KR20110076448A - Carbide ceramic heating plate and the manufacturing of the same - Google Patents

Abstract

PURPOSE: A carbide ceramic heating plate and a method for manufacturing the same are provided to improve the adhesion of nickel and a silicon-carbon compound substrate by introducing the electroless plating pre-processing process and the electroless plating process of the nickel. CONSTITUTION: The surface of a silicon-carbon compound substrate is processed with plasma. The surface of the substrate is primarily etched, and the primarily etched substrate is degreased. The degreased surface of the substrate is secondarily etched. Catalyst is applied to the secondary etched substrate. An electroless plating process using nickel is applied to the substrate, and a nickel pattern is formed on the substrate. A sodium hydroxide diluted solution is used as an etching solution.

Description

Carbide ceramic heating plate and the manufacturing method of the same

The present invention relates to a carbide ceramic hot plate and a method of manufacturing the same, and more particularly, a) plasma treatment of a silicon-carbon compound substrate surface; b) first etching the surface of the substrate; c) degreasing and second etching the first etched substrate; d) adding a catalyst to the degreased and secondary etched silicon-carbon compound substrate; e) electroless plating nickel on the catalyzed silicon-carbon compound substrate; And f) forming a nickel pattern on the nickel-electroless plated silicon-carbon compound substrate, wherein the first etching of step b) is performed by dissolving 200 to 400 g of sodium hydroxide per 1 liter of pure water. It proceeds by using the sodium hydroxide diluent as an etching solution and maintaining the etching time for 20 to 40 minutes, and the arithmetic mean value Ra of the surface roughness of the silicon-carbon compound substrate is 0.6 to 0.8 by the first etching and the second etching of step c). Provided are a carbide ceramic hot plate and a method of manufacturing the same.

Recently, due to the large-diameter tendency of wafers, the diameter has increased to 300mm, 450mm, etc., and as the diameter increases, the defective rate of the final wafer product is increasing as compared to the past, and thus, in order to improve the yield of the wafer, There is an increasing need to precisely control the temperature of the baking hot plate.

As a hot plate (hot plate) material, an aluminum-nitrogen compound sintered body was used. Since the aluminum-nitrogen compound has good thermal conductivity, high insulation, and no toxicity, it is a promising material as an insulating material or a package material in the semiconductor industry. Although it can be recognized, there is a problem that noise is seriously generated in the instrument in the equipment when high voltage is applied because of high insulation resistance, and there is a problem that an error may occur in various control devices in the equipment. Therefore, it is necessary to develop alternative materials to solve this noise problem.

Thus, in order to reduce the occurrence of noise, carbide ceramics having low insulation resistance and some conductivity were considered, and among them, a silicon-carbon compound sintered body was selected.

Since silicon carbide has high thermal conductivity, medium insulation, and no toxicity, it is attracting attention as an insulating material or a tool material in the semiconductor industry. In addition, it does not deteriorate until high temperature, which not only decreases the strength but also has excellent chemical resistance, which is used as a heat-resistant material, and has similar characteristics to that of a wafer, so it is a dummy wafer (test wafer polished on one side) of the semiconductor process. It is also promising as.

Meanwhile, in the present invention, an electroless plating process is used. Instead of plating by receiving electrical energy from the outside, electroless plating is carried out to reduce the metal ions in the aqueous metal salt solution by electrocatalytically by adding a reducing agent. It is defined as a plating method performed by depositing a metal on the surface of a sieve, also called chemical plating or autocatalyst plating. At this time, a reducing agent such as formaldehyde or hydrazine in the aqueous solution supplies electrons to reduce metal ions to metal molecules, and this reaction takes place on the surface of the catalyst. The most commonly used plating metal bodies include copper, nickel-phosphorus, nickel-boron alloys, and the like. Electroless plating has the advantage that the plating layer is dense and uniform thickness of about 20㎛ compared to the electroplating, and can be applied to various substrates such as plastics or organics as well as conductors.

In general, the electroless plating method performed on a printed circuit board (PCB) undergoes a pretreatment step of degreasing, etching, and activating treatment. In the case of using a ceramic substrate, chemical resistance varies depending on firing conditions and composition, and thus appropriate pretreatment. It is necessary to use the method. In particular, when using a silicon-carbon compound substrate, development of a pretreatment method for improving the adhesion between the plated metal and the substrate is further required.

