JP2005228834A - Electrode embedding member for plasma generator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode embedding member for use of a plasma generator capable of uniformly processing silicon wafers by keeping a plasma density distribution constant in generating the plasma, by applying high frequency to a plasma generating electrode to process the silicon wafer and having high durability against halogen-based corrosive gas. <P>SOLUTION: The electrode embedding member having the plasma generating electrode placed in a ceramic substrate has a surface on at least a wafer holding side with roughness of 0.05-10 μm by surface roughness Ra defined by JIS B 0601. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrode burying member for a plasma generator used for processing a silicon wafer or the like under a plasma generating atmosphere in the field of a semiconductor manufacturing apparatus or the like.

  In general, a semiconductor manufacturing apparatus such as an etching apparatus or a chemical vapor deposition apparatus is provided with a stainless steel heater or an indirect heating heater using infrared rays. However, in the case of semiconductor manufacturing equipment, highly reactive fluorine-based and chlorine-based halogen-based corrosive gases are used as deposition gas, etching gas, and cleaning gas. The heater which reacts with these corrosive gases has a problem of generating particles in the apparatus. In order to solve such a problem, conventionally, the resistance heating element of the heater is embedded in a ceramic substrate.

In such semiconductor manufacturing apparatuses, in many cases, a predetermined treatment is applied to a silicon wafer or the like. At that time, the halogen-based corrosive gas is introduced into the apparatus and plasma is generated. Therefore, as a member to be installed in the apparatus, a material having excellent resistance to corrosion and durability against halogen-based corrosive gas as well as plasma resistance is required. For example, in a conventional plasma generator, a plasma generating electrode and a heater electrode are embedded in a ceramic substrate, and the ceramic substrate is made of aluminum nitride having excellent corrosion resistance and durability against halogen-based corrosive gas and plasma. It is supposed to be used (Patent Document 1). According to Patent Document 2, a wire mesh electrode made of molybdenum (Mo) or tungsten (W) is used as the plasma generating electrode embedded in the ceramic substrate.
JP 2002-329774 A Japanese Patent No.3359582

  In the case where a conventional metal mesh electrode made of molybdenum (Mo) or tungsten (W) is used as a plasma generating electrode, the distance between the electrode and the silicon wafer holding surface (hereinafter referred to as “processed surface”) depends on the location. There is a problem of being different. In other words, the wire mesh electrode is formed by braiding a metal wire, so the distance from the electrode surface to the silicon wafer processing surface of the ceramic substrate is different between the part where the wire intersects and the other part. Become. For example, when processing a silicon wafer by applying a high frequency to such an electrode to process a silicon wafer, when the cations of the reactive gas in the plasma state are directed toward the plasma generating electrode in the ceramic substrate, Like the thunder, the wire moves toward the closest distance, so that the wire of the wire mesh electrode crosses and concentrates on the shortest distance to the silicon wafer processing surface. Due to the above phenomenon due to the presence of such small irregularities, the plasma generation density is not constant, so that uniform processing of the silicon wafer becomes difficult.

  Furthermore, conventionally, when forming a plasma generating electrode member, a conductive paste layer serving as a plasma generating electrode is formed by printing a tungsten carbide (WC) paste on a green sheet or by a punching pattern of a tungsten carbide green sheet. The conductive paste filling layer is formed by filling the portion that becomes the through hole with the conductive paste. Next, the green sheets subjected to these treatments are stacked and fired by hot pressing. At this time, the conductive paste filling layer serving as a terminal deforms the plasma generating electrode, and as a result, the portion becomes a projection having a large uneven shape. Therefore, the cation plasma concentrates on the protrusion having the shortest distance to the silicon wafer processing surface, and this phenomenon makes the plasma density non-uniform, which makes it difficult to uniformly process the silicon wafer. I had it.

  An object of the present invention is to apply a high frequency to a plasma generating electrode, generate plasma, and process a silicon wafer so that the silicon wafer can be processed uniformly by keeping the plasma generation distribution (density) constant. It is another object of the present invention to provide an electrode burying member for a plasma generator having high durability against a halogen-based corrosive gas.

As a result of diligent research on the solution of the above-described problems that the prior art has, the inventors have developed the present invention having the gist configuration described below.
That is, the inventors of the present invention have an electrode embedding member in which an electrode for generating plasma is disposed in a ceramic substrate, and at least the surface on the wafer holding side of the electrode has a surface roughness Ra of 0.05 as defined in JIS B 0601. An electrode embedding member for a plasma generator characterized by having a roughness in the range of ˜10 μm is proposed.

  The plasma generating electrode is preferably formed of conductive carbide ceramics or conductive nitride ceramics.

  Furthermore, the inventors have provided that in the electrode embedding member in which the electrode for plasma generation is disposed in the ceramic substrate, the electrode is provided with protrusions regularly arranged on at least the surface on the wafer holding side. A featured electrode burying member for a plasma generator is also proposed.

  In addition, it is preferable that the protrusion has a height of 100 μm to 200 μm, and the electrode is formed of conductive carbide ceramics or conductive nitride ceramics.

  According to the electrode embedded member for a plasma generator according to the present invention, it is possible to generate a plasma generation distribution (plasma density) uniformly and stably by the electrode embedded in the substrate, and at the same time, halogen-based corrosiveness. An electrode embedding member for a plasma generating apparatus that is excellent in durability against gas and can maintain such quality in a stable state for a long period of time can be provided at low cost.

  As described above, as an electrode burying member used in a halogen-based corrosive gas and a plasma generation atmosphere, a wire mesh electrode has been adopted for the plasma generation electrode embedded therein, but the wire is braided. In this case, the distance between the electrode surface and the silicon wafer processing surface is different (small unevenness) between the portion where the wire intersects and the portion where the wire does not intersect, resulting in non-uniform plasma generation distribution. Also, when electrodes are printed and laminated on a ceramic green sheet and fired by hot pressing, electrode deformation occurs at the terminal connection part, and the distance between the electrode surface and the silicon wafer processing surface is partially different (large unevenness) As a result, there is a problem that the plasma generation distribution becomes non-uniform.

  In this regard, according to the inventors' research, it has been found that it is effective to roughen the surface of the plasma generating electrode as a countermeasure against the former (small unevenness). That is, the surface roughness of the electrode surface is formed in the range of 0.05 to 10 μm, preferably 3 to 10 μm in terms of Ra. More preferably, it is formed in the range of 3 to 5 μm. On the other hand, as a countermeasure against the latter (large unevenness), the plasma generation distribution (density) on the surface of the silicon wafer is controlled by regularly arranging protrusions having a height of 100 μm to 200 μm on the wafer processing surface of the plasma generating electrode. It was kept uniform.

