Method for forming regular polymer thin films using atmospheric plasma deposition
Abstract
Problem to be solved.To propose a polymer thin film forming method which alleviates at least some of the drawbacks existing in the prior art. The present invention provides a method of forming a regular polymer thin film on a substrate using atmospheric plasma discharge. In particular, the method allows the deposition of functional polymer thin films that require a high degree of regularity and linear polymer structure. [Selection diagram] Fig. 2

Term
8.6 yearsto projected expiry
Projected expiry 6 May 2035, counted from filing; an application has no term until it is granted.
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24 claims: 1 independent, 23 dependent
- 1基板上にポリマー薄膜を形成する方法であって、 少なくとも1つのポリマー形成材料(10)を含む混合物を提供するステップと、 前記混合物(20)に大気プラズマパルスシーケンスを印加することによって、前記混合物が接触した基板の表面部分上にポリマー薄膜を形成するステップとを含み、 各プラズマパルスが、1ナノ秒間ないし1マイクロ秒間の、前記プラズマが放電される持続時間t ON と、1マイクロ秒間ないし1秒間の、前記プラズマが放電されない持続時間t OFF とを示し、 プラズマパルスのデューティサイクルt ON /(t ON +t OFF )が、1%よりも低いことを特徴とする方法。
- 2前記デューティサイクルが、0.1%よりも低いことを特徴とする請求項1に記載の方法。
- 3各プラズマ放電が、1ナノ秒間ないし1マイクロ秒間でプラズマ放電絶縁破壊電圧まで上昇する電圧パルスによって発生させられることを特徴とする請求項1または2に記載の方法。
- 4前記電圧パルスの電圧上昇率が、少なくとも10V・ns -1 であることを特徴とする請求項3に記載の方法。
- 5前記電圧パルスが、1kHzより低い周波数、好適には100Hzより低い周波数で繰り返されることを特徴とする請求項3または4に記載の方法。
- 6前記電圧パルスが、矩形波電圧パルスであることを特徴とする請求項3ないし5のいずれか1項に記載の方法。
- 7前記矩形波が、バイポーラ矩形波であることを特徴とする請求項6に記載の方法。
- 8前記矩形波が、正または負のユニポーラ矩形波であることを特徴とする請求項6に記載の方法。
- 9前記電圧パルスの持続時間が、1ナノ秒間ないし1秒間であることを特徴とする請求項3ないし8のいずれか1項に記載の方法。
- 10各プラズマ放電が、マイクロ波パルスによって生成されることを特徴とする請求項1または2に記載の方法。
- 11前記ポリマー形成材料が、モノマーを含むことを特徴とする請求項1ないし10のいずれか1項に記載の方法。
- 12前記モノマーが、不飽和基(例えば、アリル基、ビニル基またはアクリル基などの二重結合やエチニルなどの三重結合)を含む少なくとも1つの重合性基を含む分子であるか、または環状構造を有する分子であることを特徴とする請求項11に記載の方法。
- 13前記混合物が、ガス、蒸気、液体、エアロゾルまたは固体であることを特徴とする請求項1ないし12のいずれか1項に記載の方法。
- 14前記混合物が、少なくとも1つの有機溶媒を含むことを特徴とする請求項1ないし13のいずれか1項に記載の方法。
- 15前記基板の前記表面部分が、絶縁材料、半導電性材料または導電性材料を含むことを特徴とする請求項1ないし14のいずれか1項に記載の方法。
- 16前記基板及び/またはプラズマ堆積チャンバが、-50~20°Cの温度で提供されることを特徴とする請求項1ないし15のいずれか1項に記載の方法。
- 17前記基板及び/またはプラズマ堆積チャンバが、20~100°Cの温度で提供されることを特徴とする請求項1ないし15のいずれか1項に記載の方法。
- 18前記プラズマプロセスガスが、アルゴン、二酸化炭素、ヘリウム、水素、窒素及び酸素を含む群から選択された少なくとも1つのガスを含むことを特徴とする請求項1ないし17のいずれか1項に記載の方法。
- 19前記プラズマプロセスガスが、少なくとも1つのポリマー形成材料を含むことを特徴とする請求項1ないし18のいずれか1項に記載の方法。
- 20前記基板及びプラズマが、Ar、He、N 2 または空気が少なくとも99%を占める大気を含む容器内において提供されることを特徴とする請求項1ないし19のいずれか1項に記載の方法。
- 21前記プラズマプロセスガスが、ガス状または蒸気状の重合開始剤を含むことを特徴とする請求項1ないし20のいずれか1項に記載の方法。
- 22前記ガス状開始剤が、過酸化物、アリールケトン及びアルキルアゾ化合物を含む群から選択されることを特徴とする請求項21に記載の方法。
- 23前記プラズマプロセスガスが、酸化剤を含むことを特徴とする請求項1ないし22のいずれか1項に記載の方法。
- 24前記酸化剤が、臭素、臭素化合物、塩素、塩化物化合物、亜塩素酸塩化合物、塩素酸塩化合物、クロム酸塩化合物、クロム酸、二クロム酸、重クロム酸化合物、過塩素酸塩化合物、フッ素、フッ化物化合物、六価クロム化合物、過酸化水素、次亜塩素酸塩化合物、次亜ハロゲン酸塩化合物、無機過酸化物、ヨウ素、ヨウ化物化合物、硝酸塩化合物、硝酸、亜酸化窒素、四酸化オスミウム、酸素、オゾン、ペルオキシ二硫酸、ペルオキシモノ硫酸、硝酸カリウム、酸化銀、過ホウ酸ナトリウム、硫酸及び水を含む群から選択されることを特徴とする請求項23に記載の方法。
Independent claims24
93 paragraphs, as filed
0001The present invention relates to the field of polymer thin film formation. In particular, the present invention relates to the formation of regular polymer films using plasma deposition techniques.
0002A polymer is a long-chain organic molecule in which a large number of small monomer units are repeatedly connected. The properties of polymers are very diverse and can be tailored to a particular application by proper selection of monomer identity and its composition and microstructure.
0003It is known to use chemical vapor deposition (CVD) to form an organic coating on a substrate. The CVD technique allows conformal thin films to be formed on different substrate materials with different shapes. The deposited membrane is substantially free of impurities such as solvents, initiators or plasticizers used in wet chemistry. CVD of organic coatings is usually achieved by a thermal or plasma activation process. In addition, under certain conditions, variants of CVD, such as initiated chemical vapor deposition (iCVD) and oxidized CVD (oCVD), can be used to deposit the monomer layer on the substrate. It is also known that it can be done. Such known processes usually give good results, but the conditions under which the process is carried out usually require a closed / pressurized vessel in the coating apparatus. It is inconvenient to require the above-mentioned container, as the container requires an expensive and technically relevant coating device, which often interferes with the practical application of the CVD process.
0004Known plasma-induced CVD (PE-CVD) processes can be performed at either low or atmospheric pressure. These were investigated for the deposition of organic coatings. Highly functional group retention has been achieved from soft plasma discharges, including pulsed plasma discharges, which makes the resulting organic coating suitable for adhesive applications. However, the so-called plasma-polymers produced during PE-CVD usually exhibit highly branched and cross-linked three-dimensional structures consisting of randomly recombined fragments, in which respect they are synthesized by conventional methods. Distinguished from the polymer. The complex structured plasma-polymers obtained by PE-CVD can be, for example, gas sensitive, optically active, temperature sensitive, or conductive, so-called. Not suitable for applications that include smart functional layers. Such functional layers require linear and regular polymer structures.
0005Atmospheric plasma-induced CVD technology means the use of high voltage alternating current (AC), for example in atmospheric dielectric barrier discharge (AP-DBD). The AP-DBD process can be run at room temperature and has been used for individual applications such as thin film deposition, surface cleaning, sterilization and decontamination, and enhanced wettability and adhesion. According to the prior art, regular monomer layer deposition using the AP-DBD process has not been achieved. The AC AP-DBD process relies on current discharge for tens of microseconds, which causes many random side-crosslinking reactions and the formation of many new chemical groups. Under the current channel known as electron shock and filament, pinholes and non-uniformity are formed in the deposited thin film. Therefore, such known processes are difficult to control, especially when obtaining the regularity structure required in functional polymer thin films.