On the other hand, the conventional metal wiring formation method was a method of sequentially proceeding nickel-gold plating after printing in a silkscreen method using a silver paste. In addition to the above method, a method of forming a pattern using a photoresist on a pretreated ceramic substrate and optionally allowing a metal to be plated is also known. However, although the above-mentioned method has to make the vertical cross-sectional shape of the pattern to be formed into a rectangular shape having a uniform thickness corresponding to the rectangular via hole cross section, it is somewhat rounded and does not have a uniform thickness. Because of poor workability and tension due to the characteristics of the silk screen, there is a problem that the dimensions such as the cumulative pitch compared to the design value become unstable, resulting in poor electrical properties or poor reliability. Furthermore, in order to form a metal pattern having a finer line width, the above-mentioned problems become more serious, and there is a problem that it is difficult to apply to form a fine pattern substantially.

Therefore, in the present invention, in order to manufacture a carbide ceramic hot plate, a substrate material for plating nickel is selected. In particular, silicon carbide, which has not been tried before, is selected, and a pretreatment method suitable for a silicon-carbon compound substrate is developed to produce silicon-carbon. By enabling nickel electroless plating on the compound substrate and improving its adhesion, a nickel electroless plating film having a uniform thickness was obtained by using a nickel plating solution containing a specific complexing agent, and using a photolithography process. By forming a fine nickel pattern, a carbide ceramic hot plate having a low resistance deviation of the nickel pattern and a manufacturing method thereof have been developed.

Accordingly, an object of the present invention is to use a silicon-carbon compound substrate selected from carbide ceramics, which have high thermal conductivity and heavy insulation properties, which can significantly reduce noise generation compared to conventional aluminum-nitrogen compound substrates. The present invention provides a carbide ceramic hot plate and a method of manufacturing the same.

In addition, another object of the present invention is to introduce an electroless plating pretreatment method and an electroless plating method of nickel suitable for the silicon-carbon compound substrate represented by the secondary etching, thereby providing high and uniform adhesion to the silicon-carbon compound substrate. A carbide ceramic hot plate capable of forming a nickel thin film having a thickness and a method of manufacturing the same are provided.

In addition, another object of the present invention is to use a electroless plated nickel thin film in a method suitable for the silicon-carbon compound substrate and to form a pattern using a photolithography process to enable a fine nickel pattern and less resistance variation of the nickel pattern The present invention provides a carbide ceramic hot plate and a method of manufacturing the same.

In order to achieve the object as described above, the present invention comprises the steps of: a) plasma treatment of the silicon-carbon compound substrate surface; b) first etching the surface of the substrate; c) degreasing and second etching the first etched substrate; d) adding a catalyst to the degreased and secondary etched silicon-carbon compound substrate; e) electroless plating nickel on the catalyzed silicon-carbon compound substrate; And f) forming a nickel pattern on the nickel-electroless plated silicon-carbon compound substrate, wherein the first etching of step b) is performed by dissolving 200 to 400 g of sodium hydroxide per 1 liter of pure water. It proceeds by using the sodium hydroxide diluent as an etching solution and maintaining the etching time for 20 to 40 minutes, and the arithmetic mean value Ra of the surface roughness of the silicon-carbon compound substrate is 0.6 to 0.8 by the first etching and the second etching of step c). Provided are a method for producing a carbide ceramic hot plate and a carbide ceramic hot plate produced by the method.

Prior to step a), performing a grit or bead blasting process on the silicon-carbon compound substrate surface.

Removing the foreign matter present on the surface of the silicon-carbon compound substrate after the plasma treatment of step a) is preferably further included.

Degreasing and secondary etching step of step c), the degreasing step of removing contamination of the silicon-carbon compound substrate surface using an organic acid or an inorganic acid; And an etching step of etching the surface of the silicon-carbon compound substrate with 0.5 to 10% by weight of a fluoride salt solution.

The fluorinated solution is preferably a fluorinated salt solution in which NaF and NH ₄ F are mixed in a weight ratio of 1: 1 to 100.

The nickel electroless plating is preferably performed by immersing a silicon-carbon compound substrate treated with a conditioning solution in a plating solution containing nitrilotris (methylene) triphosphonic acid (NTPA) as a nickel salt, a reducing agent and a complexing agent. .

