygen in a 1:2 argon:oxygen ratio at a process pressure of 243 mTorr. The HMCTS monomer was heated to 120° C. The plasma power was 40 W. The HMCTS film was 0.5 microns thick. FIG. 18 illustrates two SEM micrographs of the polymer formed from HMCTS at two levels of magnification and shows the uniform smoothness of the film.

[0095] The corrosion current of electrodes coated with Films A-G were measured. Coated PCBs received two corrosion exposures. The PCBs were subjected to an initial corrosion exposure, were dried, and then were subjected to a second corrosion exposure. Corrosion current was measured by standard techniques using a FLUKE true RMS multimeter placed in series in the circuit.

[0096] The results of the corrosion current after the initial corrosion exposure are shown in Table 2.

TABLE-US-00002 TABLE 2 Corrosion current after initial corrosion exposure Film A PETMS/ Film B Film C Film D Film E Film F Film G V PFDTES PETMS PETMS HMCTS HMCTS HMCTS HMCTS (dc) (mA) (mA) (mA) (mA) (mA) (mA) (mA) 2 0.00009 0.00009 0.00009 0.00008 0.00010 0.00010 0.00008 4 0.00017 0.00036 0.00018 0.00008 0.00015 0.00012 0.00009 6 0.00037 0.00051 0.00050 0.00008 0.00054 0.00014 0.00023 8 0.00084 0.00081 0.05800 0.00010 0.00060 0.00012 0.00024 10 0.00103 0.00130 0.00050 0.00011 0.00088 0.00015 0.00036

[0097] The results of the corrosion current after the second corrosion exposure are shown in Table 3.

TABLE-US-00003 TABLE 3 Corrosion current after second corrosion exposure Film A PETMS/ Film B Film C Film D Film E Film F Film G V PFTES PETMS PETMS HMCTS HMCTS HMCTS HMCTS (dc) (mA) (mA) (mA) (mA) (mA) (mA) (mA) 2 0.00018 0.00027 0.00041 0.00008 0.00020 0.00011 0.00017 4 0.00040 0.00085 0.00169 0.00012 0.00064 0.00014 0.00032 6 0.00061 0.00145 0.00234 0.00008 0.00076 0.00015 0.00045 8 0.00078 0.00223 0.00290 0.00010 0.00077 0.00020 0.00036 10 0.00092 0.00337 0.00324 0.00014 0.00099 0.00024 0.00063

[0098] Films A-G demonstrate corrosion current that is approximately 100 to 1,000 times lower than current commercially available films. The polysiloxane films provide significantly better protection from water than existing films.

[0099] The contact resistance as a function of pogo pin load of electrodes coated with Films A-G was measured. Contact resistance was measured as described in Example 4.

[0100] FIG. 10 illustrates a graph of contact resistance as a function of pogo pin load for two measurements of Film A. The solid light gray and dark gray lines show the load as a function of pogo pin compression for each measurement of the polymer formed from PETMS/PFDTES. The triangle-shaped and diamond-shaped data points represent the contact resistance of the polymer formed from PETMS/PFDTES. As compared with Example 4, the contact resistance of Film A is 10 to 20 times greater than the uncoated electrodes and the commercially available fluorinated films. It was theorized that the presence of fluorinated material in Film A is not dense and enables measurable electrical contact resistance, even though the corrosion current is very low.

[0101] FIG. 11 illustrates a graph of contact resistance as a function of pogo pin load for Film D. The solid line shows the load as a function of pogo pin compression. The diamond-shaped data points represent the contact resistance. Film D was greater than 1-micron thick, was soft and friable, and had a rough surface morphology. When the pogo pin compressed Film D, the contact resistance resembled that of an uncoated electrode, even though the corrosion current was very low. It was theorized that normal pressure on Film D disrupts the local film structure surrounding large topographic structures, enabling electrical flow.

[0102] The contact resistance for Films B, C, E, F and G was also measured. The resistance as a function of pogo pin load was infinite. Thus, Films A-F demonstrate contact resistance that is significantly better than current commercially-available films.

[0103] The results of the corrosion current and contact resistance experiments show polysiloxane films of the present application create electron-rich barriers to ionic diffusion and electron conduction that substantially improve protection against moisture damage and ingress. The films represent a marked improvement over commercially-available technologies.