Modified copper surface, heteroaromatic silane compounds and their usage for increasing adhesion strength between copper and an organic material and reducing halo and wedge void formation

Abstract

This invention relates to a method for improving the adhesion strength between the surface of copper, copper alloy or copper oxide and the surface of organic materials.

Description

Technical Field

[0001] This invention relates to a method for improving the adhesion strength between the surface of copper, copper alloy or copper oxide and the surface of organic materials and reducing the formation of halo and wedge-shaped pores. Prior Technology

[0002] In the semi-additive stacking sequence used to produce integrated circuit (IC) substrates, one of the key tasks is to form strong bonds between adjacent layers that inherently lack natural adhesion. The fundamental challenge here is to form strong bonds between copper traces and the dielectric material used for stacking layers or the final solder mask coating, without negatively impacting the performance of the final product.

[0003] Previously, the most commonly used adhesion promoter systems provided highly rough copper surfaces; these rough surfaces then served as key to mechanical bonding with dielectric materials (e.g., organic resin systems) and copper traces. However, this type of system, which maximizes the copper surface area for removing minimal amounts of copper, is no longer acceptable. As conductor features become increasingly smaller, forming reliable structures with desired line and spatial tolerances becomes more challenging, making the introduction of adhesion promoter steps based on highly surface roughening entirely undesirable.

[0004] Furthermore, the second challenge lies in the upcoming 5G systems, where signal integrity is strongly correlated with surface roughening. As the frequency and rate of data transmission for electrical signals increase, the signal path moves to the outermost layer of the copper trace. Clearly, if this "layer" is highly roughened to improve adhesion to the stacked layers, the risk of signal loss or slowdown is much higher. Any such loss will compromise the ability to operate within the required high-frequency range.

[0005] To overcome these challenges, it is desirable to develop methods for treating copper surfaces and / or dielectric materials, which enhance the adhesion between the two materials without etching and / or roughening the copper surface.

[0006] Heteroaromatic silane compounds are frequently used in the manufacture of electronic components, particularly in surface treatment solutions, such as for treating copper surfaces and organic material surfaces as preparation for further processing steps.

[0007] US 2016 / 0368935 A1 relates to azole silane compounds, surface treatment solutions using azole silane compounds, surface treatment methods and their uses.

[0008] JP 2018016865 A discloses a triazole surface treatment agent containing silane compounds.

[0009] JP 2014240522 Series A relates to copper surface treatment liquids, surface treatment methods and their applications.

[0010] JP H06279461 A relates to a surface treatment agent for copper foil used in copper-clad laminates for printed circuits.

[0011] The article "Corrosion protection of copper with 3-glycidoxypropyltrimethoxysilane-based sol-gel coating through 3-amino-5-mercapto-1,2,4-triazole doping," Journal of Research on Chemical Intermediates, Vol. 42, No. 2, pp. 1315-1328, 2015, reveals a study on corrosion protection of copper in neutral media through the formation of a sol-gel coating on the copper surface. It shows that the sol-gel coating on copper, based on 3-amino-5-mercapto-1,2,4-triazole doped with 3-glycidoxypropyltrimethoxysilane, forms thiolate bonds with copper.

[0012] WO2019 / 243180 discloses azole silane compounds, their synthesis, and their uses in individual solutions and surface treatments.

[0013] WO2020 / 178146 discloses the use of azole silane compounds in methods for improving the adhesive strength between the surface of a metal, metal alloy or metal oxide and the surface of an organic material.

[0014] WO 2019 / 058773 A discloses tetrazolium silanes, methods for synthesizing such tetrazolium silanes, and their use in surface treatment.

[0015] JP2016169300A (JP6436819B2) reveals that 2,4-diamine is trisubstituted It does not contain silicon.

[0016] 2,4,6-Triamine trisubstituted It is disclosed in Chem. Eur. J. 2009, 15, 6279-6288 and JP 2017002402 A (JP6370836B2). Its use in epoxy resins is disclosed in JP6392273.

[0017] In "The role of oxide structure on copper wire to the rubber adhesion," Applied Surface Science, Vol. 161, pp. 355-364, 2000, the adhesion of millimeter-sized copper wire to rubber was studied. The bonding depends on the reaction of copper oxide with sulfur.

[0018] "Reliability prediction in electronic packages using molecular simulation", Electronic Components and Technology Conference, pp. 1314-1317, 2005, reveals molecular dynamics (MD) simulations of the interaction between epoxy molding compounds (EMC) and copper oxides.

[0019] The adhesive strength is related to the physical and chemical strength of the bond between the adhesive layer and the surface of copper, copper alloy or copper oxide.

[0020] Another aspect related to adhesive strength is avoiding the formation of wedge-shaped voids. This means that after typical processing steps such as lamination, curing, and laser treatment, and after desmearing and reduction steps, a wedge-shaped structure forms at the interface between the substrate and the laminate. These so-called wedge-shaped voids are undesirable because they promote the peeling of the laminate. Wedge-shaped voids are often thought of as halos around drilled holes (blind microvias), indicating the propagation of chemicals into the substrate. Summary of the Invention

[0021] Therefore, based on the above problems, the objective of this invention is to provide a method for treating copper surfaces and / or dielectric materials, wherein the adhesion between the two materials is improved, preferably without etching and / or roughening the copper surface.

[0022] The additional task is to provide a method that does not exhibit the disadvantages mentioned above regarding adhesive strength and wedge-shaped porosity formation. Simple Explanation of the Diagram

[0023] Figure 1: Top-view SEM images of copper foil after different immersion times in alkaline treatment solution (at different magnifications of 2500x and 5000x). Figure 2: Ra and RSAI values ​​obtained from AFM studies of copper foil after different processing steps: initial, after differential etching (DE), after alkaline treatment, and after alkaline treatment + silane coating. Figure 3: The thickness of copper oxide formed on copper foil after different alkaline treatment times was determined by integrating individual potential ranges using DSCV, in nm. Figure 4: FTIR grazing incidence measurement - peak integration of Cu₂O signal versus alkaline surface treatment time on copper foil. Integration was performed within 683–616 cm⁻¹. Figure 5: STEM image of a Cu panel treated with alkaline solution (immersion for 300 s) and coated with silane. a) EDS analysis of oxide particles was performed in three different regions. Small amounts of elements were obtained from the microscope: Mo → TEM-sample holder; Al, Zr → EDX detector; Pt, Ga → FIB preparation; Fe, Co, Pb → TEM column. b) STEM image at 200 mV, nanobeam diffraction (NBD) line scan. Figure 6: Example of halo measurement. Implementation

[0024] The aforementioned objectives are achieved by a method for improving the adhesion strength between the surface of copper, copper alloys, or copper oxides and the surface of organic materials and / or modifying the wedge-shaped porosity behavior therebetween. This method includes... (i) Providing a substrate, wherein the copper, copper alloy, or copper oxide is disposed on at least one side of the substrate. This is followed by at least one of the following steps. (ic) Processing the substrate to obtain a substrate comprising copper oxide on at least one side of the substrate, wherein the copper oxide comprises copper (I) and copper (II) in a ratio of 90:10 or higher (mol / mol), preferably 95:5 or higher (mol / mol), and even more preferably 98:2 or higher (mol / mol), and preferably the copper oxide is substantially composed of copper (I) oxide; and / or (ii) Make at least one section of the substrate in contact with the following: (a) At least one silane compound of formula (I); (I) in Ring structure The group is composed of the following components: and its mixtures; X and Y are independently chosen from the following groups: NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, SCH₃, and OCH₃; The E series is selected from the following groups: -S-, -NH-, and -NH-(CH2)m-NH-; Series A is selected from the following groups: NH, N(NH₂), and S; The Z series is selected from the following groups: and , m is an integer in the range of 2 to 12. n is an integer in the range 1 to 12. o represents an integer in the range of 2 to 12. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or A mixture of (a) and (b), If both steps (ic) and (ii) are performed, then step (ic) is performed before step (ii). (iii) Apply the organic material, The prerequisite is that the cyclic structure in the silane compound of formula (I) is... Tie Then implement steps (ic) and (ii).

[0025] Our experiments have surprisingly shown that the adhesion strength between copper, copper alloys, or copper oxides and organic materials can be improved without etching or significant removal of the copper, copper alloys, or copper oxides. This demonstrates that the relative surface area (RSAI) of the copper, copper alloys, or copper oxides is increased, while the average surface roughness (Ra) is not. In other words, after step (i), the average surface roughness of the copper, copper alloys, or copper oxides is substantially the same as at the beginning of step (i). This distinguishes the method of the present invention from many known methods, especially etching methods, that aim to increase the total surface area through roughening. Therefore, the method of the present invention is preferably a non-etching method.

[0026] The preferred embodiment of the method of the present invention is that, in step (i), the copper, copper alloy, or copper oxide comprises a copper, copper alloy, or copper oxide circuit, preferably a copper, copper alloy, or copper oxide circuit. In this case, the copper, copper alloy, or copper oxide circuit is structured. This preferably means that organic material simultaneously exposes a non-conductive (preferably organic) region and a conductive copper, copper alloy, or copper oxide region on the same side. This is best within the context of the method of the present invention.

[0027] The preferred embodiment is the method of the present invention, wherein in step (i), copper, a copper alloy, or a copper oxide is formed on a substrate at least one layer. As described above, this layer or such layers may be structured and may form or be a circuit.