<p num="0006"> An object of the present invention is to propose a method of forming a polymer thin film that alleviates at least some of the drawbacks present in the prior art.</p>
<p num="0007"> An object of the present invention is to provide a method for forming a polymer thin film on a substrate. The method is -With the step of providing a mixture containing at least one polymer-forming material, -A step of forming a polymer thin film on the surface portion of a substrate by applying an atmospheric plasma pulse sequence to the mixture and bringing the mixture into contact with the surface portion of the substrate. It is noteworthy in that it includes. Here, each plasma pulse has a duration t of plasma discharge for 1 nanosecond (ns) to 1 microsecond (μs).<sub>ON</sub>And the duration t of plasma not being discharged for 1 microsecond to 1 second<sub>OFF OFF</sub>And t<sub>ON</sub>/ (t<sub>ON</sub>+ t<sub>OFF OFF</sub>The duty cycle of the plasma discharge pulse given by) is less than 1%. The duty cycle may also be lower than 0.1%.</p><p num="0008"> The atmospheric plasma pulse sequence may preferably be a periodic sequence.</p><p num="0009"> Preferably, each plasma discharge can be generated by a voltage pulse that raises the plasma discharge dielectric breakdown voltage in 1 nanosecond to 1 microsecond. Alternatively, pulsed microwave discharge can be used to induce a pulsed discharge of plasma. The plasma discharge may be a uniform dielectric barrier discharge, a corona discharge or an arc discharge.</p><p num="0010"> Preferably, the voltage rise rate of the voltage pulse is at least 10 V · ns in absolute value.<sup>-1</sup>Can be. Preferably, the same applies to the voltage drop rate of the voltage pulse.</p><p num="0011"> The voltage pulse is preferably repeatable at frequencies below 1 kHz, preferably below 100 Hz.</p><p num="0012"> The voltage pulse may further be a square wave voltage pulse. In addition, the duration of the square voltage pulse may preferably be 1 nanosecond to 1 microsecond. The square wave may be a bipolar square wave or a positive or negative unipolar square wave.</p><p num="0013"> Preferably, the polymer forming material may be a monomer. The monomer can be derived from, for example, a molecule containing at least one polymerizable group containing an unsaturated group (eg, a double bond such as an allyl group, a vinyl group or an acrylic group, or a triple bond such as ethynyl), or a molecule having a cyclic structure. It may be selected.</p><p num="0014"> The monomers that can be deposited by the methods described herein can be listed virtually indefinitely, including: N-isopropyl suitable for the growth of temperature responsive polymers: Acrylamide (NIPAAm); heptadecafluorodecyl methacrylate (HFDMA) suitable for the preparation of superhydrophobic surfaces; perfluoroalkyl methacrylate (PFEMA) suitable for the preparation of icy surfaces; hexa suitable for the preparation of water purification films Fluoropropylene oxide (HFPO); Diethylene glycol divinyl ether (DEGDVE) suitable for cross-linking linear polymer chains to prevent dissolution of linear polymer chains and enhance stability; Epoxy functionalization for adhesive and bonding applications Glycydyl methacrylate (GMA) suitable for layer deposition; 1-ethyl-3-vinylimidazolium bis (trifluoromethylsulfonyl) imide ([EVIm] [TFSI]) suitable for the formation of polymerizable ionic liquid (PIL) 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (V3D3) suitable for depositing ultra-thin polymer insulating layers; depositing tertiary amine functionalized polymers for bonding and bonding applications Suitable for diethylaminoethyl methacrylate (DEAEMA); 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane (V4D4) suitable for deposition of lithium ion-doped thin film polymers. ); Acrylic acid 1H, 1H, 2H, 2H-perfluorodecyl (PFDA) suitable for making proton exchange membrane fuel cells (PEMFC); suitable for forming biocompatible polymers for use as polyelectrolytes in bioapplications Acrylic acid (AA); Vinylpyrrolidone (VP) suitable for depositing hydrogel materials; Methacrylic acid (MAA) suitable for applications requiring a carboxylic acid moiety; Methacrylic acid suitable for forming hydrophobic photoresponsive polymer thin films. o-Nitrobenzyl (oNBMA); Propagil Methacrylate (PMA) suitable for depositing click active polymer thin films;Hydroxyethyl methacrylate (HEMA) suitable for depositing hydrogel thin films with hydrophilic hydroxyl moieties and high swelling capacity; ethylene glycol diacryllate (EGDA) suitable for preparing pH responsive monomer layers; for forming gas separation membranes Suitable divinylbenzene (DVB); 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) suitable for forming superhydrophilic surfaces; methyl methacrylate (MMA) suitable for deposition of light-shielding monomer layers; pH-responsive layer Di (ethylene glycol) di (vinyl ether) suitable for the preparation of di (ethylene glycol) di (vinyl ether); 2- (dimethylamino) ethyl methacrylate suitable for the deposition of twin ion thin films; ethylene glycol dimethacrylate suitable for the preparation of back-penetration membranes; char formation Diethylaryl phosphate (DEAP) suitable for deposition of protective coatings; zinc 5,10,15,20- (tetra-4-ethenylphenyl) porphyrin suitable for colorigenic gas sensing applications; suitable for the formation of thin film catalysts Chromium 5,10,15,20- (tetra-4-ethynylphenyl) porphyrin; Ion 5,10,15,20- (tetra-4-vinylphenyl) porphyrin; High density functionalizable-NHChromium 5,10,15,20- (tetra-4-ethynylphenyl) porphyrin suitable for forming thin film catalysts; ion 5,10,15,20- (tetra-4-vinylphenyl) porphyrin; high-density functional group Can be transformed into-NHChromium 5,10,15,20- (tetra-4-ethynylphenyl) porphyrin suitable for forming thin film catalysts; ion 5,10,15,20- (tetra-4-vinylphenyl) porphyrin; high-density functional group Can be transformed into-NH<sub>2</sub>Aminostyrene (AS) suitable for the preparation of groups-based surfaces; 1-vinyl-2-pyrrolidone (VP) suitable for the deposition of hydrophilic, biocompatible and antifouling monomer layers; suitable for the preparation of antifouling surfaces 2- (Diisopropylamino) ethyl methacrylate (DMAEMA); 2- (diisopropylamino) ethyl methacrylate (PDPAEMA) suitable for creating surfaces that can switch between superhydrophobic and superhydrophilic states; microfluidic channels Cyclohexyl methacrylate (CHMA) suitable for coating of; Methyl methacrylate ether (MeMA) suitable for depositing polymer electrolyte thin films for lithium ion batteries; Meta-diethynylbenzene suitable for depositing semi-conductive polymer thin films ( MDEB); ethylene glycol suitable for depositing water-soluble polymer thin films; diethylaminoethyl acrylate (DEAEA); dimethylaminomethylstyrene (DMAMS); maleic anhydride (MA); hexavinyldisiloxane (HVDSO); ethylacrylic acid; Propyl acrylate; butyl acrylate; pentyl acrylate; hexyl acrylate; 2-hydroxyethyl methacrylate; vinyltrimethylsilicon (VTMS); vinylidene difluoride (VDF); neopentyl methacrylate (NPMA); cyclohexyl methacrylate (CHMA) Ethylene dimethacrylate (EDMA); 4-vinylpyridine (4VP); dimethylacrylamide; 2-hydroxyethyl methacrylate; perfluoroalkylethyl methacrylate; pentafluorophenyl methacrylate (PFM); trivinylpentamethyltrisiloxane ( TVTSO); dimethylaminoethyl methacrylate; perfluoroalkylethyl methacrylate (PFEMA); vinyl alcohol (VA); ethylene glycol dimethacrylate (EGDMA); n-vinyl-2-caprolactam (NVCL); 2,4,6 ,-Trimethyl-2,4,6,-trivinylcyclotrisilazane; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasilazane;Vinyl acetate; vinyl chloride; styrene; and propylene suitable for adhesive applications.</p><p num="0015"> The mixture and / or polymer-forming material may preferably be a gas, vapor, liquid, aerosol or solid.</p><p num="0016"> The mixture can preferably contain at least one organic solvent. Organic solvents include, for example, acetic acid, acetone, acetonitrile, n-pentanol, n-butanol, 2-methyl-2-propanol, butyl acetate, chlorobenzene, chloroform, cyclohexane, dichloromethane, diethyl ether, 1,2, -dichloroethylene, Diisopropyl ether, dioxane, dimethylformamide, ethanol, ethylacetate, ethylmethylketone, heptane, hexane, isopropyl alcohol, 3-methyl-1-butanol, methanol, pentane, n-propyl alcohol, pentachloroethane, 1,1,2, It can be selected from the group containing 2,-tetrachloroethane, 1,1,1, -trichloroethane, tetrachloroethylene, tetrachloromethane, tetrahydrofuran, toluene, trichlorethylene, water and xylene.</p><p num="0017"> The surface portion of the substrate that comes into contact with the mixture can preferably include an insulating material, a semi-conductive material or a conductive material.</p><p num="0018"> The substrate and / or plasma deposition chamber can preferably be provided at a temperature of -50 to 20 ° C. The substrate and / or plasma deposition chamber can preferably be provided at a temperature of 20-100 ° C.</p><p num="0019"> Preferably, the process gas can include at least one gas selected from the group comprising argon, carbon dioxide, helium, hydrogen, nitrogen and oxygen.</p><p num="0020"> Preferably, the plasma process gas can include at least one polymer forming material.</p><p num="0021"> Preferably, the substrate and plasma are Ar, He, N.<sub>2</sub>Alternatively, it can be provided in a container containing air, which is at least 99% air.</p><p num="0022"> The plasma process gas can preferably contain a gaseous polymerization initiator. The gaseous initiator can further be preferably selected from the group comprising peroxides, aryl ketones and alkyl azo compounds.</p><p num="0023"> The plasma process gas can preferably contain an oxidant. Oxidizing agents include bromine, bromine compounds, chlorine, chloride compounds, chlorite compounds, chlorate compounds, chromate compounds, chromic acid, dichromic acid, dicychromic acid compounds, perchlorate compounds, Fluorine, fluoride compounds, hexavalent chromium compounds, hydrogen peroxide, hypochlorite compounds, hypohalite compounds, inorganic peroxides, iodine, iodide compounds, nitrate compounds, nitrates, nitrogen phosphite, quaternary It can be selected from the group comprising osmium oxide, oxygen, ozone, peroxydisulfate, peroxymonosulfate, potassium nitrate, silver oxide, sodium perborate, sulfuric acid and water.