EP1509480A1 - Procede pour l elaboration d un substrat mineral modifi e en surface, et substrat obtenu - Google Patents

Procede pour l elaboration d un substrat mineral modifi e en surface, et substrat obtenu

Info

Publication number
EP1509480A1
EP1509480A1 EP03755999A EP03755999A EP1509480A1 EP 1509480 A1 EP1509480 A1 EP 1509480A1 EP 03755999 A EP03755999 A EP 03755999A EP 03755999 A EP03755999 A EP 03755999A EP 1509480 A1 EP1509480 A1 EP 1509480A1
Authority
EP
European Patent Office
Prior art keywords
substrate
mineral substrate
organic
silica
organotrihydrosilane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03755999A
Other languages
German (de)
English (en)
French (fr)
Inventor
Gérard LANNEAU
Michel Granier
Johanne Moineau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Universite Montpellier 2 Sciences et Techniques
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Montpellier 2 Sciences et Techniques
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Universite Montpellier 2 Sciences et Techniques filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP1509480A1 publication Critical patent/EP1509480A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a process for the preparation of a mineral substrate modified at the surface by organic groups, as well as the modified substrates obtained.
  • SAMs Self-assembled monolayers
  • These SAMs monolayers have great stability and resistance to various disturbances, in particular to corrosion or to the presence of solvents, because the organic molecules are fixed to the silica by covalent bonds.
  • Various techniques for grafting an organic layer onto the surface of a silica substrate are known: organization of the layer by physisorption, for example grafting an alkane onto a gold or silver substrate, from alkane thiols; organization of the layer by chemisorption, for example grafting of an alkane onto a platinum substrate from alcohols or amines, or onto alumina substrate from carboxylic acid; grafting of organic groups onto a substrate comprising surface OH groups, by covalent bonding from organosilanes such as alkylchlorosilanes, alkylalkoxysilanes or alkylaminosilanes (cf. in particular A. Ulman, Chem.
  • organosilanes such as alkylchlorosilanes, alkylalkoxysilanes or alkylaminosilanes
  • the object of the present invention is to provide a process for obtaining surface-modified silica substrates by depositing a dense, homogeneous and well-organized layer.
  • the process according to the invention consists in bringing a mineral substrate carrying silanol functions on its surface into contact with a solution of an organotrihydrosilane in an organic solvent, at a temperature below 30 ° C.
  • a wafer-type silicon substrate carrying a layer of silica on its surface can be obtained by various methods.
  • a first method consists in removing the native silica layer by soaking the silicon substrate in an HF solution containing at least 10% by volume of HF in ultra-pure water under ultrasound, rinsing with ultrapure water. , then treat with ozone under UV.
  • Such treatment which is particularly preferred, is described in particular by JR Vig, J. Vac. Sci. Technol., 1985, 3, 1027-1034.
  • a second method consists in subjecting said silicon substrate to a flow of oxygen at a high temperature, for example at 1150 ° C., as described in particular by DL Angst, Langmuir, 1991, 7, 2236-2242.
  • the silicon substrate is subjected to chemical oxidation by the basic route: after cleaning the surface of the substrate with a solvent under ultrasound, the substrate is left in a mixture H 2 0, NH 4 OH, H 2 0 2 5/1/1, then rinsed with deionized water, dried and rehydrated (Cf. for example "JD Legrange, et al., Langmuir, 1993, 9, 1749-1753").
  • the silicon substrate is subjected to an acidic chemical oxidation: the substrate is cleaned with a basic solution, then immersed in an acid mixture of the H 2 S0 4 / H 2 ⁇ 2 type (Cf. AK Kakkar , et al., Langmuir, 1998, 14, 6941-6947).
  • the actual grafting step that is to say bringing the organotrihydrosilane into contact with the silica substrate, is carried out in a neutral atmosphere (preferably under argon), using an organotrihydrosilane solution in a aprotic solvent.
  • aprotic solvents it is preferable to use those which have a low hygroscopic character.
  • the organotrihydrosilane can be chosen from the compounds XE-SiH 3 in which E is a spacer segment and X represents H or a reactive terminal function.
  • X can be chosen from any function capable of allowing the attachment of other organic groups (for example an inated group, a halogen, an epoxy, a pyridyl, an ester, a tosylate (p-toluenesulfonyl), a hetero- cumulene (such as an isocyanate, isothiocyanate or carbodiimide) or a metal complexing agent (for example a crown ether, a cryptand, a calixarene which is a macrocycle obtained by condensation of a phenolic derivative with formaldehyde).