[0028] The preferred embodiment of the method of the present invention is that, in step (i) (and / or more preferably after step (ii)), the copper, copper alloy, or copper oxide circuit includes lines with a linewidth of 100 µm or less, preferably 75 µm or less, and more preferably 55 µm or less. In some cases, the method of the present invention is preferred, wherein, in step (i) (and / or more preferably after step (ii)), the copper, copper alloy, or copper oxide circuit includes lines with a linewidth of 30 µm or less, preferably 20 µm or less, and most preferably 10 µm or less.

[0029] [Includes steps] [(ic)] [Method] [-] [Copper formation] [(I)] [Oxides] [] Surprisingly, copper oxide surfaces with high copper (I) content exhibit both good adhesion behavior and a flat (or smooth) surface compared to copper (II). This is surprising because the typical paradigm is that "the rougher the surface, the better the adhesion." For the reasons mentioned above, rough surfaces are not desirable for demanding electronic applications.

[0030] Therefore, it has been found that the potential problem can be solved by providing a method for improving the adhesion strength between the surface of copper, copper alloys or copper oxides and the surface of organic materials and / or improving the wedge-shaped porosity behavior therebetween. This method includes... (i) Providing a substrate, wherein the copper, copper alloy, or copper oxide is disposed on at least one side of the substrate. The following steps (ic) Processing the substrate to obtain a substrate comprising copper oxide on at least one side of the substrate, wherein the copper oxide comprises copper (I) and copper (II) in a ratio of 90:10 or higher (mol / mol), preferably 95:5 or higher (mol / mol), and even more preferably 98:2 or higher (mol / mol), and preferably the copper oxide is substantially composed of copper (I) oxide; (iii) Apply the organic material.

[0031] It has been found that the copper (I) oxide surface of the present invention can be obtained when step (ic) is carried out by contacting at least one section of the copper, copper alloy or copper oxide with an alkaline aqueous solution containing one or more chelating agents.

[0032] Therefore, the preferred step (ic) includes contacting at least one section of the copper, copper alloy or copper oxide with an alkaline aqueous solution containing one or more chelating agents.

[0033] The alkaline solution used in the method of this invention is an alkaline aqueous solution. In the context of this invention, "aqueous" means that the solution contains water. Preferably, the solution used in the method of this invention contains water, wherein greater than 50 vol%, more preferably 70 vol%, more preferably 80 vol%, even more preferably 90 vol%, and most preferably 95 vol%, of the total volume of the oxidizing solution. Most preferably, the solution contains water, provided that water is the sole solvent.

[0034] The term "alkaline" means that the pH of the solution is greater than 7, preferably 9 or above, even more preferably 11 or above, and most preferably 12.5 or above. Preferably, it refers to the solution in step (ic) of the method of the present invention, wherein the pH is in the range of 8 to 14, more preferably in the range of 9 to 14, even more preferably in the range of 10 to 14, still even more preferably in the range of 11 to 14, and most preferably in the range of 12 to 14.

[0035] To obtain an alkaline pH, the solution contains hydroxide ions at a concentration preferably in the range of 0.1 mol / L to 2.0 mol / L, more preferably in the range of 0.2 mol / L to 1.8 mol / L, even more preferably in the range of 0.3 mol / L to 1.6 mol / L, still even more preferably in the range of 0.4 mol / L to 1.5 mol / L, and most preferably in the range of 0.5 mol / L to 1.2 mol / L. These concentrations result in a preferred strongly alkaline oxidizing solution, for example, pH 13 or higher.

[0036] The preferred embodiment is a solution containing one or more hydroxide ion sources, preferably one hydroxide ion source.

[0037] Preferred sources of hydroxide ions are inorganic hydroxides, organic hydroxides, or mixtures thereof. Inorganic hydroxides are preferably selected from the group consisting of ammonium hydroxide and alkali metal hydroxides, and more preferably from the group consisting of ammonium hydroxide, sodium hydroxide, and potassium hydroxide. Preferred organic hydroxides are alkyl ammonium hydroxides, more preferably tetraalkyl ammonium hydroxides, and even more preferably tetramethyl ammonium hydroxides.

[0038] The alkaline aqueous solution contains one or more copper chelating agents. The chelating agents are typically used to chelate copper ions that dissolve when the alkaline solution is applied to a copper surface, thus preventing the formation of insoluble copper hydroxide. Typically, the chelating agents used for copper ions prevent or at least significantly reduce the formation of this hydroxide. Therefore, the method of the present invention is preferred, wherein the alkaline solution additionally contains one or more chelating agents for chelating copper ions, preferably one or more chelating agents containing at least one carboxyl group and at least one hydroxyl group.

[0039] The preferred embodiment of the present invention is the method wherein, in the alkaline solution, one or more chelating agents comprise sugars, preferably monosaccharides.

[0040] Even more preferred is the method of the present invention, wherein one or more ligating agents for ligating copper ions comprises gluconic acid and / or its salts, and preferably the sole ligating agent for ligating copper ions in an alkaline solution is gluconic acid and / or its salts.

[0041] The preferred embodiment of the present invention is the method wherein, in the alkaline solution, the total concentration of one or more chelating agents is in the range of 5 mmol / L to 400 mmol / L, more preferably in the range of 10 mmol / L to 300 mmol / L, more preferably in the range of 15 mmol / L to 200 mmol / L, even more preferably in the range of 20 mmol / L to 100 mmol / L, still even more preferably in the range of 25 mmol / L to 80 mmol / L, and most preferably in the range of 30 mmol / L to 60 mmol / L. The above concentrations are preferably applicable to the aforementioned preferred chelating agents, preferred gluconic acid, and their salts.

[0042] The preferred embodiment is the method of the present invention, wherein in step ic, the temperature of the alkaline aqueous solution is in the range of 20°C to 80°C, more preferably in the range of 25°C to 75°C, even more preferably in the range of 30°C to 70°C, and even more preferably in the range of 35°C to 65°C, and most preferably in the range of 40°C to 60°C.

[0043] In some embodiments of the present invention, it is preferable if the alkaline aqueous solution used in step (i) additionally contains sodium chlorite or an oxidizing agent.

[0044] It has been found that step (ic) can be applied as an impregnation process. Impregnation application means that the solution is provided in the form of a bath, in which copper, copper alloy, or copper oxide is impregnated. It has been further found that a contact time of 40 s or longer is preferred. The preferred contact time in step (ic) is 40 s to 900 s, the more preferred contact time in step (ic) is 60 s to 500 s, and even more preferred contact time in step (ic) is 90 s to 450 s.

[0045] In an alternative, step (ic) has been found to be applicable as a spray application. Spray application refers to transferring the solution to a spray dispenser and then spraying it onto copper, copper alloys, or copper oxides. It has been further found that a contact time of 10 s has produced good results. Therefore, a contact time of 10 s or longer is preferred. A preferred contact time in step (ic) is 20 s to 200 s, and a more preferred contact time in step (ic) is 30 s to 150 s.

[0046] [Includes steps] [(ii)] [Method] [-] [Applying silane compounds] [] According to another embodiment of the present invention, the above objective is achieved by a method for improving the adhesion strength between the surface of copper, copper alloy, or copper oxide and the surface of organic materials and / or improving the wedge-shaped porosity behavior therebetween, the method comprising... (i) Providing a substrate, wherein the copper, copper alloy, or copper oxide is disposed on at least one side of the substrate. The following steps (ii) Make at least one section of the substrate in contact with the following: (a) At least one silane compound of formula (I); (I) in Ring structure The group is composed of the following components: and its mixtures; X and Y are independently chosen from the following groups: NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, SCH₃, and OCH₃; The E series is selected from the following groups: -S-, -NH-, and -NH-(CH2)m-NH-; Series A is selected from the following groups: NH, N(NH₂), and S; The Z series is selected from the following groups: and , m is an integer in the range of 2 to 12. n is an integer in the range 1 to 12. o represents an integer in the range of 2 to 12. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or A mixture of (a) and (b), If steps (ic) and (ii) are performed, then step (1-c) is performed before step (ii); (iii) Apply the organic material.

[0047] The contact in step (ii) can be applied as an impregnation application. Impregnation application means that the solution is provided in the form of a bath in which copper, copper alloy, or copper oxide is impregnated.

[0048] In an alternative, step (ii) may be applied as a spray application. Spray application means transferring the solution to a spray dispenser and then spraying it onto copper, copper alloys, or copper oxides.

[0049] In an alternative, step (ii) can be applied as a coating application, such as bar coating, spin coating, and curtain coating.

[0050] The method of the present invention is preferably carried out at a temperature of 5°C to 60°C, more preferably 10°C to 40°C, and even more preferably 20°C to 30°C.

[0051] [three] [ ] [Silane compounds] [] One embodiment of the method of the present invention relates to a specific three as defined above. Silicon compounds. In many cases, the third aspect of the invention... A silane compound is preferred, wherein Y represents NH and N (NH₂), preferably NH. In other cases, the third aspect of the invention... A silane compound is preferred, wherein Y represents S. Of the two, a nitrogen-containing Y is preferred over a Y where Y is S.

[0052] The third invention The silane compound is preferred, wherein X represents NH 2, NH(NH 2), NH(CH 2) oNH 2, SH, SCH 3 or OCH 3, wherein o is an integer in the range of 2 to 12; more preferably NH 2, NH(NH 2), NH(CH 2) oNH 2, SH or SCH 3, wherein o is an integer in the range of 2 to 12; even more preferably NH 2.

[0053] The present invention of the best of the series (II) compounds Silane compounds, (II) in m is an integer in the range of 2 to 10. n is an integer in the range 1 to 10. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl.