In general, a plasma generating apparatus applies a high-frequency voltage between a plasma generating electrode and another plasma generating electrode separately provided above a wafer processing member when processing a silicon wafer or the like. And a predetermined process is applied to the silicon wafer or the like by supplying a film forming or etching gas. At this time, since the plasma generating electrode side embedded in the ceramic substrate becomes a negative pole, the cations dissociated into a plasma state between the pair of plasma generating electrodes are on the plasma generating electrode side embedded in the ceramic substrate Move towards. At this time, since the cations in the plasma state have the same properties as lightning, they exhibit the property of being concentrated on the closest electrode by the lightning rod effect.
Therefore, if the gap between the electrode for plasma generation embedded in the member and the other electrode for plasma generation installed above the wafer processing surface of the electrode is made constant, the local concentration of plasma is reduced. It can be avoided. The above lightning rod effect is a phenomenon that occurs when the distance difference exceeds about 10 μm on average.

Therefore, in the present invention, the roughened surface provided on the surface of the plasma generating electrode has a surface roughness Ra in the range of 0.05 to 10 μm, preferably 3 to 3 in terms of surface roughness Ra specified in JIS-B 0601. It was decided to form in the range of 10 μm, more preferably 3-5 μm. Instead of this, in the present invention, large protrusions having a height of about 100 μm to 200 μm are intentionally provided on the entire processed surface of the electrode wafer in a regular and uniform arrangement. In this way, it is possible to control the extreme lightning rod effect of plasma by subjecting the electrode surface to a roughening treatment or intentionally providing a protrusion.
In addition, although it is an idea about a protrusion, by making this into the height of the above-mentioned range and making it a regular and uniform arrangement on the entire plate surface, the lightning rod effect is actively used, thereby sporadic. By making the lightning rod effect inconspicuous, the plasma generation distribution is made uniform on the contrary.

  In the present invention, the surface of the plasma generating electrode is controlled to a roughness of about 10 μm or less in terms of average roughness (Ra). Surface roughening methods include, for example, 400 mesh, wire diameter 0.018 (mm), 400 mesh, wire diameter 0.023 (mm), 350 mesh, wire diameter 0.025 (mm), 325 mesh, wire diameter 0.028 (mm), 300 There is a method of printing a conductive paste on a ceramic green sheet by a screen printing method using a stainless steel screen having a mesh, a wire diameter of 0.030 (mm), 270 mesh, and a wire diameter of 0.035 (mm). When screen printing is performed using the mask formed of the mesh and the wire diameter, a mesh mark remains on the printed surface after the conductive paste is printed. This mark forms irregularities in the range of 0.05 to 10 μm after lamination and sintering by a hot press method.

  Moreover, about the large protrusion 12b with a height of 100-200 micrometers arranged regularly on the surface, the hole of 3.3 mm in diameter is formed by punching in the ceramic green sheet of thickness 150-250 micrometers, and the electrode for plasma generation in this hole When the ceramic paste of the same composition is filled and a laminated body is formed, it is laminated on the plasma generating electrode green sheet and fired, so that the surface of the plasma generating electrode has a height of 100 to 200 μm and a diameter of 3 mm. Protrusions are formed.

  By the way, in the conventional electrode embedding member used in a halogen corrosive gas and a plasma generation atmosphere, for example, a member having C-containing aluminum nitride as a ceramic substrate, the contained C and the electrode embedded in the ceramic substrate, for example, for plasma generation Mo and W, which are constituent materials of the electrode, react and generate carbides when exposed to high temperatures. As a result, the volume resistivity of the member is increased and the plasma density becomes non-uniform. In this regard, in the present invention, conductive ceramics are employed as the material constituting the plasma generating electrode. Thus, when the conductive ceramic is used as the substrate material, the increase in the volume resistivity can be suppressed.

  In other words, conductive ceramics have low reactivity with carbon (C), so that even when used for a long time at firing or above 500 ° C. (temperature of plasma CVD film formation) This is because the contained C does not react and the resistance value hardly changes with time. Among these, conductive carbide ceramics are characterized by being able to maintain the plasma density stably and uniformly over a long period of time because they are pre-carburized and do not react with C and there is no change in resistance value over time. .

In addition, when a metal such as Mo or W is used as the electrode as in the conventional case, the lattice vibration of the metal rapidly increases as the temperature rises, so that the free movement of electrons is hindered. . As a result, when the volume resistivity is increased and the voltage is constant, there is a problem that the current flow rate is decreased and it is difficult to increase the temperature.
On the other hand, in the case of conductive ceramics, particularly conductive carbide ceramics, the volume resistivity decreases as the temperature increases, so that a large current can be input at a high temperature, and plasma is easily generated. Therefore, the conductive carbide ceramic is advantageous as a plasma generating electrode used at a high temperature of 200 ° C. or higher.

  The conductive ceramics preferably has a particle size of 0.1 to 10 μm. This is because if the thickness is less than 0.1 μm, oxidation tends to occur. On the other hand, if it exceeds 10 μm, it becomes difficult to sinter and the resistance value increases. In addition, the definition of this particle size defines the range of the minimum minor axis and the maximum major axis in an arbitrary two-dimensional sectional view as described above.

  From the above, in the present invention, it is preferable to embed a plasma generating electrode made of conductive carbide ceramics in an insulating nitride ceramic substrate. Insulating nitride ceramics used as a substrate have excellent heat resistance and mechanical properties, as well as excellent corrosion resistance and durability against halogen-based corrosive gases and plasmas, as well as high thermal conductivity and excellent temperature followability. . In addition, since this insulating nitride ceramic has a thermal expansion coefficient close to that of the conductive ceramic electrode to be embedded, the occurrence of cracks due to thermal shock does not occur. In addition, this insulating nitride ceramic has a higher volume resistivity at high temperatures than that of insulating carbide ceramics, so that a large current flows without causing an electrical short circuit. And plasma can be generated uniformly. In this sense, in the present invention, it is preferable to use conductive carbide ceramics as the material for the plasma generating electrode for the insulating nitride ceramic substrate.

  In the present invention, a heater electrode may be embedded in the nitride ceramic substrate together with the plasma generating electrode. The reason is that the electrode can be prevented from being exposed to a corrosive plasma gas atmosphere, and the temperature can be controlled more quickly when it is inside the ceramic substrate.