</p><p num="0024"> The present invention provides a method of forming a functional so-called smart polymer thin film that requires regularity and a linear polymer structure. By using the method according to the present invention, conventional linear polymers or copolymer thin films can be grown by chain polymerization, free radical polymerization, precision free radical polymerization, step-growth polymerization, controlled oxidation polymerization, and ring-opening polymerization. This process can operate at atmospheric pressure or near atmospheric pressure, which reduces the need for equipment with sealed and pressure regulated deposit vessels. This also allows the process to be used on substrates with complex shapes, as it is easy to adapt known processing vessels for use in the process according to the invention. The method according to the present invention does not necessarily require an initiator or oxidant as in the case of known CVD processes. The present invention relies on a very short current discharge, which can be triggered, for example, by a voltage pulse with a fast rise time. Therefore, it uses less energy than known AP-DBD methods that use AC sinusoidal pulsed plasma at much higher duty cycles. Less energy is therefore absorbed by the substrate and the temperature of the substrate is not significantly altered by the effects of pulsed plasma discharge. This in turn allows for temperature control of the substrate during deposition. For example, the substrate can be heated, which facilitates the desorption of shorter polymer chains and smaller oligomers. Alternatively, the substrate can be cooled during deposition, thereby promoting the condensation of monomers on the surface of the substrate and increasing the deposition rate. Due to the fast voltage rise time, the square wave AP-DBD according to the present invention is performed by different discharge current pulses in the voltage rise and fall phases. The short current discharge generated is dominated by high-energy electrons and efficiently triggers the formation of free radicals that initiate the free radical polymerization process. Short current discharge duration is t<sub>OFF OFF</sub>Allows the use of duty cycles well below 0.1% while maintaining the millisecond range. The effect of plasma discharge on the resulting thin film chemistry is thus minimized. On the other hand, the free radical polymerization reaction that occurs during more than 99.9% of the deposition process works very favorably. Therefore, the present invention is used to grow a thin film composed of well-defined and defect-free polymer repeating units.</p><p num="0025"> As far as the inventor of the present application is known, there has been no scientific evidence that ignition of an ultrashort atmospheric plasma discharge using a very low repetition frequency can induce a linear polymerization process.</p><p num="0026"> Hereinafter, the present invention will be described through various preferred embodiments and with reference to the drawings.</p>
0027<figref num="1">It is a flowchart which shows the main method step according to the preferred embodiment of this invention.</figref><figref num="2">It is the schematic of the preferable embodiment of the apparatus for carrying out this invention.</figref><figref num="3">It is the schematic of the preferable embodiment of the apparatus for carrying out this invention.</figref><figref num="4">It is the schematic of the preferable embodiment of the apparatus for carrying out this invention.</figref><figref num="5">The applied voltage and associated plasma current discharge measured when using the preferred embodiments of the present invention are shown.</figref><figref num="6">The applied voltage and associated plasma current discharge measured while using the prior art method are shown.</figref><figref num="7">The dependence of the polymer thin film growth rate on the discharge pulse duty cycle for preferred embodiments and prior art methods of the present invention is shown.</figref><figref num="8">The amount of increase in polymer thin film thickness per growth cycle as a function of cycle duration for preferred embodiments of the present invention and prior art methods is shown.</figref><figref num="9">The FTIR spectra of the glycidyl methacrylate monomer and the poly (glycidyl methacrylate) polymerized by the conventional method are shown.</figref><figref num="10">The FTIR spectra of polymer thin films grown from various duty cycles using preferred embodiments of the present invention are shown.</figref><figref num="11">The FTIR spectra of polymer thin films grown from various duty cycles using prior art methods are shown.</figref><figref num="12">The XPS spectra of polymer thin films grown from various duty cycles using preferred embodiments of the present invention are shown.</figref><figref num="13">The results of AP-MALDI-HRMS for the samples obtained using the preferred embodiments of the present invention are shown.</figref><figref num="14">The size exclusion chromatogram of the polymer thin film formed using the preferred embodiment of the present invention is shown.</figref><figref num="15">The results of MALDI-MS for the samples obtained using the preferred embodiments of the present invention are shown.</figref><figref num="16">It consists of (a) to (c), where (a) and (b) show different frequency voltage pulsations used according to preferred embodiments of the present invention, and (c) is shown in (a) and (b). It shows various discharge currents related to pulsation.</figref><figref num="17">The mass deposition rates observed using the preferred embodiments of the present invention are shown.</figref><figref num="18">The mass deposition rate efficiency considering the energy used in 1 second observed using the preferred embodiments of the present invention for various duty cycles is shown.</figref><figref num="19">The relative atomic concentrations of the polymer membranes deposited using the preferred embodiments of the present invention, as well as DEAP and polyDEAP, are shown.</figref><figref num="20">High resolution XPS spectra of C1s contributions of conventional polymerized poly DEAP and plasma polymerized DEAP with a duty cycle of 0.001% according to preferred embodiments of the present invention are shown.</figref><figref num="21">The FTIR spectra of the DEAP plasma polymer formed using the preferred embodiment of the present invention and the poly DEAP synthesized by a known free radical polymerization method are shown.</figref><figref num="22a">The AP-MALDI-HRMS spectrum of the polymer thin film formed by using the preferred embodiment of the present invention is shown.</figref><figref num="22b">The AP-MALDI-HRMS spectrum of the polymer thin film formed by using the preferred embodiment of the present invention is shown.</figref><figref num="22c">The AP-MALDI-HRMS spectrum of the polymer thin film formed by using the preferred embodiment of the present invention is shown.</figref>
0028FIG. 1 is a flowchart showing the main steps of a preferred embodiment of the present invention. In the first step 10, a mixture containing at least one polymer-forming material is provided. The mixture may consist solely of the polymer-forming material itself, but may instead include other components, such as organic solvents. The inclusion of such additional components may affect, for example, the rate of film formation and the porosity of the deposited layer. The polymer-forming material is advantageously a monomer, the selection of which is such that the regularity and linear polymer chains containing the monomer exhibit the properties required for the intended application. Monomers that can be deposited by the methods described herein can be listed virtually indefinitely, including: N-isopropyl suitable for the growth of temperature-responsive polymers: Acrylamide (NIPAAm); heptadecafluorodecyl methacrylate (HFDMA) suitable for the preparation of superhydrophobic surfaces; perfluoroalkyl methacrylate (PFEMA) suitable for the preparation of icy surfaces; hexagon suitable for the preparation of water purification films Fluoropropylene oxide (HFPO); Diethylene glycol divinyl ether (DEGDVE) suitable for cross-linking linear polymer chains to prevent dissolution of linear polymer chains and enhance stability; Epoxy functionalization for adhesive and bonding applications Glycidyl methacrylate (GMA) suitable for layer deposition; 1-ethyl-3-vinylimidazolium bis (trifluoromethylsulfonyl) imide ([EVIm] [TFSI]) suitable for the formation of polymerizable ionic liquid (PIL) 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (V3D3) suitable for depositing ultra-thin polymer insulating layers; depositing tertiary amine amine functionalized polymers for bonding and bonding applications Suitable for diethylaminoethyl methacrylate (DEAEMA); 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane (V4D4) suitable for deposition of lithium ion-doped thin film polymers. );<sub>2</sub>Vinyl acetate; vinyl chloride; styrene; and propylene suitable for adhesive applications. One of ordinary skill in the art can select the polymer-forming material according to the requirements of a particular application. Such applications preferably include the use of smart or highly functional monomeric layers and / or coatings. The substrate on which the polymer thin film is formed is, for example, a conductive or semi-conductive material. Alternatively, the substrate may be any insulating material. The substrate may be, for example, a metal such as glass or steel. Furthermore, the substrate can have a planar or three-dimensional shape. Depending on the means and shape used to bring the substrate into contact with the mixture, the latter can be provided in the form of a gas or vapor, or as a liquid, as an aerosol or as a solid.