The step e) may include forming a photoresist pattern on the electroless plated nickel layer using a dry film; Etching nickel using the corrosion solution; And peeling off the photoresist pattern.

It is preferable that the corrosion solution contains HCl and NaClO ₃ .

In addition, in order to achieve the object of the present invention as described above, there is provided a carbide ceramic hot plate produced by the above-described manufacturing method.

According to the present invention as described above, by introducing an electroless plating pretreatment method and an electroless plating method of nickel suitable for the silicon-carbon compound substrate, the adhesion between the nickel and the silicon-carbon compound substrate can be improved, and the uniform thickness There is an effect that can form a nickel thin film having.

In addition, according to the present invention, by using an electroless plated nickel thin film in a method suitable for a silicon-carbon compound substrate and forming a pattern using a photolithography process, a fine nickel pattern is possible, and the effect of the resistance variation of the nickel pattern is small. There is.

According to the present invention, in the pretreatment step of nickel electroless plating, the surface of the silicon-carbon compound substrate is treated with oxygen plasma, and surface etching is performed by using a diluted sodium hydroxide solution to improve the roughness of the surface. It was confirmed that the adhesion between the plating film and the silicon-carbon compound substrate was improved.

In addition, the silicon-carbon compound substrate was etched using an etchant in which sodium fluoride and ammonium fluoride were mixed in an appropriate range as the fluoride salt, thereby further improving the adhesion of the nickel electroless plated film to the substrate. In addition, it was confirmed that the nickel plating film was more uniformly formed when nitrilotris (methylene) triphosphonic acid (NTPA) was used as the complexing agent in the plating solution during nickel electroless plating.

The oxygen plasma refers to plasma formed using oxygen gas or a mixed gas of oxygen gas and another gas, and the nickel plating includes all of nickel alloy plating for plating only nickel alone or plating nickel and other components together. can do. Examples of the nickel alloys include nickel-phosphorus and nickel-boron alloys.

In addition, after forming a nickel film by electroless plating on the silicon-carbon compound substrate treated by the above pretreatment method, a pattern is formed by a photolithography process, and the nickel film is etched according to the formed pattern to form a nickel pattern. In addition to manufacturing a nickel pattern, it is possible to provide a silicon-carbon compound substrate on which a nickel pattern with a low resistance variation is formed.

Accordingly, the present invention provides a silicon-carbon compound substrate having a nickel pattern with excellent adhesion to the substrate and a low resistance variation using a nickel electroless plating process and a pattern forming process suitable for the silicon-carbon compound substrate, and a method of manufacturing the same. It is to.

Hereinafter, the present invention will be described in more detail based on the embodiments and the accompanying drawings.

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art.

Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.

A method of manufacturing a carbide ceramic hot plate according to the present invention comprises the steps of: a) plasma treatment of a silicon-carbon compound substrate surface; b) degreasing and surface etching the plasma treated silicon-carbon compound substrate; c) adding a catalyst to the degreased and surface etched silicon-carbon compound substrate; d) electroless plating nickel on the catalyzed silicon-carbon compound substrate; And e) forming a nickel pattern on the silicon-carbon compound substrate on which the nickel is electroless plated. The surface etching of step b) includes 200 to 400 g of sodium hydroxide dissolved in 1 L of pure water. The sodium diluent is used as an etchant and the etching time is maintained for 20 to 40 minutes, and the arithmetic mean value Ra of the silicon-carbon compound substrate is 0.6 by performing both the first etching and the second etching of step c). It should be in the range of ~ 0.8.

The above process can be understood more clearly and simply by the nickel plating process of FIG. 1 and the nickel plating process of FIG. 2. However, the gold plating process is a conventional process, and a detailed description thereof will be omitted.

In addition, when the nickel-plated silicon-carbon compound obtained through such a process is shown as a schematic diagram, it can be understood as shown in FIG.

Dividing the above process in more detail as follows.

The plasma treatment step of step a) means to treat the surface of the silicon-carbon compound substrate using a plasma of a gas containing oxygen gas, thereby removing the organic material present on the surface of the substrate and at the same time It modifies the state to improve adhesion to the electroless plating nickel film.

A grit or bead blasting process may be performed prior to the plasma treatment to further increase the surface roughness of the silicon-carbon compound substrate, in which case the surface area participating in the reaction may be increased to provide nickel. The adhesion of the electroless plating film can be further improved.