[0054] The preferred compounds are those of formulas (IIa) and (IIb). (IIa) (IIb)

[0055] In the substitution, the best are compounds of formula (III) of this invention. Silane compounds, (III) in m is an integer in the range of 2 to 10. n is an integer in the range 1 to 10. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl.

[0056] The best are compounds of formula (IIIa). (IIIa)

[0057] In the context of this invention, the term "independently" (or a similar expression) combined with a variable means that the selected feature for that variable in a first compound is independent of the selected feature for that variable in a second compound, and if a compound contains the same variable at least twice, then they are selected independently of each other and therefore may be different. This principle also applies to other "independently" terms.

[0058] [Tetraazole silane compounds] [] One embodiment of the method of the present invention relates to a specific tetrazolium silane compound as defined above. In many cases, the tetrazolium silane compound of formula (IV) of the present invention is preferred. (IV) Where n is an integer in the range of 1 to 10. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl.

[0059] The preferred form of this invention is the tetrazolium silane compound of formula (IVa). (IVa).

[0060] [Triazole] [ / ] [Thiadiazole silane compounds] [] One embodiment of the method of the present invention relates to a specific triazole or thiadiazole silane compound as defined above. In many cases, the triazole or thiadiazole silane compound of formula (V) is preferred. (V) in X represents NH₂, NH(NH₂), NH(NHU), NH(CH₂), NH₂, SH, SCH₃, OCH₃, NHU, or SU. Y represents NH, N(NH₂), N(NHU), or S. U independently represents CH 2-CH(OH)-CH 2-O-(CH 2) n-Si(OR) 3, where R independently represents (CH 2-CH 2-O) pZ, where independently n is an integer in the range 1 to 10. o represents an integer in the range of 2 to 12. p is 0, 1, 2, 3 or 4, and Z represents H or C1 to C5 alkyl.

[0061] Preferably, X represents NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, SCH₃, or OCH₃, where o is an integer in the range of 2 to 12; more preferably, NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, or SCH₃, where o is an integer in the range of 2 to 12; even more preferably, NH₂.

[0062] The preferred form is the thiadiazole or triazole silane compound of the present invention, which is a compound of formula (Va) or (Vb). (Va) (Vb).

[0063] [Synthesis of Silane Compounds] [] three The synthesis of silane compounds is disclosed in internal reference P21 / 002, a co-pending application, which is incorporated herein by reference.

[0064] The synthesis of the triazole silane / thiadiazole compound is disclosed in WO2019 / 243180, which is incorporated herein by reference.

[0065] The synthesis of tetrazolium silane compounds has been disclosed in US 2020 / 0399290.

[0066] Another objective of this invention is to provide alternative synthetic methods for tetrazolium silane compounds.

[0067] This invention also relates to a method for synthesizing the tetrazolium silane compound of formula (IV): (IV) Where n is an integer in the range of 1 to 10. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl. The synthesis method includes the following steps: (i) Provided (VI) compounds (VI), (ii) Provide silane compounds of formula (VII) (VII), Where n is an integer in the range of 1 to 10. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl. (iii) Reacting the compound of formula (VI) with the silane compound in a solvent to produce the compound of formula (IV) as defined above, and (iv) Hydrolyze the compound of formula (IV) obtained in step (iii) as appropriate, such that at least one of R is (CH 2-CH 2-O) mZ, where m = 0 and Z = H.

[0068] The above description of the tetrazolium silane compound of the present invention (preferably as described in the preferred embodiment) is also preferably applicable to the synthesis method of the present invention, for example, regarding the preferred tetrazolium silane compound of the present invention.

[0069] Step (iv) is optional and includes the presence of at least some water to hydrolyze the compound obtained in step (iii) of the method of the present invention. Preferably, this water is added after step (iii) in an additional step (e.g., step (iv)). If this compound (m = 0 and Z = H) is desired, then step (iv) is not optional.

[0070] The most preferred embodiment is the synthesis method of the present invention, wherein in step (iii), the solvent comprises an organic solvent, more preferably one or more organic solvents, and most preferably one or more water-miscible organic solvents.

[0071] In many cases, the synthesis method of the present invention is preferred, wherein in step (iii), the solvent is one or more solvents selected from the group consisting of: glycol ethers and mixtures thereof, preferably selected from the group consisting of: - HO-(CH 2-CH 2-O) pT, where p series 1, 2, 3 or 4, preferably 1 or 2, and T represents C1 to C5 alkyl, preferably C3 to C5 alkyl. and its mixtures, even better Choose from the group consisting of: diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof.

[0072] Generally, glycol ethers are preferred over alcohols as defined above (see above for the reasons). Therefore, the various synthetic methods of the present invention are preferred.

[0073] The preferred method is the synthesis method of the present invention (particularly as previously described), wherein the solvent in step (iii) is substantially free of, and preferably free of, water.

[0074] Preferably, the solvent in step (iii) is one or more organic solvents, and after step (iii) of the method of the present invention, the mixture of the present invention is obtained (see above for the mixture). The above-mentioned properties of the mixture of the present invention also apply to the synthesis method of the present invention.

[0075] The preferred method of synthesis of the present invention is wherein the total molar ratio of compound (VI) to compound (VII) is in the range of 1:0.7 to 1:1.3, more preferably in the range of 1:0.80 to 1:1.2, even more preferably in the range of 1:0.9 to 1:1.2, and most preferably in the range of 1:0.95 to 1:1.05. If the total molar ratio is significantly lower than 1:0.7, the synthesized product contains excessive unreacted precipitates, which is undesirable, as the desired species is a tetrazolium silane compound comprising both tetrazolium and silane moieties. This principle also preferably applies to the mixtures, storage solutions, and working solutions of the present invention.

[0076] The preferred method is the synthesis method of the present invention, wherein in step (iii), the temperature is in the range of 50°C to 100°C, and more preferably in the range of 60°C to 90°C.

[0077] The preferred method of synthesis of the present invention is wherein, in step (i), the tetrazolium compound of formula (III) is provided as a suspension. This means that the tetrazolium compound of formula (III) is preferably suspended in at least one solvent, such that the tetrazolium compound and the at least one solvent form the suspension. For this purpose, the at least one solvent is preferably one or more organic solvents, preferably one or more water-miscible organic solvents. Preferably, the at least one solvent used to form the suspension is the same as the solvent used in step (iii). Most preferably, the tetrazolium compound of formula (III) is suspended in one or more solvents selected from the group consisting of C1 to C4 alcohols, glycol ethers and mixtures thereof, preferably selected from the group consisting of: - C1 to C3 alcohols, - Cyclic and non-cyclic ethers, such as diethyl ether, tetrahydrofuran, 1,4-dioxane and mixtures thereof, preferably 1,4-dioxane, tetrahydrofuran and mixtures thereof. - HO-(CH 2-CH 2-O) pT, where p series 1, 2, 3 or 4, preferably 1 or 2, and T represents C1 to C5 alkyl, preferably C3 to C5 alkyl. and its mixtures, even better The best choice is a group consisting of: methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof. Choose from the group consisting of: diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof.

[0078] The preferred method is the synthesis method of the present invention, wherein in step (iii), the reaction is carried out for 1 hour to 48 hours, more preferably 3 hours to 30 hours, and even more preferably 5 hours to 24 hours.

[0079] The method of the present invention is preferred, wherein the silane compound and (if applicable) silane oligomer can be present as a mixture. Alternatively, more than one compound can be present as a mixture. Generally, organic solvents promote solubility. Therefore, the present invention also relates to mixtures comprising, and preferably consisting of, the following: (a) - one or more silane compounds (as set forth herein, preferably as preferred), and / or - One or more silane oligomers (as described herein, preferably as the preferred embodiment), (b) - One or more organic solvents.

[0080] The method of the present invention is preferred, wherein the mixture of the present invention substantially does not contain, and preferably does not contain, halide ions.

[0081] In the context of this invention, the term "substantially free of" a subject matter (e.g., a compound, material, etc.) means that the subject matter is completely absent or present only in a very small and inconsequential amount without affecting the intended purpose of this invention. For example, this subject matter may be unintentionally added or used, for example, as an unavoidable impurity. "Substantially free of" preferably means 0 to 50 ppm, more preferably 0 to 25 ppm, even more preferably 0 to 10 ppm, and even more preferably 0 to 5 ppm, and most preferably 0 to 1 ppm, based on the total weight of the mixture (if defined for the mixture). 0 ppm means that the individual subject matter is completely absent, which is preferred. This principle also applies to other forms of the invention, such as the storage solution of the invention (see below) and the working solution of the invention (also see below).

[0082] The preferred embodiment is the mixture of the present invention, wherein, based on the total weight of the mixture, the total amount of all silane compounds and oligomers of the present invention together is in the range of 5 wt.-% to 30 wt.-%; more preferably in the range of 8 wt.-% to 26 wt.-%; more preferably in the range of 12 wt.-% to 24 wt.-%; even more preferably in the range of 15 wt.-% to 23 wt.-%; and most preferably in the range of 17 wt.-% to 21 wt.-%

[0083] The preferred embodiment is the method of the present invention, wherein one or more organic solvents of the mixture comprises a solvent selected from the group consisting of: acetone, 1,3-dioxolane, acetonitrile, 1,4-dioxane, methanol, ethanol, 1-propanol, 2-propanol, terbutanol, prop-2-en-1-ol, ethyl lactate, ethylene glycol monomethyl ether acetate, N,N-dimethylformamide, 2-butoxyethanol, di(propylene glycol) methyl ether, tetrahydrofurfuryl alcohol, N-methyl-2-pyrrolidone, 2-(2-methoxyethoxy)ethanol, γ-butyrolactone, ethylene glycol, propylene glycol, dipropylene glycol, ε-caprolactone, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, tetrahydrothiophene-1-oxide, diethylene glycol monobutyl ether acetate, propylene carbonate, cyclobutane, glycerol, and mixtures thereof.

