TW201202378A - Methods of treating metal surfaces and devices formed thereby - Google Patents

Abstract

Embodiments of the present invention relate generally to methods of treating metal surfaces to enhance adhesion or binding to substrates, and devices formed thereby. In some embodiments of the present invention, methods of achieving improved bonding strength without roughening the topography of a metal surface are provided. The metal surface obtained by this method provides strong bonding to resin layers. The bonding interface between the treated metal and the resin layer exhibits resistance to heat, moisture, and chemicals involved in post-lamination process steps, and therefore can suitably be used in the production of PCB's. Methods according to some embodiments of the present invention are especially useful in the fabrication of high density multilayer PCB's, in particular for PCB's having circuits with line/spacing of equal to and less than 10 microns. Methods according to other embodiments of the present invention are particularly useful in the coating of metal surfaces in a wide variety of applications.

Description

201202378 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The specific embodiments of the present invention are generally directed to methods of treating metal surfaces to enhance adhesion or bonding to substrates and other materials, and apparatus for forming the same. In certain embodiments, the present invention relates to the manufacture of printed circuit boards (PCBs) or printed wiring boards (PWBs). More particularly, it relates to the treatment of metal surfaces such as, but not limited to, copper surfaces to enhance copper surfaces and organic materials. The method of attachment between them, as well as the device formed by it. In certain embodiments of the invention, 'providing a method of achieving improved bond strength without roughening the morphology of the metal surface. The metal surface obtained by this method provides a strong bond to the resin layer. [Prior Art] The miniaturization, portability and increasing functionality of consumer electronics continue to drive the development of printed circuit board manufacturing toward smaller and more compact boards. Part of the key features of increasing the number of layers, reducing core and laminate thickness, reducing copper wire width and line spacing, making smaller diameter vias, and microvia interconnect high density interconnect (HDI) packages or multilayer PCBs. The copper circuit forming the circuit layout of PC B is typically fabricated by an erase program or an overlay program or a combination thereof. In the erasing process, a desired copper pattern is formed by etching down a thin copper foil laminated on a dielectric substrate, wherein the copper foil is covered by a photoresist and forms a desired circuit in the photoresist after exposure. The latent image, the non-circuit area of the photoresist is washed away in the photoresist and the underlying copper is etched away with an uranium engraving agent. In the stacking process, a copper pattern is formed upward from the bare dielectric substrate in the pass-through circuit pattern of the photoresist formed in -5-201202378. Other copper circuit layers are bonded by a partially cured dielectric resin (often referred to as a "prepreg") to form a multilayer assembly in which the copper circuit conductive layer and the dielectric resin are interleaved. Heat and pressure are then applied to the assembly to cure the partially cured resin. A perforation is drilled and copper is plated to electrically connect all of the circuit layers, thus forming a multilayer PCB. Methods of making multilayer PCBs are well known in the art and are described in many publications, such as the "Printed Circuits Handbook" sixth edition by CF Coombs, Jr. (McGraw-Hill Professional, 2007) and MW Jawitz. The "Printed Circuit Board Materials Handbook" (McGraw-Hill, 1997). Regardless of the PCB structure and manufacturing method, the most basic is the good adhesion between the copper circuit layer and the resin insulating layer. A poorly attached circuit board cannot withstand the high temperatures of solder remelting and subsequent soldering, resulting in failure of the delamination and electrical properties of the board. The surface of the copper circuit was smooth when it was just patterned, but the smooth surface could not adhere well to the resin layer. It is theoretically known to increase the contact area between two dissimilar materials to increase the adhesion strength. In order to improve the bond between the copper and the resin, most conventional approaches rely on highly roughened copper surfaces to increase their surface area and introduce micro-valves and ridges as mechanical bond anchors on the surface to promote adhesion to the resin. One of the most widely known and used approaches is the so-called "black oxide procedure" which forms a black oxide layer with a rough surface on top of the copper surface. The black oxide consists of needle-shaped dendrites or whiskers of a mixture of copper oxide and copper oxide of up to 5 microns in length. This large crystal structure provides a large surface area and mechanical anchoring effect, thus providing good bonding. -6- 201202378

Meyer's U.S. Patent Nos. 2,3,64,993, 2,460,896 and 2,460,898 are the first to describe the use of an alkaline chlorite solution to oxidize a copper surface to a black oxide layer. Some examples of the early application of this method to copper-resin bonding in PCBs include U.S. Patent Nos. 2,955,974, 3,1 77,1 03, 3,1 98,672, 3,240,662, 3,374, 1 29 and 3,481,777. While such a needle-shaped oxide layer greatly increases surface area and bonding, the dendrites are fragile and susceptible to damage during the lamination process, resulting in failure of bonding within the oxide layer. Subsequent improvements to the oxide program have placed the focus on optimizing the reactant concentration and other program parameters in order to reduce the crystal size and thus the thickness of the oxide layer to improve mechanical stability. U.S. Patent Nos. 4,409,037 and 4,8,44,981 show some significant improvements in this aspect, which have a specific concentration level and a hydroxide to chlorite ratio of an alkaline chlorite solution. Description of the recipe. U.S. Patent No. 4,512,8,18, the disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire portion U.S. Patent No. 4,7,2,79, the disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire all Other methods of forming a black oxide layer include the use of hydrogen peroxide, as described in U.S. Patent No. 3,344,8,8, the disclosure of which is incorporated herein by reference. The copper surface is oxidized by thermal oxidation as described in U.S. Patent No. 3,677,828, and a phosphoric acid-dichromate solution as described in U.S. Patent No. 3,83,433. The problem associated with this oxide roughening pathway is that the copper oxide is soluble in the acid; and the severe delamination of the bonded surface occurs during later processing steps involving the use of the acid. For example, the perforation as previously mentioned drills the multi-layer board and is plated with copper to provide interconnection of the circuit layers. The pores of the holes are often formed from resinous dross from the borehole and must be removed by a desmear process involving permanganate engraving and then acid neutralized. The acid can dissolve copper oxide a few millimeters from the surface of the pore. The evidence is that a red ring is formed around the perforation due to the pink color of the underlying copper. The formation of the pink ring corresponds to local delamination and represents a severe flaw in the PCB. These have become major bottlenecks in the manufacture of multilayer PCBs and have been thoroughly investigated to seek further improvements in the oxide layer to make them less susceptible to acid attack and such local delamination. Most of the current solutions to the pink ring problem involve post-treatment of copper oxide. For example, U.S. Patent No. 3,6,77,82,8, the disclosure of which is incorporated herein by reference to the entire disclosure of the entire disclosure of the disclosure of the entire disclosure of the disclosure of the entire disclosure of the disclosure of the entire disclosure of the disclosure of the entire disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the entire disclosure of the disclosure of method. U.S. Patent No. 4,7,7,43,9 discloses a procedure for improving the acid resistance of copper oxide by contacting copper oxide with a solution containing an amphoteric element forming an acid oxide such as selenium dioxide. U.S. Patent No. 4,7,75,444 describes a procedure for forming a copper oxide layer which is then treated with chromic acid to stabilize and/or prevent the copper oxide from being dissolved in the acid. Many studies have shown that 7K is formed by first forming copper oxide on the surface of the copper and then reducing the copper oxide to copper oxide or a copper-rich surface to improve acid resistance. U.S. Patent No. 4,642,161 teaches the use of a borane reducing agent of the formula BH3NHRR, wherein R and R' are each selected from the group consisting of ruthenium, CH3 and CH2CHd/f, to be reduced by the borane reducing agent shown in 201202378. method. U.S. Patent No. 5,006,200 describes a group selected from the group consisting of diamines (仏::4), formaldehyde (11 (:110), sodium thiosulfate (Na2S203), and sodium borohydride (NaBH4). U.S. Patent No. 5,721,014 No. 5,750,087, 5,753,309, and a reducing agent consisting of a borane compound such as morpholine borane, pyridine borane, piperidine borane, etc., from 〇99/02452. The most common method for the reduction of copper oxide to copper pentoxide is by using the reducing agent dimethylamine borane (DMAB), which has reduced the radius of the pink ring to a certain extent, but since the copper oxychloride is in acid It is not completely insoluble, so the route is still limited and does not completely solve the problem. Many efforts have been made to solve the above mentioned problems, as shown in, for example, U.S. Patent Nos. 5,492,595 and 5,736,065, A method of reducing copper to metallic copper while maintaining the needle-like structure of the oxide. However, such a needle-like structure is mechanically unstable and is mashed during the lamination process. Subsequent development of an alternative oxide coating process has been developed. Some of the exemplary procedures are described in U.S. Patent Nos. 5,53,094, 0,946,02732, 5,807,493, 6,746,621 B2, 5,869,130, 6,554,948, and 5,800,859. A highly roughened copper surface is created by a controlled uranium that combines a conventional oxide procedure with a roughened underlying copper surface to simultaneously oxidize it. In many instances, the organic layer is simultaneously coated as a corrosion inhibitor or adhesion promoter. A micro-roughening procedure using an etch comprising hydrogen peroxide, a mineral acid, and a corrosion inhibitor such as triazole is described in U.S. Patent No. 5,800,859. U.S. Patent No. 6, 2012, No. 6, 716, No. 6, 182, No. 6, 946, No. 7,108,79 5 82, 7,211,204 82, and 7,351,353 81, the use of an oxidizing agent, a pH conditioner, a morphological modifier, a homogeneity enhancer, and an azole inhibitor The composition provides a similar way to roughen the copper surface. For the same purpose, U.S. Patent Nos. 5,532,094, 5,700,3 89, 5,807,493, 5,885,476, 5,965,036 No. 6,426,02081, and 6,746,62 1 82 describe a microetching composition consisting of an oxidizing agent (such as hydrogen peroxide), a source of copper ions, an organic acid, a source of tooth ions, and an azole-type inhibitor. Equal routes have improved acid resistance, however interfacial bonding is primarily achieved by mechanical anchoring, and the adhesion strength decreases rapidly as the surface roughness of the treated copper surface decreases. Therefore, there is still a need for improvement 〇 In addition, it is difficult to manufacture a reproducible oxide layer. A significant problem with the formation of oxides is that their growth is difficult to control. Conventional techniques for controlling the growth of oxide layers use time or temperature as a means of promoting or stopping oxide growth. This prior art approach suffers from problems of poor reliability and reproducibility. It is readily apparent that although many approaches have been developed to improve the adhesion between the copper surface and the dielectric resin, these approaches rely on the creation of highly roughened surfaces to promote adhesion. It is generally accepted that the copper surface must be roughened in the prior art to increase the surface area bound or attached to the epoxy or dielectric resin. However, this approach is severely limited because the width and/or line spacing of the copper wire is limited to prevent further miniaturization of the circuit. In addition, the oxide layer formed by the prior art method suffers from problems of reproducibility and poor reliability. The current trend toward higher density and thinner line width circuits with increased number of layers has created a need for higher bonding strength of copper and dielectric resins while maintaining a smooth surface. Clearly, there is a need for further progress and development in the art. In addition, protective coatings are used in almost every industry where metal surfaces are exposed to the atmosphere, hunger