  • organic groups for example an inated group, a halogen, an epoxy, a pyridyl, an ester, a tosylate (p-toluenesulfonyl), a hetero
  • the spacer group E makes it possible to confer particular properties on the film obtained by implementing the method.
  • Group E is chosen from the radicals making it possible to obtain an organized monolayer.
  • a long chain alkylene type E radical allows interchain interaction.
  • the radicals E of the alkylene type very particularly preferred are those which have from 8 to 24 carbon atoms.
  • a radical E comprising two triple bonds -C ⁇ C- allows crosslinking.
  • a radical E comprising a conjugated aromatic chain confers non-linear optical properties.
  • a radical E of the pyrrole, thiophene or polysilane type confers electronic conduction.
  • a radical E of the heterosubstituted polyaromatic type confers photo / electroluminescence properties.
  • a radical E of the heterosubstituted polyaromatic type confers photo / electroluminescence properties.
  • a group E of the alkyl or fluoroalkyl type in particular an alkyl or fluoroalkyl group having from 3 to 24 carbon atoms, makes it possible to use the layers obtained in chromatography or in electrophoresis.
  • the organotrihydrosilane solution preferably contains from 10 ⁇ 3 to 10 "1 mole / 1. Solutions in which the concentration of organotrihydroxilane is of the order of 10 -2 mole / 1 are particularly preferred.
  • the duration of the grafting is preferably between 4 and 24 hours, a duration of around 12 hours allows good results to be obtained.
  • the reaction medium must be maintained at a temperature below 30 ° C.
  • the limit value depends on the substituent XE-. This limit value tends to decrease when the number of carbon atoms of the substituent decreases. The determination of the limit value for a given substituent is within the reach of the man of job. Useful information can be found in particular in Brzoska et al, (Langmuir, 1994, 10, 4367), which mentions the existence of a critical temperature Te controlling the quality of the self-assembled monolayers obtained from different alkyltrichlorosilanes.
  • the limit temperature is generally less than 30 ° C. For example, the temperature must be less than 30 ° C if R is C ⁇ sH 37 and less than 10 ° C if R is C ⁇ 2 H 25 .
  • organosilane XE-SiH 3 as a coupling agent allows the initial formation of an Si-O-Si bond by direct condensation between the Si-H function of the reagent with a Si-OH silanol function carried by the surface. of the substrate. This grafting method considerably limits the formation of aggregates, which are detrimental to the deposition of a homogeneous layer.
  • the use of XE-SiH 3 also has the advantage of producing easily eliminated by-products, namely H 2 . There is no risk of finding anionic entities or protic compounds inherent in the processes of the prior art using chlorosilanes or alkoxysilanes on the treated substrate.
  • the silica substrate modified according to the method of the present invention comprises on its surface a monolayer of XE- segments fixed by covalent Si-O-Si bond, said layer comprising X functions uniformly distributed over the surface and accessible.
  • the method of the invention consists in depositing an organic monolayer on a surface layer of initially very hydrophilic silica, the contact angle being less than 10 °. After grafting, the wettability of the o
  • FIG. 1 illustrates the state of a drop of water on a hydrophilic surface, the angle ⁇ being less than 90 °.
  • FIG. 2 illustrates the state of a drop of water on a hydrophobic surface, the angle ⁇ being greater than 90 °.
  • the images obtained by AFM show that the surface is homogeneous and has a very low average surface roughness (RMS), generally less than 0.2 nm.
  • RMS average surface roughness
  • the roughness of the treated substrate is independent of the nature of the grafted organic group, it remains very close to that of the initial untreated substrate.
  • the substrate coated with a monolayer obtained by the proposed process is generally characterized by a good recovery rate and a good organization of the chains on its surface.
  • the covalent bond by which the substrate is attached to the organic group is of the -SiH 2 O-Si- type.
  • the presence of SiH 2 groups is revealed by the si-H vibration band at 2150 cm -1 . This band is not found on the substrates modified according to the methods of the prior art using an alkyltrichlorosilane or an alkyltrialkoxysilane comprising the same alkyl group.