Meanwhile, in step b), a dilute solution of sodium hydroxide was used as an etching solution. This is to improve or control the surface roughness. When surface etching is performed under the same concentration and conditions as described above, the nickel plated film and the surface of the silicon-carbon compound are used. It is possible to realize the surface roughness that can provide the optimum adhesion.

If sodium hydroxide is out of the range of the above range, if the concentration is lower than the range does not show the effect of etching, if the concentration is higher than the range, the erosion rate is very fast, so it is not easy to control the holding speed of the etching process, the impression after dipping Continued erosion can occur even after this. That is, it will be referred to as the optimum concentration condition for the etching of the silicon-carbon compound, there is a critical significance in this regard.

In addition, in the case where the surface etching time is out of the above range, if the time is shorter than the range, the effect of etching does not appear, and if the time is longer than the range, the etching is overetched. Can vary. Therefore, the above time range will be a critical meaning of the time that allows the nickel plated film is best plated on the surface of the silicon-carbon compound substrate.

In addition, the surface roughness has the same range as above, and as a result of measuring the adhesion of the nickel plated film to the silicon-carbon compound surface by using a tape test, the highest adhesion is obtained when the surface roughness ranges. It was found. Therefore, the above surface roughness value is an optimum surface roughness value that allows the nickel plated film to be in close contact with the silicon-carbon compound surface, and the upper limit and the lower limit will have critical significances, respectively. In this case, the "peel test" means a nickel plating film is formed on the surface of the silicon-carbon compound substrate, and repeated testing is performed by forcibly peeling it off using a tape.

In addition, after the plasma treatment of step a) may further comprise the step of removing the foreign matter present on the surface of the silicon-carbon compound substrate, there may be a number of methods, it is best to remove by a mechanical method using a brush or the like desirable. The above method is particularly suitable for removing foreign substances generated in the plasma treatment or blasting process. If the foreign substance is not removed, a defect may occur in which the nickel electroless plating layer may not come into close contact with the substrate.

Step c) is a degreasing step of removing contamination of the silicon-carbon compound substrate surface using an organic acid or an inorganic acid; And an etching step of etching the silicon-carbon compound substrate surface with 0.5 to 10% by weight of a fluorine salt solution, wherein step d) comprises treating the silicon-carbon compound substrate surface with a conditioning solution and catalyzing the surface of the silicon-carbon compound substrate. It is preferable to use Pd as the catalyst, wherein, in this case, it is composed of the step of forming a Sn-Pd seed layer, and then removing the Sn to form an activated Pd nucleus.

In addition, the step of forming the activated Pd nucleus is characterized by treating with an accelerator solution containing 0.5 to 10% by weight of a fluorine compound mixed with HF and HBF ₄ . In the case of treating with an accessory solution containing a fluorine compound according to the present invention, the growth rate of the electroless nickel plated film was superior to that of the conventional hydrochloric acid or sulfuric acid based solution.

Pretreatment processes for electroless nickel plating on silicon-carbon compound substrates include plasma surface treatment, front face, degreasing, primary etching, secondary etching, conditioning, pre-dip, and catalyzing ), The process of accelerating, and the cleaning process between each step and steps. In the present invention, the method further comprises the step of treating the silicon-carbon compound substrate with an oxygen plasma before the degreasing process.

As described above, the plasma surface treatment is a step of improving the adhesion to the nickel electroless plating film by removing an organic substance on the surface of the silicon-carbon compound substrate and modifying the surface state with an oxygen-containing gas plasma.

The grease removing is performed to remove organic and inorganic contaminants such as fingerprints, oils, and discoloration on the ceramic surface and to remove the ceramic residue, and it is preferable to use a neutral or acid based chemical. Avoid pasting the paste applied to the ceramic material. In the degreasing process, it is preferable to control the temperature and the treatment time according to the composition of the ceramic material and the degree of contamination, and it is preferable to use a degreasing agent that is easy to wash with water.