0029During the subsequent step 20, a polymer thin layer is formed on the surface portion. To that end, an atmospheric plasma pulse sequence is applied to the mixture. Low frequency and ultrashort pulsed atmospheric plasma discharges have little effect on the temperature of the monomers, reactors and substrates. The temperature of the monomer mixture, the reactor chamber and the substrate can all be adjusted independently. This involves the formation of free radicals that come into contact with the surface of the substrate or interact with other radicals present on the surface portion of the substrate. The pulsed plasma is characterized by the characteristics of the discharge pulse. Specifically, each pulse has a duration t during which the plasma is discharged.<sub>ON</sub>And the duration t that the plasma is not discharged<sub>OFF OFF</sub>And. The total duration of the pulse is t<sub>ON</sub>And t<sub>OFF OFF</sub>Given by the sum of. Discharge time t<sub>ON</sub>Is very short, in the range of 1 ns to 1 μs, but with an inactivity time t<sub>OFF OFF</sub>Is much longer, about 1 μs to 1 second (s). These two durations are chosen so that the discharge time is much shorter than the rest time. Therefore, the duty cycle of the plasma pulse is t<sub>ON</sub>/ (t<sub>ON</sub>+ t<sub>OFF OFF</sub>), Advantageously lower than 1%, preferably lower than 0.1%. A thin layer is formed in 1 to 100 seconds, depending on the pulsating frequency of the plasma.
0030During the period when the plasma is discharged, various ions, metastable atoms, electrons and radicals are generated and the initiation reaction begins. On the other hand, in a much longer period when the plasma is not discharged, ions, semi-stable atoms and electrons disappear rapidly, but the formed free radicals ensure the polymerization of components containing polymerizable groups. .. According to the present invention, this second step works very favorably.
0031Here, the principle underlying the present invention will be described as a general theory. Further details will be described in preferred embodiments described herein.
0032FIG. 2 shows a schematic representation of an exemplary and non-limiting embodiment of the device 100 for performing a method according to the present invention. The stage 113 conveys the substrate 105, and the surface portion of the substrate 105 is coated along the direction X. A portion of the substrate 105 passes through the plasma zone 109, where the substrate is exposed to pulsed atmospheric pressure plasma. In the illustrated embodiment, the dielectric barrier discharge plasma is provided by two electrodes 108 arranged side by side and a system having a slot between the electrodes, through which the process gas G is directed toward the substrate 105. Can be made to. The mixture 103 containing the polymer-forming material is gaseous. The mixture 103 is carried near the substrate 105 together with the process gas G. Both electrodes 108 are coated with a dielectric layer 110. Upon exposure to a pulsed dielectric barrier discharge plasma, the polymer-forming material forms a monomer layer on the substrate 105. A pulsed plasma is evoked by a high voltage pulse generator 120 functionally coupled to the electrodes. The generator 120 is operated to apply a voltage pulse with a rise time capable of reaching the plasma discharge breakdown voltage within 1 nanosecond to 1 microsecond, preferably within 1 nanosecond to 0.1 microsecond. .. The generator is operated to generate a substantially rectangular ultrashort high voltage pulse with a duty cycle of less than 1%, preferably less than 0.1%. Such signal generators are available in the art and are known to those of skill in the art and are therefore not described in further detail in the context of the present invention. The pulsation frequency is less than 10 kHz, preferably less than 1 kHz, more preferably less than 100 Hz. After passing through the plasma zone 109, the substrate 105 contains a polymer thin film 111, which contains a regular and linear polymer structure. Although not shown, the above steps can be performed several times. In addition, the method is at or near atmospheric pressure, i.e. 5.
0033The device 200 for carrying out the present invention shown in FIG. 3, which is another embodiment, is the same as the embodiment shown in FIG. 2 except for the following. The mixture 203 containing the polymer-forming material is deposited, sprayed, or evaporated on a portion of the substrate 205 using a spray nozzle 204. The pretreated substrate is then exposed to pulsed plasma 209. Both zones do not overlap or are spatially different.
0034Specifically, by using the AP-DBD procedure described in FIG. 3, the afterglow region surrounds the plasma discharge. Therefore, the formed layer will first be exposed to an afterglow region that is softer than a direct plasma discharge, in which the polymerization process will have already begun. The lateral extension of the afterglow region can be, for example, 1-20% of the extension of plasma zone 209.
0035Any type of atmospheric pressure plasma discharge, including, but not limited to, dielectric barrier discharge, corona discharge, arc discharge, etc., can be used to perform a method of forming a polymer thin film on a substrate. The discharge is initiated between at least two electrodes, one of which can be a coated substrate. When a discharge is generated between the high voltage electrode and the substrate, the substrate is believed to be directly exposed to the plasma discharge. The embodiments shown in FIGS. 2 and 3 schematically illustrate an apparatus in which the substrate is directly exposed to plasma discharge. Such embodiments are particularly suitable for coating flat substrates.
0036FIG. 4 shows a schematic representation of an exemplary and non-limiting embodiment of a remote discharge device 300 for performing a method according to the invention on a 3D substrate 305. Discharge begins in the reactor 310 between at least two electrodes, one of which is the high voltage electrode and the other of which is the ground electrode. Upstream of substrate 305, plasma discharge 309 is triggered remotely. If the discharge occurs upstream of the substrate, the substrate is exposed to plasma discharge afterglow or plasma jets (also called inductive streamers). Remote discharge is particularly suitable for processing 3D substrates.
0037In all configurations, the polymer forming material can be directly exposed to the plasma discharge, or plasma discharge afterglow region, or plasma jet region.
0038In the following preferred embodiments, two different experimental procedures for carrying out the method according to the present invention and the results obtained using them will be described.
00391. Atmospheric pressure plasma initiation chemical vapor deposition using ultra-short square pulse dielectric barrier discharge
0040In the following, expandable methods for atmospheric pressure plasma-initiated chemical vapor deposition of conventional polymers according to the present invention will be described. Ultrashort pulse dielectric barrier discharges are used to deposit the monomer layer, which allows for high deposition rates at low plasma duty cycles of 0.01%. FTIR and XPS reveal excellent retention of unstable functional epoxy groups. The polymer structure of the thin film is demonstrated by matrix-assisted laser desorption / ionization high-resolution mass spectrometry. Size Exclusion Chromatography (SEC) reveals the suitability of the monomer layer deposition method according to the present invention, up to 30,000 g · mol<sup>-1</sup>The polymer molecular weight of was obtained.
00411.1. Experimental part
00421.1.1. Atmospheric pressure plasma initiation Chemical vapor deposition and materials
0043As described above, poly (glycidyl methacrylate), PGMA and ppGMA thin films polymerized in the atmospheric dielectric barrier discharge reactor were deposited. We investigated two different electrical excitations to cause plasma discharge.
0044On the one hand, an AHTPB10F generator manufactured by EFFITECH® (Gif-sur-Yvette, France), which produces a 1 μs square peak of 2 kV, was used to generate an ultrashort square pulse DBD according to the present invention. The duty cycle of 0.01 to 1% was investigated by changing the peak repetition frequency from 100 Hz to 10,000 Hz.
0045On the other hand, an AC current DBD was generated using a Corona generator 7010R manufactured by SOFTAL Corona & Plasma GmbH (Hamburg, Germany), which produces a 1 kV 10,000 Hz sine wave signal. AC discharge t<sub>ON</sub>Was maintained at 1 ms and the duty cycle (DC) of 0.1 to 100% was investigated. Discharge current and voltage signals were measured using a current probe (Lecroy®, CP030) and a high voltage probe (Lecroy®, PPE 20 kV). Waveforms were recorded using an oscilloscope (Lecroy®, Wavesurfer 42XS, 400MHz). Using a classical bubbler system, the liquid monomer glycidyl methacrylate (GMA) (Sigma Aldrich®, 97%) was injected into the reactor using it without further purification. Argon (Air Liquide (registered trademark), 99.999%) used as a process and carry gas was added to 15 l · min.<sup>-1</sup>I flushed it to the bubbler. 20 l · min of total argon flow through the reactor throughout all experiments<sup>-1</sup>Maintained in. Aluminum substrates (Eurofoil® and silicon wafer substrates from Dudelange, Luxembourg) (Siltronix®, Archamps, France), 95: 5 nitrogen: oxygen (Air Liquide) (Registered Trademark), 99.999%) AP-DBD Plasma (1W cm)<sup>-2</sup>) Was washed by exposure for 30 seconds. For comparison, PGMA powder polymerized by the conventional method (Sigma-Aldrich Corporation (registered trademark), Mn ~ 20,000 g · mol<sup>-1</sup>) Was also characterized.
