TWI499655B - A modified agent for a self-assembled film of a silane group, and a glass surface metallization method using the modifier - Google Patents

Description

Modifier for aralkyl group layer self-assembled film, and glass surface metallization method using the same

The invention proposes a modification scheme for the molecular agglomeration phenomenon of the self-assembled film of the alkylene group layer on the surface of the substrate, and the proposed modification scheme is a modifier, which can agglomerate the molecules of the alkyl group layer on the surface of the substrate. The phenomenon is completely eliminated, the surface roughness of the alkylene group layer is lowered, and the surface of the alkylene group layer is flat-density-uniform (hereinafter referred to as optimization), and the functionality can be introduced and constructed on the terminal functional group of the optimized alkyl group layer. A film (single layer film or multilayer film) is used to modify the surface of the substrate.

It is known that a decane molecule can form a self-assembled film (SAM) by chemical adsorption on a substrate having a hydroxyl group, and this self-assembled film can change the surface characteristics of the substrate.

The mechanism by which a decane molecule forms a self-assembled film on a substrate is generally considered to be a hydroxyl group formed by hydrolysis of a decane molecule, and the formed hydroxyl group is dehydrated by a hydroxyl group on the substrate to form a -Si-O-Si-covalent bond, and chemically The adsorption mode is deposited on the substrate. However, not all of the decane molecules form a bond with the surface of the substrate, but are interconnected into a network or self-polymerized to form a larger group, and several decane molecules in the network or self-polymerized group are bonded to the substrate. According to the scanning electron microscope, the self-assembled film on the surface of the substrate has convex agglomerates of different sizes (as shown in the first figure), and the surface flatness of the self-assembled film is not good.

Since the terminal functional groups of the self-assembled film can be bonded to other functional functional groups, The functional film can be constructed on a self-assembled film. It is known that the flatness, compactness, and uniformity of the self-assembled film have an absolute influence on the flatness, compactness, uniformity, and function of the functional film. Self-assembled films with poor surface uniformity can also cause unevenness of the functional film attached thereto, and the uneven functional film negatively affects its function. Therefore, controlling the flatness, compactness, and uniformity of the self-assembled film is an important issue.

In the past, the preparation of flattened self-assembled films requires strict control of the various factors of the reaction system. The inclusions include substrate surface cleanliness, base surface hydroxyl density, reaction water content, atmospheric humidity, reaction temperature, reaction concentration, solvent type, decane chain length, and terminal functional groups. However, it is quite difficult to strictly control the above factors, and the final self-assembled film is still difficult to achieve the desired flatness.

The problem to be solved by the present invention is that the flatness, compactness, and uniformity of the self-assembled film of the alkylene group layer on the surface of the substrate are not good due to the phenomenon of molecular agglomeration. According to the above problem, the present invention proposes a modification scheme. The modification scheme is a modifier of a self-assembled film of an alkylene group layer, and the molecular agglomeration phenomenon of the self-assembled film of the alkyl group layer on the surface of the substrate can be completely eliminated by the modifier, and the self-assembled film of the alkylene group layer is reduced. The surface roughness is such that the surface of the self-assembled film of the alkylene group layer is flat-density-uniform (hereinafter referred to as optimization). The surface of the substrate can be modified by introducing and constructing a functional film on the terminal functional group of the optimized oxime group layer self-assembled film.

The invention further applies the modifier to the metallization process of the surface of the glass substrate, and uses the modifier to optimize the self-assembled film of the sulfonyl group layer on the surface of the glass substrate, and uses the optimized self-assembled film as the foundation of the metal film. , the metal film is bonded to the glass base with good adhesion The surface of the board exhibits optimized (flat-dense-uniform) and gloss as mirror-like surface properties.