environment or complex interfaces. In prior art techniques, the coating is typically applied after thorough cleaning and pretreatment of the metal surface (which is done to create a surface to be bonded to the coating). These pretreatment steps can be simple acid or alkaline cleaning, solvent cleaning, and oxidation and/or reduction to increase the surface area and/or the sugar content of the surface. In addition, many conventional treatments involve the deposition of other metals, such as chromium or titanium, which serve as a better anchor for subsequent deposition of additional organic layers. Finally, organic (molecular) reactants have been used to derivatize the surfaces of such metals to provide an excellent attempt for additional adhesion to such coatings. All of these prior art procedures are time consuming and expensive, and significant advantages can be provided by minimizing the number of steps and procedures for preparing chemical concentrations and complexity of the metal for coating. SUMMARY OF THE INVENTION Accordingly, certain embodiments of the present invention provide methods of treating a smooth metal surface to enhance adhesion between the metal surface and the organic layer. The metal surface treatment procedure provided by a specific example of the present invention to increase the bond strength without significantly roughening the metal surface is distinct and contrary to conventional prior art techniques. In some embodiments of the invention, a method of achieving improved bond strength between materials without roughening the metal surface is presented. -11 - 201202378 In some embodiments, a method of treating a metal surface to promote adhesion or bonding between the metal surface and an organic layer is provided, characterized by: forming a metal oxide layer on the metal surface The metal surface is stabilized and the metal oxide layer is then conditioned with molecular reactants and/or reducing agents to achieve a selective oxide thickness and morphology. In some embodiments, a method of treating a metal surface to promote adhesion or bonding between the metal surface and an organic material is provided, characterized in that a metal oxide layer or a stabilization layer is formed on the metal surface, and Limiting the formation of a metal oxide layer by a self-limiting reaction between a metal oxide and a molecular reactant or a surface modifying compound (sometimes referred to as a suppressing compound). In some embodiments, the roughness of the stabilizing layer Up to about 0. 14 Ra and exhibits a morphology comprising particles having an average particle diameter in the range of 200 nm or less, and a thickness in the range of about 1 Torr to 200 nm. In some embodiments, the stabilization layer consists essentially of copper oxide. In some embodiments, a molecular layer is formed over the stabilization layer. In another embodiment, a specific embodiment of the present invention provides a printed circuit board comprising: at least one metal layer; at least one epoxy layer; and stability formed between the metal layer and the epoxy layer Layer. In other embodiments of the invention, a method of combining a smooth metal surface with a resin is proposed, wherein the bonding interface has the desired resistance to heat & moisture and chemicals involved in the post lamination process step, and thus in many applications It is especially suitable for multilayer PCB lamination. In some embodiments of the present invention, a method of manufacturing a high density multilayer P C B having a line and/or -12 - 201202378 line pitch width equal to or less than 10 microns is proposed. In other embodiments, the invention can be used in a wide variety of applications. In one of such examples, a specific example of the invention can be used to form a protective coating. In other embodiments, 'a specific example of the present invention provides a method of manufacturing a printed circuit board' which comprises the steps of: pre-cleaning a copper surface with a base and/or a peroxide solution; by forming a copper oxide layer on the copper surface And stabilizing the copper surface; terminating the formation of the copper oxide layer by a self-limiting reaction between the copper oxide and one or more surface modifiers or inhibiting the chelate; and bonding the treated copper surface to the resin. In some embodiments, one or more molecules can be coupled to the copper oxide layer, the one or more organic molecules comprising one or more bonding groups that are configured to bond to the copper oxide surface and/or one or A plurality of thermally stable matrices constructed to attach groups attached to the resin. In yet another embodiment, a specific embodiment of the invention provides a method of controlling the growth of an oxide layer on a surface of a metal, the method comprising: self-limiting by an oxide layer and one or more surface modifying compounds The reaction stops the growth of the oxide layer. Additionally, other embodiments of the invention provide a reducing composition comprising: one or more reducing agents; and one or more molecular reactant compounds. Additionally, other embodiments of the invention provide oxidant compositions comprising one or more oxidizing agents; and one or more surface modifying agents or inhibiting compounds. DETAILED DESCRIPTION OF THE INVENTION It is to be understood that the foregoing general description and the following description are only illustrative and illustrative of the invention. In addition, the singular forms of the present invention are to be construed as being limited to the singular forms of the present invention, and the use of the "or" means "and/or does not wish to "include", "include" and "have" DETAILED DESCRIPTION OF THE INVENTION In many embodiments, a particularly metal substrate, such as, but not limited to, an epoxy or resin based forming a stabilization layer that is firmly attached to the organic material provides for the manufacture of the coating and is significantly superior to the particular printed circuit board. The stabilizer layer has a smoother shape, so that it is surprisingly and unexpectedly attached to it. In fact, the previous central teachings and pathways have to be sufficiently adhered to the surface of the metal oxide. The stabilization layer having the desired thickness and morphology has the ability to adhere to subsequent organic materials deposited thereon. That is, 'in certain embodiments, the modified metal oxide modifies the growth and stability of the oxide layer. The reaction or the parent is carried out to carry out the oxidation step and the reduction step, or the second usually 'oxide growth is very difficult to control. Prior art compounds The steps are to reduce the thickness of the oxide, to further form, etc. The specific embodiment of the invention provides significant innovation by using a surface modifying agent that controls or limits the oxide growth process with the oxygen. This can be attributed to the oxidation. The solution is added to the solution to slow the growth of the oxide and then blocked to complete. Or 'can be used in a standard oxidation reaction, and then in the case, unless otherwise." The surface layer of the board) and the electronic prenatal technology are superior to the roughening of the organic material technology method in order to form a layer and the unique method of stability is formed by using a selective controller. It is often necessary to post-oxidize the oxidant to form a compound to modify the surface to further oxidize the reduction step which has been modified by adding <14-201202378 plus a surface modifier to provide stabilization. Specific examples of the invention use the reaction to control growth rate, thickness, oxide morphology, and all of these embodiments can be accomplished in a single step. The resulting metal oxide film exhibits the desired thickness and morphological properties as soon as it is formed, without the need for a post-treatment step. Eliminating post-processing steps significantly reduces the complexity of the program and provides significant cost savings. Moreover, embodiments of the present invention provide methods of controlling the growth of a ruthenium oxide layer on a metal surface. More specifically, in certain embodiments, the growth of the oxide layer is terminated by a self-limiting reaction between the oxide layer and one or more surface modifiers or inhibiting compounds. A significant advantage is that the specific embodiment of the present invention provides a stable, controllable process range. This range of custom procedures provides a robust and repeatable program. In particular, the present invention is a major advancement because the continuous oxide growth of the metal oxide layer in the prior art method is one of the main failure mechanisms of conventional PCB boards. The metal surface is stabilized by exposing the metal surface to an oxidizing agent. In an exemplary embodiment, the oxidizing agent is selected from any one or more of the group consisting of sodium chloride, sodium hydroxide, hydrogen peroxide, permanganate, ozone, or mixtures thereof. The step of stabilizing the metal surface can be carried out at a temperature ranging from room temperature to about 8 (TC). After oxidation, the metal oxide layer can be conditioned with a reducing agent. In some embodiments, the reducing agent is selected from the following Any one or more of: borane, morpholine boron, pyridium borane, piperidine borane or dimethylamine boron. The metal oxide layer can be conditioned at room temperature. The temperature is carried out at a temperature in the range of about 50 ° C. In some embodiments, the overall method 201202378 is carried out in the range of about 5 to 20 minutes. In addition, certain embodiments of the invention provide for conditioning after conditioning. The oxidized surface is contacted with one or more organic molecules comprising one or more bonding groups configured to bond to the metal surface and one or more attachments configured to attach to the organic material a thermally stable matrix of a group. In an exemplary embodiment, the one or more organic molecules are the surface modifier or inhibiting compound. In some embodiments, a metal surface is treated to promote the metal surface and A method of attaching or joining between machine materials, characterized in that a stabilization layer is formed on the surface of the metal, and the formation of the stabilization layer is caused by the self between the metal oxide and the surface modifier or inhibitor compound Controlled by a limited reaction. Significant progress is achieved in accordance with a specific embodiment of the invention, the formation of an oxide layer and the control of its growth, including termination, in one step. A particular advantage is that the metal oxide layer (sometimes Also known as the stabilization layer) exhibits unique and desirable features. In some embodiments, the formed stabilization layer has a thickness of about 200 nanometers or less. In some embodiments, the stabilization The morphology of the layer is composed of a substantially amorphous structure. In an exemplary embodiment, the formed stabilization layer has particles having a particle size in the range of 200 nm or less. In other exemplary embodiments, the formation The stabilization layer has particles having a particle size in the range of 15 nanometers or less. In some embodiments, the formed stabilization layer has substantially randomly oriented particles. Usually (but not completely), The stabilization layer consists of copper oxide and a molecular reactant. -16- 201202378 To begin the formation of the stabilization layer, the oxidation is initiated by exposing the metal surface to an oxidant. In some embodiments, the oxidant The solution consists of one or more oxidizing agents and one or more surface modifying agents may be added. In the exemplary embodiment, the one or more oxidizing agents consist of sodium chlorite, hydrogen peroxide, permanganate. Perchlorate, persulfate, ozone, or mixtures thereof. Any suitable concentration of oxidizing agent solution may be used. In some embodiments, the oxidizing agent solution consists essentially of one or more oxidizing agents in the solution. The surface modifier is selected from the group consisting of a compound that reacts with the stabilization layer in a self-limiting reaction. In some embodiments, the surface modification compound is selected to oxidize the metal when forming a metal oxide. The surface reaction of the object controls the reaction rate. Optionally, a functional group may be added to the surface modifying compound to provide additional bonding to an organic material such as, but not limited to, an epoxide or the like. After the oxidation begins, the oxide begins to grow on the top surface of the metal surface. After forming the stabilization layer, the surface modifying compound begins to react with the oxygen containing moiety on the surface of the metal. This will slow down and block further oxidation, thus achieving a self-limiting reaction of the oxide formation. Additionally, certain embodiments of the invention provide for contacting the metal surface with one or more organic molecules comprising one or more bonding groups configured to bond to the metal surface and one or more A thermal stabilization matrix is constructed that is attached to the attachment of the organic material. In an exemplary embodiment, the one or more surface