00461.1.2. Analytical technology
0047Scanning electron microscope (SEM) observation and film thickness measurement were performed by Hitachi (registered trademark) SU-70 FE-SEM. Prior to SEM observation, the non-conductive sample was sputter coated with 5 nm platinum to prevent charging and twisting. Fourier Transform Infrared Spectroscopy (FTIR) analysis was performed with a Bruker® Hyperion 2000 spectrometer equipped with a Ge-ATR-liquid crystal. X-ray photoelectron spectroscopy (XPS) analysis was achieved with a Kratos® Axis-Ultra DLD instrument using a monochromatic Al Kα X-ray source (hυ = 1486.6 eV) with a path energy of 20 eV. AP-MALDI manufactured by MassTech Inc. combined with LTQ / Orbitrap Elite manufactured by Thermo Scientific (registered trademark) (San Jose, CA) Atmospheric matrix-assisted laser desorption / ionization high-resolution mass spectrometry (AP-MALDI-HRMS) analysis was performed using a PDF + ion source. Before analysis, α-cyano-4-hydroxysilicate skin acid (10 mg · mL)<sup>-1</sup>The sample surface was modified by directly spotting 0.2 μL of a solution of (50: 50 v / v methanol / water containing 0.1% trifluoroacetic acid) on the sample surface. Once evaporated, the solution results in co-crystallization of the workpiece and matrix from the sample surface, thereby promoting ionization efficiency and limiting laser-induced fragmentation. Differential Refractometer (RID), and up to 400,000 g · mol<sup>-1</sup>Size exclusion using Agilent Technologies® (Diegem, Belgium) 1200 series system with PLgel MIXED-D 5mm SEC column designed for poly (styrene) equivalents of molecular weight Chromatography (SEC) was performed. OmniSEC® software version 4.6.1 (Malvern Instruments, UK) was used for data acquisition and processing. Calculated number average molecular weight and weight average molecular weight (Mn and weight average molecular weight, respectively) using a set of poly (methyl methacrylate) standards purchased from Sigma-Aldrich® (St. Louis, Missouri) and conventional calibration methods. Mw) was calculated. Samples are HPLC grade THF (1 mg · ml)<sup>-1</sup>), 1 mL · min<sup>-1</sup>Was analyzed at the flow rate of. Bruker® Autoflex III Mass Spectrometer with Triple Frequency Nd-YAG Laser (λ = 355nm) Operated at 50Hz Pulse Repeats (Bruker Dartonics) MALDI-MS mass spectra were recorded using Daltonics), Leipzig, Germany). Ions were accelerated by a positive voltage of 19 kV using a pulse ion extractor (based on the mass range of interest (approximately 10 ns in this case)). A time-of-flight mass spectrometer was operated in reflector mode and ions were detected using a microchannel plate detector. Calibration was performed using both matrix peak (internal calibration) and poly (ethylene glycol) standard material (external calibration, solvent-free coating, CHCA as matrix, LiTFA as cationized salt). FlexControl® software version 3.0 (Burker Daltonics) is used for instrument control and data acquisition, and FlexAnalysis® software version 3.0 (Burker Daltonics) and mMass version 5.5 are used for data processing. Was used. Α-Cyano-4-hydroxycinnamic acid (CHCA) was purchased from Bruker Daltonix® (Leipzig, Germany). Lithium trifluoroacetate (LiTFA), trans-2- [3- (4-tert-butylphenyl) -2-methyl-2-propenilidene] malononitrile (DCTB) and poly from Sigma-Aldrich® (St. Louis, Missouri) (Ethethylene glycol) Standard substance (Mn = 600, 1,000, 2,000 and 3,000 g · mol<sup>-1</sup>) Was purchased. All samples followed a solvent-free preparation consisting of a step of grinding the matrix (CHCA for calibrator, DCTB for assay) with polymer and LiTFA-doped salt at room temperature for about 5 minutes using a mortar and pestle. .. The matrix / polymer / salt molar ratios were largely optimized for each sample. The solid mixture thus produced was applied to several MALDI targets and then pressed with a small spatula to form a thin film for mass spectrometry.
00481.2. Results and discussion
00491.2.1. Short rectangular pulse dielectric barrier discharge for free radical polymerization of PGMA layer
0050To illustrate the benefits of ultra-short rectangular pulse dielectric barrier discharge, a second series of thin films was deposited using sinusoidal alternating current with argon and GMA steam supplied in the same AP-DBD reactor. In each case, different t<sub>ON</sub>, T<sub>OFF OFF</sub>And the duty cycle has been investigated and summarized in Tables I and II. For short square pulse and alternating current AP-DBD experiments, t<sub>ON</sub>Was maintained at 1 μs and 1 ms, respectively. For the short square pulse AP-DBD test, a maximum plasma off time of 9999 μs (DC can be investigated up to 0.01%) was investigated, but for an AC current AP-DBD, a maximum of 999 ms t was investigated.<sub>OFF OFF</sub>That is, 0.1% DC was considered.
0051<img id="000003" he="70" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" />
0052<img id="000004" he="83" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" />
00535 and 6 show the gas-applied external voltage and current density measured for the short square pulse and AC current AP-DBD, respectively. Although the short square pulse AP-DBD is observed to operate in uniform mode with different discharge current pulses during voltage rise and fall phases (Figure 5), the AC AP-DBD has many cluttered filament current peaks. The filament discharge that it has is shown (Fig. 6). A fast voltage rise of up to 2 kV in 30 ns has a duration of about 100 ns and an amplitude of 0.6 mA · cm.<sup>-2</sup>Induces a first positive discharge current pulse that is. Negative current peaks of the same duration and amplitude occur during voltage drop.
00541.2.2. Polymerization Poly (glycidyl methacrylate) (PGMA) layer characterization
0055The atmospheric dielectric barrier discharge deposition of glycidyl methacrylate results in a macroscopically smooth and adhesive thin film deposition over the entire length of the substrate, regardless of the various electrical excitations (Tables I and II) investigated in this embodiment. Brought. All deposited membranes were stable when immersed in water and absolute ethanol and when wiped. Apart from the apparent difference in growth rate, the membranes were indistinguishable from each other. By SEM, it was confirmed that all the deposited films covered the entire substrate and were smooth and free of particle formation.
0056The dependence of film formation rate on plasma electrical excitation and duty cycle was investigated by cross-sectional SEM. The deposition rate obtained from the alternating current AP-DBD (Fig. 7) reached its maximum at 10% DC, consistent with that observed in previous studies. The amount of film thickness increase per cycle (Fig. 8) is t<sub>OFF OFF</sub>It shows the existence of the sedimentary reaction that occurs inside, and t<sub>OFF OFF</sub>It has been shown to reach a plateau of 140 pm per cycle when is over 100 ms. This indicates the termination of free radical polymerization of GMA due to the radical combination reaction that occurs over a long rest period. As a result, in AC AP-DBD, t of 315ms or more<sub>OFF OFF</sub>That is, at DCs lower than 0.3%, the film formation rate is almost zero. The maximum deposition rate obtained for the square pulse AP-DBD was also obtained for 0.1% DC, which is two orders of magnitude lower than that observed in the AC experiment. Furthermore, from the short rectangular pulse AP-DBD, the maximum is 6.3 nm · s.<sup>-1</sup>Higher deposition rates were obtained. The use of short square pulses is fairly short t less than 1ms<sub>OFF OFF</sub>In the meantime, the concentration of free radicals remains high and contributes to polymer propagation. t<sub>OFF OFF</sub>When was longer than 1 ms, a decrease in slope was observed in the plot of film thickness increase as a function of cycle duration. This indicates a slowdown in the free radical polymerization process due to the reduction of available free radicals.
0057Observation of growth rate is t<sub>ON</sub>And t<sub>OFF OFF</sub>The occurrence of various mechanisms inside was shown. It is well known that the combination of these mechanisms affects the chemical composition and structure of the resulting thin film. Various junction configurations in the deposited membrane were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and compared to those of liquid GMA monomers and conventional polymerized PGMA powders (Figs. 9-11). The strong and narrow absorption band attributed to the C = O expansion and contraction of the ester group is 1722 cm regardless of the plasma electrical excitation.<sup>-1</sup>Was observed in. The C = O bond should also be present in the GMA monomer and PGMA powder spectra and should not change upon cross-linking, and the C = O bond was used to normalize the entire spectrum. Interestingly, the FTIR spectra of the thin films (ie A3, A4 and A5) obtained from the lowest DC are consistent with those obtained for PGMA polymerized by conventional methods. These samples are 755 cm<sup>-1</sup>, 843cm<sup>-1</sup>, 905cm<sup>-1</sup>And 1253 cm<sup>-1</sup>It clearly showed excellent retention of the pendant epoxy group with the presence of a well-margined FTIR absorption band in. The increase in DC resulted in peak intensity loss and peak spread due to the breakdown and formation of functional groups in the broader distribution of chemical bonds. 1448cm<sup>-1</sup>, 1483cm<sup>-1</sup>, 2933cm<sup>-1</sup>And 2999 cm<sup>-1</sup>CH in<sub>3</sub>Other peaks due to the vibrational mode were also observed to widen with increasing DC. Interestingly, in the FTIR spectrum of the deposited membrane, GMA monomer (1637 cm) presumed to cause polymerization<sup>-1</sup>A C = C stretch band from the methacrylate group of) was observed.