  For the plasma generating electrode used in the present invention, it is desirable to use a sintered body obtained by firing particles of tungsten carbide (tungsten carbide). The size of the tungsten carbide particles as the raw material is one having a particle diameter in the range of 1 μm to 10 μm in an arbitrary two-dimensional sectional view, for example, a sectional view in the thickness direction of the ceramic substrate (minimum minor diameter: 1 μm, maximum Long diameter: 10 μm) is desirable. The reason is that when the particle size is less than 1 μm, it is highly reactive and easily oxidizes, so it reacts with oxygen in the ceramic substrate during use, resulting in a high resistance value. This is because the crystallinity is lowered, the resistance value is still high, and the current density in the electrode varies and uniform plasma cannot be generated.

  In the present invention, the thickness of the ceramic substrate is preferably about 5 mm to 20 mm. If the reason is less than 5 mm, the strength of the ceramic substrate itself is lowered, so that the ceramic substrate is easily damaged. On the other hand, if it exceeds 20 mm, the temperature responsiveness in the ceramic substrate deteriorates, and the temperature cannot be controlled.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a partial cross-sectional view showing an example of an electrode embedding member for a plasma generator according to the present invention. As shown in this figure, an electrode embedding member 10 of a plasma generator having a configuration suitable for the present invention mainly comprises a ceramic substrate 11 and a plasma generating electrode 112 embedded in the substrate 11. It is.
Further, if necessary, a ceramic terminal protection cylinder 17 is bonded to this member on the bottom surface (surface opposite to the wafer processing surface) 11b of the substrate, while the upper surface of the ceramic substrate 11 is connected. (Processing surface) 11a is formed with a plurality of convex portions 11c for supporting the front wafer, and further, a heater electrode 12 is embedded in the ceramic substrate 11, and at the end of the heater electrode 12, It is preferable to form a through hole 13 and a bag hole for exposing the through hole 13 to the substrate bottom surface 11b.

Further, another through hole 113 and a bag hole for exposing the through hole 113 to the substrate bottom surface 11b are also formed immediately below the end of the plasma generating electrode 112. These through holes 13 and 113 are connected to the external terminal 23 through a brazing material layer (not shown).
Here, the through hole refers to a hole in which a conductor is formed on an inner wall portion of a hole used for electrically connecting a plasma generating electrode, a heater electrode, an electrostatic electrode and the like to an external terminal.

  In the plasma generator 10 shown in FIG. 1, the heater electrode 12 embedded in the ceramic substrate 11 shows a circuit example in which the heater electrode 12 is continuously arranged concentrically from the vicinity of the center of the substrate toward the outer periphery. In this example, the end of is formed near the center of the ceramic substrate 11.

  When the above-mentioned electrode burying member for a plasma generator is used in a semiconductor manufacturing apparatus, the ceramic substrate 11 is usually in a support container having a bottom plate, and the surface opposite to the terminal protection cylinder 17 is in close contact with the bottom plate. To be fixed. Thereby, the inner side and the outer side of the terminal protection cylinder 17 are isolated in an airtight state, and even if the periphery of the ceramic substrate 11 is exposed to a corrosive gas atmosphere such as a reactive gas or a halogen gas, the terminal The external terminals 23 and the like housed inside the protective cylinder 17 are not corroded even if they are in direct contact with the corrosive gas. In addition, since the terminal protection cylinder 17 also functions to firmly support the ceramic substrate 11, even when the ceramic substrate 11 is heated to a high temperature, it is not warped by its own weight. As a result, damage to the heated object such as a semiconductor wafer can be prevented, and the heated object can be heated to a uniform temperature.

  In addition, it is desirable that the lead wire 26 connected to the temperature measuring element 180 is also accommodated in the terminal protection cylinder 17. If the lead wire 26 is provided outside the terminal protection cylinder 1, it is desirable to protect the lead wire 26 with an insulator or the like in order to prevent corrosion caused by a reactive gas or a halogen gas.

  In the present invention, as one structure of the plasma generating electrode 112, in the case of a single layer, on the wafer processing surface side, in the case of a plurality of layers as shown in FIG. As described above, the surface side is a rough surface 112a that is small unevenness. Furthermore, in the present invention, as another structure of the plasma generating electrode 112, in the case of a single layer, the wafer processing surface side is at least the uppermost layer in the case of a plurality of layers as shown in FIG. On the wafer processing surface side, a projection 112b made of large irregularities as described above is formed. The material of the electrode 112 is preferably composed of conductive ceramics. As the conductive ceramic, for example, a metal that has already become tungsten carbide or molybdenum carbide is used as an electrode material, not a metal that has been carbonized by firing during use. These conductive ceramics may be used alone or in combination of two or more. Among these, tungsten carbide is more preferable.

  As for the arrangement of the plasma generating electrode 112 made of the conductive ceramic, the roughness top of the roughened surface 112 is preferably about 5 μm to 300 μm in distance from the projection top. In the present invention, the measured value of the thickness of the electrode layer is obtained by cutting the ceramic substrate 11 in which the plasma generating electrode is embedded in a direction perpendicular to the wafer processing surface, and the plasma generating electrode observed at that time. In order to prevent the variation of the boundary between the boundary and the ceramic substrate depending on the location, arbitrary 10 points are measured and the average value is used. If this thickness is less than 5 μm, the degree of variation in the thickness of the electrode layer is greatly affected, so that the variation in resistance value is large and the plasma distribution is not constant, so the vapor phase growth surface formed on the wafer surface The thickness variation of becomes large. On the other hand, if it exceeds 300 μm, cracks occur at high temperatures.

  As a method of forming the plasma generating electrode layer, it is preferable to use a conductor green sheet or a conductor paste. In the case of a conductor green sheet, it is desirable that the conductor green sheet is punched into a pattern, and then laminated on an insulating green sheet serving as a ceramic substrate and fired. The conductor green sheet contains conductive ceramic particles, and may contain various resins, solvents, thickeners and the like.

  Examples of the resin used for the green sheet include an epoxy resin and a phenol resin. Examples of the solvent include isopropyl alcohol. Examples of the thickener include cellulose. Can be used, but is not limited to these examples.

  In addition, when a conductive paste is employed when forming the plasma generating electrode layer made of the conductive ceramic, a conductive paste layer is formed on the insulating ceramic green sheet using a screen printing method. Thereafter, another ceramic green sheet that is not printed is further laminated and fired, whereby the plasma generating electrode layer can be embedded in the ceramic substrate.