  • the present invention is described in more detail with the aid of the following examples, to which it is not however limited.
  • Example 1 A series of silicon substrates coated with an organic layer were prepared by treatment with octadecyl trihydrosilane.
  • cut silicon disks (1,0,0) were used to obtain rectangular plates of 1 x 2 cm 2 .
  • each wafer was soaked in a concentrated HF solution for a few seconds, until the surface became completely hydrophobic. Then, each plate was rinsed with ultra-pure water, then treated with ozone under UV.
  • Each plate thus treated was immediately introduced into a Schlenck tube containing 20 ml of a 10 ⁇ 2 M solution of octadecyltrihydrosilane in CC1 4 , and kept in the tube for 24 h at a temperature of 15 ° C, without shaking. .
  • the platelets were extracted from the Schlenck tubes, washed with CCl 4 , with absolute ethanol, then with chloroform, each washing being carried out under ultrasound, for a period of the order of 5 min.
  • the platelets thus obtained can be stored in an ambient atmosphere, without undergoing degradation.
  • the contact angle on the surface of the platelets is 98 ° ⁇ 2, which indicates a hydrophobic and homogeneous surface.
  • silicon wafers were treated with octadecyltrichlorosilane, for comparison.
  • the substrates treated according to the invention have a Vsi-H band at 2150 cm "1 which does not exist for the substrates obtained from C ⁇ 8 H 37 SiCl 3 and which corresponds to the existence of Si-H bonds in a type environment
  • the images obtained in AFM for the wafers of the invention show a homogeneous surface with a very low roughness, of the order of 0.15 - 0.20 nm.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schlenck tube. Two series of tests were carried out at 5 ° C and 20 ° C respectively. The analyzes carried out on the platelets gave identical results.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schlenck tube. Two series of tests were carried out at 5 ° C and 20 ° C respectively. The analyzes carried out on the platelets gave identical results.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schlenck tube. Two series of tests were carried out at 5 ° C and 20 ° C respectively. The analyzes carried out on the platelets gave identical results.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schl
  • Example 1 The procedure of Example 1 was reproduced, but replacing the octadecytrihydrosilane with phenyltrihydrosilane, all the other conditions being identical.
  • the contact angle measured on the surface of the modified inserts is 74 ° ⁇ 4.
  • the images obtained in AFM for the wafers of the invention show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
  • FIG. 3 illustrates the surface condition of the wafer after grafting of p-methylstilbényltrihydrosilane.
  • the contact angle measured on the surface of the modified inserts is 85 ° + 3.
  • the images obtained in AFM for the platelets show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
  • the contact angle measured on the surface of the modified wafers is 75 ° + 4.
  • the images obtained in AFM for the platelets show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
  • FIG. 4 illustrates the surface condition of the wafer after the post-grafting reaction of p-bromotoluene.
  • the platelets thus obtained can be stored in an ambient atmosphere, without undergoing degradation.
  • the method according to the invention has been implemented for a silica substrate in the form of colloidal silica.
  • the substrate is an activated silica sold by the company Merck under the name Silica Merck 60F.
  • 0.5 g of the activated silica was treated with 1 g of octadecyltrihydrosilane in 20 ml of CCl 4 at 19-20 ° C for 24 h with magnetic stirring.
  • the powder obtained was filtered, washed 2 times with 20 ml of CC1 4 , then 4 times with 20 ml of THF to remove any physisorbed silanes.
  • grafted silane is characterized by infrared and NMR spectroscopy.
  • An IR band at 2165 cm ⁇ 1 and a signal at -31 ppm in NMR 29 Si show the presence of -0-SiR (H) -0- functions. This result supposes the hydrolysis of a consecutive Si-H bond fixing the organosilane on the surface.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP03755999A 2002-05-31 2003-05-20 Procede pour l elaboration d un substrat mineral modifi e en surface, et substrat obtenu Withdrawn EP1509480A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0206736A FR2840297B1 (fr) 2002-05-31 2002-05-31 Procede pour l'elaboration d'un substrat mineral modifie en surface, et substrat obtenu
FR0206736 2002-05-31
PCT/FR2003/001515 WO2003101905A1 (fr) 2002-05-31 2003-05-20 Procede pour l'elaboration d'un substrat mineral modifie en surface, et substrat obtenu