0058X-ray photoelectron spectroscopy (XPS) showed that all films contained only carbon and oxygen elements. No evidence of nitrogen contamination from the open air reactor ambient air and silicon or aluminum from the substrate was detected. Figure 10 shows the carbon C1s core level of the membrane obtained from various short rectangular pulse AP-DBD conditions. For membranes obtained from DCs below 0.3%, the C1s husk level envelope can be overlaid on one of the PGMAs, which means that there are five different carbon environments, namely CH (285.00eV). ), C (CH<sub>3</sub>) (CH<sub>2</sub>)<sub>2</sub>(C = O) (285,67eV), O-CH<sub>2</sub>-CO (286,71eV), epoxide CH-O-CH<sub>2</sub>It is clarified that (287.02eV) and C (= O) O (289.15eV) exist in a ratio close to the ratio of PGMA. Regardless of the supply of electrical excitation, the increase in DC resulted in a clear decrease in epoxy group contribution at 287.02 eV. All of these observations are consistent with the FTIR analysis already described in this embodiment.
0059The FTIR and XPS spectra of the membranes obtained from the lowest DC conditions have been shown to be consistent with those obtained for commercially available PGMA (FIGS. 9-12). However, such techniques only provide information on the retention of groups and cannot be used to determine the structure of the polymer. Atmospheric matrix-assisted laser desorption / ionization high-resolution mass spectrometry (AP-MALDI-HRMS) experiments were performed to determine the molecular composition of plasma-polymerized samples. AP-MALDI-HRMS is associated with poly (GMA) oligomers relative to the sample with a duty cycle of 0.1% or less for the square wave pulse AP-DBD and 0.3% or less for the AC current AP-DBD. A mass spectrum showing the signal to be used is given. A detailed AP-MALDI-HRMS analysis of the sample (ie A3) obtained from the square wave pulse AP-DBD and 0.1% duty cycle is shown in Figure 13 and the main ions of interest are summarized in Table III. The spectrum is occupied by the intact oligomer of poly (GMA). The base peak corresponds to the protonated dimer of GMA having a proton as the terminal group. Such oligomers can be detected up to hexamer under these conditions. In addition to this intact oligomeric distribution, a remarkable signal is given to the monomer (C).<sub>7</sub>H<sub>11</sub>O<sub>3</sub><sup>+</sup>, M / z = 143.0704), oligomers with one or two hydroxyl end groups, and oligomers with modified repeating units. Changes in the two main repeat units can be observed. As a first modification, 2,3-dihydroxypropyl methacrylate (DHPMA) (m / z = 161.08095 ([C)) by hydrolyzing the epoxy ring of the monomer.<sub>7</sub>H<sub>12</sub>O<sub>4</sub>+ H]<sup>+</sup>)) Can be formed. From this DHPMA monomer, GMA reacts and the general formula is [H (DHPMA).<sub>n</sub>(GMA)<sub>m</sub>H + H]<sup>+</sup>It is possible to form the distribution of oligomers measured at m / z = 305.15948, 447.22246 and 589.28562 corresponding to poly (GMA) having and having one hydrolyzed epoxy ring. As a second modification, one ester group can be hydrolyzed to give one carboxylic acid repeating unit (isobutyric acid (IBA)). As a general formula [H (IBA)<sub>n</sub>(GMA)<sub>m</sub>H + H]<sup>+</sup>Such oligomers with, for example, correspond to the signals detected at m / z = 231.12266 and 317.15951, where one GMA repeat unit is attached to one or two isobutyric acid repeat units, respectively.
0060GMA Plasma Initiation Chemistry Solubility of thin film (A5) obtained from square wave pulse AP-DBD and 0.01% DC to obtain information on the molar mass and molar mass distribution of the molecular structures synthesized during vapor phase deposition. Size exclusion chromatography (SEC) analysis was performed on the part. As a result, the SEC chromatogram recorded from the differential index detector was polymerized by the conventional method for comparison with PGMA (Mn = 20,000 g · mol).<sup>-1</sup>) Is shown in FIG. 14 together with the chromatogram. Multimodal distributions are easily detected for plasma-polymer samples, very short chains are observed as strong peaks just before the solvent peaks, some oligomers are seen as shoulders of the above peaks, and longer poly (GMA). Species were detected as a wide distribution. Conventional calibration using PMMA standards is an accurate mass measurement (Mn = 21,139 g · mol) for commercially available PGMA samples, probably due to their close chemical composition and structure.<sup>-1</sup>, Mw = 50,512g mol<sup>-1</sup>And Mp = 33,524g mol<sup>-1</sup>) Was found to be provided. Assuming that the polymer chains produced in the plasma-polymer are more similar in shape to each other than the polymer chains produced under conventional wet polymerization, up to 30,000 g · mol in the soluble part of the A5 sample.<sup>-1</sup>Species could be detected slightly, but the values of Mn, Mw and Mp are approximately 2,753 g · mol, respectively.<sup>-1</sup>, 9,086g mol<sup>-1</sup>And 3,253g mol<sup>-1</sup>Found in.
0061<img id="000005" he="159" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" />
0062A MALDI-MS experiment was performed on the THF-soluble part of the membrane (sample A5) obtained from the square wave pulse AP-DBD and the 0.01% duty cycle. The results are shown in Fig. 15. Three protonated PGMA-like distributions briefly described as a PGMA backbone with H / H, H / OH and OH / OH as α / ω end groups were detected (Table IV). An additional amount resulting from the disproportionation reaction and shifted by -2 Da from the above main distribution was also observed, but other distributions with undefined terminal groups were also slightly detected, so the molars of α / ω terminal groups were observed. Listed in Table IV along with mass. Further experiments with triple detection (RID, viscometer, and right-angle / low-angle light scattering) were tried to prove the deviation and branching of the linear PGMA reference compound to kinetics, but of sufficient quality. No signal was recorded.
0063<img id="000006" he="147" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" /><img id="000007" he="248" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" /><img id="000008" he="70" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" />
00641.2.3. Free radical plasma initiation Chemical vapor deposition
0065Numerous previous studies have reported how plasma electroexcitation frequencies can affect the morphological and chemical properties of AP-DBD-deposited membranes. SEM and AFM observations have clearly shown whether electrical excitation can favor or prevent the formation of particles, non-uniformities or pinholes in the coating. In parallel, longer plasma t<sub>OFF OFF</sub>Chemical studies revealed better monomeric structure retention when the period was used. Higher functional group retention is usually t<sub>OFF OFF</sub>It is induced by the monomer-free radical polymerization that occurs in it. In contrast, the shorter plasma t<sub>OFF OFF</sub>Causes a high rate of random side-crosslinking reactions, leading to the formation of new chemical groups. By using plasma DCs lower than 0.1% using the present invention, free radical polymerization of methacrylate functional groups containing monomers was improved. In the classic AC AP-DBD, such a low duty cycle is plasma t in the range of hundreds of milliseconds.<sub>OFF OFF</sub>Means the use of, resulting in a very slow growth rate.
0066In contrast, the ultra-short rectangular pulse dielectric barrier discharge is t<sub>OFF OFF</sub>Can allow the use of DC well below 0.1% while maintaining the range of milliseconds. The result is a high growth rate that exceeds even the maximum speed achieved with AC AP-DBD. A short and uniform current discharge (100ns) dominated by high energy electrons that efficiently induces the formation of free radicals that will initiate the free radical polymerization process due to the fast voltage rise time (30ns). ) Is obtained. The effect of the plasma discharge, which occurs twice every 1-10 ms for 100 ns, on the chemistry of the resulting thin film is thus minimized. On the other hand, free radical polymerization reactions that occur only during 99.9% or more of the deposition process are very advantageous. Therefore, a thin film consisting of polymer repeating units of known composition, etc., as observed by MALDI-HRMS, for example, is grown.
0067As shown in this study, ultra-short rectangular pulse dielectric barrier discharges are particularly suitable for the deposition of thin films with high epoxy group retention. Thanks to the use of nanosecond to microsecond pulsed AP-DBDs, other unstable functional groups that are easily cleaved in the PE-CVD process can also be retained. Beyond the benefits of functional group retention, ultra-short rectangular pulsed dielectric barrier discharges have also been shown to result in the formation of homomonomer layers. The plasma deposition method described in this embodiment opens a new path towards chemical vapor deposition of functional homopolymers and copolymers. The plasma-initiated chemical vapor deposition technique (PiCVD) currently under investigation for the deposition of conductive polymers as thin films will also be suitable for deposition of responsive conductive layers that require a linear polymer structure. ..