[0084] The preferred embodiment is the method of the present invention, wherein one or more organic solvents of the mixture comprises a solvent selected from the group consisting of: methanol, ethanol, 1-propanol, 2-propanol, tributanol, di(propylene glycol) methyl ether, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

[0085] In rare cases, the method of the present invention is preferred, wherein one or more organic solvents of the mixture comprises a solvent selected from the group consisting of glycol ethers, preferably selected from the group consisting of di(propylene glycol) methyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

[0086] This invention also relates to a storage solution, which comprises (a) - one or more silane compounds of the present invention (as set forth herein, preferably as described herein), and - One or more silane oligomers of the present invention, as appropriate (as set forth herein, preferably as the preferred embodiment). (b) - Water as needed, (c) - One or more water-miscible organic solvents, The prerequisite is that if water is present, the pH is 9 or higher.

[0087] Preferably, the storage solution of the present invention substantially does not contain, or preferably does not contain, halide ions. Only in rare cases are halide ions present due to the intentional addition of halide ions, or more preferably due to the intentional addition of chloride ions.

[0088] The preferred embodiment is the storage solution of the present invention, wherein, based on the total weight of the storage solution, the total amount of all silane compounds of the present invention (as described throughout this document, preferably as described herein) and all silane oligomers of the present invention (as described throughout this document, preferably as described herein) together is in the range of 0.2 wt.-% to 30 wt.-%; more preferably in the range of 0.5 wt.-% to 28 wt.-%; more preferably in the range of 0.7 wt.-% to 25 wt.-%; even more preferably in the range of 0.8 wt.-% to 22 wt.-%; and most preferably in the range of 0.9 wt.-% to 20 wt.-%

[0089] The aforementioned storage solution may contain water, depending on the circumstances. Preferably, it is the storage solution of the present invention, wherein the storage solution is alkaline and, based on the total weight of the storage solution, water is present in a total amount ranging from 10 wt.-% to 80 wt.-%; more preferably from 15 wt.-% to 78 wt.-%; even more preferably from 20 wt.-% to 76 wt.-%; still more preferably from 33 wt.-% to 74 wt.-%; and most preferably from 38.6 wt.-% to 70 wt.-%

[0090] The storage solution contains one or more water-miscible organic solvents. This organic solvent promotes the desired solubility of the individual silane compounds and their oligomers, particularly if present at a relatively high concentration (e.g., up to and about 15 wt.-%, see above). Therefore, the storage solution of the present invention is preferred, wherein, based on the total weight of the storage solution, one or more water-miscible organic solvents are present in a total amount ranging from 5 wt.-% to 89.5 wt.-%, more preferably from 10 wt.-% to 84.2 wt.-%, more preferably from 14 wt.-% to 79 wt.-%, even more preferably from 18 wt.-% to 65.5 wt.-%, and most preferably from 24 wt.-% to 59 wt.-%.

[0091] In many cases, the storage solution of the present invention is preferred, wherein the total weight of water is less than the total weight of all water-miscible organic solvents.

[0092] As mentioned above, the storage solution is alkaline if water is present. In the context of this invention, this means a pH of 9 or higher. Preferably, the storage solution of this invention has a pH of 9.6 or higher, more preferably in the range of 10.5 to 14, more preferably in the range of 11 to 14, and most preferably in the range of 12 to 14. If the pH is significantly lower than pH 9, the solubility of the silane compound and its oligomers decreases, even reaching a point where undesirable precipitation occurs. Acidic pH is unsuitable for storage purposes because precipitation is observed at this pH in many cases with relatively high concentrations of the silane compound and its corresponding oligomer of this invention. As learned from WO2019 / 243180, for azole silanes, undesirable phase separation and degradation of the azole silane compound are frequently observed if the pH is significantly higher than 13. In contrast, the present invention... Silane solutions exhibit good phase stability at high pH values.

[0093] Furthermore, the silane solutions of this invention exhibit good stability over a wide temperature window, i.e., no phase separation and no degradation. Specifically, these solutions are stable from -5°C to 50°C.

[0094] In the context of this invention, pH refers to a temperature of 25°C.

[0095] In the alkaline storage solution of the present invention, the alkaline pH is preferably obtained by using at least one alkaline hydroxide, and most preferably by using sodium hydroxide.

[0096] The alkaline pH not only allows for relatively high concentrations of these silane compounds and their oligomers in the storage solution, but also strongly maintains the silane compounds of the present invention in their monomeric state and significantly reduces the formation of the silane oligomers of the present invention. However, if such an oligomer is formed in the alkaline storage solution of the present invention, it is usually rapidly hydrolyzed into its monomeric form due to the alkaline pH. This is desirable in the storage solution of the present invention.

[0097] The preferred embodiment is the storage solution of the present invention, wherein the total weight of all silane compounds of the present invention is greater than the total weight of all silane oligomers of the present invention.

[0098] In some cases, the storage solution of the present invention is preferred, wherein for at least 80 wt.-%, more preferably at least 90 wt.-%, and most preferably at least 95 wt.-%, of the total weight of all silane compounds of the present invention, Z is H and p is 0. This means that in the storage solution, the silane compounds are mainly present in their hydrolyzed form containing SiOH- groups.

[0099] The aforementioned storage solutions are particularly suitable for transporting and / or storing one or more silane compounds of the present invention. However, for utilizing these compounds, for example as surface treatment solutions in the production of electronic components, individual working solutions are preferred. Therefore, the present invention further relates to working solutions with a pH in the range of 2 to 14, wherein the solution contains... (a) - one or more silane compounds of the present invention (as set forth herein, preferably as described herein), and / or - One or more silane oligomers of the present invention (as set forth herein, and preferably as the preferred embodiment), (b) - Water as needed, (c) - One or more water-miscible organic solvents, In the working solution, based on the total weight of the working solution, the total amount of all silane compounds of the present invention (as set forth herein, preferably as described herein) and all silane oligomers of the present invention (as set forth herein, preferably as described herein) together is 10 wt.% or less.

[0100] Particularly preferred are the working solutions of the present invention, provided that the working solution contains at least one of the silane oligomers of the present invention (as set forth herein, and preferably as described herein). This is particularly preferred for freshly prepared working solutions.

[0101] The term "10 wt.-% or less" does not include 0 wt.-%. This means that the total amount is always > 0 wt.-%, preferably at least 0.1 wt.-%.

[0102] The preferred embodiment is the working solution of the present invention, wherein, based on the total weight of the working solution, the total amount of all silane compounds of the present invention (as described throughout this document, preferably as described herein) and all silane oligomers of the present invention (as described throughout this document, preferably as described herein) together is in the range of 0.1 wt.-% to 6 wt.-%; more preferably in the range of 0.2 wt.-% to 5 wt.-%; more preferably in the range of 0.3 wt.-% to 4 wt.-%; even more preferably in the range of 0.4 wt.-% to 3.7 wt.-%; and most preferably in the range of 0.5 wt.-% to 3.5 wt.-%.

[0103] Our experiments show that the individual presence of one or more silane compounds and one or more silane oligomers of the present invention varies over time. In a freshly prepared working solution, the total weight of the silane compounds of the present invention is typically higher than the total weight of the silane oligomers. However, over time, when using the working solution, the total weight of these silane oligomers increases significantly, possibly even to the point that the total weight of the silane oligomers exceeds the total weight of the silane compounds. Furthermore, the disposal of the working solution of the present invention also affects the total weight of the compounds and oligomers, respectively. For example, significant drag-out during use of the working solution and corresponding replenishment with fresh working solution typically results in a decrease in the steady-state conditions of the silane compounds relative to the silane oligomers.

[0104] Preferably, the working solution of the present invention comprises - One or more silane compounds of the present invention (as set forth herein, preferably as described herein), and - One or more silane oligomers of the present invention (as set forth herein, preferably as the preferred embodiment). Therefore, individual working solutions comprising at least one compound and at least one oligomer are preferred.

[0105] The working solution of the present invention has a pH in the range of 2 to 14. Preferably, the working solution of the present invention has a pH in the range of 3.5 to 14, and more preferably in the range of 4.0 to 13.5.

[0106] The preferred embodiment is the working solution of the present invention, wherein, based on the total weight of the working solution, the aqueous system is present in a total amount ranging from 5 wt.-% to 90 wt.-% more preferably from 10 wt.-% to 85 wt.-% and even more preferably from 15 wt.-% to 80 wt.-% of the total amount.

[0107] To ensure the complete dissolution of the silane compounds and silane oligomers of the present invention in the working solution of the present invention, one or more water-miscible organic solvents are present. Preferably, the working solution of the present invention contains one or more water-miscible organic solvents in a total amount ranging from 5 wt.% to 90 wt.%, more preferably from 10 wt.% to 85 wt.%, and even more preferably from 15 wt.% to 80 wt.%, based on the total weight of the working solution.

[0108] As mentioned above, in the context of this invention, the silane compounds and silane oligomers of this invention are initially free of halides. This means, on the one hand, that these compounds and oligomers are inherently free of halogen atoms because they do not utilize halogen-containing precipitates, and on the other hand, that halide ions are not present in the direct synthesis environment. However, in a few cases, the working solution of this invention preferably contains a precisely defined amount of halide ions. Therefore, in some cases, the working solution of this invention preferably further contains... (d) - Halogen ions, preferably chloride ions.