Publications (1)

Publication Number Publication Date
EP1509480A1 true EP1509480A1 (fr) 2005-03-02

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Application Number Title Priority Date Filing Date
EP03755999A Withdrawn EP1509480A1 (fr) 2002-05-31 2003-05-20 Procede pour l elaboration d un substrat mineral modifi e en surface, et substrat obtenu

Country Status (6)

Country Link
US (2) US20050214546A1 (ja)
EP (1) EP1509480A1 (ja)
JP (1) JP4509776B2 (ja)
AU (1) AU2003260556A1 (ja)
FR (1) FR2840297B1 (ja)
WO (1) WO2003101905A1 (ja)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4614330B2 (ja) * 2005-01-31 2011-01-19 独立行政法人科学技術振興機構 有機基で修飾されたシリコン基板の製造方法
GB201012661D0 (en) * 2010-07-28 2010-09-15 Dow Corning Organosilicon hydrophobing agents

Family Cites Families (13)

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Publication number Priority date Publication date Assignee Title
ES457293A1 (es) * 1976-03-30 1978-02-01 Union Carbide Corp Un procedimiento mejorado para preparar etileno solo o con una o mas alfaolefinas.
US5783299A (en) * 1986-01-21 1998-07-21 Seiko Epson Corporation Polarizer plate with anti-stain layer
JP2632956B2 (ja) * 1988-08-26 1997-07-23 キヤノン株式会社 平面膜の形成方法
JP2741815B2 (ja) * 1991-02-19 1998-04-22 松下電器産業株式会社 化学吸着膜の製造方法
JPH04345633A (ja) * 1991-05-23 1992-12-01 Matsushita Electric Ind Co Ltd 有機機能性累積膜およびその製造方法
JP2002507146A (ja) * 1997-05-28 2002-03-05 グローバル サーフィス アクチェンゲゼルシャフト 表面をコーティングする方法
US6284317B1 (en) * 1998-04-17 2001-09-04 Massachusetts Institute Of Technology Derivatization of silicon surfaces
KR20010042451A (ko) * 1999-02-10 2001-05-25 모리시타 요이찌 유기박막, 그 제조방법 및 그 제조장치와 액정배향막, 그제조방법 및 그 제조장치와 액정배향막을 사용한액정표시장치 및 그 제조방법
FR2792628B1 (fr) * 1999-04-22 2001-06-15 Saint Gobain Vitrage Substrat texture susceptible de constituer un vitrage, procede pour son obtention
US6331329B1 (en) * 1999-05-17 2001-12-18 University Of Massachusetts Surface modification using hydridosilanes to prepare monolayers
JP3933857B2 (ja) * 1999-10-04 2007-06-20 松下電器産業株式会社 薄膜、その製造方法及びその製造装置と、薄膜を用いた液晶表示装置及びその製造方法
JP2001170521A (ja) * 1999-12-15 2001-06-26 Matsushita Electric Ind Co Ltd 有機薄膜、その作製方法およびそれに用いる製膜装置
JP2001031447A (ja) * 2000-01-01 2001-02-06 Matsushita Electric Ind Co Ltd 機能性フロートガラスおよびその製造方法

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Also Published As

Publication number Publication date
FR2840297A1 (fr) 2003-12-05
FR2840297B1 (fr) 2005-03-25
JP2005528262A (ja) 2005-09-22
AU2003260556A8 (en) 2003-12-19
JP4509776B2 (ja) 2010-07-21
WO2003101905A1 (fr) 2003-12-11
AU2003260556A1 (en) 2003-12-19
US20080318068A1 (en) 2008-12-25
US20050214546A1 (en) 2005-09-29

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