The first etching is as described above, the second etching may be carried out using an etchant consisting of an organic acid, an inorganic acid, but using those containing sodium fluoride (NaF), ammonium fluoride (NH ₄ F), etc. It is preferable. The content of the fluorine salt contained in the etching solution of the present invention is preferably 0.5 to 10% by weight. When the content of the fluorine salt is less than 0.5% by weight, the surface area increase effect due to etching is insignificant and the adhesion of nickel is not improved. When the content exceeds 10% by weight, partial etching occurs due to overetching, so that the catalyst of the post-process is not easily adsorbed, and thus the local adhesion is very poor. The etchant according to the present invention is preferably a fluoride salt solution in which sodium fluoride (NaF) and ammonium fluoride (NH ₄ F) are mixed in a weight ratio of 1 to 1 to 100, and when the weight ratio is greater than 100, the phenomenon is locally etched. If a lot appears, and the weight ratio is less than 1, the surface roughness (roughness) does not increase much, so that the problem with the nickel may be somewhat inferior.

Conditioning is a process of imparting hydrophilicity so that the catalyst can be adsorbed on the ceramics in the catalytic process of the ceramics as described below, which contains a cationic surfactant, an anionic surfactant, and amino alcohol. Use conditioning liquid. Surfactant components are preferably treated by dipping without agitation because the chemicals decompose due to air bubbles when air stirring, product shaking, and mechanical stirring are performed. After conditioning, the washing is carried out by hot water at 50 to 70 ° C. It is preferable to perform three steps of water washing.

The pre-dip is a process for preventing contamination of the catalyst chemical tank and dilution of the concentration by preventing water from flowing into the catalyst chemical tank. The pre-dip is not necessarily a process but is preferably used. . The chemicals preferably use sulfuric acid and ammonium chloride mixtures except metal (Pd-Sn) in the catalyst chemicals.

The catalytic process (catalyzing) is, for example, to form a Sn-Pd seed layer on a ceramic substrate, and is composed of _first salt (SnCl ₂ H ₂ O) and palladium chloride (PdCl ₂ ) as main components. The colloidal particles are uniformly electrodeposited on a metal paste filled in a ceramic surface and via holes. Since the non-hydrochloric acid-based catalyst is a wild colloidal solution compared to the high hydrochloric acid catalyst, it is preferable to use a non-hydrochloric acid-based additive to form a fine catalyst to uniformly deposit the electroless copper plating. In addition, the catalyst has a very low concentration and is unstable, so it must be avoided if impurities such as ammonium persulfate, hydrogen peroxide, ferric chloride, ferric chloride, surfactants, direct sunlight, water, etc. are mixed or activated charcoal promotes chemical decomposition. It is desirable to prevent air from entering as much as possible.

The accelerating process is a step of forming activated Pd nuclei by removing Sn introduced during the catalytic process. Sn ⁺² -Pd ⁺² complex salt is adsorbed in the catalizing process, and the complex salt adsorbed in the next washing process is hydrolyzed to coexist with divalent tin ions, Sn (OH) Cl, tetravalent tin and palladium salts. The precipitated first and second tin salts can be dissolved and removed in an accelerating process to generate the activated pure Pd nuclei. If the accelerator treatment is insufficient, it is preferable to treat it sufficiently because unplating occurs during electroless plating, the deposition rate decreases, or the adhesion decreases. The accelerator may be a solution containing an inorganic acid or a base, and hydrochloric acid, sulfuric acid, and hydrofluoric acid may be used as the inorganic acid, and sodium hydroxide may be used as the base. However, when using an accelerator containing an inorganic acid of hydrofluoric acid, It was found that the coating film speed of the plating process was improved. The content of the preferred hydrofluoric acid-based inorganic acid is preferably 0.5 to 10% by weight in the accelerator solution. If the concentration is less than 0.5% by weight, unplating of the electroless nickel film may occur, and when the concentration exceeds 10% by weight, there is a problem in that the surface roughness of the nickel is increased.

In the nickel electroless plating process, the silicon-carbon compound substrate on which the Pd nucleus is formed is immersed in an electroless plating solution containing a nickel salt, a reducing agent, a complexing agent, and the like, and Pd promotes reduction of nickel ions in the plating solution as a catalyst. Precipitating nickel and once the nickel precipitates, the precipitation reaction is continued by the self-catalytic action of the nickel itself as a catalyst. Nickel chloride, nickel sulfate, nickel acetate, and the like are used as the nickel salt, and sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, hydrazine, and the like are used as reducing agents, and complexing with nickel ions as a complexing agent. Although a compound having this is used, in the present invention, by using nitrilotris (methylene) triphosphonic acid (NTPA) as a complexing agent, a more uniform nickel electroless plating film can be formed. The content of the complexing agent is in the range of 1 to 100 g / L, preferably 5 to 50 g / L in the plating liquid.