[0109] However, in other cases, the working solution of the present invention is preferably free of chloride ions, and more preferably free of halide ions.

[0110] One or more water-miscible organic solvents are present in the storage solution and the working solution of the present invention. Preferably, the storage solution (as described throughout this document, preferably as a preferred embodiment) or the working solution (as described throughout this document, preferably as a preferred embodiment) of the present invention, wherein one or more water-miscible organic solvents comprise water-miscible organic solvents selected from the group consisting of: C1 to C4 alcohols, ethers, glycol ethers, and mixtures thereof, preferably selected from the group consisting of: - C1 to C3 alcohols, - Cyclic and non-cyclic ethers, such as diethyl ether, tetrahydrofuran, 1,4-dioxane and mixtures thereof, preferably 1,4-dioxane, tetrahydrofuran and mixtures thereof. - HO-(CH 2-CH 2-O) pT, where p-series 1, 2, 3, or 4, preferably 1 or 2, and T represents C1 to C5 alkyl, preferably C3 to C5 alkyl. and its mixtures, even better Choose from the following groups of components: methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof, or even better. Choose from the group consisting of: diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof.

[0111] The water-miscible organic solvents defined above also apply to the synthesis method of this invention (see below).

[0112] In each case, glycol ethers are preferred over alcohols. Glycol ethers generally offer improved stability compared to these alcohols. Furthermore, alcohols typically exhibit lower flash points compared to glycol ethers, which makes them potentially hazardous in terms of fire hazard. A relatively high flash point is generally desirable to prevent ignition. Therefore, glycol ethers generally offer the desired solubility, stability, and safety. This principle also preferably applies to the mixtures of the present invention, the storage solutions of the present invention, and the synthetic methods of the present invention (see below).

[0113] The preferred embodiment is the storage solution of the present invention (as described throughout this document, preferably as a preferred embodiment) or the working solution of the present invention (as described throughout this document, preferably as a preferred embodiment), wherein all silane compounds of the present invention (as described throughout this document, preferably as a preferred embodiment) and all silane oligomers of the present invention (as described throughout this document, preferably as a preferred embodiment) account for at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, even more preferably at least 93 wt.-%, most preferably at least 95 wt.-%, and even most preferably at least 98 wt.-%. Preferably, no other silane compounds or oligomers are present besides those described herein. This also means that the absolute total amount of silane compounds and silane oligomers together is best suited for use (as defined above), provided that no other silane compounds and silane oligomers are present in the storage solution and working solution of the present invention, respectively.

[0114] Furthermore, the preferred embodiment is the storage solution of the present invention (as described throughout this document, preferably as a preferred embodiment) or the working solution of the present invention (as described throughout this document, preferably as a preferred embodiment), wherein all silane compounds of the present invention (as described throughout this document, preferably as a preferred embodiment) and all silane oligomers of the present invention (as described throughout this document, preferably as a preferred embodiment) account for at least 51 mol-%, preferably at least 60 mol-%, more preferably at least 70 mol-%, most preferably at least 80 mol-%, and even more preferably at least 90 mol-%, of all compounds containing at least one silicon atom in the storage solution and the working solution, respectively.

[0115] Due to the method of this invention, the adhesion strength (e.g., peel strength) between copper and organic materials can be improved without using any etching and cleaning steps. However, in some cases, especially where the surface roughness of the copper surface does not affect circuit quality, other etching and cleaning steps can be performed. In this case, the adhesion strength between copper and organic materials can be further improved.

[0116] The method of the present invention preferably includes the following steps prior to step (ii): (ia) contacting at least one section of the copper, copper alloy or copper oxide with an etching cleaning solution, preferably an etching cleaning solution containing one or more acids and / or one or more oxidants, more preferably an etching cleaning solution containing a mixture of inorganic acids and peroxides (preferably a mixture of sulfuric acid and hydrogen peroxide).

[0117] According to the present invention, it is preferable when the oxidant is a peroxide, and more preferably when the peroxide is hydrogen peroxide.

[0118] According to the present invention, it is preferable that the etching cleaning solution contains corrosion inhibitors in addition to acid and / or one or more oxidants.

[0119] The method of the present invention preferably includes, prior to step (ii), the following step: (ib) contacting at least one section of the copper, copper alloy, or copper oxide with a (preferably second) etching cleaning solution. In the case where step (ib) is performed after step (ia), the etching cleaning solution used is a second etching cleaning solution. In the case where step ib is performed without a prior etching cleaning step, the etching cleaning solution used is a first etching cleaning solution.

[0120] According to the present invention, the second etching cleaning solution comprises an iron(III) salt or an iron(III) complex, more preferably comprising ferric sulfate (Fe₂(SO₄)₃), ferric chloride (FeCl₃), ferric bromide (FeBr₃), ferric nitrate (Fe(NO₃)₃), ferric acetate (Fe(OC(O)CH₃)₃), (Fe(OH)₃), or mixtures thereof, and even more preferably comprising ferric sulfate (Fe₂(SO₄)₃). The iron ions are preferably contained at a concentration in the range of 1 to 100 g / L, more preferably 1 to 50 g / L, and more preferably 1 to 30 g / L.

[0121] In an alternative, according to the present invention, the second etching cleaning solution comprises an inorganic acid, more preferably sulfuric acid, hydrochloric acid, or a mixture thereof, and even more preferably sulfuric acid.

[0122] According to the present invention, during step ia, the typical removal amount of copper, copper alloy or copper oxide is less than 2 µm, the preferred removal amount is 0.1 µm to 1.5 µm, the more preferred removal amount is 0.2 µm to 1.2 µm, and even more preferably, the removal amount is 0.4 µm to 1.1 µm, and the optimal removal amount is 0.5 µm to 1.0 µm; and the resulting average surface roughness Ra has a maximum value of 100 nm.

[0123] According to the present invention, during step ib, the typical amount of copper, copper alloy or copper oxide removed is less than 20 nm and the resulting average surface roughness Ra has a maximum value of 10 nm and a preferred maximum value of 5 nm.

[0124] The method of the present invention preferably includes, prior to step (ii), the following step: (ic) contacting at least one section of the copper, copper alloy, or copper oxide with a solution, preferably a sodium hydroxide solution. It is preferred if the solution contains a copper binder.

[0125] In some embodiments of the present invention, it is preferable if the solution used in step ic additionally contains sodium chlorite or an oxidizing agent. It is particularly preferable to use sodium chlorite or an oxidizing agent in the solution used in step ic if an iron(III) salt or iron(III) complex is not used in step ib, or if step ib is not carried out during the method of the present invention.

[0126] The order of steps (ia), (ib), and (ic) may vary. The method of this invention can be performed in the following order: (ia), (ib), (ic), or (ia), (ic), (ib), or (ib), (ia), (ic), or (ic), (ia), (ia), or (ic), (ia), (ib), (ia). The order (ia), (ib), (ic) is preferred. Alternatively, steps (ia), (ib), and (ic) may not be performed in the method of this invention, or one or both may be performed.

[0127] The method of the present invention is preferred, wherein the organic material applied in step (iii) is an organic polymer.

[0128] The method of the present invention is preferred, wherein the organic material is applied in step (iii) by laminating the organic material onto at least the contact area of ​​copper, copper alloy or copper oxide.

[0129] The method of the present invention preferably includes an additional step after step (iii): (iv) subjecting the substrate and organic material to heat treatment at a temperature in the range of 142°C to 420°C, preferably in the range of 145°C to 300°C, and more preferably in the range of 150°C to 220°C.

[0130] The method of the present invention is preferred in that, after step (ii), after step (ia), after step (ib), and / or after step (ic), at least one section of copper, copper alloy, or copper oxide is rinsed, wherein the copper, copper alloy, or copper oxide is preferably rinsed with water. It is preferable that the water used during rinsing after step (ii) has a pH value in the range of 2 to 14, preferably in the range of 4 to 10, more preferably in the range of 5 to 9, even more preferably in the range of 6 to 8, and most preferably in the range of 6.5 to 7.5.

[0131] The method of the present invention is preferred, wherein, after step (ii), after step (ia), after step (ib), and / or after step (ic), at least one section of copper, copper alloy, or copper oxide is dried.

[0132] In an alternative, the method of the present invention is preferred, wherein after step (ii), at least one section of copper, copper alloy, or copper oxide is not baked. This can be shown (Table 4 below) by avoiding the baking step, which results in improved halo formation compared to a baked sample.

[0133] The method of the present invention preferably includes the following steps in this order: (i) A substrate is provided, wherein at least one side of the substrate comprises copper, a copper alloy, or a copper oxide. (ia) Where appropriate, at least one section of the copper, copper alloy, or copper oxide shall be brought into contact with an etching cleaning solution, preferably an etching cleaning solution containing one or more acids and / or one or more oxidizing agents, more preferably an etching cleaning solution containing a mixture of inorganic acids and peroxides, and where appropriate, at least one section of the copper, copper alloy, or copper oxide shall be rinsed (preferably with water). (ib) If necessary, at least one section of the copper, copper alloy, or copper oxide may be brought into contact with a second etching cleaning solution, wherein the second etching cleaning solution preferably contains ferric sulfate and / or sulfuric acid, and if necessary, at least one section of the copper, copper alloy, or copper oxide may be rinsed (preferably with water). (ic) If necessary, contact at least one section of the copper, copper alloy, or copper oxide with an alkaline solution, and if necessary, subsequently rinse at least one section of the copper, copper alloy, or copper oxide (preferably with water). (ii) Contacting at least one section of the copper, copper alloy or copper oxide with the following: (a) At least one silane compound of formula (I); (I) in Ring structure The group is composed of the following components: and its mixtures; X and Y are independently chosen from the following groups: NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, SCH₃, and OCH₃; The E series is selected from the following groups: -S-, -NH-, and -NH-(CH2)m-NH-; Series A is selected from the following groups: NH, N(NH₂), and S; The Z series is selected from the following groups: and , m is an integer in the range of 2 to 12. n is an integer in the range 1 to 12. o represents an integer in the range of 2 to 12. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or A mixture of (a) and (b), The prerequisite is that the cyclic structure in the silane compound of formula (I) is... Tie Then implement steps (ic) and (ii). And, if necessary, rinse at least one section of the copper, copper alloy, or copper oxide (preferably with water). (iii) Apply organic material such that during step (ii) it interacts with the three Silane compounds and / or trisilanes At least one segment of the copper, copper alloy, or copper oxide in contact with the silane oligomer is in contact with the applied organic material. and (iv) Subject the substrate and organic material to heat treatment at a temperature ranging from 142°C to 420°C, preferably from 145°C to 300°C, and even more preferably from 150°C to 220°C, as appropriate.