modifier molecules are surface active moieties -17-201202378. In some embodiments, a metal surface is treated to promote adhesion or bonding between the metal surface and the organic material. The method is characterized in that the surface of the metal is stabilized by forming a stabilization layer on the surface of the metal, and then the stabilization layer is conditioned with a reducing agent to achieve a selective oxide thickness and morphology. A particular advantage is that the metal oxide layer (sometimes referred to as the stabilization layer) exhibits unique characteristics. In some embodiments, the stabilization layer has a thickness of about 200 nm or less after conditioning. In some embodiments, the morphology of the metal oxide layer is comprised of a substantially amorphous structure. In an exemplary embodiment, the stabilization layer has a highly distributed particle structure' and the particle size of the particles after conditioning is in the range of 200 nanometers or less. In other embodiments, the stabilization layer has particles and the particle size of the particles Ιαα after conditioning is in the range of 1 〇 〇 nanometer or less. In some embodiments, the metal oxide has particles and the particles are substantially randomly oriented after conditioning. Usually (but not completely), the stabilization layer consists of copper oxide. The metal surface is stabilized by exposing the metal surface to an oxidizing agent. In an exemplary embodiment, the oxidizing agent is selected from any one or more of the group consisting of sodium chlorite, hydrogen peroxide, permanganate, perchlorate, persulphate, ozone, or mixtures thereof. The step of setting the surface of the metal can be carried out at a temperature ranging from room temperature to about 80 °C. Alternatively, the metal surface can be stabilized by thermal oxidation and electrochemical anodization. After stabilization, the stabilization layer was conditioned with a reducing agent. In some specific examples, the instant agent is selected from any one or more of the following: awake, thio-18 - 201202378 sodium sulphate, sodium borohydride, and the formula BH3NHRR' (wherein R and R 'A group selected from the group consisting of ruthenium, CH3 and CH2CH3", such as borane reducing agent, such as dimethylamine borane (DMAB), borane, such as morpholine borane, pyridium borane Piper steep boron hospital. The conditioning of the stabilization layer can be carried out at a temperature ranging from room temperature to about 50 °C. In some embodiments, the overall process time is in the range of about 2 to 20 minutes. In addition, certain embodiments of the present invention provide for contacting the metal surface with one or more organic molecules after conditioning, the organic molecules comprising one or more bonding groups configured to bond to the metal surface and One or more thermally stable matrices that are configured to attach to the organic material (such as a PCB epoxide, etc.). In an exemplary embodiment, the one or more organic molecules are surface active moieties. Any suitable surface active moiety can be used. In some embodiments, the surface modifier moiety is selected from the group consisting of a macrocyclic pro-anthracene group, a macrocyclic complex, a sandwich coordination complex, and a polymer thereof. Alternatively, the surface modifier moiety can be composed of porphyrin. The one or more organic molecules may be selected from the group consisting of porphyrins, porphyrin macrocycles, extended porphyrins, shrinking porphyrins, linear porphyrin polymers, porphyrin sandwich coordination complexes, porphyrin arrays, decanes. , tetraorganodecane, amine, sugar, or any combination of the above. In certain embodiments, the one or more attachment groups are comprised of an aryl functional group and/or an alkyl attachment group. When the attachment group is an aryl group, the aryl functional group may be composed of a functional group selected from any one or more of the following: -19-201202378: acetate, alkylamino, allyl, amine, amine Base, bromo, bromomethyl, carbonyl, carboxylate, carboxylic acid, dihydroxyphosphonium, epoxide, ester, ether, ethynyl, indolyl, hydroxy, hydroxymethyl, iodo, decyl,锍Methyl, Se-ethenyl selenyl, Se-ethyl selenomethyl, S-acetylthio, S-acetylthiomethyl, oxyseleno, 4,4,5,5 - Tetramethyl-1,3,2-dioxaborane-2-yl, 2-(trimethyldecyl)ethynyl, vinyl, and combinations thereof. When the attachment group is composed of an alkyl group The alkyl attachment group comprises a functional group selected from any one or more of the group consisting of acetate, alkylamino, allyl, amine, amine, bromo, bromomethyl, carbonyl, carboxylate , carboxylic acid, dihydroxyphosphonium, epoxide, ester, ether, ethynyl, methionyl, hydroxy, hydroxymethyl, iodine, decyl, fluorenylmethyl, Se-ethyl seleno selenyl, Se -Ethyl selenylmethyl, S-acetylthio, S-acetylthiomethyl , oxyseleno group, 4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl, 2-(trimethyldecyl)ethynyl, ethyl stilbene, and combination. In another embodiment, the at least one attachment group consists of an alcohol or a phosphonate. In other embodiments, the at least one attachment group can be composed of any one or more of the following: amines 'alcohols, ethers, other nucleophiles, phenylacetylenes, phenylallyls, phosphines Acid esters, and combinations thereof. Typically, in certain embodiments, the organic molecule is comprised of a thermal stabilization unit or matrix having one or more bonding groups X and one or more attachment groups Y. In a specific example, the organic part is divided. The heat-resistant metal is bonded to the molecule and may be composed of one or more "surface-active portions" which are also referred to as "redox active moieties" -20-201202378 or "ReAMs" in the related application. A specific example of the present invention includes the use of a composition of molecular components of a surface active moiety, which are generally described in the following U.S. Patent Nos.: 6208553, 6381169, 6657884, 6324091, 6272038, 6212093, 6451942, 6777516, 6674121, 6642376, 6728129, the following US Early Publications Nos.: 20070108438, 20060092687, 20050243597, 20060209587, 20060195296, 20060092687, 20060081950, 20050270820, 0 20050243597, 20050207208, 20050185447, 20050162895, 20050062097, 20050041494, 20030169618, 20030111670, 20030081463, 20020180446, 20020154535, 20020076714, 2002/0180446, 2003/0082444, 2003/0081463, 2004/0115524 ' 2004/0150465 , 2004/0 1 20 1 80 , 2002/0 1 05 8 9 , U. S. S. N. s 1 0/766,3 04, 10/834,630 ' 10/628868, 10/456321, 10/723315, 10/800147, 10/795904, 10/754257, 60/687464, the contents of which are cited in full The way to break into this article. It should be noted that although the heat resistant molecules are sometimes referred to as "redox moieties" or "ReAMs" in the related applications listed above, the term surface active portion is more appropriate in the present application. Generally, in some embodiments, several types of surface active moieties are useful in the present invention, all of which have a multidental ligand as a substrate, including a macrocyclic moiety and a non-macrocyclic moiety. A number of suitable ligands and complexes, as well as suitable substituents, are described in the references cited above. In addition, many multidental ligands may include substituents (generally referred to herein as "R" groups) and include those described in earlier US Publication No. 21 - 201202378 2007/0108438 With respect to definitions, the definition of substituents in this case is specifically incorporated herein by reference. Prior to the application of the ligands are divided into two categories: the use of nitrogen, oxygen, sulfur, carbon or sulfur atoms (depending on the metal ion) as a coordination atom (in the literature usually refers to the σ (α) donor) ligand And organometallic ligands, such as metallocene ligands (generally referred to in the literature as π-donor, and are described as Lm in U.S. Patent Publication No. 2,197,086,843). In addition, a single surface active moiety may have two or more redox active subunits, such as shown in Figure 13A of U.S. Patent Publication No. 2 0 0 7 / 0 1 0 8 4 38, which uses porphyrins. And ferrocene. In certain embodiments, the surface active moiety is a macrocyclic ligand comprising both a macrocyclic proligand and a macrocyclic complex. By "macrocyclic proligand" herein is meant a cyclic compound containing a donor atom (sometimes referred to herein as a "coordinating atom") oriented such that it can bind to a metal ion and is large enough to surround the metal atom. . Typically, the donor atom is a heteroatom, which includes, but is not limited to, nitrogen, oxygen and sulfur, with the former being preferred. However, those skilled in the art will also appreciate that different metal ions preferentially bind to different heteroatoms, and thus the heteroatoms used may depend on the desired metal ion. Moreover, in some embodiments, a single macrocycle may contain different types of heteroatoms. A "macrocyclic complex" is a macrocyclic proligand having at least one metal ion; in some embodiments, the macrocyclic complex comprises a single metal ion 'only as described above' a multinuclear complex ( Including multinuclear macrocyclic complexes) is also included. A wide variety of macrocyclic ligands are used in the present invention, including electron conjugation -22-201202378 and non-electron conjugated macrocyclic ligands. A broad schematic diagram of a suitable macrocyclic ligand is shown and described in Figure 15 of U.S. Patent Publication No. 2007/0108438. In certain embodiments, the rings, bonds, and substituents are selected to form a compound that is electronically conjugated and has at least two oxidation states. In certain embodiments, the macrocyclic ligands of the present invention are selected from the group consisting of porphyrins (especially porphyrin derivatives as defined above) and 1,4,7,10-tetrazo A heterocyclic dodecane derivative. A particularly good subset of the macrocycles of the invention includes porphyrins, including porphyrin derivatives. Such derivatives include one or more carbon atoms of an indole- or porphyrin ring having an ortho-fused or ortho-perifused to the extra ring of the P-porphyrin nucleus. A derivative of a porphyrin or a porphyrin nitrogen atom replaced by an atom of another element (substituted by an atom of another element) (a replacement of the nitrogen structure) has a -, or a core atom located around the porphyrin a derivative of a substituent other than hydrogen, one or more of the porphyrins being a saturated derivative (hydroquinones such as chlorin (bacteria), bacteriochlorin) ), isobacteriochlorin, isohydroiochlorin, chlorpheniramine, corphin, pyrrocorphin, etc., having one or more atoms inserted into the porphyrin ring Derivatives (including pyrrole and pyrromethylene units) (expanded porphyrins), derivatives having one or more groups removed from the porphyrin ring (shrinked B porphyrins, such as porphyrins, Corr (1), and combinations of the foregoing derivatives (eg, phthalocyanines) , Azaline cyanine, and porphyrin isomers). Further suitable porphyrin derivatives include, but are not limited to, chlorophylls, including etiophyllin, pyrophylline (-23-201202378 pyrroporphyrin), rhodoporphyrin (rhod ο porphyri η), leaves Oral porphyrin, erythropoietin, chlorophyll a and b, and heme, including porphyrin (deuteroporphyrin), heminin (deuterohemin), hemin, iron heme, protoporphyrin, chlorination Heme, hematoporphyrin, mesoporphyrin, faecal porphyrin, uruporphyrin and turacin, and tetraarylazadipyrromethine 歹[J Those skilled in the art will appreciate that each unsaturated position (whether carbon or heteroatom) may include one or more substituents as defined herein, depending on the desired price of the system. Further, the inclusion in the definition of "porphyrin" is a porphyrin complex comprising a ruthenium front ligand and at least one metal ion. The metal suitable for the porphyrin compound depends on the hetero atom used as the coordinating atom, but is usually selected from transition metal ions. The term "transition metal" as used herein generally refers to the 3S element of Groups 3 to 12 of the Periodic Table. Typical transition metals are characterized by their valence electrons or their electrons associated with other elements in more than one shell, and thus often exhibit several common oxidation states. In a specific embodiment, the transition metal of the present invention includes, but is not limited to, one or more of the following: niobium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, lanthanum, chromium, cerium, molybdenum , 鐯, 钌, money, IG, silver, pot, feed, molybdenum, crane, bismuth, hungry, antimony, platinum, palladium, gold, mercury, furnace 'and/or its oxides, and/or its nitrides, and / or its alloy, and z or a mixture thereof. There are also many macrocycles based on 1,4,7,10-tetraazacyclododecane derivatives. Figures 17 and 13C of US Publication No. 2007/0108438 describe -24-201202378 many loosely 1,4,7,10-tetraazacyclododecane/1,4,8,11-tetrazene heterocycle The cyclam derivative is a macrocyclic pro-ligand of the substrate which can be extended by inclusion of a carbon or heteroatom independently selected. In certain embodiments, at least one R group is a surface active subunit, preferably conjugated to the metal. In certain embodiments, when two at least one R group are surface active subunits, two or more adjacent R2 groups form a cyclic group or an aryl group. In the present invention, the at least one R group is a surface active subunit or moiety. Moreover, in some embodiments, macrocyclic complexes that rely on organometallic ligands are used. In addition to the pure organic compounds used as the surface active moiety and the various transition metal coordination complexes having an 8-atom organic ligand with a donor atom as a heterocyclic ring or an exocyclic substituent, there are currently a wide variety of Transition metal organometallic compounds having a π-bonded organic ligand are available (for details, see Advanced Inorganic Chemi stry, 5th edition, Cotton & Wilkinson, John Wiley & Sons, 198, Chapter 26; Organometallics, A Concise Introduction, Elschenbroich et al., 2nd edition, 1 992, 30 VCH; and Comprehensive Organometalli c Chemistry II, A Review of the Literature 1982-1994, edited by Abel et al., Vol. 7, Nos. 7, 8, 1 . 