In the nickel pattern forming method according to the present invention, a nickel thin film having a thickness of 0.1 μm to 10 μm is formed on the silicon-carbon compound substrate pretreated by the pretreatment method as described above using the nickel plating solution. More preferably, the nickel thin film is a nickel-phosphorus alloy thin film.

The step f) is a step of forming a nickel pattern on the nickel-electroless plated silicon-carbon compound substrate, a photolithography process using a photoresist or dry film as a photosensitive polymer to form a photosensitive polymer pattern, Etching the nickel and removing the photosensitive polymer.

The photoresist is applied by a spin coating method, and the dry film is attached to the substrate by heating at a temperature of 60 to 100 ° C. on a substrate on which a nickel electroless plating film is formed using a photosensitive polymer film. Forming a pattern on the photoresist or dry film is performed through the steps of exposing and developing using a mask.

In more detail, a method of using a dry film may include attaching a dry film, attaching a pattern film having a pattern to a substrate with a dry film, exposing a substrate with a PT film, and exposing the substrate. Peeling the dry film of the exposed portion of the substrate.

Etching the nickel after forming the pattern with the photosensitive polymer uses a method of etching and dissolving nickel using a corrosion solution. In the preparation method according to the present invention, the nickel corrosion solution preferably contains HCl and NaClO ₃ , the HCl concentration in the corrosion solution is preferably 0.7 to 1.3 mol / L, and the NaClO ₃ is 5.0 to 99 CAP.

After etching the nickel, the photosensitive polymer is removed to form a nickel pattern. Gold is electroless plated thereon to complete a silicon-carbon compound substrate having a nickel pattern.

The present invention will be described in more detail with reference to the following Examples. However, the following examples are only examples of the present invention, and the scope of the present invention is not limited thereto.

It should be recalled again that the following manufacturing flow of the present invention relates to a method of plating nickel on a silicon-carbon compound substrate to be used as a hot plate.

Preparation Example 1 Preparation of Silicon-Carbon Compound Substrate Plated with Nickel Electroless Plating

Silicon-carbon compound substrate (density: 3.1 g / cm3, bending strength: 490 MPa, hardness: 20 kPa, volume resistivity: 1 x 10 x 8 kcal / cm, thermal conductivity: RT 158 W / mk, size: Φ 315, 3.5 mmt roughness: Ra 0.7 μm) was used to prepare a nickel electroless plated substrate through a pretreatment process. The remaining constituents not described below are deionized water.

The silicon-carbon compound substrate plasma processing equipment (Co. Quaternary South Korea, Plasma Desmear System) under 0.25 Torr by introducing a nitrogen, CF ₄ and oxygen gas, respectively ^{100Kgf / cm 2, 200gf / cm} 2, 1200gf / After injection of cm ² , power was applied (3000 LF / W) to form a plasma, and plasma treatment was performed for 1200 seconds.

In order to remove the surface foreign matter of the plasma-treated silicon-carbon compound substrate, the foreign material on the surface was removed with a brush (0.15 A pressure) by introducing into a front treatment facility (Korea Machinery, Alumina).

The silicon-carbon compound substrate face-treated with the brush was firstly etched using a sodium hydroxide dilution solution containing 200 to 400 g of sodium hydroxide per pure water as an etching solution, and the etching time was maintained for 20 to 40 minutes. The surface roughness arithmetic mean value Ra of the board | substrate was made into the range of 0.6-0.8. In the present invention, the secondary etching was performed as described below separately from the primary etching, which is to introduce a plurality of etching processes for strengthening the adhesion during nickel plating, the silicon during plating through the plurality of etching processes- The desired surface roughness can be obtained to enhance the adhesion of nickel to the surface of the carbon compound, which will be referred to as uniqueness of the present invention.

The primary etched silicon-carbon compound substrate was immersed in a degreasing solution containing 2% by weight of sulfuric acid and 0.1% by weight of nonylphenylpolyethylene oxide at 45 degrees for 6 minutes, washed with water, and then washed with 0.1% by weight of sodium fluoride and fluorinated. Secondary etching was performed for 7 minutes at 45 degrees in an aqueous solution containing 5.0% by weight of ammonium.