  The conductive ceramic paste preferably contains various resins, solvents, thickeners, and the like in addition to the conductive ceramic particles in order to use a screen printing method. As the resin, for example, an epoxy resin, a phenol resin, or the like is used. As the solvent, for example, isopropyl alcohol or the like is used. As the thickener, for example, cellulose or the like is used. It is not limited to.

  In the electrode embedding member of the present invention, an electrostatic electrode may be further formed on the ceramic substrate 11 in addition to the plasma generating electrode 112. In this case, the plasma generating apparatus includes a heating unit. Functions as an electrostatic chuck.

  In the electrode embedding member of the present invention, the ceramic material constituting the ceramic substrate 11 (in addition, silicon carbide exhibits insulating properties when the purity is high, while it is conductive due to the conductivity of carbon when the purity is low. Therefore, it is desirable to use high-purity silicon carbide when used as the ceramic substrate, for example, nitride ceramics, carbide ceramics, oxide ceramics, etc. can be used. Examples of the nitride ceramics include aluminum nitride, silicon nitride, boron nitride, titanium nitride and the like. Examples of the carbide ceramic include silicon carbide, zirconium carbide, boron carbide, titanium carbide, tantalum carbide, and tungsten carbide. Examples of the oxide ceramic include alumina, silica, cordierite, mullite, zirconia, and beryllia. These ceramic materials may be used alone, or may be a mixture of two or more.

  Among these, it is desirable to use nitride ceramics or carbide ceramics. The reason is that nitride ceramics and carbide ceramics have a smaller coefficient of thermal expansion than metals and have a much higher mechanical strength than metals. Therefore, even if the thickness of the ceramic substrate is reduced, it is warped or distorted by heating. This is because the ceramic substrate can be made thin and light. Also, since the ceramic substrate has high thermal conductivity, if the thickness is reduced, the substrate surface temperature quickly follows the temperature change of the heater electrode when the temperature of the heater electrode is changed by changing the voltage and current amount. Temperature control becomes easy. It is more preferable to use nitride ceramics for the substrate. The reason is that nitride ceramics are excellent in heat resistance and mechanical properties and have high thermal conductivity, and aluminum nitride is particularly preferable. This is because aluminum nitride has a high thermal conductivity of 180 W / m · K at room temperature, and the temperature followability of the ceramic substrate is most excellent.

It is preferable to use a ceramic substrate containing a sintering aid. As the sintering aid, for example, an alkali metal oxide, an alkaline earth metal oxide, a rare earth oxide, or the like is used. Among these, the use of CaO, Y ₂ O ₃ , Na ₂ O, Li ₂ O, Rb ₂ O is desirable.

  The ceramic substrate preferably contains 200 ppm or more of carbon. The reason is that such a ceramic substrate can accurately measure the surface temperature through the measurement of brightness (N) by a thermoviewer. Here, the brightness N is an ideal black brightness of 0, an ideal white brightness of 10, and the perception of the brightness of the color between these black brightness and white brightness. Each color is divided into 10 so as to have a uniform rate, and is displayed with symbols N0 to N10.

  The ceramic substrate 11 preferably has a porosity of 5% or less. The reason is that it is possible to suppress a decrease in thermal conductivity and warpage at high temperatures. The porosity can be measured by the Archimedes method.

  2 (a) to 2 (c) are plan views showing the shape of the plasma generating electrode embedded in the electrode generating member for a plasma generating apparatus of the present invention. FIG. 2 (a) is a circular plane type plasma. Examples of generating electrodes, shown in FIGS. 2 (b) and 2 (c), generate a plasma having a mesh pattern formed by regularly drilling circular or square openings 112h in a circular plane type. It is an example of the electrode for use.

  2B and 2C is a planar electrode layer made of a plate-like body having a large number of openings 112h. In addition to the rough surface 112a and the protrusion 112b, a large number of electrodes are used. Since these openings 112h have a synergistic effect, the ceramic particles flow when the ceramic green sheets are laminated, and the bonding strength of the ceramic is improved and the strength is improved. Further, due to the difference in thermal expansion coefficient between the ceramic substrate 11 and the plasma generating electrode 112, stress may be generated in the vicinity of the contact portion and the ceramic substrate 11 may be damaged. However, when the opening 112h is provided, the stress is dispersed. Therefore, it is useful in that the above risk is avoided.

  The electrode for a plasma generator shown in FIG. 2C is a mesh mesh, and the aperture ratio is adjusted to about 4 to 40%. The surface may be a rough surface having an average surface roughness (Ra) of about 8 μm by screen printing, or a protrusion 112b may be formed in some cases.

  FIG. 3 shows a multilayer structure in which a plurality of plasma generator electrodes 112 are stacked in a ceramic substrate 11. In general, when a high frequency is applied to a plasma generating electrode, it is difficult for the high frequency to flow if the layer thickness of the electrode is thin. Occur. Therefore, there is a possibility of causing damage to the ceramic substrate. Therefore, it is advantageous in that such a problem can be avoided by using a multilayer structure of two or more layers.

  FIG. 4 is a cross-sectional view showing a form in which the circular plasma generating electrode 112 and the like are divided into a plurality of parts.

  It should be noted that when the heater electrode is embedded in the ceramic substrate, it is desirable that at least one layer is embedded at a position from the bottom surface of the substrate to 60% in the thickness direction. The reason is that heat diffuses well during propagation to the heating surface, and it is easy to make the temperature distribution on the heating surface uniform.

A conductive ceramic pad (through hole) is connected to the plasma generating electrode 112 and the heater electrode 113, and a metal (W, Mo) external terminal receiver is further connected to the pad. The external terminal receiver is provided with a screw on the outer peripheral portion that contacts the ceramic pad, and the external terminal receiver and the ceramic are joined and fixed via the screw. A screw is also formed on the external terminal receptacle, and this screw is screwed onto a Ni electrode that is a power supply terminal.
The ceramic substrate 11 is preferably provided with a bottomed hole drilled toward the heating surface on the bottom surface, and a temperature measuring element such as a thermocouple is attached to the bottomed hole. The temperature of the heater electrode can be measured by this temperature measuring element, and the temperature can be controlled by changing the voltage and current based on the data.

  In the present invention, as shown in FIG. 1, it is desirable that a through hole 15 for inserting a lifter pin (not shown) is provided in a portion away from the center of the ceramic substrate. The lifter pins can be moved up and down by placing an object to be heated such as a semiconductor wafer on the lifter pins, so that the semiconductor wafer can be transferred to a transfer machine (not shown) or transferred. A semiconductor wafer is received from a machine.