0 & Chapter 11, Pergamon Press, hereby incorporated by reference.) Such organometallic ligands include cyclic aromatic compounds such as cyclopentadienide [C5H5 (-1)] and various cyclic substituted and ring fused derivatives such as ruthenium (-1) ions. (indenylide ( -1 ) ion )' they produce a class of bis(pentadienyl) metal compounds (ie, erb-25-201202378 metal): see, for example, Robins et al. at J_Am.  Chem.  Soc.  104:1882-1893 (1982); and Gassm an et al.  Am.  Chem.  Soc.  1 08:4228-4229 (1 986), which is incorporated herein by reference. Among them, ferrocene [(C5H5) 2Fe] and its derivatives have been used in various chemical reactions (c〇nnelly et al., Chem.  Rev.  96:877-9 1 0 (1 996), incorporated herein by reference) and electrochemical reactions (Geiger et al., Advances in Organometallic Chemistry 23: 1 · 93; and Geiger et al., Advances in Organometallic Chemistry 2 4:8 7, a typical example of a bow | Other organometallic ligands that may be suitable include cyclic aromatic hydrocarbons such as benzene to produce bis( arene) metal compounds and cyclic substituted and ring fused derivatives thereof, of which bis(phenyl)chrome is a typical example. Other non-cyclic η-bonding ligands such as allyl (-1) ions or butadiene produce organometallic compounds that may be suitable, and all such ligands are bonded to other 7 c-bonds and 8-bonds. The ligands together form a general type of organometallic compound having a metal-carbon bond. These electrochemical studies with bridged organic ligands and additional non-bridged ligands, as well as various dimers and oligomers with compounds having no metal-metal bonds, are useful. In some embodiments, the surface active moiety is a interlayer coordination complex. The term "interlayer coordination compound" or "interlayer coordination complex" refers to a compound of the formula L-Mn-L wherein each L is a heterocyclic ligand (as described below), each of which is a metal, η 2 or greater, most preferably 2 or 3, and each metal is between a pair of ligands and is bonded to one or more heteroatoms in each of the ligands (usually a plurality of heteroatoms) Atoms, for example 2, 3, 4, 5) -26- 201202378 (depending on the oxidation state of the metal). Thus, the interlayer coordination metal is bonded to an organometallic compound of a carbon atom, such as a ligand in a ferrocene interlayer coordination compound, which are generally arranged in a stacked orientation (ie, often cofacially oriented and mutually Axis alignment, such as the ligand may or may not rotate relative to each other in this axis) (see Ng and J i ang (1 9 9 7) Chemical Society Reviews 26: 442, incorporated herein by reference) . The interlayer coordination complex package is not limited to "two-layer interlayer coordination compound" and "three-layer interlayer coordination". The synthesis and use of interlayer coordination compounds are described in U.S. 6,212,093; 6,451,942; 6,777,516; and the polymerization of such molecules is described in WO 2005/086826, all of which are incorporated herein by reference. And the base of the "single giant ring" complex. In addition, polymers of such interlayer compounds are also used; this U. S. S. N,212,093; 6,451,942; 6,777,516, dyad and triad: and the molecular cooperatives describe WO 2005/08 6826, all of which are incorporated by reference. Included in this article. The surface active moiety comprising a non-macrocyclic chelating agent is attached to the metal ion to form a non-macrocyclic chelating compound due to the presence of the metal such that the plurality of proligands are joined together in multiple oxidation states. In some embodiments, a ligand prior to administration of nitrogen is used. The ligands are well known in the art prior to the appropriate administration of nitrogen and include, but are not limited to, NH2; NFIR; NRR1; pyridine; pyridoxine; isoniazid, amide; Therefore, Tongwei, for example, 43 3 - including the patent cooperation, especially including the method of plant 2 to provide a combination of limited azole; -27- 201202378 卩 卩 π π π π π π π π π π Steep and substituted derivatives; morpholines, especially 1,10-morpholine (abbreviated as phe η) and substituted derivatives of morpholines, such as 4,7-dimethylmorpholine and dipyridinol [3,2-a:2,,3,-c] morphine (abbreviated as dppz); dioxin D morphine; 1,4,5,8,9,1 2 -hexaazatriene Benzene (abbreviated as hat); 9,1 0 • phenanthrene diimide (abbreviated as phi); 1,4,5,8-tetraazaphene (abbreviated as tap); 1,4,8,11-four Azacyclotetradecane (abbreviated as 1,4,8,11-tetraazacyclotetraoxane) and isocyanide. Substituted derivatives (including fused derivatives) can also be used. It should be noted that the macrocyclic ligand which is non-coordinating to saturate the metal ion and which needs to be added with other pre-ligands is regarded as a non-macrocyclic ligand which acts for this purpose. Those skilled in the art will appreciate that many "non-macro" ligands may be covalently attached to form a coordinating saturated compound, but lack a cyclic structure. The use of carbon, oxygen, sulfur and phosphorus to impart sigma ligands is also well known in the art. For example, a suitable sigma carbon system is disclosed in C 〇 11 ο η and Wilkenson Advanced Organic Chemistry > 5th ed., John Wiley & Sons, 1988, which is incorporated herein by reference: Page 38. Similarly, suitable oxygen ligands include crown ethers, water, and others known in the art. Phosphides and substituted phosphines are also suitable; see page 38 of the Cotton and Wilkensoesee article. The ligands containing oxygen, sulfur, phosphorus and nitrogen are attached in such a manner that the hetero atom is a coordinating atom. In addition, some specific examples use polydentate ligands which are multinuclear ligands, for example, which are capable of bonding more than one metal ion. They can be giant rings or non-giant rings. The molecular element herein may also comprise a polymer of the surface active -28-201202378 moiety as described above; for example, a porphyrin polymer (a polymer comprising a porphyrin complex), a macrocyclic complex polymerization may be used. , a surface active moiety comprising two surface active subunits, and the like. The polymers may be homopolymers or heteropolymers' and may comprise different mixtures (blends) of any number of monomeric surface-active moieties, wherein "monomers" may also include two or more subunits. A surface active moiety (eg, a sandwich coordination compound, a porphyrin derivative substituted with one or more ferrocenes, etc.). The surface active moiety polymer is described in WO 2 5/0 8 6 826, which is incorporated herein in its entirety by reference. In a particular embodiment, the attachment group Y comprises an aryl functional group and/or an alkyl attachment group. In a particular embodiment, the aryl functional group comprises a functional group selected from the group consisting of an amine group, an alkylamino group, a bromo group, an iodo group, a hydroxyl group, a hydroxymethyl group, a decyl group, a bromomethyl group. ,vinyl,allyl,S-ethinylthio,Se-ethylmercaptomethyl, ethynyl, 2-(trimethyldecyl)ethynyl, fluorenyl, fluorenylmethyl, 4,4 , 5,5-tetramethyl-1,3,2-O diborane-2-yl' and dihydroxyphosphonium. In a particular embodiment, the alkyl attachment group comprises a functional group selected from the group consisting of bromo, iodine, hydroxy, methionyl, vinyl, fluorenyl, oxyseleno, S-acetyl Sulfuryl-S-acetyl-selenyl, ethynyl, 2-(trimethyldecyl)ethynyl, 4,4,5,5-tetramethyl-1,3,2-dioxaborane · Base, and dihydroxyphosphonium. In a particular embodiment, the attachment group comprises an alcohol or a phosphonate. In certain embodiments, the surface moieties are decane characterized by A(4_x)SiBxY' wherein each A is independently a hydrolyzable group, such as a hydroxy or alkoxy group, wherein x = 1 to 3' And B is independently an alkyl or aryl group, -29-201202378 which may or may not contain an attachment group γ as described above. Specific examples of the invention are applicable to many organic substrates. In an exemplary embodiment, the organic substrate may be composed of any one or more of the following: an electronic substrate, a PCB substrate, a semiconductor substrate, a photovoltaic substrate, a polymer, a ceramic, a carbon, an epoxy resin, a glass reinforced epoxy resin, and a phenol. , polyimine resin, glass reinforced polyimine, cyanate esters, esters, teflon, plastics, coatings and mixtures thereof. In another embodiment, a specific embodiment of the present invention provides a printed circuit board comprising: at least one metal layer; at least one epoxy layer: and a stability formed between the metal layer and the epoxy layer Layer. In some embodiments, the stabilization layer is comprised of a metal oxide having a thickness in the range of about 200 nanometers or less. In other embodiments, the stabilization layer is comprised of a metal oxide that exhibits a substantially amorphous structure. In other embodiments, the stabilization layer is composed of a metal oxide having a thickness of about 150 nm or less and exhibiting a substantially amorphous structure. Generally, the stabilization layer is composed of a stabilizer layer having particles. It is constructed in which the particle diameter of the particles is in the range of 200 nm or less. In another specific example, the particle size of the particles is in the range of 100 nm or less. Typically (but not completely), the metal oxide consists of copper oxide. A particular advantage is that the specific embodiment of the invention provides a means of treating a "smooth" metal substrate. In some embodiments, the invention enables the use of a smooth metal substrate 'which means a metal substrate that has not been roughened beforehand. In the case of a copper substrate, such a substrate can come from a wide variety of sources. For example, copper substrates suitable for use in the method of the present invention include, but are not limited to, electrolytic or electroplated copper, electroless copper, and rolled copper, and are not limited by the method of preparing them. In some embodiments, the roughness of the metal layer is about 0. 13 μηι Ra. In some embodiments, the formed copper oxide (or "treated smooth copper surface") or the stabilized layer of the present invention has a roughness of about 0. 14 pm Ra, thus confirming that the method of the invention does not significantly roughen the surface. In other embodiments, a printed circuit board comprising a polymeric material, such as a ruthenium epoxy resin, is proposed, which may contain a large amount of tantalum material, such as glass, yttria or other materials, the surface of which is chemically Attachment materials, such as porphyrins, are modified to significantly alter their chemical affinity for metals such as, but not limited to, copper to promote strong adhesion between the polymer composite and the metal layer. A second layer of chemical attachment layer can be applied to the metal surface to promote adhesion to the subsequent polymer (epoxy/glass) layer. In some embodiments, the PCB is a multilayer conductive structure. For example, in one embodiment, a printed circuit board is provided comprising: at least one metal layer; an organic molecular layer attached to the at least one metal layer; and an epoxy layer on top of the organic molecular layer. In some embodiments, the at least one metal layer exhibits 1. Peel strength of 0 kg/cm and surface roughness of less than 150 nm. In some embodiments, the at least one metal layer additionally comprises a patterned metal line formed thereon, wherein the patterned metal line has a width equal to or less than 25 microns. Further, the width of the patterned metal line is equal to or less than 15 μm, 1 μm or 5 μm. In another embodiment of the present invention, an epoxy tree brush circuit board having one or more layers of -31 - 201202378 metal layers and one or more layers formed on the metal layer is proposed, characterized in that: Or more layers of metal to show a peel strength greater than 1. 