00681.3. Conclusion
0069The previously known CVD method adopted to obtain the monomer layer implies the use of reduced pressure, but the ultrashort rectangular pulsed dielectric barrier discharge is a simple one-step process for homopolymer deposition. Provide atmospheric and room temperature processes. Thanks to the fast voltage rise time (30 ns), a short and uniform discharge dominated by high-energy electrons occurred and free radical polymerization of GMA was initiated. The effect of plasma on GMA monomers is minimized by using a low duty cycle of 0.01%, t<sub>OFF OFF</sub>The free radical polymerization reaction that occurred inside worked very favorably on the deposited PGMA layer. FTIR and XPS showed excellent retention of unstable functional epoxy groups. Matrix-assisted laser desorption / ionization high-resolution mass spectrometry demonstrated the polymer structure of the thin film. Maximum 30,000g mol<sup>-1</sup>A monomer layer having a weight average molecular weight of Ultra-short rectangular pulsed dielectric barrier discharges open new avenues for chemical vapor deposition of functional homopolymers and copolymers and are currently under investigation for the deposition of conductive polymers as thin films.
00702. Conventional poly (diethylaryl phosphate) atmospheric pressure plasma initiation chemical vapor deposition using unipolar nanosecond square pulse dielectric barrier discharge
0071In this embodiment, the possibility of depositing conventional polymers by AP-PiCVD via free radical polymerization is described thanks to the ultra-short square pulse DBD.
00722.1 Experimental part
00732.1.1 Material
0074DEAP (diethyl allyl phosphate) was obtained from Sigma-Aldrich® and used without further purification (98%).
00752.1.2 Coating deposit
0076The configuration of the direct dielectric barrier discharge used in this study is summarized below. A discharge was generated between the two planar parallel high voltage electrodes (15 mm x 74 mm each) covered by an alumina dielectric barrier and the movable stage as a ground electrode. Prior to plasma treatment, the plasma chamber was pumped to a vacuum of 20 Pa and then filled with the desired gas mixture (argon in this case) to atmospheric pressure. By repeating this procedure three times, high gas purity and homogeneity of the discharge were ensured. The distance between the high voltage electrode and the substrate was maintained at 1 mm. Organophosphate precursors (DEAP, C7H15O4P) were injected into the discharge using a bubbler system with cylinders and frits. To prevent the precursor from condensing on the inner surface of the gas tube, the precursor was thermostat-controlled (298K) and the gas tube was slightly heated (308K). The concentration of precursor is approximately 20 ppm. The total flow rate was maintained at 5 standard liters per minute (slm) in all experiments and the atmospheric pressure was kept constant by slight pumping. During the deposition process according to the present invention, plasma was initiated using the Effitech® generator AHTPB10F, which generates ultra-short square pulses. There is also another type of generator (Corona Generator, SOFTAL electronic® GmbH) for initiating plasmas with a standard 10kHz sinusoidal signal, as is known in the art. Using. In that case, t from continuous wave (CW) respectively<sub>on</sub>And t<sub>off</sub>Coatings were deposited using various modulated sinusoidal electrical excitations up to pulsed waves (PW) with different on-time and off-time pulses named. The off time was set to 30 ms to renew the gas mixture between the electrodes before each on time.
0077The coated substrate was a 275 μm thick silicon wafer (intrinsic, double-sided mirror-polished, Syltronics®). First, N by washing the substrate with acetone and alcohol in an ultrasonic bath prior to each operation and plasma activating for 30 seconds just prior to deposition.<sub>2</sub>: O<sub>2</sub>(95: 5%) Atmospheric dielectric barrier discharge occurred.
00782.1.3. Thin film characterization technology
0079Samples were weighed using a ME-36S microbalance manufactured by Sartorius®. Samples were weighed three times before and after each deposition to measure mass deposition rates.
0080The coating thickness was evaluated by spectroscopic ellipsometry (AutoSE®, Horiba Scientific) at an angle of incidence of 70 ° over a spectral range of 440-1000 nm. The polarization model used assumes that the sample is made up of a 2 nm thick silicon oxide layer (natural oxide film) and a semi-infinite silicon substrate topped with a plasma thin film. The plasma polymerized layer was simulated using the law of dispersion, assuming that it was uniform, non-porous, and isotropic. The roughness was assumed to be negligible.
0081FTIR analysis with Bruker® Hyperion 2000 spectrometer in transmission mode or liquid N<sub>2</sub>This was done either with a cooled mercury cadmium mercury (MCT) detector. 4cm<sup>-1</sup>The spectrum was obtained by averaging 500 scans with the spectral resolution of. A Savitzky-Golay filter smoothed the signal, taking into account 20 points at each of the individual points for a smoothing routine.
0082X-ray photoelectron spectroscopy (XPS) measurements with a monochromatic Al Kα X source (hν = 1486.6 eV) operating at 150 W and a Kratos® Axis-Ultra DLD XPS system with a hemispherical energy spectrometer. went. Path energies were fixed at 160 eV for survey scans and 40 eV for inner shell level spectra in a 300 x 700 μm analytical region. The charge was compensated using a static eliminator. All spectra were calibrated at 285.0 eV using the carbon 1 peak aliphatic contribution. No etching step was performed prior to the analysis. The XPS spectrum was processed by Casa XPS® software and the Shirley-type background was subtracted from the spectrum. The peak coincided with a Gaussian / Lorenz type (70% -30%) straight line.
0083A 2', 4', 6'-trihydroxyacetophenone monohydrate (THAP) matrix solution at a concentration of 30 mg / mL in acetone was applied to the plasma polymer coating. Atmospheric pressure ion source (AP-) coupled to a hybrid linear trap / orbitrap analyzer (LTQ-Orbitrap Elite®, Thermo Fisher Scientific GmbH, Bremen, Germany) MALDI-MS analysis was performed using MALDI, MassTech (registered trademark), Columbia, Maryland, USA. The mass spectrometer was operated in positive ion mode with a fixed mass resolution of 120,000 (FWHM). For the desorption / ionization method, the ion source was equipped with an Nd: YAG laser (λ = 355 nm) and operated at a repetition rate of 200 Hz. Internal calibration was performed using a matrix ion signal as the rock mass of the protonated dimer THAP at m / z = 335.07614 and found that mass accuracy was usually better than 2 ppm.
00842.2 Results and reviews
00852.2.1. Electrical characterization of ultra-short square pulse dielectric barrier discharge
0086The originality of this study is to investigate the benefits of ultra-short square pulse DBDs for PiCVD of organic coatings. Electrical measurements were made to characterize the discharge. FIG. 16 (a) shows the different pulsation frequencies used from 50 Hz to 10 kHz. In fact, the square wave moves back and forth between the minimum and maximum amplitude values at a repetition rate equal to the frequency. At this time, it is possible to adjust the duration of the plasma off time (minimum amplitude value) by using the frequency of the signal. For example, a frequency at 50 Hz has a repeat rate equal to 20 ms, while a frequency at 10 kHz has a repeat rate equal to 0.1 ms. In this study, the pulse discharge duration was kept constant at 245 ns. At this time, the investigated frequency range allows investigation of the effect of off-time on the deposition mechanism, but to limit monomer fragmentation and to promote reaction group activation as a starting step, nano A rectangular pulse of seconds was selected.
0087Figure 16 (b) shows the applied voltages for the various electrically excited frequencies used in this study. The voltage pulse has a duration of 245 ns and a rise time of 45 ns. For each voltage pulse, two current pulses with a period of 40-70 ns are observed (Fig. 16 (c)). The first current pulse is generated when the applied voltage exceeds the breakdown voltage of the gas, and the second pulse represents the discharge that occurs at the falling end of the voltage pulse. Since the current trace of filament discharge consists of many narrow spikes, the smooth curve of the current pulse indicates diffusion discharge. Therefore, these repeatable ultrashort pulses generate a uniform discharge in a very short time, resulting in the rapid generation of two discharge currents. This is suitable for preventing the monomer from being greatly fragmented and for maintaining the structure of the monomer.
0088However, even if nanopulses can promote structure retention, the frequency of repetition must be considered. In fact, if nanopulses are considered as the starting step, then a propagation step must be present to cause the polymerization. At this time, the plasma is no longer needed and the off time should play this role. To demonstrate this, various plasma-off durations were used. The frequency was changed to perform the various off periods as described above, and a duty cycle (DC) of 0.001 to 0.2% was performed.
00892.2.2 characterization of thin film growth rate
0090The growth rate of the coating was measured in weight and film thickness according to the conditions shown in Table V.
0091<img id="000009" he="70" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" />
0092First, it can be seen that the mass deposition rate follows the same tendency as the film thickness deposition rate. It can be seen that the deposition rate increases up to a frequency of 1 kHz and then decreases at 10 kHz. Therefore, the effect of off-time on deposition kinetics can be considered.
0093To clarify this effect, it is interesting to plot the deposition rate that occurs during the time the plasma is off. Figure 17 shows t<sub>off</sub>It represents the mass deposition rate per period (left, solid line) and during the 1 microsecond off period (right, dashed line). The growth rate of the coating is 6 pg · cm at a frequency of 10 kHz.<sup>-2</sup> T<sub>off</sub>Equal to 721 pg · cm at 50 Hz<sup>-2</sup> T<sub>off</sub>Reach, so obviously t<sub>off</sub>Increases with the duration of.