  A plurality of projections (but different from the projections 112b provided on the electrodes) 11c for supporting the wafer are formed on the surface of the ceramic substrate on the wafer processing surface side by embossing. In addition, the surface of the protrusion 11c may be roughened by blasting. In addition, by supporting the semiconductor wafer on the processed surface of the substrate through the protrusions 11c formed on the substrate, the wafer or the like can be held at a distance of 10 to 300 μm from the processed surface. .

  The terminal protection cylinder 17 is substantially cylindrical, but the outer wall contour shape in a cross section perpendicular to the wall surface of the cylinder is preferably, for example, circular, elliptical, polygonal or the like. Usually, since the ceramic substrate has a disk shape, it is desirable that the contour shape of the outer wall in the cross section of the ceramic body is circular.

  Hereinafter, a method for manufacturing an electrode embedding member for a plasma generator according to the present invention will be described with reference to FIG. 5 showing an example of a manufacturing method centering on a portion of the plasma generating device 10, particularly an electrode embedding member.

(1) Green Sheet Production Step First, a ceramic powder is mixed with a binder, a solvent, and the like to prepare a paste, which is formed into a sheet shape by a doctor blade method, and a green sheet 110 is produced. As the ceramic powder, aluminum nitride or the like can be used, and if necessary, a sintering aid such as yttria, a compound containing Na, Ca, or the like may be added. The binder is preferably at least one selected from the group consisting of an acrylic binder, ethyl cellulose, butyl cellosolve, and polyvinyl alcohol. As the solvent, α-terpineol and / or glycol is desirable.

  The thickness of the green sheet 110 is preferably about 0.1 to 2.0 mm, and a predetermined portion of the green sheet 110 to be a through hole for connecting to the heater electrode and the plasma generating electrode is formed, or the green sheet is preliminarily formed. A through-hole or a bottomed hole may be formed after the laminate is prepared and fired.

(2) Step of Printing Tungsten Carbide Paste on Green Sheet A conductor paste layer 122 that becomes a plasma generating electrode 112 by printing a tungsten carbide (WC) paste on the green sheet 110 or punching out the tungsten carbide green sheet in a pattern. And a portion of the through hole that is filled with a conductive paste forms a conductive paste filling layer 133. Then, a heater electrode (carbonized WC heating element pattern layer) 12 formed by punching a tungsten carbide (WC) green sheet is sandwiched between the green sheets 110, and a tungsten carbide (WC) heater electrode pattern layer 120 serving as the heater electrode 12 is formed. The conductive paste filling layer 130 filled in the end portion and the portion that becomes the through hole is printed and formed, and the conductive paste is printed thereon to form the conductive paste layer 122 that becomes the high-frequency electrode 112, A conductor paste filling layer 133 is formed by filling a portion to be a through hole with a conductor paste.
At this time, the conductor paste layer 120 to be the heater electrode 12 is printed so that the end portion of the conductor paste layer 120 is filled with the conductor paste filling layer 130 filled in the through hole, and the conductor paste layer to be the plasma generating electrode 112. The layer 122 is printed so that the end portion of the layer 122 and the conductor paste filling layer 133 filled in the portion to be the through hole overlap. As these conductor pastes, those containing metal particles or conductive ceramic particles are preferably used.

  As said metal particle, a tungsten carbide particle, a molybdenum carbide particle, etc. are preferable, and those with an average particle diameter of 0.1-10 micrometers are preferable. The reason is that when the particle size is less than 0.1 μm or exceeds 10 μm, it is difficult to print the conductor paste.

  Examples of such a conductive paste include 85 to 87 parts by weight of metal particles or conductive ceramic particles; 1.5 to 10 parts by weight of at least one binder selected from the group consisting of acrylic, ethyl cellulose, butyl cellosolve, and polyvinyl alcohol; A composition (paste) in which 1.5 to 10 parts by weight of a solvent composed of α-terpineol and / or glycol is mixed can be used. The conductor paste used for the conductor paste filling layers 130 and 133 filled in the portions to be through holes and the conductor paste used for the conductor paste layers 120 and 122 may have the same composition or different compositions. A thing may be used.

  Next, the process of roughening the plasma generating electrode will be described. When roughening the surface of the electrode for plasma generation to Ra: 0.05-10μm, 400 mesh, wire diameter 0.018 (mm), 400 mesh, wire diameter 0.023 (mm), 350 mesh, wire diameter 0.025 (mm) , 325 mesh, wire diameter 0.028 (mm), 300 mesh, wire diameter 0.030 (mm), 270 mesh, wire diameter 0.035 (mm), 200 mesh, wire diameter 0.040 (mm), 120 mesh, wire diameter 0.080 (mm) A method of printing a conductive paste on a ceramic green sheet by a screen printing method using a stainless steel screen or the like. When screen printing is performed using the mask formed of the mesh and the wire diameter, a mesh mark remains on the printed surface after the conductive paste is printed. These marks become irregularities in the range of 0.05 to 10 μm after lamination and sintering by a hot press method. In addition, in order to form a large protrusion 112b, a hole having a diameter of 3.3 mm is formed in a ceramic green sheet having a thickness of 150 to 250 μm by punching, and this hole is filled with a ceramic paste having the same composition as the plasma generating electrode. When the body is formed, a projection having a height of 100 to 200 μm and a diameter of 3 mm is formed on the surface of the plasma generating electrode by laminating and firing on the plasma generating electrode green sheet.

(3) Green sheet laminating process A laminating process for embedding a plasma generating electrode having a surface roughness of 10 μm or less is performed by forming an electrode pattern on a green sheet 110 on which a conductive paste layer 122 to be a plasma generating electrode 112 is screen-printed. In the illustrated example, the green sheet 110 in which no layer is formed is laminated in two layers, and on the other hand, the green sheet 110 in which only the conductive paste filling layer 133 that becomes the connection conductor 113 is formed under the green sheet 110 is illustrated in the illustrated example. Overlay two layers.
Further, a green sheet 110 on which the heater electrode 12 pattern layer 120 is formed is further superimposed under the green sheet 110, and a conductive paste filling layer 130, preferably a cylindrical body, is further formed thereunder. A sheet 110 is laminated, and a green sheet 110 that has not been processed is further laminated thereon (FIG. 5A).