0 kg/cm and a surface roughness smaller than the specific example of the present invention enables a very small line width to be formed. In an example, the metal layer is a patterned metal formed thereon, the patterned metal lines having a width equal to or less than 25 microns. In a bulk example, the metal layer comprises patterned gold formed thereon having a width equal to or less than 15 microns and less than 1 〇 micron. In yet another embodiment, a pattern can be formed in which the width of the patterned metal line is equal to or less than 5 microns. In other embodiments, the present invention contemplates the manufacture of a printed electrical method comprising the steps of: using a base and/or Or a surface of the peroxide solution; stabilized by forming a copper oxide layer on the surface of the copper: terminating the formation of copper oxide by copper oxide with one or more surface modifiers or inhibiting the self-limiting reaction of the compound; Treated copper grease combined. In some embodiments, one or more molecular copper layers can be coupled, the one or more organic molecules comprising a bonding group with one or more bonded to the surface of the copper oxide and one or more attached to the resin. A thermally stable substrate to which the group is attached. Referring to Fig. 1A, there is illustrated an exemplary embodiment of a simplified pattern of smooth metal-resin 1 〇〇 A comprising a smooth metal substrate 1 〇 2 bonded to 104. A stabilization layer of a dense oxide layer bonded to the organic layer 1 〇 8 is formed on top of the metal! 〇6 is corroded or chemically attacked. In some embodiments, it may be that the printing of the lipid layer is less than 15 nm. Some specific lines are formed in other genus lines, and further the metal slab is pre-cleaned between the copper surface. The surface and the tree are combined with the oxidized structure to bond with the interface resin substrate or do not prevent the metal needs but not -32 - 201202378 must be additionally conditioned or layered with the organic molecular layer 108 to form a functional with the resin The activity of the base Y reaction binds to position X to promote chemical bonding to form a covalent bond. In this exemplary embodiment, the smooth metal/resin interface 100A has a roughened copper-resin interface 100B having a prior art interface with a mechanical anchor as shown in FIG. 1B. Better adhesion strength and resistance to heat, moisture and chemical attack. Referring to Figure 2, in order to further illustrate the features of the present invention, the figure shows a sample experimental procedure flow and the process includes four main steps: (1) surface pretreatment 200, (2) surface stabilization and conditioning And optionally functionalized 210, (3) random surface reduction (if necessary) 220, (4) vacuum lamination 240, and (5) heat treatment (if necessary) 260. The specific sub-steps and experimental data are shown for illustrative purposes only and are not intended to limit the scope of the invention in any way. Figure 2 also shows the procedure for performing the peel strength test, but it is only shown to illustrate the test procedure. The generalized method steps of the present invention do not include a peel test step. Ο In the exemplary method illustrated in Figure 2, surface pretreatment 200 is performed by cleaning, cleaning, soft etching, and acid cleaning, and the substrate is cleaned and dried. Next, the surface is stabilized at step 210. In this particular example, the surface is stabilized by surface oxidation. The step of surface oxidation includes exposing the metal surface to an oxidant solution comprising one or more oxidizing agents and one or more surface active moieties. This step produces a stabilization layer of the desired thickness and morphology. Optionally, the functionalization can be carried out, followed by washing and drying of the substrate. If necessary, an optional reduction can be performed in step 220. In a -33-201202378 body example, the pH was adjusted to 12. The sample was treated with 3 5 t of a 40 g/L dimethylamine borane (DMAB) reduction bath for 2 hours. This densifies the oxide layer and removes excess oxide. At this point, the stabilization layer can be functionalized using molecular reactants. The sample is then rinsed and dried with hot air, after the stabilization step 210 and the optional reduction step 220, at step 240 by assembling the laminate film onto the stabilization substrate, applying vacuum lamination, and optionally Vacuum pressure was applied to perform vacuum lamination. A random heat treatment 260 is then performed to cure or anneal the laminated composition. The peel strength test is then carried out as needed. Referring to Figures 3A and 3B, there are shown two separate specific examples of the present invention. For example, in Figure 3A, metal 300 is treated with standard surface oxidation to form oxide layer 310. The oxide layer is grown by a conventional method such as by thermal oxidation. After the oxide layer 310 is formed, the oxide layer 310 is reduced to form the stabilization layer 2020 of the present invention. A molecular reagent is optionally added to the reducing agent to form a stabilization layer 320. Fig. 3B shows another embodiment where the metal 305 is treated with a molecular reagent optionally added to the oxidizing agent during the oxidation step to limit the growth of the oxide layer, thereby forming the stabilization layer 36. In both instances, the adhesion of the subsequent layers is enhanced by the presence of the stabilization layer 3 2 0, 360 without causing significant roughening of the metal surface. In other embodiments, the invention can be used in a wide variety of applications. In one of such examples, a specific example of the invention can be used to form a protective coating. In some embodiments, a method of adding a molecular component of a modified surface to one of the treatment solutions (eg, an oxidation bath or a reduction bath) such as -34-201202378 is provided, which greatly simplifies the metal surface machining. Learning from the presence of reactants (such as oxidizing agents or reducing agents) is shorter and provides more uniform coverage and stability. It can substantially cost the pre-processing program and provide a degree of smoothness to the surface of the modified metal such as greater smoothness and/or adhesion to the enhanced layer and subsequent layer. The MI modified surface can be used as is, or other predetermined defects can be used ( Modifications such as decane chemicals provide additional functionality. The present examples can also be used with other materials that form stable oxides, including cerium oxide, aluminum oxide or oxidized pins. A short list of applications in accordance with examples of the present invention includes, but is not limited to, the following: a substrate that incorporates a hard-and-scratch-resistant hard coating, a coating solution for the coating, and a coated polymer decane couple for the substrates Manufacture of oxide particles; organic/inorganic hybrid polyimine compound resistant to atomic oxygen; coating of automotive power cable, and surface-treated inorganic composition for liquid crystal display panels for manufacturing such compositions ; metal plate adhesive. The adhesive can have a high shear strength. The metal composite panel using the adhesive has high damping for the damping/muffling sheet; the decane water repellent coating for the glass plate of the vehicle or building window. The water repellent glass sheet of the vehicle or the glazing is manufactured by covering the surface of the glass with a repellent coating on the surface; the method of the present invention reduces the extra-surface feature (reliability) due to the use of the MI. The gold procedure for the coating of these other specific substrates; the degree of sealing of the material with a high stripping factor and the covalent bond of the substrate -35-201202378 compatible for protein separation Preparation of gelatin-epoxy resin decane anodized aluminum composite film. The coating should have good hydrophilicity and biocompatibility, and can be widely used for various chemical separations; fabrication of resin-coated substrates, prepregs, and resin-coated metal foils 表面 Non-aggregated surface-treated inorganic powders. The inorganic powder is surface-treated with an organic compound having a polar portion and a non-polar portion and being liquid at ambient temperature. The powder may also be surface treated with a decane coupling agent f. Dispersing the surface-treated inorganic powder in a resin composition used as an EMC (epoxy resin molding compound), a liquid sealant, a substrate material, an adhesive for an electronic component, a resin compound or a coating; for a long-lasting surface Derivatized polyfunctional decane polymers and their antimicrobial properties. It requires covalent surface immobilization and polymer crosslinking to form a permanent coating on both reactive and non-reactive surfaces. The polymer containing a reactive methoxyalkyl group forms a strong Si-0-Si bond with the surface of the oxide, thereby fixing the polymer chains at multiple points; and the packaging material has good adhesion between the plastic substrate and the inorganic layer. A transparent transparent gas barrier film; an aluminum electrode foil surface which must be resistant to negative substances and reacted with a decane coupling agent, which can be used as an electrode of a battery pack and/or a capacitor; a melt blown nonwoven fabric modified by functional microparticles. The manufacturing method requires the surface-modified functional microparticles to be combined with the melt and extruded by the conventional procedure; the nanostructured fuming metal oxide for the thermal interface paste, which has a heat of -36-201202378 A thermally conductive solid component in a paste. It is more advantageous with carbon black but in terms of its non-conductivity. In the absence of smoke, the object is ineffective. By coating the microparticles with decane, the paste is more effective in use; a chromium-free composition that is beneficial to the surface treatment of the steel sheet, which imparts excellent corrosion resistance, processability, and processability to the steel sheet. , powder and lubricating properties. a surface-intercal composition having excellent powder coating properties, comprising an acrylic urethane resin, a colloid, a decane coupling agent, a cerium oxide and an isocyanate crosslinking agent to coat the coated steel sheet Method of manufacturing a semiconductor device comprising receiving a Si film formed on a substrate by using a porous film containing a metal-coated cerium oxide, aluminum oxide and/or oxygen on a substrate; using a trialkoxy decane pair Scratch-resistant and abrasion-resistant polyacrylic acid nano/microparticle hybrid composite surface modification to promote the identification of fluorinated polymer coated galvanized steel with good lubricating properties; decane-modified alumina naphthalene Scratch-resistant coating of rice particles with improved scratch resistance coating material containing organic binder, acrylic two-component polyurethane or UV-curable adhesive 'and decane-modified alumina nanoparticles, It is prepared by depolymerizing a binder containing a particle such as silicon carbide or chlorohydrate in the presence of it, and simultaneously or afterwards; as effective as the oxidative viscosity is reduced. It applied the end of the treatment solution and for producing a composite oxide coating and esters by hydration of the coating made of aluminum clad material sheet and I-. Such as an aqueous agent, adding an organic solvent, aluminum decane -37-201202378

Ti〇2 nanoparticle (nano-ti02) is an Al2〇3, SiO 2 S decane coupling agent coated by chemical liquid deposition; improved electroless copper plating with high adhesion to nickel plating. The electroless plating method is carried out by the following steps: (1) treating the substrate to be plated with a decane coupling agent; (2) immersing the treated substrate in Ni for electroless Ni plating on the treated surface of the substrate a plating bath, and (3) immersing the Ni-plated substrate in a Cu plating bath of PHS 10 to electrolessly plate Cu on the Ni plating layer. The adhesion of the Ni plating layer to the substrate is high, and the adhesion of the Cu plating layer to the Ni plating layer is high; and the stability of the decane modifier on the alumina nanoporous film is improved. The stability of the decane covalently bonded to the nanoporous alumina membrane can be improved by the A1-0-Si bond. The MI treatment prior to the decaneization greatly improves the stability of the immobilized molecule; the bonding strength of the modified resin to the Ti substrate coated with cerium oxide; and the application of a nylon composite containing copper oxide particles to obtain a material having a high coefficient of friction. The existing procedural methods include (1) treating copper oxide particles and alumina particles with a decane coupling agent in acetone, drying and honing; (2) treating carbon fibers in air for oxidation; (3) mixing and treating in a ball mill Copper oxide particles, alumina particles, carbon fibers, and nylon for 6 to 8 hours; then performing a standard process; and illustrating a modified coating for a lamp comprising a network structure obtainable by conversion of an organically modified decane by a sol-gel procedure The cerium oxide particles obtainable from the acid-stabilized colloidal cerium oxide dispersion are incorporated in the network structure in a large amount. -38-201202378 [Embodiment] Experiment A number of experiments were carried out as follows. The examples are for illustrative purposes only and are not intended to limit the invention in any way. EXAMPLES Example 1: Treatment of a Smooth Copper Substrate This example illustrates an exemplary approach to treating a smooth copper substrate in accordance with certain