[0134] The method of the present invention is preferred, wherein the substrate is a non-conductive substrate and / or the organic material is a non-conductive organic material, preferably a non-conductive organic polymer.

[0135] The method of the present invention is preferred, wherein the method includes steps (ic) and (ii). Therefore, the preferred method is a method for improving the adhesion strength between the surface of copper, copper alloy, or copper oxide and the surface of an organic material and / or improving the wedge-shaped porosity behavior therebetween, comprising... (i) Providing a substrate, wherein the copper, copper alloy, or copper oxide is disposed on at least one side of the substrate. Subsequently (ic) Processing the substrate to obtain a substrate comprising copper oxide on at least one side of the substrate, wherein the copper oxide comprises copper (I) and copper (II) in a ratio of 90:10 or higher (mol / mol), preferably 95:5 or higher (mol / mol), and even more preferably 98:2 or higher (mol / mol), and preferably the copper oxide is substantially composed of copper (I) oxide; and (ii) Make at least one section of the substrate in contact with the following: (a) At least one silane compound of formula (I); (I) in Ring structure The group is composed of the following components: and its mixtures; X and Y are independently chosen from the following groups: NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, SCH₃, and OCH₃; The E series is selected from the following groups: -S-, -NH-, and -NH-(CH2)m-NH-; Series A is selected from the following groups: NH, N(NH₂), and S; The Z series is selected from the following groups: and , m is an integer in the range of 2 to 12. n is an integer in the range 1 to 12. o represents an integer in the range of 2 to 12. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or A mixture of (a) and (b), Step (ic) is performed before step (ii); (iii) Apply the organic material.

[0136] The preferred method is one in which at least one segment of the substrate is in contact with both (a) the silane of formula (I) and (b) at least one amino acid in step (ii).

[0137] Example A. A method for improving the adhesion strength between the surface of copper, copper alloy, or copper oxide and the surface of an organic material and / or improving the wedge-shaped porosity behavior therebetween, comprising: (i) A substrate is provided, wherein at least one side of the substrate comprises copper, a copper alloy, or a copper oxide. This is followed by at least one of the following steps. (ic) Processing a substrate to obtain a substrate comprising copper oxide on at least one side of the substrate, wherein the copper oxide comprises copper (I) and copper (II) in a ratio of 90:10 or higher (mol / mol), preferably 95:5 or higher (mol / mol), and even more preferably 98:2 or higher (mol / mol), and preferably the copper oxide is substantially composed of copper (I) oxide; and / or (ii) Make at least one section of the substrate in contact with the following: (a) At least one silane compound of formula (I); (I) in Ring structure The group is composed of the following components: and its mixtures; X and Y are independently chosen from the following groups: NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, SCH₃, and OCH₃; The E series is selected from the following groups: -S-, -NH-, and -NH-(CH2)m-NH-; Series A is selected from the following groups: NH, N(NH₂), and S; The Z series is selected from the following groups: and , m is an integer in the range of 2 to 12. n is an integer in the range 1 to 12. o represents an integer in the range of 2 to 12. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or A mixture of (a) and (b), If both steps (ic) and (ii) are performed, then step (ic) is performed before step (ii). (iii) Apply organic materials, The prerequisite is that the cyclic structure in the silane compound of formula (I) is... Tie Then implement steps (ic) and (ii).

[0138] B. According to the method of Example A, Step (ic) comprises contacting at least one segment of copper, copper alloy, or copper oxide with an alkaline aqueous solution containing one or more chelating agents; preferably, the one or more chelating agents contain at least one carboxyl group and at least one hydroxyl group; more preferably, the one or more chelating agents contain sugars, preferably monosaccharides; even more preferably, the one or more chelating agents for chelating copper ions contain gluconic acid and / or its salts; most preferably, the only chelating agent for chelating copper ions in the alkaline solution is gluconic acid and / or its salts.

[0139] C. The method according to Example B, wherein the alkaline aqueous solution in step (ic) has a pH in the range of 7.5 to 14.0, preferably in the range of 10.0 to 14.0.

[0140] D. The method according to embodiment B or C, wherein step (ic) is an application as an impregnation and the contact time is 40 s or longer, preferably the contact time in step (ic) is 40 s to 900 s, more preferably the contact time in step (ic) is 60 s to 500 s, and even more preferably the contact time in step (ic) is 90 s to 450 s.

[0141] E. The method according to embodiment B or C, wherein step (ic) is applied as a spray coating and the contact time is 10 s or longer, preferably the contact time in step (ic) is 20 s to 200 s, and more preferably the contact time in step (ic) is 30 s to 150 s.

[0142] F. The method according to any of the foregoing embodiments includes the following steps (ii) Make at least one section of the substrate in contact with the following: (a) At least one silane compound of formula (I); (I) in Ring structure The group is composed of the following components: and and its mixtures; X and Y are independently chosen from the following groups: NH₂, NH(NH₂), NH(CH₂)₀NH₂, SH, SCH₃, and OCH₃; The E series is selected from the following groups: -S-, -NH-, and -NH-(CH2)m-NH-; The Z series is selected from the following groups: and , m is an integer in the range of 2 to 12. n is an integer in the range 1 to 12. o represents an integer in the range of 2 to 12. R independently represents (CH2-CH2-O)pT, where independently p is 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or A mixture of (a) and (b).

[0143] G. The method according to any of the foregoing embodiments, wherein the organic material applied in step (iii) is an organic polymer.

[0144] H. According to any of the methods in the foregoing embodiments, the organic material is applied in step (iii) by laminating the organic material onto at least the contact area of ​​copper, copper alloy or copper oxide.

[0145] I. According to any of the methods in the foregoing embodiments, if step (ii) is performed, the following steps are additionally included before performing step (ii): (ia) Contacting at least one section of copper, copper alloy or copper oxide with an etching cleaning solution, preferably an etching cleaning solution containing one or more acids and / or one or more oxidants, more preferably an etching cleaning solution containing a mixture of inorganic acids and peroxides.

[0146] J. According to any of the methods in the foregoing embodiments, if step (ii) is performed, the following additional steps are included before performing step (ii): (ib) Contact at least one section of copper, copper alloy or copper oxide with (preferably second) an etching cleaning solution containing an inorganic acid, preferably sulfuric acid.

[0147] K. According to any of the methods in the foregoing embodiments, wherein after step (ii), after step (ia), after step (ib) and / or after step (ic), at least one section of copper, copper alloy or copper oxide is rinsed, wherein the copper, copper alloy or copper oxide is preferably rinsed with water.

[0148] L. The method according to any of the foregoing embodiments A to K, wherein after step (ii), after step (ia), after step (ib) and / or after step (ic), drying of at least one section of copper, copper alloy or copper oxide is performed.

[0149] M. The method according to any of the foregoing embodiments A to K, wherein after step (ii), at least one section of copper, copper alloy or copper oxide is not baked.

[0150] N. The method according to any of the foregoing embodiments includes an additional step after step (iii): (iv) subjecting the substrate and organic material to heat treatment at a temperature in the range of 142°C to 420°C, preferably in the range of 145°C to 300°C, and even more preferably in the range of 150°C to 220°C.

[0151] O. According to any of the methods in the foregoing embodiments, wherein after step (ii), after step (ia), after step (ib) and / or after step (ic), at least one section of copper, copper alloy or copper oxide is rinsed, wherein the copper, copper alloy or copper oxide is preferably rinsed with water.

[0152] P. According to any of the methods in the foregoing embodiments, the contact time in step (ii) is 5 seconds to 30 minutes, preferably 7 seconds to 20 minutes, more preferably 10 seconds to 10 minutes, even more preferably 12 seconds to 5 minutes, and most preferably 15 seconds to 120 seconds. The invention is further explained by the following non-limiting examples.

[0153] [Example] [Composite] [(IV)] [Tetraazole silane compounds] [:] [] Synthetic tetrazolium silane compounds of formula (IV-a): (IVa) 4.92 g (57.8 mmol) of 2H-tetrazole-5-amine was suspended in 84.3 ml of diethylene glycol monobutyl ether (DEGBE). This suspension was heated to 80 °C. At this temperature, 13.67 g (57.8 mmol) of 3-glycidoxypropyltrimethoxysilane was added. The reaction mixture was maintained at 80 °C for 15 hours.

[0154] Subsequently, a reaction product was obtained at a concentration of approximately 20 wt.% in DEGBE. The product thus obtained was used without further purification.