In addition, the stacking step of embedding the plasma generating electrode having large protrusions is performed by projecting into a hole having a thickness of 150 to 250 μm and a diameter of 3.3 mm on the green sheet 110 on which the conductive paste layer 122 to be the plasma generating electrode 112 is formed. The ceramic green sheet 110 filled with the conductive paste for use is laminated, and the green sheet 110 on which only the conductive paste filling layer 133 is formed is overlaid thereon.
Further, a green sheet 110 on which the heater electrode 12 pattern layer 120 is formed is overlaid on the green sheet 110, and further on the green sheet 110, a conductor paste filling layer 130, preferably a cylindrical body, is formed. A sheet 110 is laminated, and a green sheet 110 that has not been processed is further laminated thereon (FIG. 5 (a) ′).

  In the above example, the number of green sheets 110 to be laminated on the upper side of the green sheet 110 on which the conductive paste layer 120 is formed is larger than the number of green sheets 110 to be laminated on the lower side, so You may make it eccentric in the direction of a bottom face side. Specifically, it is desirable that the upper green sheet 110 is stacked on the order of 20 to 50, and the lower green sheet 110 is stacked on the order of 10 to 50.

(4) Baking process of green sheet laminated body Next, the green sheet laminated body is pressurized and heated to bake the green sheet 110 and the conductive paste layers 120 and 122 serving as the internal plasma generating electrode and heater electrode. Then, the ceramic substrate 11, the heater electrode 12, which is a resistance heating element, the plasma generating electrode 112, the through holes 13, 113, and the like are manufactured (FIG. 5B).
A desirable lower limit of the heating temperature for the firing is 1000 ° C., and a desirable upper limit is 2100 ° C. Heating is performed in an inert gas atmosphere or in a vacuum. As the inert gas, for example, argon, nitrogen or the like can be used. A desirable lower limit of the pressure of pressurization is 10 MPa, and a desirable upper limit is 20 MPa.

  A portion to be a through hole into which a lifter pin for transporting an object to be heated such as a semiconductor wafer is inserted is formed after the green sheets 110 are laminated and fired. Formation is performed by drilling. Next, the bag hole 19 is formed in the bottom surface 11b of the ceramic substrate 11 by drilling.

(5) Manufacturing process of substantially cylindrical terminal protection cylinder Ceramic powder, such as aluminum nitride powder, is put in a substantially cylindrical forming mold and is cut as necessary. The substantially cylindrical ceramic body 17 is manufactured by sintering at ˜2100 ° C. and normal pressure. At this time, it is desirable that the substantially cylindrical ceramic body to be manufactured is substantially cylindrical. The heating for the sintering is performed in an inert gas atmosphere or in a vacuum. As the inert gas, for example, argon, nitrogen or the like can be used. Next, the end surface of the ceramic body 17 is polished and flattened.

(6) Joining process of ceramic substrate and ceramic body In a state where the end surface of the terminal protection cylinder 17 is in contact with the vicinity of the center of the bottom surface of the ceramic substrate 11, the ceramic substrate 11 and the terminal protection cylinder 17 are heated, Join. At this time, the ceramic body 17 is joined to the bottom surface of the ceramic substrate 11 so that the through holes 13 and 113 in the ceramic substrate 11 are accommodated inside the inner diameter of the ceramic body 17 (FIG. 5C).

  As a method for joining the ceramic substrate 11 and the terminal protection cylinder 17, for example, the sintering aid is set so that the concentration of the sintering aid inside the ceramic substrate 11 and the concentration of the sintering aid inside the terminal protection cylinder 17 are different. It can be said that the method of containing an agent and bringing them into contact at the joining position and then joining them by heating is a preferred method because the joining strength between the ceramic substrate 11 and the terminal protection cylinder 17 is excellent. In this case, the sintering aid moves from a member having a high concentration of sintering aid to a member having a low concentration, and particles grow across the interface to form a firm joint surface.

Moreover, as another method of joining the ceramic substrate 11 and the terminal protection cylinder 17, for example,
a. A method (diffusion bonding) in which a solution containing a sintering aid for a ceramic material constituting these is applied to the bonding surfaces of the ceramic substrate 11 and the terminal protection cylinder 17 and fired,
b. A method of firing the ceramic substrate 11 and the terminal protection cylinder 17 after applying a ceramic paste whose main component is the same as that of the ceramic constituting the ceramic substrate 11 and the terminal protection cylinder 17;
c. Brazing using gold brazing, silver brazing, etc.
d. A method of bonding using an adhesive such as oxide glass,
Etc.

(7) Attaching an external terminal or the like A pin 19a with a tungsten screw is screwed into a bag hole 19 formed inside the terminal protection cylinder 17 through a brazing material 19c, and a Ni rod 19b with a brazing material is pinned with a tungsten screw. (Fig. 6) and then heated to 900-1100 ° C.

  Further, a thermocouple 26 or the like as a temperature measuring element is inserted into the bottomed hole 14 formed in the bottom surface of the ceramic substrate 11, and the manufacture of the electrode embedding member 10 of the present invention is completed.

(Example 1)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, the green sheet was dried at 80 ° C. for 5 hours, and then a portion to be a through hole was formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment of (1), the above-mentioned conductor paste is screen-printed using a 400 mesh mask with a wire diameter of 0.018 mm and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut out into a 330 mm disk shape, and a ceramic plate-like body having a heater electrode with a thickness of 25 μm and a width of 10 mm inside and a through hole with a surface roughness of 2 μm on the surface of the plasma generating electrode was obtained.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.

(Example 2)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, the green sheet was dried at 80 ° C. for 5 hours, and then a portion to be a through hole was formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment in (1), the above-mentioned conductor paste is screen-printed using a mask of 350 mesh and wire diameter of 0.025 mm, and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut out into a 330 mm disk shape, and a ceramic plate-like body having a heater electrode with a thickness of 25 μm and a width of 10 mm inside and a through hole with a surface roughness of 2 μm on the surface of the plasma generating electrode was obtained.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.

(Example 3)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, the green sheet was dried at 80 ° C. for 5 hours, and then a portion to be a through hole was formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment of (1), the above-mentioned conductor paste is screen-printed using a 400 mesh mask with a wire diameter of 0.023 mm, and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut out into a 330 mm disk shape, and a ceramic plate-like body having a heater electrode with a thickness of 25 μm and a width of 10 mm inside and a through hole with a surface roughness of 2 μm on the surface of the plasma generating electrode was obtained.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.

Example 4
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, the green sheet was dried at 80 ° C. for 5 hours, and then a portion to be a through hole was formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment of (1), the above-mentioned conductor paste is screen-printed using a mask of 325 mesh and wire diameter of 0.028 mm, and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut out into a 330 mm disk shape, and a ceramic plate-like body having a heater electrode with a thickness of 25 μm and a width of 10 mm inside and a through hole with a surface roughness of 2 μm on the surface of the plasma generating electrode was obtained.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.