The modifier of the present invention is obtained by mixing a metal compound MX and an acidic solution at a predetermined concentration ratio. The metal compound MX, M may be an alternative of a monovalent or multivalent (divalent, trivalent) metal cation, and the preferred monovalent metal cation is K ⁺ , Na ⁺ . Preferred divalent metal cations are selected from the group consisting of Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Sn ²⁺ , Cu ²⁺ , Co ²⁺ , and Ni ²⁺ . Preferred trivalent metal cations are Fe ³⁺ , Al ³⁺ . The anion X which can be coordinated to a monovalent or polyvalent metal cation is one of Cl ^- , NO ₃ ^- , Br ^- , I ^- , ClO ₄ ^- . When the trivalent metal cation is Fe ³⁺ , the anion to which it can coordinate does not include I ⁻ . The acidic solution NZ, N may be H ⁺ , and Z may be an alternative to Cl ^- , SO ₄ ^2- , NO ₃ ^- , CH ₃ COO ^- . The concentration of the metal compound is 0.1-0.5 M, the concentration of the acidic solution is 0.1-0.5 M, and the pH is 1-4.

A glass surface metallization method using the modifier, mainly on a glass substrate The step of optimizing the modified amino decane self-assembled film between the surface modification procedure and the copper plating process on the surface of the glass substrate, contacting the amine decane self-assembled film on the surface of the glass substrate with the modifier, and self-assembling the amino decane The self-polymerizing group of the membrane disintegrates and detaches, thereby forming an optimized aminodecane self-assembled film. The optimized self-assembled film is used as the foundation of the metal film, so that the metal film can be bonded to the surface of the glass substrate with good adhesion, and is optimized (flat-density-uniform) and the gloss is mirror-like. Surface properties.

The first figure is a scanning electron micrograph of an aminopyridinium self-assembled film without the use of the modifier of the present invention.

The second figure is a scanning electron micrograph of an aminopyridinium self-assembled film using the modifier of the present invention.

The third figure is a comparative diagram of a copper plating layer which is not used with the modifier of the present invention and the modifier of the present invention.

The fourth figure is a schematic diagram of tape adhesion test on the copper plating layer on the surface of the glass substrate.

The modifier for the self-assembled film of the alkylene group layer of the present invention is obtained by mixing a metal compound MX and an acidic solution at a predetermined concentration ratio. The metal compound MX, M may be an alternative of a monovalent or multivalent (divalent, trivalent) metal cation, and the preferred monovalent metal cation is K ⁺ , Na ⁺ . Preferred divalent metal cations are selected from the group consisting of Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Sn ²⁺ , Cu ²⁺ , Co ²⁺ , and Ni ²⁺ . Preferred trivalent metal cations are Fe ³⁺ , Al ³⁺ . The anion X which can be coordinated to a monovalent or polyvalent metal cation is one of Cl ^- , NO ₃ ^- , Br ^- , I ^- , ClO ₄ ^- . When the trivalent metal cation is Fe ³⁺ , the anion to which it can coordinate does not include I ⁻ . The acidic solution NZ, N may be H ⁺ , and Z may be an alternative to Cl ^- , SO ₄ ^2- , NO ₃ ^- , CH ₃ COO ^- . The concentration of the metal compound is 0.1-0.5 M, the concentration of the acidic solution is 0.1-0.5 M, and the pH is 1-4.

The modifier of the invention is optimized for the self-assembled film of the sulfonyl group layer on the surface of the substrate, and in order to prove the effectiveness of the modifier of the invention, the amino decane self-assembled film is prepared on the surface of the glass substrate, and then the amino decane is further prepared. The self-assembled film was brought into contact with the modifier of the present invention, and the surface state of the aminopyridinium self-assembled film before and after the modification was observed by a scanning electron microscope.

A method for preparing an aminopyridinium self-assembled film on a surface of a glass substrate, as in a known manner, firstly, the glass substrate is pickled or alcohol-washed to have an OH group on the surface of the glass substrate; then the glass substrate is contacted with a decane solution. An amino decane self-assembled film is formed on the surface of the glass substrate. The decane solution is dissolved in an anhydrous solvent in the present invention, and the solvent is selected from the group consisting of toluene, methanol and ethanol, and the concentration is 1-5 wt%. The glass substrate is taken out from the decane solution and contacted with an anhydrous solvent to terminate the self-assembly behavior of the molecule, and the glass substrate is washed and dried to complete the glass substrate. Surface modification.

Next, the glass substrate with the amino decane self-assembled film and the modifier of the present invention Contacting at room temperature (25 ° C), using the modifier to optimize the modification of the amino decane self-assembled film, including contact immersion or spraying, the contact time is 3-5 minutes; The substrate was taken out, washed with pure water, and dried.