[0155] ESI-MS confirmed the formation of compounds containing three methoxy groups attached to silicon atoms. Additionally, compounds containing one, two, or three DEGBE moieties, rather than individual methoxy groups, have also been identified.

[0156] [Sample Preparation] [] The samples (each containing several identical samples) were prepared as follows.

[0157] Table 1 provides an overview of the reaction steps, which will be described in more detail later. Table 1 step deal with composition temperature Typical stay time Remark (i) Provide copper substrate annealing (Optional) 160℃ Ventilated drying oven, 1 hour (ia) Differential Etching 25ml / l Hyperflash 25 50ml / l H₂SO₄ 450% 65ml / l H₂O 235% 30℃ Depends on the etching rate Target etching depth is 0.5µm and 1µm Three-stage cascade flushing water dry (Optional) Until dry (ib) H₂SO₄ 45% 130ml / l H₂SO₄ 450% Ambient temperature 30 s Three-stage cascade flushing water Ambient temperature 20 s (ic) alkaline aqueous solution pH 14 50℃ 30 – 600 s rinse water Ambient temperature 20 s Drying (optional) Until dry Hot air dryers, such as air guns and hair dryers (ii) Adhesion promoter Different silanes Ambient temperature 60 s See AP table Three-stage cascade flushing water Ambient temperature 30 seconds each dry Until dry Hot air dryers, such as air guns and hair dryers (ii-a) bake (Optional) 130 30 min Ventilated drying oven (iii) laminated See Table 2

[0158] [step] [(i)] [:] [] Copper foil with a copper surface (150 mm x 75 mm x 35 µm, internally electroplated) was used. For the example, a substrate-free copper foil was used under simplified laboratory conditions.

[0159] For studies of wedge-shaped apertures and / or halos, electroplated copper panels are used.

[0160] The preparation conditions are as follows: Types of electrolytic copper plating: Foil (adhesion test) Panel (wedge-shaped aperture) Electrolytes: Cupracid AC Electroplating parameters: 103min 1.5 A / dm² = 35µm copper plating thickness

[0161] [step] [(ia)] [:] The copper surface of the copper foil was treated at 30°C with 25 ml / l Hyperflash 25, 50 ml / l H 2SO 450%, and 65 ml / l H 2O 235% to achieve an etching depth of 0.5 or 1 µm. After etching and cleaning, the etch-cleaned copper surface was rinsed with water for approximately 30 seconds and dried as needed. This yielded a etch-cleaned and rinsed copper surface.

[0162] [step] [(ib)] [:] [] Clean the copper surface of the copper foil at room temperature for 20-30 seconds using 5 vol% sulfuric acid.

[0163] [step] [(ic)] [:] [] The copper surface of the substrate was treated with a sulfur-alkaline aqueous solution (50°C, immersion, 300 sec or 50°C, spraying, 30 sec). After treatment, all copper foil surfaces were rinsed with cold water for approximately 30 seconds.

[0164] [step] [(ii):] [] The copper surface of the substrate is immersed at 25°C in a solution containing trioxide. The coating solution contains silane compounds and solvents for up to 60 seconds. If water is present, the pH of the coating solution is 7 (triazole and tetraazole silanes) (adjusted with sulfuric acid if necessary) or as high as 13.5 (triazole silanes). (Silane). Details are given in Table 2.

[0165] Subsequently, the copper surfaces of all the copper foils were rinsed with water for approximately 30 seconds and then dried. This yielded the silanized and dried copper surfaces of the copper foils.

[0166] [step] [(ii-a)] [:] [] The copper foil is then annealed at 130°C for 30 minutes to remove residual moisture from the surface. Note: This heat treatment step is also known as baking. These substrates with copper surfaces then undergo film lamination (see below).

[0167] [step] [(iii)] [:] [] In the lamination step, the insulating film (see Table 2) is vacuum laminated onto the copper foil of all samples in a clean room with a room temperature of 20 to 25°C and a relative humidity of 50 to 60% by using a vacuum laminator.

[0168] The conditions for vacuum lamination are as follows: 100℃, vacuum: 3 hPa for 30 sec, pressure: 0.5 MPa for 30 sec.

[0169] After lamination, a laminated copper surface is obtained. Table 2 - Overview of Conditions Sample Step (ic) [None / Immersion / Spraying] time [s] Step (ii) [Yes / No] silane time [s] C1 (Comparison) none n / a none n / a n / a 1a Immersion 30 none n / a n / a 1b Spraying 30 none n / a n / a 2a Immersion 60 none n / a n / a 2b Spraying 60 none n / a n / a 3a Immersion 120 none n / a n / a 3b Spraying 120 none n / a n / a 4a Immersion 300 none n / a n / a 4b Spraying 300 none n / a n / a 5 Immersion 30 have (IVa) 60 s 6 Immersion 60 have (IVa) 60 s 7 Immersion 120 have (IVa) 60 s 8 Immersion 300 have (IVa) 60 s 9 Immersion 300 have (Vb) 60 s 10 Immersion 300 have (IIa) 60 s (IVa): (Vb): (IIa)

[0170] [Surface Morphology] [] Surface morphology was measured using field emission scanning electron microscopy (FESEM). FEI NOVA Nanolab 600 and FEI Helios Nanolab 660 microscopes were used to study the surface and cross-sections of the FIB preparation.

[0171] SEM Scanning electron microscopy (SEM) images show the changes in surface structure after different time steps (ic) (Figure 1). Oxide particles are formed on the surface at 30 s (sample 1). With longer processing times according to step (ic), the Cu surface becomes "flat" due to the growth of oxide particles.

[0172] AFM Surface roughness was measured using atomic force microscopy (AFM): for each sample, the surface was imaged in five 20 µm × 20 µm measurement windows. The average roughness RA and the relative increase in surface area RSAI were calculated. Figure 2 illustrates the increase in roughness due to alkaline treatment and its invariance after the application of silane.

[0173] Characterization of copper oxides [] DSCV Characterization of copper oxides was performed using dual-scan cyclic voltammetry (DSCV). The method was used for the quantification of Cu oxides. During the first scan, copper and cuprous oxide were reduced to Cu to provide the corresponding cathode current. During the third scan, the background current was measured in the same cathode direction as in the first scan. The background current was subtracted from the cathode current of the first scan to calculate the amount of charge required to reduce the corresponding Cu oxide species. The experiment was conducted at RT in LiCl (4 M) solution, with a potential range of -0.5 to -1.6 V (relative to Ag / AgCl (3 M KCl)), a scan rate of 100 mV / s, and 3 scans. o For a scan rate of 100 mV / s: § CuO: -0.5 to -1.08 V (relative to Ag / AgCl (3M KCl)) § Cu₂O: -1.08 to -1.3 V (relative to Ag / AgCl (3M KCl)) The oxide layer thickness (d) in nm is calculated using Faraday's law.

[0174] Measurement results show that Cu(II) oxide remained at the "zero" level. In contrast, Cu(I) oxide increased (Figure 3).

[0175] FTIR The substrate surface was characterized using Fourier-transform infrared spectroscopy (FTIR) with grazing incidence units. Changes in the surface oxide state during alkaline treatment were evaluated. (Figure 4)

[0176] EDS Elemental analysis of the samples was performed using energy-dispersive X-ray spectroscopy (EDS). Thin layers were prepared for scanning transmission electron microscopy (STEM) and further used for EDX measurements. Details are given in Figures 5a) to 5b) and the corresponding descriptions.

[0177] EDS analysis was performed at three different regions of the oxide particles.

[0178] It has been found that the ratio of Cu to O is 2:1, which indicates that oxide particles formed by alkaline solutions have Cu₂O properties.

[0179] HRTEM Nanobeam diffraction (NBD) measurements in high-resolution transmission electron microscopy (HRTEM) mode are the most advantageous technique for routine strain analysis (simple experimental setup, nanoscale spatial resolution, and high measurement sensitivity (std. dev. ~ 0.1%)).

[0180] Line scanning was performed at nine locations along the height of the oxide particles. All the obtained patterns were almost identical → the same mass of oxide was expected along the particle height.

[0181] [Adhesion tested via peel strength test] [wearing] [Evaluate] [:] For the selected specimens obtained after lamination, the peel strength was measured: (1) Initially, (2) After 96 hours of HAST (HAST conditions: 130℃, 85% rh, HAST chamber: EHS-221M). (3) After 12 IR reflow cycles (thermal reliability, simulated peak temperature of 260°C for the welding process) To determine peel strength, several strip segments were prepared from each sample by bonding individual copper foils to a rigid plate (of the same size as the copper foil) with the plate facing the insulating film. This yielded a copper surface with a structurally reinforced insulating film.

[0182] The copper surfaces with the obtained structurally reinforced insulating film are then cured in an oven: copper surfaces with GL102 material are cured at 200°C for 90 minutes, and copper surfaces with GX-T31 material are cured at 190°C for 90 minutes.

[0183] Subsequently, each copper surface with the structurally reinforced insulating film is cut into strip segments (10x100 mm, Bugard drilling / wiring).

[0184] Strip segments were placed on a peel strength tester (Roell Zwick Z010) to individually assess the peel strength required to detach the copper surface from its respective structure of hydrogenated insulating film (angle: 90°, speed: 50 mm / min). Generally, the higher the peel strength required to avoid delamination, the better the adhesion.