embodiments of the present invention. As described above, the method of the present invention makes it possible to use a treated metal substrate, meaning a metal substrate which has not been roughened beforehand. In an example, the metal surface is copper and more specifically a smooth copper surface, meaning a copper substrate that has not been roughened beforehand. Such a copper substrate can be formed from a wide variety of sources. For example, copper substrates suitable for use in the method of the present invention include, but are not limited to, electrolytic or electroplated copper, electroless copper, and rolled copper, and are not limited by the method of preparing them. In Example 1, the electrolytic copper substrate was first cleaned at 40 ° C for 4 minutes with a 40 g/L sodium hydroxide solution, and then rinsed with water. The copper substrate was further cleaned with a 1 wt% hydrogen peroxide solution at RT for 1 minute, and cleaned with a 3 wt% sulfuric acid solution at RT for 1 minute, and then rinsed with water. It was then stabilized by rinsing with water at 6 (TC in a 140 g/L chlorite solution with 12 g/L sodium hydroxide and less than 1% surface modifying compound for 6 minutes). The substrate was then treated in a reduction bath of 40 g/L dimethylamine borane (DM AB) adjusted to 12.6 at 35 ° C for 2 minutes. The sample was then rinsed and dried with hot air. The surface morphology and thickness of the stabilization layer were adjusted by changing the concentration of the treatment solution -39-201202378, temperature and duration' and characterized by SEM, XRD and Auger depth profile. The sample was then rinsed and It is dried by hot air. Figure 4A is an example SEM micrograph of 50,000 times magnification showing a conventional electrolytic copper surface with needle-like particles and oriented grain growth reflecting the long-range regularity of the crystal structure (ie, smooth copper) The morphology of the surface, or in other words the 'unroughened copper surface.' In contrast, the morphology of the surface of the electrolytic copper treated according to the method of the present invention formed with a stabilization layer is shown in Figure 4B. 4B shows the past The stabilization layer on the copper surface exhibits finer particle morphology, non-directional particle growth, and higher uniformity. In contrast, Figure 4C shows a conventional black oxide surface that exhibits a thicker and brittle fibrous structure. 4D is an exemplary SEM micrograph of a conventional microetched copper surface showing a highly uniform micro-valley and ridge morphology. The table data of Figure 5 compares the surface roughness expressed by both Ra and Rz, and demonstrates the invention The treatment does not roughen the copper surface, which is different from the conventional oxidation and reduction procedure for a substantially large roughened surface. The stabilized layer of the treated smooth copper surface prepared according to Example 1 is further characterized by Eugene electron spectroscopy (AES) To determine the surface composition and the thickness distribution of the layer. Referring to Figure 6, the AES depth analysis of the treated smooth copper surface shows that the stabilization layer contains mixed copper and copper oxide (presumably - cuprous oxide), and its thickness is Approximately 100 nm. Conversely, the conventional black oxide layer extends over a distance of 1 000 nm. The thickness of the stabilization layer must be in the range of about 100 to 200 nm to ensure good bonding strength. Referring to Figures 7A and 7B', the growth of the stabilization layer is characterized by an example of a copper substrate according to a specific example of the invention -40 - 201202378. Under various conditions, a surface modifying compound is used according to a specific example of the present invention. The depth analysis of the formed copper oxide layer is shown in Fig. 7. As shown, the atomic composition of the outer surface of the layer is approximately 50% copper and 5% oxygen. When it is moved into the substrate through the surface layer The composition is close to 100% copper. The self-limiting nature of the process is shown in Figure 7B, which shows that the growth of the oxide layer is substantially flat after a particular oxidation time, in this example after about 0 minutes. Example 2: Confirmation of Resin Bonding Enhancement on Smooth Copper Substrate This example illustrates an exemplary approach to enhance epoxy adhesion on a smooth copper substrate. As shown in Figure 8, the treated Cu test strips were tiled onto a temporary backing. As shown in the schematic steps shown in Figures 9A through 9D, a 35 μm thick commercially available cumulative (BU) epoxy (or dielectric) laminate film that has been stabilized under ambient conditions for at least 3 hours is tiled in Cu. Top of the bar. The assembly was then vacuum laminated at 〇 loot: vacuum for 30 seconds and pressurization at 3 Kg/cm 2 for 3 sec seconds. This lamination step was repeated twice to form a total of 3 layers of B U film. It is noted that the copper surface changes from reddish to light brown or green after surface treatment and then turns black after lamination, which means that a chemical bonding reaction has taken place. The surface of the resin contains chemically reactive groups such as hydroxyl groups, amines, epoxides and others which can react with the oxygen-rich copper surface by forming bonds. In order to quantify the adhesion strength, as shown in Fig. 9B, a rigid backing substrate (reinforcing material) was laminated on top of the BU film. The assembly was then heat treated or cured in a convection oven at rc 8 (rc -41 - 201202378 for 90 minutes. Next, the assembly was cut into small squares to remove the temporary backing substrate and divided into peel strengths Test and use of the independent test piece for the test of the High Accelerated Stress Test (HAST). The adhesion strength of the formed laminate is 90 degrees on the 10 mm wide peeling strip by the dynamometer of the peel tester. The peel angle and the peel speed of 5 〇mm/min were quantified. More specifically, the peel strength was tested on the initial formation and then on the substrate after pre-conditioning and remelting. The pre-conditioning system was carried out at 125 ° C for 25 hours, then It was carried out at 30 ° C and 60% relative humidity (R Η ) for 1 292 hours. The remelting system was carried out three times at 260 ° C. Thereafter, the H AST test was carried out at 1 30 ° C and 85% RH. Figures 10A and 10B illustrate the effect of this treatment on the retention of peel strength after the HAST test. The smooth control group (i.e., without the stabilization layer of the present invention) has a peel strength of 88% after HAST and is conventionally roughened. The control group showed a loss of 40%. Processing a smooth copper substrate (i.e., having a stabilization layer formed in accordance with the present invention) not only exhibits a higher initial peel strength, but also exhibits a higher retention rate with only a 26% loss. The table data of Figure 10B also confirms The enhancement of peel strength stability is achieved without changing the surface roughness. This result is superior to the teachings of the prior art and is currently unpredictable by the teachings of the prior art. Significant advantages are embodiments of the present invention that provide a stable, controllable process Scope. This custom range provides a robust and repeatable procedure. Figure 11 illustrates the peel strength reproducibility or robustness and HAST of a sample of five batches of a smooth copper surface of a laminated epoxy treated according to a specific embodiment of the present invention. Stability. Figure 1 2 A and 1 2 B show the -42-201202378 laminated treated copper surface with a stabilized layer according to a specific example of the invention compared to a standard roughened surface before and after the HAS SEM The top view further demonstrates that the method of the present invention does not significantly roughen the copper surface and that no significant delamination occurs after the remelting and HAST reliability tests. Figure 1 3 A And s E Μ micrograph of the surface of the stripped copper with 1 3 B, which shows that the copper-resin interface of the smooth copper control group (Fig. 13 A) breaks just at the copper surface, whereas the method formed according to the invention has stability The interface of the treated layer of smooth copper (Fig. UB) is broken in the resin. This surprising result confirms that the bond strength between the resin and the treated copper surface of the present invention is stronger than that of the overall resin material itself. Example 3: Confirmation of Thin Line Patterning and Electrical Insulation Reliability A device was formed to illustrate that patterning of thin lines can be achieved by a specific example of the present invention. More specifically, the same process processing and lamination line and line pitch according to Embodiment 1 and Embodiment 2 have the same size (5〇/5〇, 3 0/3 0, Ο 20/20, 10/10 And a comb pattern of 8/8 μηα). The SEM cross-sectional view again confirmed that the copper wire was not roughened by the method of the present invention and was not delaminated after the remelting and H A S Τ test. After remelting and HAST, the electrical insulation resistance of 2 V remains above 1〇12 Ω, which is seven orders of magnitude higher than the PCB manufacturing specification. Table 1 below summarizes these results. Good results have been obtained on these structures' showing that the present invention significantly improves the ability to pattern copper lines with fine line pitches'. This is a significant advancement in the art. -43- 201202378 Table 1. Thin-line patterning and electrical insulation reliability line/line spacing size (μιη) 2V insulation resistance after HAST without HAST X 1〇12Ω 50/50 micron qualified 1.27 30/30 micron qualified 1.30 20/20 micron qualified 1.43 1 (V10 micron qualified 1.29 8/8 micron qualified 1.10 Example 4: Laser drilling of laminated epoxy resin surface and hole cleaning/plating compatibility confirmed to form a mine The device for passing through holes is then further processed to demonstrate process compatibility. More specifically, the smooth copper substrate is processed and laminated in accordance with the same process as described in Example 1 and Example 2. Drilling through C02 and UV lasers A via array of diameters of 30, 40, 50, 75, 100' 150, and 200 μm. The via structure is then lightly etched and acid cleaned or desmeared, followed by electroless copper plating and then electroplated. 14 shows an SEM section of a laser via formed on the surface of a laminated smooth treated copper in accordance with an embodiment of the present invention, which demonstrates no undercut and delamination after the desmear and plating procedure Example 5: Solder bond reinforcement on a smooth copper substrate This example demonstrates an exemplary approach to enhance solder resist adhesion on a smooth copper substrate. The smooth copper test strip is treated in accordance with the same process as described in Example 1 and tiled on a temporary back as shown in FIG. Lining. As shown in Fig. 9 ,, a commercially available solder mask-44 - 201202378 (SR) laminate film which has been stabilized under ambient conditions for at least 3 hours is laid on top of the copper strips. The assembly was then vacuum laminated at a vacuum of 75 ° C for 30 seconds and at 1 Kg/cm 2 for 60 seconds. The assembly was then subjected to a UV exposure of 400 mJ/cm 2 followed by a convection oven at 1 50 Curing at ° C for 60 minutes and UV curing at 1 μm/cm 2 . To quantify the adhesion strength, a rigid backing substrate (reinforcing material) is laminated as shown in step 2 of Figure 9 B. The top of the SR film. The assembly is then cut into small squares to remove the temporary backing substrate, which is then divided into separate test pieces for peel strength test and high accelerated stress test (HAST). More specifically The peel strength was tested on the initial formation and on the substrate after preconditioning, remelting and hast. 15A and 15B illustrate the effect of the treatment method of the present invention on the retention of peel strength after the HAST test. The peel strength of the untreated smooth control group after the HAST decreased by 87%, and the conventional roughened control group showed a loss of 69%. The apparently controlled system, the treated smooth copper surface formed according to the specific examples of the present invention not only shows a higher initial peel strength, but also shows a higher retention rate, which has only a 22% loss. The table data of Figure 15B also confirms The increase in peel strength stability was not significantly changed under the surface roughness. Example 6: UV patterning of Cu surface of laminated SR and verification of via cleaning/plating compatibility A device having a via array and a copper wire was formed and then further processed to confirm processing compatibility. More specifically, the smooth copper substrate was processed and laminated in the same manner as described in Example 5. A through-hole array having a bottom diameter of 80 to 440 μm and a copper-45-201202378 line having a line width of 62 to 500 μm are formed by UV exposure and development. Fig. 1A shows the copper line pattern and via array, and Fig. 6B shows the ball grid array (B G A ) pattern. The