0094However, it is also important to consider the effectiveness of the deposition rate, that is, the deposition rate over the same period. At this time, two different periods of on time and off time can be clearly determined. Nevertheless, since the plasma on time is set to be constant for all the investigated conditions, only the deposition rate during the off period at the same time was investigated. Therefore, different results can be observed as the deposition rates that occur during the 1 ms off time reach their maximum during the 1 kHz frequency (1 ms). The deposition that occurs during the on time is t<sub>off</sub>Since it is negligibly small compared to the time of off time, the deposition rate per 1 microsecond of off time is t.<sub>on</sub>It can be thought of as the propagation rate of the species activated in it. In fact, the ultrashort plasma pulse provides an energy source that activates the monomer and becomes a radical via the allyl reactive group. During the off time, the radicals generated will propagate and will be gradually exhausted over time. As can be seen, the propagation of the activated species reaches its maximum rate with a duty cycle of 0.02%, which is the amount of radicals 1 ms after the plasma off time and therefore t.<sub>off</sub>It can mean that the deposition rate in is reduced.
0095Furthermore, considering that most of the deposition mechanism occurs during the off period, the on period can be shortened to prevent fragmentation of the monomers and to save energy in the deposition process. It is interesting to show it clearly. Figure 18 shows the evolution of mass deposition rates as a function of duty cycle, taking into account the energy used during the plasma-on time. For comparison, classic AC DBD coatings were achieved with duty cycles of 3% and 100%. Considering that the energy consumed per second is the same, it can be clarified that the square pulse DBD enables a higher deposition rate than the AC DBD. The deposition rate that occurs in the shortest duty cycle is the most efficient deposition process in terms of deposition rate per energy consumption. At this time, it can be considered that the ultra-short square pulse is an energy saving process as compared with AC AP-DBD.
0096Propagation is t<sub>off</sub>It is clear that different mechanisms occur in the gas phase due to their non-linearity with respect to duration, and it should be possible to determine various trends in the chemistry of the coating.
0097Table VI reports the relative atomic concentrations of the coating as a function of duty cycle measured in XPS. To better understand these results, the atomic concentration of polyDEAP polymerized by conventional methods has been added.
0098The XPS element concentration shown in FIG. 19 confirms the possibility of adjusting the chemistry of the coating depending on the duty cycle used. For comparison, a conventional polymerized poly DEAP is included. High organic content is present for low duty cycles, but the amount of carbon clearly decreases as the duty cycle increases. After the decrease in carbon, the amount of oxygen continues to increase, while the concentration of phosphorus is almost constant. A low duty cycle is clearly required to prevent significant modification of the monomer in comparison to the elemental concentration of poly DEAP used as a reference.
0099<img id="000010" he="70" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" />
0100The high-resolution XPS spectrum of conventional poly-DEAP is realized in one of the "softest" plasma conditions, which has been proven to retain more monomeric structure, ie, at a frequency of 50 Hz (Figure 20). ). Table VII shows the relative concentrations of each coating's contribution to the carbon 1 contribution.
0101<img id="000011" he="51" wi="169" file="JP2017526518A_D0001.tif" img-format="tif" img-content="drawing" />
0102Again, the properties of polyDEAP are exactly the same as the coating contributions achieved by AP-PECVD. Due to the potential contribution of the end groups obtained from the AIBN radical, the contribution of nitrile was assumed for polyDEAP.
0103The FTIR spectrum shown in FIG. 21 allows further analysis of the retention structure of various coatings.
0104The DEAP polymers obtained by conventional free radical polymerization and nanopulse DBD were analyzed according to the conditions already described. You can outline different categories. The first category (DC = 0.001% and DC = 0.002%) consists of spectra with a fingerprint that is relatively close to the polyDEAP pattern. Ν (POC) and δ (CH) according to the poly DEAP spectrum<sub>3</sub>)<sub>rocking</sub>Since the band to which it belongs is preserved, the structure retention of the monomer is supported. Only slight spreads and differences in strength of the band should be noticed. The second category includes the highest duty cycle (DC = 0.02% and 0.2%) and is slightly different from the standard. 1105cm<sup>-1</sup>Δ (CH) at (DC = 0.02%)<sub>3</sub>)<sub>rocking</sub>The disappearance of the oscillatory band and the redshift of the PO groups associated with indicates that the organic properties of the coating have been lost, which correlates the observations with the elemental composition of the coating.
0105So far, it has been shown that using unipolar square nanopulses with a duty cycle of 0.001% is the best way to obtain a coating with high monomeric structure retention. Therefore, high-resolution mass spectrometry was performed to clarify the chemical structure of the coating in comparison with the standard poly DEAP.
0106After deposition of matrix THAP, mass spectra were obtained in cation mode by AP-MALDI-MS. The molecular structure was identified and assigned thanks to the high mass accuracy (<2ppm) provided by the Orbitrap® analyzer. The mass spectrum shown was obtained after subtraction of the matrix THAP signal. Figures 22a to 22c show the chemical formula: [H (C).<sub>7</sub>H<sub>15</sub>PO<sub>4</sub>)<sub>n</sub>H + H]<sup>+</sup>The molecular structure of the poly DEAP corresponding to is described in the number of repeating units "n" (Fig. 22a), the mass spectrum in the mass range m / z = 100 to 1000 (Fig. 22b), and the mass range m / z = 360 to 410. It is shown together with the mass spectrum (Fig. 22c) corresponding to the enlarged view. The mass spectrum shows the proton end groups [H (C).<sub>7</sub>H<sub>15</sub>PO<sub>4</sub>)<sub>n</sub>H + H]<sup>+</sup>It was occupied by poly DEAP proton adducts with. Furthermore, oligomers with high mass accuracy (<1 ppm) and repeating units up to n = 9 (data not shown) were detected. Only oligomers of repeating units up to 5 are shown (Fig. 22b). The enlarged view is m / z = 363.13319 [H (C)<sub>7</sub>H<sub>15</sub>PO<sub>4</sub>) (C<sub>5</sub>H<sub>11</sub>PO<sub>4</sub>) H + H]<sup>+</sup>Attributable, low mass deviation -0.075 ppm C<sub>2</sub>H<sub>2</sub>At neutral loss and m / z = 407.15928 [H (C)<sub>7</sub>H<sub>15</sub>PO<sub>4</sub>)<sub>2</sub>OH + H]<sup>+</sup>It shows two changes in the molecular structure corresponding to the hydroxyl end groups with a low mass deviation of -0.373 ppm, respectively. Both of these changes were also detected in oligomers with repeating units up to n = 9.
0107For unipolar square nanopulses, it has already been demonstrated that two discharge currents of 40 ns and 70 ns are generated at the rising and falling edges of each pulse. These ultrashort pulses produce a uniform discharge with a low gas temperature and medium output, but with a very high electron density due to the fast rising pulse. The generation of high-energy electrons increases ionization and results in the efficient formation of important radical species. In addition, nanopulse discharge is an energy-saving process because the power dissipated during discharge is low and short.
0108It is known that the faster the rate of rise, the better the plasma reacts, as more excited atoms can enhance the ionization and excitation process of the plasma. An organic coating was formed by applying these discharges to the monomer. The deposition rate of the coating was measured and several deposition mechanisms were clarified. In fact, 1 μs t<sub>off</sub>The deposition rate in is increased up to a duration of up to 1 ms (1000 Hz) and then decreased. Therefore, the energy species / propagation ratio is optimal for a 1 ms off time. At this time, up to 1 ms, different energy species exist, and therefore, it can be considered that the reaction species that improve the crosslinked plasma polymer structure and the free radicals that favor the classical free radical propagation are mixed. At this time, after 1 ms, only free radicals still exist and enable classical polymerization. It's a long t<sub>off</sub>That is why (50Hz) gives poly DEAP.
01092.3 Conclusion
0110In the embodiments of the present invention described, a unipolar rectangular nanopulse was used to polymerize diethyl allyl phosphate via free radical polymerization, thanks to a novel method, plasma-initiated chemical vapor deposition (PiCVD). While ultrashort pulses generate radicals, the off period allows radical propagation and DEAP polymerization.
0111The originality of this study is to perform organic coating via free radical polymerization thanks to the ultra-short square pulse DBD.
0112The components of the embodiments described may be interchangeable and complementary to each other, or may be combined in any suitable manner. In addition, one of ordinary skill in the art may adopt these components while remaining within the scope of the invention as defined by the appended claims, taking into account specific conditions, procedures or uses.
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Numbers
- Publication
- 2017526518
- Application
- 2016566663
Titles2
- Japanese
- 大気プラズマ堆積を用いて規則性ポリマー薄膜を形成する方法
- English
- A method of forming a regular polymer thin film using atmospheric plasma deposition
Classification
- CPC, 6
- B05D1/62
- B05D3/0486
- H01J37/32192
- H01J37/32348
- H01J37/3467
- H01J2237/3321
- IPC, 5
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- H10P14 68
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