(Example 5)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, the green sheet was dried at 80 ° C. for 5 hours, and then a portion to be a through hole was formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment of (1), the above-mentioned conductor paste is screen-printed using a 300 mesh mask with a wire diameter of 0.030 mm, and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut out into a 330 mm disk shape, and a ceramic plate-like body having a heater electrode with a thickness of 25 μm and a width of 10 mm inside and a through hole with a surface roughness of 2 μm on the surface of the plasma generating electrode was obtained.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.

(Example 6)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, the green sheet was dried at 80 ° C. for 5 hours, and then a portion to be a through hole was formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment of (1), the above-mentioned conductor paste is screen-printed using a mask of 270 mesh and wire diameter of 0.035 mm, and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut out into a 330 mm disk shape, and a ceramic plate-like body having a heater electrode with a thickness of 25 μm and a width of 10 mm inside and a through hole with a surface roughness of 2 μm on the surface of the plasma generating electrode was obtained.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.

(Example 7)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, after the green sheet was dried at 80 ° C. for 5 hours, 10 portions or the like that would become through holes with a diameter of 3 mm were formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment in (1) above, the above-mentioned conductor paste is screen printed using a mask of 200 mesh and wire diameter of 0.040 mm, and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut into a 330 mm disk shape, and a ceramic electrode having a heater electrode with a thickness of 25 μm and a width of 10 mm inside and a through hole with a surface roughness of 10 μm on the surface of the plasma generating electrode was obtained.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Example 8)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of alcohol composed of 1 part by weight and 1-butanol and ethanol were mixed, molding was performed by a doctor blade method to produce green sheets having thicknesses of 0.47 mm and 0.15 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching on a green sheet having a thickness of 0.47 mm in order to form external terminals.
(3) Further, 50 circular through holes having a diameter of 3.3 mm were formed by punching a 150 μm thick green sheet dried at 80 ° C. for 5 hours to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle diameter of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled into a through hole provided to form a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, 150 μm protrusions were formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, and a 100 μm protrusion is formed on the surface of the plasma generating electrode, and a ceramic plate having a through hole It was.
(9) Next, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the nickel electrode rod on the surface of the ceramic plate-like body A hole was formed.
(10) Blasting was performed on the wafer processing surface of the electrode embedding member manufactured by the steps (1) to (9) so that the roughness (Ra) was 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

Example 9
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce green sheets having a thickness of 0.47 mm and 0.17 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Further, a green sheet having a thickness of 170 μm dried at 80 ° C. for 5 hours was formed by punching 50 circular through-holes having a diameter of 3.3 mm in order to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to form a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for heater electrodes. (5) Average particle diameter of 3 μm A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of molybdenum carbide particles, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of an α-terpineol solvent, and 0.2 parts by weight of a dispersant. Further, a conductive paste was filled into a through hole provided to form a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. In this way, a 170 μm protrusion was formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk shape, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, a 120 μm protrusion formed on the surface of the plasma generating electrode, and a ceramic plate having a through hole It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Example 10)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce green sheets having a thickness of 0.47 mm and 0.20 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Further, a green sheet having a thickness of 200 μm dried at 80 ° C. for 5 hours was formed by punching 50 circular through-holes having a diameter of 3.3 mm in order to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle diameter of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled into a through hole provided to form a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, 200 μm protrusions were formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk shape, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, a 150 μm protrusion formed on the surface of the plasma generating electrode, and a ceramic plate having a through hole It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Example 11)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce green sheets having a thickness of 0.47 mm and 0.22 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Further, a green sheet having a thickness of 220 μm dried at 80 ° C. for 5 hours was formed by punching 50 circular through holes having a diameter of 3.3 mm in order to form the electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A plasma paste electrode conductive paste was prepared by mixing 100 parts by weight of titanium nitride particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
Further, a conductive paste was filled into a through hole provided to form a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, a projection of 220 μm was formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut into a disk shape of 330 mm, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, and a projection of 180 μm is formed on the surface of the plasma generating electrode, and a ceramic plate having a through hole It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Example 12)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce green sheets having a thickness of 0.47 mm and 0.25 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Further, a green sheet having a thickness of 250 μm dried at 80 ° C. for 5 hours was formed by punching 50 circular through holes having a diameter of 3.3 mm in order to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle diameter of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled into a through hole provided to form a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, 200 μm protrusions were formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk shape, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, and a 200 μm protrusion formed on the surface of the plasma generating electrode, and a ceramic plate-like body with a through hole It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Comparative Example 1)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of alcohol composed of 1 part by weight and 1-butanol and ethanol were mixed, molding was performed by a doctor blade method to produce green sheets having thicknesses of 0.47 mm and 0.15 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching on a green sheet having a thickness of 0.47 mm in order to form external terminals.
(3) Further, 50 circular through holes having a diameter of 3.3 mm were formed by punching a 150 μm thick green sheet dried at 80 ° C. for 5 hours to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle diameter of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled into a through hole provided to form a protrusion on the surface of the plasma generating electrode to form a filling layer.
As a result, the electrode surface had a surface roughness of Ra: about 150 μm.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, 150 μm protrusions were formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, and a 100 μm protrusion is formed on the surface of the plasma generating electrode, and a ceramic plate having a through hole It was.
(9) Next, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the nickel electrode rod on the surface of the ceramic plate-like body A hole was formed.
(10) Blasting was performed on the wafer processing surface of the electrode embedding member manufactured by the steps (1) to (9) so that the roughness (Ra) was 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Comparative Example 2)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of an alcohol composed of 1 part by weight and 1-butanol and ethanol was mixed, molding was performed by a doctor blade method to produce a green sheet having a thickness of 0.47 mm.
(2) Next, the green sheet was dried at 80 ° C. for 5 hours, and then a portion to be a through hole was formed by punching.
(3) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle size of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(4) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer.
(5) On the green sheet after the treatment in (1), the above-mentioned conductor paste is screen-printed using a mask of 120 mesh and wire diameter of 0.080 mm and dried in air at 25 ° C. for 8 hours or more.
(6) The green sheets of (1) to (5) having been subjected to the above treatment and a tungsten carbide pattern sheet were laminated and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot pressed at 1840 ° C. under a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This was cut into a 330 mm disc shape, and a ceramic plate-like body having a heater electrode with a thickness of 25 μm and a width of 10 mm inside, and a through hole with a surface roughness of 20 μm on the surface of the plasma generating electrode.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.