patterned structure is then subjected to a mild etching and acid cleaning or desmear process followed by electroless Ni and then Au immersion deposition. Figure 17 shows the SEM cross section of the SR through hole formed on the laminated smooth copper. It confirmed no delamination after the desmear and plating procedure. Good results have been obtained on these structures, meaning that the processing method of the present invention significantly improves the ability to pattern SR with fine line spacing, which is a significant advancement in the art. In summary, many specific examples of the invention are presented herein. In some embodiments, a method of treating a metal surface to promote adhesion between the metal surface and an organic material is provided, characterized in that a metal oxide layer is formed on the metal surface, and the metal oxide layer is formed. It is controlled by a self-limiting reaction between the metal oxide and the surface modifying compound. The formation of the metal oxide layer can be controlled such that the metal oxide layer has a thickness of about 200 nm or less, or optionally has a thickness in the range of about 100 nm to 200 nm. The formation of the metal oxide layer can be controlled such that the metal oxide layer has a morphology consisting of a substantially amorphous structure. In some embodiments, the metal oxide layer has particles having a particle size in the range of 250 nm or less, or optionally in the range of 200 nm or less. The particles are substantially randomly oriented after conditioning. The metal oxide layer may be composed of copper oxide. In some embodiments, the metal oxide layer is formed by exposing the surface of the metal to an oxidizing agent. The oxidizing agent may be selected from any one or more of the following: sodium chlorite, hydrogen peroxide, peroxyacid salt, perchlorate, persulfate, ozone or a mixture thereof. -46 - 201202378 In certain embodiments, the surface modifying compound is selected from the group consisting of compounds which react with the surface of the metal oxide to form a reaction rate upon formation of the metal oxide. The surface modifying compound can be selected such that it eventually slows down and terminates the oxidation reaction. The process can be carried out at a temperature ranging from room temperature to about 80 °C. In some embodiments, the self-limiting reaction will stabilize after about 5 to 15 minutes. In other embodiments, a method of treating a metal surface to promote adhesion between the base metal surface and an organic material is provided, the method comprising the steps of: oxidizing the metal surface to form a metal oxide layer on the metal surface; And terminating the growth of the metal oxide layer by a self-limiting reaction between the metal oxide layer and the surface modifying compound. In some embodiments, the step of oxidizing and terminating the oxidation additionally comprises exposing the surface of the metal to a solution comprising an oxidizing agent and a surface modifying compound. Optionally, some methods additionally comprise contacting the metal surface with one or more organic molecules, wherein the organic molecules comprise one or more bonded oxime groups and one or more constructed structures bonded to the metal surface A thermally stable matrix of attachment groups attached to the organic material. In some embodiments, the one or more organic molecules are surface active moieties. In some embodiments, the one or more organic molecules are selected from the group consisting of porphyrins, porphyrin macrocycles, extended porphyrins, shrinking porphyrins, linear porphyrin polymers, p-porphyrin sandwich coordination complexes , or p-porphyrin array. The surface active moiety can be selected from the group consisting of a macrocyclic proligand, a macrocyclic complex, a sandwich coordination complex, and a polymer thereof. The attachment group can be formed from an aryl functional group and/or an alkyl attachment group -47-201202378. In certain embodiments, the aryl functional group consists of a functional group selected from one or more of the following: acetate, alkylamino, allyl, amine, amine, bromo, bromo Base, carbonyl, carboxylate, carboxylic acid, dihydroxyphosphonium, epoxide, ester, ether, ethynyl, decyl, hydroxy, hydroxymethyl, iodo, decyl, fluorenyl, Se-B Mercapto selenyl, Se-ethyl selenomethyl, S-acetylthio, S-acetylthiomethyl, oxyselenos 4,4,5,5-tetramethyl-1,3 , 2-dioxaboran-2-yl, 2-(trimethyldecyl)ethynyl, vinyl, and combinations thereof. In certain embodiments, the alkyl attachment group comprises a functional group selected from any one or more of the group consisting of acetate, alkylamino, allyl, amine, amine, bromo, bromomethyl , carbonyl, carboxylate, carboxylic acid, dihydroxyphosphonium, epoxide, ester, ether, ethynyl, decyl, hydroxy, hydroxymethyl, iodo, decyl, fluorenyl, Se-acetyl Selenium, Se-ethenyl selenomethyl, S-acetylthio, S-acetylthiomethyl, oxyseleno, 4,4,5,5-tetramethyl-1,3, 2 -Bismoborane-2-yl, 2-(trimethyldecyl)ethynyl, vinyl, and combinations thereof. In one example, the at least one attachment group is comprised of an alcohol or phosphonate. In other embodiments, the at least one attachment group consists of any one or more of the following: amines, alcohols, ethers, other nucleophiles, phenyl acetylenes, phenylallyl groups, Phosphonates, and combinations thereof. In some embodiments, a method of forming a coating on a metal surface is provided, characterized in that a metal oxide is formed on the surface of the metal, and the metal oxide layer is formed by the metal oxide and the surface modifying compound. Controlled by a self-limiting reaction between them. In another embodiment, a method of forming a coating on a metal surface is disclosed in the method of -48-201202378, comprising the steps of: oxidizing a metal surface to form a metal oxide layer on the metal surface; and using the metal oxide layer A self-limiting reaction with the surface modifying compound terminates the growth of the metal oxide layer. Furthermore, a method of forming a coating on a metal surface is provided, comprising the steps of: stabilizing the metal surface; and conditioning the stabilized metal surface 0. In another embodiment of the invention, a printed circuit board is proposed 0 includes: at least one metal layer; at least one epoxy layer; and a stabilization layer formed between the metal layer and the epoxy layer. The stabilization layer can be composed of a metal oxide having a thickness of about 200 nm or less. In some embodiments, the stabilization layer is comprised of a metal oxide that exhibits a substantially amorphous structure. In some embodiments, the stabilization layer is comprised of a metal oxide having a thickness of about 200 nanometers or less and exhibiting a substantially amorphous structure. The stabilization layer may additionally be composed of a metal oxide layer having particles, wherein the particles have a particle size in the range of 250 nm or less, or optionally the particle size is 200 nm or less. The scope. In some embodiments, the metal oxide consists of copper oxide. The metal layer can have a roughness of up to about 0.14 μηι Ra, and the metal oxide layer can have a roughness of up to about 〇14 μηη Ra. In some embodiments, the metal layer additionally includes a patterned metal line formed thereon, the patterned metal line having a width equal to or less than about 25 microns, optionally the patterned metal line having equal to or less than about A width of 15 microns, and optionally the patterned metal line has a width equal to or less than about 10 microns, and optionally the patterned metal line has a width equal to or less than -49 to 201202378 of about 5 microns. In other embodiments, a method of fabricating a printed circuit board is provided that includes the steps of pre-cleaning a copper surface with a base and/or a peroxide solution; and stabilizing the copper oxide layer on the copper surface. a copper surface; the formation of copper oxide is terminated by a self-limiting reaction between copper oxide and one or more surface modifying compounds; and the treated copper surface is combined with a resin. In some embodiments, a method of controlling the growth of an oxide layer on a surface of the metal is provided, comprising: terminating the oxide layer by a self-limiting reaction between the oxide layer and one or more surface modifying compounds Growing. Specific examples of the invention additionally provide oxidant compositions comprising one or more oxidizing agents; and one or more surface modifying compounds. Furthermore, a method of treating a metal surface to promote adhesion or bonding between the metal surface and an organic material is proposed, characterized in that the metal surface is stabilized by forming a stabilization layer on the surface of the metal, and then conditioned with a reducing agent. The stabilization layer achieves a selective oxide thickness and morphology. In some embodiments, the reducing agent is selected from any one or more of the group consisting of a borane, a morpholine boron, a pyridiumb 〇rane, a piperidine or a second. Metamine borane DMAB). In some embodiments, the surface of the metal is stabilized at a temperature ranging from room temperature to about 80 ° C, optionally at a temperature ranging from room temperature to about 50 ° C. In some embodiments, the overall process time is in the range of about 5 to 20 minutes. In other embodiments, a method of treating a metal surface to promote adhesion between the metal surface and an organic material is provided, comprising the steps of: naming the metal surface; and conditioning the stabilized metal surface . In one example, stabilizing the metal surface includes forming a metal oxide layer on the metal surface. In one example, the step of conditioning the metal surface comprises reducing the metal oxide layer with a reducing agent. In some embodiments, the metal oxide layer has a thickness after conditioning of about 200 nm or less. In some embodiments, the conditioned metal oxide layer is comprised of a substantially amorphous structure. The metal oxide layer has particles, and after nucleation, the particles have a ruthenium particle size in the range of 250 nm or less, optionally in the range of 200 nm or less. In some embodiments, the particles are substantially randomly oriented after conditioning. In one example, the metal oxide layer is comprised of copper oxide. In one embodiment, the metal surface is contacted with one or more organic molecules after conditioning, wherein the organic molecules comprise one or more bonding groups configured to bond to the metal surface and one or more A thermal stabilization matrix is constructed that is attached to the attachment of the organic material. In some examples of the body, the organic material may be composed of any one or more of the following: an electronic substrate, a PCB substrate, a semiconductor substrate, a photovoltaic substrate, a polymer, a ceramic, a carbon, an epoxy resin, a glass reinforced epoxy. Resins, phenols, polyimines, glass-reinforced polyimine, cyanate esters, esters, teflon, plastics, and mixtures thereof. In still another embodiment, a method of manufacturing a printed circuit board is provided, comprising the steps of: pre-cleaning a copper surface with a base and/or a peroxide solution; and stabilizing the copper oxide layer on the copper surface a copper surface; conditioning the copper oxide layer with a reducing agent; and combining the treated copper surface with the resin. -51 - 201202378 additionally an additional step of coupling one or more molecules to the copper oxide layer, the one or more organic molecules comprising one or more bonding groups configured to bond to the surface of the copper oxide and A plurality of thermally stable matrices constructed to attach groups attached to the resin. It is to be understood that the foregoing methods, apparatus, and description are illustrative. It will be appreciated that those skilled in the art will recognize other approaches and are intended to be within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other embodiments of the specific embodiments of the invention are in the 1A and 1B illustrate a specific example of a metal-resin bonding procedure according to a specific example of the present invention, and compared with a conventional roughening procedure; FIG. 2 illustrates a flow chart of an experimental procedure illustrating one specific example of the method of the present invention; 3A and 3B show simplified example reaction diagrams for two specific examples of the invention; Figures 4A through 4D show the following SEM photographs: (A) smooth copper surface before any treatment (i.e., control group); (B) according to the present A copper surface treated in accordance with one embodiment of the invention, which exhibits a smoothness of the stabilized layer of the treated surface; and (C) a conventional black oxide surface as described in the prior art; and (D) as described in the prior art Microetching roughened copper surface; -52 - 201202378 Fig. 5 is a comparison of surface roughness expressed by both Ra and rz of the copper surface shown in Figs. 4A to 4D; The stability of the stabilized layer prepared by the specific example of the present invention is a depth analysis of about 150 nm, which is compared with a conventional copper black oxide layer having a depth of usually more than 1 micrometer; FIG. 7 shows that the metal is represented by Λ and 7 B a photograph of the oxide; it clearly illustrates the Euclid depth analysis of the copper oxide in FIG. 4A, and the self-limiting parabolic growth of the treated smooth copper surface using the surface modifying compound according to the specific example of the present invention; Figure 8 is an example of a sample layout for performing a peel strength test on a copper test strip on an epoxy substrate; Figures 9A to 9D show the preparation of the sample and the degree of lamination used according to some specific examples. Simplified cross-sectional view; Figures 10A and 10B illustrate the peel strength and surface roughness of a smooth copper surface of a laminated epoxy resin treated according to an embodiment of the present invention (referred to as "smooth treated smooth"), which is compared with a control group Comparison of a smooth copper substrate and a conventional roughened copper surface; Figure 11 graphically illustrates the peel strength of a sample of five batches of a smooth copper surface of a laminated epoxy resin treated according to an embodiment of the present invention. Reproducibility and HAST Stability; Figures 12A and 12B show SEM cross-sections of a laminated treated smooth copper surface (bottom surface) before and after HAST in accordance with an embodiment of the present invention, with a standard rough surface (top surface) Comparison; and demonstrates that the method of the invention does not significantly roughen the surface and has no layer at the interface after HAST-53-201202378