[0185] The peel strength of samples 1 to 15 is shown in Table 3 below. Table 3 Sample Step (ic) Immersion [time, s] Step (ii) [Silane] Peel strength GX-T31 (N / cm) Peel strength GL102 (N / cm) initial HAST reflux initial HAST reflux C1 n / a n / a 6.6 2.1 2.1 6.4 1.6 4.7 1a 30 n / a 9.3 3.7 5.0 7.5 2.2 5.6 2a 60 n / a 9.5 4.8 4.3 7.2 2.5 4.8 3a 120 n / a 9.7 5.6 4.5 7.6 2.7 5.2 4a 300 n / a 10.2 5.8 4.8 7.9 3.3 5.6 C2 n / a (Vb) 7.5 4.4 5 n / a (IVa) 5.8 2.8 3.0 7.2 2.4 6.3 6 n / a (IIa) 8.4 4.0 5.0 6.8 3.6 5.7 7 30 (IVa) 8.6 2.9 4.0 6.1 2.9 5.8 8 60 (IVa) 8.8 4.7 4.5 6.8 4.3 6.2 9 120 (IVa) 10.2 5.6 5.6 6.9 4.9 6.5 10 300 (IVa) 9.8 8.3 7.5 7.3 4.8 6.3 11 300 (Vb) 7.3 4.6 12 30 (IIa) 8.7 6.5 6.2 6.3 3.8 5.8 13 60 (IIa) 8.9 7.4 7.2 6.5 4.2 5.8 14 120 (IIa) 9.5 7.8 7.4 6.7 4.7 6.2 15 300 (IIa) 9.4 8.5 7.8 7.5 5.0 6.5 (IVa): (Ex): (IIa)

[0186] Experiments show that the examples of the present invention exhibit good adhesive strength, which is expressed here as peel strength.

[0187] [Halo and wedge-shaped porosity assessment] [, , ] Sample preparation: To evaluate the halo effect, copper samples were prepared by adhering individual insulating films to a copper panel. This resulted in a copper surface with a structurally reinforced insulating film.

[0188] The copper surfaces with the structurally reinforced insulating film were then semi-cured in an oven in two steps: the copper surfaces with GL102 material were cured at 130°C for 30 minutes, followed by 175°C for 30 minutes; and the copper surfaces with GX-T31 material were cured at 100°C for 30 minutes, followed by 170°C for 30 minutes.

[0189] After lamination and semi-curing, the copper panel is laser-treated using a UV laser to drill blind microvias (BMVs). Subsequently, the substrate undergoes desmearing and reduction condition steps. Specifically, these include swelling treatment using Securiganth MV Sweller (Atotech) under alkaline conditions; permanganate treatment using Securiganth MV Etch P (Atotech) under alkaline conditions; and reduction conditioner treatment using Securiganth MV Reduction Conditioner (Atotech) under acidic conditions. After each step, the sample is rinsed with water.

[0190] The laminated materials exhibit thicknesses of approximately 10 µm for wedge-shaped pores and halos, and 35 µm in the case of adhesion studies.

[0191] Measurement: 1) Halo Assessment The substrate was measured using an optical microscope (200x magnification; see Figure 4). An image illustrating the halo measurement is shown in Figure 6.

[0192] The blind microvias (BMVs) studied were fabricated as test grids on a surface-treated and Ajinomoto Build-up Film (ABF) laminated test carriage using laser drilling technology. Halo data were obtained after the prepared test carriage was sent through the entire desizing process (swelling agent, permanganate, reduction modifier) ​​as described above.

[0193] Halo measurements are performed using optical microscopy supported by a camera (CCD). Therefore, the microscope must be operated in incident illumination mode. All image generation must be performed using a dark field (DF) filter setting. A magnification factor of approximately 200x is typically used.

[0194] The fully processed test mount is securely mounted on the measurement stage, and the BMV capture pad must be set to optical focus. The CCD exposure time must be adjusted to the maximum possible contrast at the halo boundary. Therefore, the capture pad should be as bright as possible.

[0195] Measure and record the visible diameter of the through-hole (or cleaning capture pad), and the halo-like boundaries appearing inside (innermost layer) and outside (outermost layer) according to Figure 6. The actual halo value can now be calculated using the following formula. 1. Outer halo (μm) = (outermost diameter (μm) - diameter of through hole (μm)) / 2 2. Internal halo (μm) = (inner diameter of halo (μm) - diameter of through hole (μm)) / 2

[0196] Typically, this process iterates at least 3 times at random test vias to achieve a minimum statistical report. Table 4 Sample Step (ic) Immersion [time, s] Step (ii) [Silane] GL102 (µm halo size) Baking (130℃, 30 min) is available. GL102 (µm halo size) No baking internal external internal External C1 n / a n / a 79.9 143 49.6 91.8 2a 60 n / a 61.9 104 39.7 71.2 4a 300 n / a 19.2 61.7 17.9 38.6 C2 (Comparison) n / a (Vb) 67.2 76.4 5 n / a (IVa) 65 85 15 41 6 n / a (IIa) 19.0 75 15 60 8 60 (IVa) 50 70 n / a n / a 10 300 (IVa) 23.1 68.7 19.5 42.0 11 300 (Vb) 22.5 74.8 12 300 (IIa) 20.0 25 (IVa): (Vb): (IIa)

[0197] The best results are obtained from the combination of step (ic) and step (ii) which contains TE silane.

[0198] Experiments show that the embodiments of the present invention exhibit good behavior in avoiding the formation of wedge-shaped voids, which are referred to herein as halo size.

[0199] 2) Wedge porosity assessment In addition, the substrate undergoes focused ion beam (FIB) cutting and subsequent scanning electron microscopy (SEM) measurement. This method allows for the analysis of copper adhesion near blind microvias (BMVs), also known as wedge-shaped apertures.

Claims

1. A method for improving the adhesion strength between the surface of copper, copper alloy, or copper oxide and the surface of an organic material and / or improving the wedge-shaped porosity behavior therebetween, comprising (i) providing a substrate having the copper, copper alloy, or copper oxide on at least one side of the substrate, and then (ii) contacting at least one segment of the substrate with: (a) at least one silane compound of formula (I); (I) wherein the ring structure is selected from the group consisting of: and mixtures thereof; X and Y are independently selected from the group consisting of: NH2, NH(NH2), NH(CH2)oNH2, SH, SCH3, and OCH3; E is selected from the group consisting of: -S-, -NH-, and -NH-(CH2)m-NH-; A is selected from the group consisting of: NH, N(NH2), and S; Z is selected from the group consisting of: and, m is an integer in the range of 2 to 12, n is an integer in the range of 1 to 12, o is an integer in the range of 2 to 12, and R independently represents (CH2-CH2-O)pT, wherein p independently refers to 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or a mixture of (a) and (b), (iii) applying the organic material, subject to the condition that if the ring structure in the silane compound of formula (I) is the same, then the following steps (ic) are performed after step (i) and before step (ii): (ic) treating the substrate to obtain a substrate containing copper oxide on at least one side of the substrate, wherein the copper oxide contains copper (I) and copper (II) in a ratio of 90:10 or higher (mol / mol).

2. The method of claim 1, wherein step (ic) comprises contacting at least one segment of the copper, copper alloy or copper oxide with an alkaline aqueous solution containing at least one bonding agent.

3. The method of claim 2, wherein the alkaline aqueous solution in step (ic) has a pH in the range of 7.5 to 14.

0.

4. The method of claim 2 or 3, wherein step (ic) is applied as an impregnation and the contact time is 40 s to 900 s.

5. The method of claim 2 or 3, wherein step (ic) is applied as a spray coating and the contact time is 10 s to 200 s.

6. The method of any one of claims 1 to 3, comprising the step (ii) contacting at least one segment of the substrate with: (a) at least one silane compound of formula (I); (I) wherein the ring structure is selected from the group consisting of: and mixtures thereof; X and Y are independently selected from the group consisting of: NH2, NH(NH2), NH(CH2)oNH2, SH, SCH3 and OCH3; E is selected from the group consisting of: -S-, -NH- and -NH-(CH2)m-NH-; Z is selected from the group consisting of: and, m is an integer in the range of 2 to 12, n is an integer in the range of 1 to 12, o is an integer in the range of 2 to 12, R independently represents (CH2-CH2-O)pT, wherein p is independently 0, 1, 2, 3 or 4, and T represents H or C1 to C5 alkyl; or (b) at least one amino acid; or a mixture of (a) and (b).

7. The method of any one of claims 1 to 3, wherein the organic material applied in step (iii) is an organic polymer.

8. The method of any one of claims 1 to 3, wherein the organic material is applied in step (iii) by laminating the organic material onto at least the contact section of the copper, copper alloy or copper oxide.

9. The method of claim 1, which further includes the following steps before performing step (ii): (ia) contacting at least one section of the copper, copper alloy or copper oxide with an etching cleaning solution.

10. The method of claim 1, which further comprises the following steps before performing step (ii): (ib) contacting at least one segment of the copper, copper alloy or copper oxide with a second etching cleaning solution containing an inorganic acid.

11. The method of any one of claims 1 to 3, 9 and 10, wherein, after step (ii), after step (ia), after step (ib) and / or after step (ic), the rinsing of at least one section of the copper, copper alloy or copper oxide is performed.

12. The method of any one of claims 1 to 3, 9 and 10, wherein drying of at least one section of the copper, copper alloy or copper oxide is performed after step (ii), after step (ia), after step (ib) and / or after step (ic).

13. The method of any one of claims 1 to 3, 9 and 10, wherein baking of the at least one section of copper, copper alloy or copper oxide is not performed after step (ii).

14. The method of any one of claims 1 to 3, 9 and 10, wherein after step (iii) the additional step is included: (iv) subjecting the substrate and the organic material to heat treatment at a temperature in the range of 142°C to 420°C.

15. The method of claim 11, wherein the copper, copper alloy or copper oxide is rinsed with water.

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