As shown in the first and second figures, the surface of the unmodified modified amino decane self-assembled film and the optimized modified amino decane self-assembled film were observed by scanning electron microscopy (SEM). The first figure shows an unmodified polyamine-based decane self-assembled film with the entire surface covered with large and small self-polymerized group bumps. The second figure shows the optimized modified amino decane self-assembled film, the self-polymerized group bumps are almost completely eliminated, and the film surface exhibits an optimized (flat-density-uniform) enthalpy state. It is inferred that the modifier of the present invention should disintegrate the self-polymerizing group bonded to the NH ₂ functional group in the amino decane self-assembled film, and the amino decane self-assembled film is bonded to the glass substrate. The Si-O bond is unaffected [the monolayer in the self-assembled film is held]; and the disintegrated self-polymerizing molecule and the modifying agent are completely separated from the glass in the step of cleaning the substrate with pure water. The surface of the substrate.

The modifier of the invention can optimize the amino decane self-assembled film on the surface of the glass substrate (flat-density-uniform). A functional film (single layer film or multilayer film) can be introduced and constructed at the terminal functional group of the optimized amino decane self-assembled film to thereby modify the surface of the substrate.

Therefore, the present invention further applies the modifier to the metallization of the surface of the glass substrate. Using the modifier to optimize the amino decane self-assembled film on the surface of the glass substrate, the optimized amino decane self-assembled film is used as a metal film construction foundation, so that the metal film can be bonded to the glass with good adhesion. The surface of the substrate and exhibits an optimized (flat-dense-uniform) and glossy surface-like surface properties.

The invention applies the modifier to the process of metallizing the surface of the glass substrate, comprising the following steps: Step 1: Hydroxylation of the surface of the glass substrate, pickling or alcohol washing the glass substrate to bring the OH group on the surface of the glass substrate; Step 2 The amino decane is formed on the surface of the glass substrate, and the glass substrate with the OH group on the surface is contacted with the decane solution to form an amino decane self-assembled film on the surface of the glass substrate; the decane solution is amine in the present invention. The decane is dissolved in an anhydrous solvent, and the solvent is selected from the group consisting of toluene, methanol and ethanol at a concentration of 1-5 wt%; after a predetermined period of contact, the glass substrate is taken out from the decane solution and contacted with an anhydrous solvent to terminate the molecular self-assembly. Behavior; the glass substrate is then washed and dried to obtain a glass substrate with an amine decane self-assembled film; in step three, the modified amino decane self-assembled film is optimized, and the amino decane self-assembled film obtained in the second step is obtained. The glass substrate is in contact with the above-mentioned modifier of the invention (stand soaking or spraying), the contact time is 3-5 min, and the temperature is 25 degrees, so that the amino decane self-assembled film on the surface of the glass substrate is optimized ( Tan-compact-uniform), obtain a glass substrate optimized for surface self-assembled film; step 4, contact with the catalyst, contact the glass substrate optimized for surface self-assembled film with the catalyst compound HY required for copper plating; H in the mordant is an alternative to Pd ²⁺ , Ni ²⁺ , Cu ²⁺ , and Ag ⁺ ; Y is an alternative to Cl ^- , SO ₄ ^2- , NO ₃ ^- , and CH ₃ COO ^- . The catalyst compound is bonded to the terminal functional group of the amino decane self-assembled film to form a catalyst layer; in step 5, electroless copper plating is used to reduce copper binding to the catalyst layer by using known electroless copper plating method to make the glass The surface of the substrate is bonded to a copper plating layer.

In order to prove the influence of the modifier of the invention on the copper plating layer, the copper plating layer not using the modifier of the invention is compared with the copper plating layer using the modifier of the invention, and the copper layer is used to reflect the image reflection. The degree of clarity is used to describe the gloss of the copper coating. The third figure (a) shows that the copper plating layer without the modifier is rough and matte, and the camera reflection of the captured image cannot be presented. It is presumed that the agglomerated molecules of the aminopyridane self-assembled film that have not been optimized and modified are touched. The reason why the dielectric layer and the copper plating layer are uneven. The third figure (b) shows that the copper plating layer using the modifier is glossy like a mirror, and the camera reflection of the captured image is clearly presented. It is presumed that the modified amino alkane self-assembled film can make the catalyst layer and the copper plating layer uniform.