In this way, by performing secondary etching, the arithmetic mean value (Ra) of the surface roughness of the silicon-carbon compound was adjusted to 0.6 to 0.8. When the surface roughness was maintained in this way, nickel could be effectively adhered to the surface of the silicon-carbon compound. there was.

Therefore, the surface roughness value of the silicon-carbon compound as described above and the secondary etching process of the present invention for implementing the same constitute a key component of the present invention.

After washing the silicon-carbon compound substrate subjected to the secondary etching process, 0.5% by weight of 3 Sodium trinitro triacetone, 0.3% by weight of lauryltrimethylammonium chloride, 0.3% by weight of triethanolamine and After immersing in a conditioning solution containing 0.1% by weight of polyethylene alkyl ester at 60 ° C for 8 minutes and washing with water, 16% by weight of sodium chloride (NaCl), 3.6% by weight of sodium bisulfate, and ammonium chloride (NH ₄ Cl) Tin chloride and chloride on the surface of the silicon-carbon compound substrate were immersed for 5 minutes at 25 degrees in a catalizing solution containing 0.4% by weight, 0.5% by weight sulfuric acid, 0.5% by weight hydrochloric acid, 1.1% by weight tin chloride and 0.01% by weight palladium chloride. Palladium particles were electrodeposited. The catalyzed silicon-carbon compound was immersed in an aqueous solution containing 0.3% by weight of HF, 1.3% by weight of HBF ₄ and 0.08% by weight of gluconic acid at 25 ° C for 8 minutes to dissolve and remove the tin salt to generate activated Pd nuclei. I was.

The activated silicon in a nickel plating bath in which a solution of nickel sulfate (17.75 wt%), sodium phosphate (10.35 wt%), sodium lactate (11.13 wt%) and pure water (60.77 wt%) was diluted to 100 ml per 1 liter of pure water The carbon compound substrate was immersed for 17 minutes at 83 degrees to form an electroless nickel plated layer having a thickness of about 4 μm. 4 is an optical photograph of a silicon-carbon compound substrate on which a nickel pattern prepared in Preparation Example 1 is formed.

In order to evaluate the adhesion of electroless nickel plating, it proceeded according to the tape test method of the adhesion test method of plating (KSD0254). In the test method, the film was cut to a depth of 1 cm × 1 cm in the center of the electroless copper plated substrate, and then 9 times the film cutting line was inserted into the 1 cm × 1 cm to the depth of contact with the substrate at an interval of 1 mm. 100 grids of 1mm in width and length were made, and the peeling test was carried out by attaching a cello tape on the grid and detaching them. The results are shown in Table 1. (Circle): No peeling, (circle): Peeling is 10 or less, (triangle | delta): Peeling is 10-30, x: It shows that peeling is more than 30.

[Production Example 2]

An electroless nickel plated silicon-carbon compound substrate was prepared in the same manner as in Preparation Example 1, except that the blasting treatment using alumina beads was further performed before the plasma treatment.

[Manufacture example 3]

Electroless nickel-plated silicon was carried out in the same manner as in Preparation Example 1, except that nitrilotris (methylene) triphosphonic acid (NTPA) was added to the nickel plating bath of Preparation Example 1 to be 10 g / L in the plating solution. Carbon compound substrates were prepared.

Comparative Example 1

An electroless nickel plated silicon-carbon compound substrate was prepared in the same manner as in Preparation Example 1, except that the plasma treatment and the front treatment were not performed.

These preparation examples and comparative examples are summarized as shown in Table 1 below, as can be seen from the results below, the adhesion between the substrate prepared according to the method of Preparation Examples 1 to 3 and electroless plated nickel. It is very good and it can be seen that the results of Preparation Examples 2 and 3 are particularly superior.

Pretreatment Peel Test Remarks Blasting plasma face Preparation Example 1 ○ ○ ○ Preparation Example 1 ○ ○ ○ ◎ Preparation Example 1 ○ ○ ○ ◎ In nickel plating solution
Add NTPA Comparative Example 1 X X X △

Example 1

The silicon-carbon compound substrate on which the nickel electroless plating film prepared in Preparation Example 1 was formed was washed with water, dried, and heated to 80 ° C., and then dried film (Morton, thickness of 25 μm, size 350 mm) was 1.0 m at 110 ° C. on a hot roller. After contacting at a speed of / min and attaching a patterned pattern film, and exposed, and exposed by spraying 1% by weight aqueous solution of Na ₂ CO ₃ (pH 10.85) at a speed of 3.0m / min, 2kgf / cm ² pressure Remove it.