Figure 1 3 A shows a photograph of the s E Μ of the stripped copper surface after two H A S T (complete and morphological modes) confirming the copper-resin interface rupture in the untreated smooth copper surface control group. Figure 1 3 shows the S EM photograph (complete and morphological pattern) of the smoothed copper surface after peeling and treated according to the specific example of the present invention after two HAS crucibles, and shows that most of the area is covered by resin, which means failure Occurs in the resin rather than the copper-resin interface; Figure 14 shows a SE Μ photograph of a cross section of a laser through hole formed on a laminated smooth copper surface according to an embodiment of the present invention, which confirms that Undercutting did not occur after the slag and plating procedure; Figure 1 5 Α and 15 Β to illustrate the peel strength and surface roughness of the smooth copper surface of the laminated solder resist treated according to the specific example of the present invention, Comparison of the substrate and the conventional roughened copper surface; FIGS. 16A and 16B show photographs of the SR pattern and the via array (16A) and the BGA pattern (16B) of the copper line; and FIG. 17 is formed in accordance with an embodiment of the present invention. A SEM photograph of the cross section of the SR through-hole formed on the surface of the treated copper was confirmed, and it was confirmed that the delamination treatment did not cause delamination. [Main component symbol description] 1 0 0 A: smooth metal-resin bonding interface 102: metal substrate 104: resin substrate 106: stabilization layer - 54 - 201202378 1 〇 8 : organic layer 100 Β : roughened copper-resin interface 300: Metal 3 1 0 : oxide layer 3 2 0 : stabilization layer 350 : metal 3 6 0 : stabilization layer 〇 200 : surface pretreatment 2 1 0 : surface stabilization and conditioning and random functionalization 220 : random surface Reduction 240: vacuum lamination 2 6 0 : heat treatment

Claims (1)

201202378 VII. Patent application scope: 1. A method for treating a metal surface to promote adhesion between the metal surface and an organic material, characterized in that: a metal oxide layer is formed on the metal surface and the metal oxide layer is The formation is controlled by a self-limiting reaction between the metal oxide and the surface modifying compound. 2. A method of treating or coating a metal surface, comprising the steps of: oxidizing a metal surface to form a metal oxide layer on the metal surface; and between the metal oxide layer and the surface modifying compound The self-limiting reaction terminates the growth of the metal oxide layer. 3. The method of claim 1 or 2, wherein the metal oxide layer is formed such that the metal oxide layer has a thickness of about 200 nm or less. 4. The method of claim 1 or 2, wherein the metal oxide layer has a thickness in the range of from about 100 nm to about 200 nm. 5. The method of claim 1 or 2, wherein the formation of the metal oxide layer is controlled such that the metal oxide layer has a morphology consisting of a substantially amorphous structure. The method of claim 1 or 2, wherein the metal oxide layer has particles having a particle diameter in the range of 250 nm or less. The method of claim 1 or 2, wherein the metal oxide layer is composed of copper oxide. 8. The method of claim 1 or 2, wherein the metal oxide - 56 - 201202378 has particles and the particles are substantially randomly oriented after conditioning. 9. The method of claim 1 or 2, wherein the metal oxide layer is formed by exposing the metal surface to an oxidizing agent. The method of claim 9, wherein the oxidizing agent is selected from any one or more of the group consisting of sodium chlorite, hydrogen peroxide, permanganate, perchlorate, persulfate, Ozone or a mixture thereof. The method of claim 1 or 2, wherein the surface modifying compound is selected from the group consisting of a compound which reacts with the surface of the metal oxide to form a reaction rate when the metal oxide is formed. 12. The method of claim 11, wherein the surface modifying compound eventually slows down and terminates the oxidation reaction. The method of claim 1 or 2, wherein the method is carried out at a temperature ranging from room temperature to about 80 °C. The method of claim 1 or 2, wherein the self-limiting reaction is stabilized after about 5 to 15 minutes. 15. The method of claim 2, wherein the step of oxidizing and terminating the oxidizing additionally comprises exposing the surface of the metal to a solution comprising an oxidizing agent and a surface modifying compound. The method of claim 15, wherein the surface modifying compound is in the oxidizing agent solution. The method of claim 2, further comprising the step of: contacting the metal surface with one or more organic molecules, wherein the organic molecules comprise one or more structures configured to interface with the metal surface </ RTI> -57-201202378 A group and one or more thermally stable matrices constructed to attach to the organic material. The method of claim 17, wherein the one or more organic molecules are surface active moieties. The method of claim 17, wherein the one or more organic molecules are selected from the group consisting of porphyrins, porphyrin macrocycles, expanded porphyrins, and contracted porphyrins (contracted) Porphyrin), a linear porphyrin polymer, a porphyrin-filled complex, or a method of the invention, wherein the surface active moiety is selected from the group consisting of the following: Groups of constituents: proligand, macrocyclic complex, sandwich coordination complex, and polymers thereof. 2 1 The method of claim 18, wherein the surface active moiety is porphyrin. The method of claim 3, wherein the one or more attachment groups are comprised of an aryl functional group and/or an alkyl attachment group. 23. The method of claim 22, wherein the aryl functional group consists of a functional group selected from any one or more of the group consisting of acetate, alkylamino, allyl, amine, amine , bromo, bromomethyl, carbonyl, carboxylate, carboxylic acid, dihydroxyphosphonium, epoxide, ester, ether, ethynyl, decyl, hydroxy, hydroxymethyl, iodo, decyl, hydrazine Methyl, S e-ethyl decyl selenyl, Se-ethyl selenomethyl, s_ acetyl thio, 3 ethyl thiomethyl, oxyseleno, 4, 4, 5, 5 - Tetramethyl-1,3,2-dipyroborane-2-yl, 2-(trimethylsilyl)ethynyl, vinyl, and combinations thereof. The method of claim 22, wherein the alkyl attachment group comprises a functional group selected from any one or more of the group consisting of acetate, alkylamine, allyl, amine , amine, bromo, bromomethyl, carbonyl, carboxylate, carboxylic acid, dihydroxyphosphonium, epoxide, ester, ether, ethynyl, decyl, hydroxy, hydroxymethyl, iodine, fluorenyl , hydrazine methyl, Se-ethyl decyl selenyl, Se-acetyl selenomethyl, s_ acetyl thio, s_ acetyl thiomethyl, oxyseleno, 4, 4, 5, 5 - tetramethyl-13,2-dioxaxolan-2-yl, 2-(trimethylenemethyl)ethynyl, vinyl, and combinations thereof. The method of claim 17, wherein the at least one attachment group is comprised of an alcohol or a squarate. The method of claim 17, wherein the at least one attachment group is composed of one or more of the following: amines, alcohols, ethers, other nucleophiles, phenylacetylene Classes, phenylallyl groups, phosphonates, and combinations thereof. The method of claim 1, wherein the organic material is an organic substrate composed of any one or more of the following: an electronic substrate, a PCB substrate, a semiconductor substrate, a photovoltaic substrate, a polymer, a ceramic, Carbon, epoxy resin, glass reinforced epoxy resin, phenol, polyimide resin, glass reinforced polyimine, cyanate ester, ester, Teflon, plastic and mixtures thereof. A printed circuit board comprising: at least one metal layer; at least one epoxy layer; and a stabilization layer formed between the metal layer and the epoxy layer. -59-201202378 2 9. The printed circuit board of claim 28, wherein the stabilization layer is composed of a metal oxide having a thickness of about 200 nm or less, 〇3 0. A printed circuit board of the eighth aspect, wherein the stabilization layer is composed of a metal oxide exhibiting a substantially amorphous structure. The printed circuit board of claim 28, wherein the stabilization layer It is composed of a metal oxide having a thickness of about 200 nm or less and exhibiting a substantially amorphous structure. The printed circuit board of claim 28, wherein the stabilization layer is composed of a metal oxide layer having particles, wherein the particles have a particle diameter of 250 nm or less. range. 3. The printed circuit board of claim 28, wherein the stabilization layer is composed of a metal oxide layer having particles, wherein the particles have a particle size of 200 nm or less. range. 34. The printed circuit board of claim 29, wherein the metal oxide is comprised of copper oxide. 3 5 . The printed circuit board of claim 28, wherein the metal layer has a roughness of up to about 0.14 Ra° 3 6 . The printed circuit board of claim 29 is the metal oxide. Roughness up to approximately 〇·14 Ra. The printed circuit board of claim 28, wherein the metal layer additionally comprises a patterned metal line formed thereon, the patterned metal line having a width equal to or less than about 25 microns. -60-201202378 3 8. The printed circuit board of claim 28, wherein the metal layer additionally comprises a patterned metal line formed thereon. The patterned metal line has a width equal to or less than about 15 microns. . The printed circuit board of claim 28, wherein the metal layer additionally comprises a patterned metal line formed thereon, the patterned metal line having a width equal to or less than about 1 〇 micrometer. The printed circuit board of claim 28, wherein the gold genus layer further comprises a patterned metal line formed thereon, the patterned metal line having a width equal to or less than about 5 microns. 4 1. A method of manufacturing a printed circuit board, comprising the steps of: pre-cleaning a copper surface with a base and/or a peroxide solution; and stabilizing the copper surface by forming a copper oxide layer on the copper surface; The formation of copper oxide is terminated by a self-limiting reaction between copper oxide and one or more surface modifying compounds; and the treated copper surface is combined with a resin. The method of claim 41, further comprising the step of: coupling one or more organic molecules with the copper oxide layer, the one or more organic molecules comprising one or more configured to A copper oxide surface-bonded bonding group and one or more thermally stable substrates configured to attach to the resin. 43. A method of treating a metal surface to promote adhesion or bonding between the metal surface and an organic material, characterized in that the metal surface is stabilized by forming a metal oxide layer on the surface of the metal, and then reduced The -0.1 - 201202378 agent conditioned the metal oxide layer to achieve a selective oxide thickness and morphology. 44. A method of manufacturing a printed circuit board, comprising the steps of: pre-cleaning a copper surface with a base and/or a peroxide solution; and stabilizing the copper surface by forming a copper oxide layer on the copper surface; Conditioning the copper oxide layer; and bonding the treated copper surface to the resin. The method of claim 4, further comprising the step of: coupling one or more organic molecules with the copper oxide layer, the one or more organic molecules comprising one or more constructed to A copper oxide surface-bonded bonding group and one or more thermally stable substrates configured to attach to the resin. 46. A method of forming a coating on a metal surface, the method comprising the steps of: stabilizing the surface of the metal; and conditioning the surface of the stabilized metal. -62 -