As shown in the fourth figure, the copper plating on the surface of the glass substrate is tested for tape adhesion (3M, #610, specification ASTM D3359-09), and the fourth image (a) is the glass surface after the glass cutting and tape test, glass There is no obvious copper layer peeling on the surface; the fourth figure (b) is the surface of the 3M tape after the tape test, and the surface of the tape has no obvious copper layer adhesion, indicating that the adhesion of the copper plating layer is good.

In summary, based on the above experimental results, it was confirmed that the modifier of the present invention has the effect described in the column of the invention.

Claims (14)

a modifier for a self-assembled film of a ruthenium alkyl group, the modifier being contacted with a self-assembled film of a ruthenium group layer to disintegrate the self-assembled film of the oxime group layer; the modifier is a mixture of a metal compound MX and an acidic solution; the metal compound MX, M may be an alternative of a monovalent or polyvalent metal cation, and X is an alternative to Cl ^- , NO ₃ ^- , Br ^- , ClO ₄ ^- ; Solution NZ, N is H ⁺ , Z may be Cl ^- , SO ₄ ^2- , NO ₃ ^- , CH ₃ COO ^- ; metal compound concentration is 0.1-0.5M, acidic solution concentration is 0.1-0.5M, The modifier has a pH of 1-4. The modifier for the self-assembled film of the alkylene group layer according to the first aspect of the invention, wherein the monovalent metal cation is one of K ⁺ and Na ⁺ . The modifier for the self-assembled film of the alkylene group layer according to the first aspect of the invention, wherein the polyvalent metal cation is a divalent metal cation. The modifier for the self-assembled film of the alkylene group layer according to the first aspect of the patent application, wherein the polyvalent metal cation is Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Sn ²⁺ , Cu ²⁺ , Co ^{2 +} , Ni ²⁺ choice. The modifier for the self-assembled film of the alkylene group layer according to the first aspect of the invention, wherein the polyvalent metal cation is a trivalent metal cation. The modifier for the self-assembled film of the alkylene group layer according to claim 1, wherein the polyvalent metal cation is Al ³⁺ . The modifier of the alkylene group layer self-assembled film according to any one of claims 1 to 6, wherein the metal compound X further comprises I ^- . The modifier for the self-assembled film of the alkylene group layer according to the first aspect of the invention, wherein the polyvalent metal cation is Fe ³⁺ . The modifier for the self-assembled film of the alkylene group layer according to the first aspect of the patent application, wherein the decane The self-assembled film of the group layer is an aminopyridinium self-assembled film. A glass surface metallization method using the modifier of the first application of the patent scope, comprising a glass substrate surface modification procedure and a copper substrate surface copper plating process; wherein the glass substrate surface modification procedure comprises a glass substrate surface hydroxylation step, And a step of forming an amino decane self-assembled film on the surface of the surface hydroxylated glass substrate; the copper plating process on the surface of the glass substrate comprises contacting the amino decane self-assembled film with a catalyst compound required for copper plating, and self-assembling the amino decane The terminal functional group of the film is bonded to a catalyst layer, and the copper plating step of reducing and bonding the copper to the catalyst layer; characterized in that: an optimization is performed between the surface modification process of the glass substrate and the copper plating process on the surface of the glass substrate. a step of self-assembling a film of a sulfhydryl decane, contacting an amine decane self-assembled film on the surface of the glass substrate with the modifier, the modifier disintegrating the self-polymerizing group of the amino decane self-assembled film; The substrate separates the disintegrated agglomerating molecules and the modifying agent from the glass substrate and the aminodecane self-assembled film. The glass surface metallization method according to claim 10, wherein the contact time of the aminodecane self-assembled film and the modifier is 3-5 min. The glass surface metallization method according to claim 10, wherein the contact temperature of the aminodecane self-assembled film and the modifier is 25 degrees Celsius. The glass surface metallization method according to claim 10, wherein the contact method of the amino decane self-assembled film and the modifier is to immerse the glass having the amino decane self-assembled film in the modifier. in. The glass surface metallization method according to claim 10, wherein the contacting method of the amino decane self-assembling film and the modifying agent is spraying the modifying agent on the surface of the amino decane self-assembling film.