After the development process, the silicon-carbon compound substrate is sprayed with a corrosion solution (HCl 1.15 mol / L, NaClO ₃ 35 CAP, specific gravity 1.365) at a speed of 2.5 m / min and a pressure of ³ kgf / cm ² to etch the electroless nickel film. After washing with water and drying, the photosensitive resin was removed with a NaOH solution to prepare a silicon-carbon compound substrate having a nickel pattern.

The nickel patterned substrate was treated with gold (Au) plating solution (high purity chemical company, IM-GOLD-IB) at 83 ° C. for 5 minutes to form an Au electroless plating layer having a thickness of 0.05 μm on the nickel electroless plating layer. As a result of measuring the resistance at 8 points of the substrate for the same pattern of the silicon-carbon compound substrate prepared, the average was found to be 205.6Ω (3.11% of deviation). Nickel pattern of the substrate produced by the manufacturing method according to the invention has the advantage that the pattern width is uniform, the resistance variation is small.

Comparative Example 2

Using a conventional Pd + Ag paste (Sungji Tech, PdAg paste) to form a pattern by the silk screen method, as in Example 1 to prepare a silicon-carbon compound substrate with a pattern formed by plating gold and the same pattern The resistance was measured at 8 points on the board with an average of 242.4 Ω (16.58% deviation). Therefore, compared with Example 1, the variation of resistance was very large and the reliability of the product was evaluated comparatively low.

1 is a process flow diagram showing a process of electroless nickel plating on a silicon-carbon compound substrate according to an embodiment of the present invention,

2 is a process flow diagram illustrating a process of forming a nickel pattern on an electroless nickel plated silicon-carbon compound substrate according to an embodiment of the present invention.

3 is a vertical cross-sectional view of a silicon-carbon compound substrate on which a nickel pattern is formed according to an embodiment of the present invention;

4 is an optical picture of a silicon-carbon compound substrate having a nickel pattern according to an embodiment of the present invention.

Claims (9)

a) plasma treating the silicon-carbon compound substrate surface; b) first etching the surface of the substrate; c) degreasing and second etching the first etched substrate; d) adding a catalyst to the degreased and secondary etched silicon-carbon compound substrate; e) electroless plating nickel on the catalyzed silicon-carbon compound substrate; And f) forming a nickel pattern on the nickel-electroless plated silicon-carbon compound substrate; It is configured to include, The first etching of step b) is performed by using a sodium hydroxide dilution solution containing 200-400 g of sodium hydroxide per pure water as an etching solution and maintaining the etching time for 20 to 40 minutes. A method for producing a carbide ceramic hot plate, characterized in that the surface roughness arithmetic mean value (Ra) of the silicon-carbon compound substrate is in the range of 0.6 to 0.8 by secondary etching. The method of claim 1, before the step a), performing a grit or bead blasting process on the surface of the silicon-carbon compound substrate. 3. The method of claim 2, Removing a foreign substance present on the surface of the silicon-carbon compound substrate after the plasma treatment of step a). The method of claim 1, Step c) and the secondary etching step, Degreasing step of removing contamination of the silicon-carbon compound substrate surface using an organic acid or an inorganic acid; And a secondary etching step of etching the surface of the silicon-carbon compound substrate with 0.5 to 10% by weight of a fluorinated salt solution. The method of claim 4, wherein The fluoride salt solution is a method for producing a carbide ceramic hot plate, characterized in that the NaF and NH ₄ F fluoride salt solution mixed in a weight ratio of 1: 1 to 100. The method of claim 1, The nickel electroless plating is performed by immersing a silicon-carbon compound substrate treated with a conditioning solution in a plating solution containing nitrilotris (methylene) triphosphonic acid (NTPA) as a nickel salt, a reducing agent and a complexing agent. Method for producing a ceramic hot plate. The method of claim 1, Step f), Forming a photoresist pattern on the electroless plated nickel layer using a dry film; Etching nickel using the corrosion solution; And Peeling off the photoresist pattern; Method for producing a carbide ceramic hot plate, characterized in that comprises a. The method of claim 7, wherein The corrosion solution is a method of producing a carbide ceramic hot plate, characterized in that containing HCl and NaClO ₃ . A carbide ceramic hot plate produced by the method of claim 1.

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