(Comparative Example 3)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of alcohol composed of 1 part by weight and 1-butanol and ethanol were mixed, molding was performed by a doctor blade method to produce green sheets having thicknesses of 0.47 mm and 0.10 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Further, 50 circular through holes having a diameter of 3.3 mm were formed by punching a 100 μm thick green sheet dried at 80 ° C. for 5 hours to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle diameter of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled in a portion to be a through hole for forming a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, protrusions of 100 μm were formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk shape, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, a projection of 80 μm is formed on the surface of the electrode for plasma generation, and a ceramic plate having a through hole It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Comparative Example 4)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of alcohol composed of 1 part by weight and 1-butanol and ethanol were mixed, molding was performed by a doctor blade method to produce green sheets having a thickness of 0.47 mm and 0.27 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Further, 50 circular through holes having a diameter of 3.3 mm were formed by punching a green sheet having a thickness of 270 μm dried at 80 ° C. for 5 hours to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A plasma paste electrode conductive paste was prepared by mixing 100 parts by weight of titanium nitride particles having an average particle size of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled in a portion to be a through hole for forming a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, 270 μm protrusions were formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk shape, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, a ceramic plate-like body having a through hole with 220 μm protrusions formed on the surface of the electrode for plasma generation It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Comparative Example 5)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of alcohol composed of 1 part by weight and 1-butanol and ethanol were mixed, molding was performed by a doctor blade method to produce green sheets having thicknesses of 0.47 mm and 0.30 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Further, a green sheet having a thickness of 300 μm dried at 80 ° C. for 5 hours was formed by punching 50 circular through holes having a diameter of 3.3 mm in order to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of tungsten carbide particles having an average particle diameter of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled in a portion to be a through hole for forming a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, a 300 μm protrusion was formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk shape, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, and a 250 μm protrusion is formed on the surface of the plasma generating electrode, and a ceramic plate having a through hole It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

(Comparative Example 6)
(1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1 μm) 100 parts by weight, yttrium oxide (Y ₂ O ₃ : yttria, average particle size 0.4 μm) 4 parts by weight, acrylic binder 11.5 parts by weight, dispersant 0.5 Using a paste in which 53 parts by weight of alcohol composed of 1 part by weight and 1-butanol and ethanol were mixed, molding was performed by a doctor blade method to produce green sheets having thicknesses of 0.47 mm and 0.35 mm.
(2) Next, this green sheet was dried at 80 ° C. for 5 hours, and then 10 circular through holes with a diameter of 3 mm were formed by punching in order to form external terminals.
(3) Furthermore, a green sheet having a thickness of 350 μm dried at 80 ° C. for 5 hours was formed by punching 50 circular through-holes having a diameter of 3.3 mm in order to form an electrode surface.
(4) 10000 parts by weight of tungsten carbide (WC-10 manufactured by Allied Material) particles having an average particle diameter of 1 μm, 1509 parts by weight of an acrylic binder (SA-545 manufactured by Mitsui Chemicals), and 175 parts by weight of a plasticizer (DOA manufactured by Kuroki Kasei) Then, 560 parts by weight of 1-butanol and 432 parts by weight of ethanol were mixed, and a tungsten carbide green sheet having a thickness of 65 μm ± 5 μm was produced by a doctor blade method. This was dried in air at 25 ° C. for 48 hours to obtain a green sheet having a thickness of 55 μm ± 5 μm, and this green sheet was punched to form a tungsten carbide pattern sheet for a heater electrode.
(5) A conductive paste for an electrode for plasma generation was prepared by mixing 100 parts by weight of molybdenum carbide particles having an average particle diameter of 3 μm, 1.9 parts by weight of an acrylic binder, 3.7 parts by weight of α-terpineol solvent, and 0.2 parts by weight of a dispersant. . Furthermore, a conductor paste was filled in a portion to be a through hole for connecting an external terminal to form a filling layer. Further, a conductive paste was filled in a portion to be a through hole for forming a protrusion on the surface of the plasma generating electrode to form a filling layer.
(6) The above-mentioned conductor paste is screen-printed on the green sheet subjected to the treatment of (1) and dried in air at 25 ° C. for 8 hours or more.
(7) The green sheets of (1) to (6) after the above treatment and the tungsten carbide pattern sheet were laminated, and pressure-bonded at 130 ° C. and a pressure of 8 MPa to form a laminate. Thus, 350 μm protrusions were formed on the surface of the plasma generating electrode, and the surface of the electrode had a surface roughness of Ra: about 150 μm.
(8) Next, the obtained laminate was degreased in nitrogen gas at 600 ° C. for 5 hours, and hot-pressed at 1840 ° C. and a pressure of 15 MPa for 6 hours to obtain a ceramic plate having a thickness of 18 mm. This is cut out into a 330 mm disk shape, and has a heater electrode with a thickness of 25 μm and a width of 10 mm inside, a 300 μm protrusion formed on the surface of the plasma generating electrode, and a ceramic plate having a through hole It was.
(9) Then, a screw groove is formed on the side surface for fixing the bottomed hole for inserting the temperature measuring element by drilling and the electrode rod made of nickel on the surface of the obtained ceramic plate-like body A hole was formed.
(10) The electrode embedding member manufactured by the steps (1) to (9), that is, the blasting was performed so that the roughness of the wafer processing surface of the ceramic heater was Ra 0.5 μm.
(11) To the ceramic heater manufactured by the steps (1) to (9), aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) is formed into a cylindrical shape by a dry rubber press method, and an oxidizing atmosphere, A columnar body made of aluminum nitride (outer diameter 80 mm, inner diameter 70 mm, length 190 mm) formed by degreasing at 600 ° C for 5 hours and then firing in nitrogen gas at 1860 ° C for 6 hours Bonding was performed by heating at 1850 ° C. in nitrogen gas.
(12) The segment 1n was drilled to form a through hole for inserting a lifter pin of a silicon wafer and a bottomed hole (diameter: 1.7 mm, depth: 10 mm) for embedding a thermocouple.
(13) A tungsten pin with an Au-Ni brazing material is fixed to the fixing hole in a fixing hole in which a screw groove is formed on the side surface for fixing the nickel electrode rod, and the tip is Au-Ni A nickel rod with a brazing material was screwed in, and the nickel rod was brazed in a nitrogen atmosphere at 1030 ° C. for 28 minutes.

Discussion of Examples and Comparative Examples Table 1 shows the relationship between the surface roughness Ra of the plasma generating electrode, the height of the protrusions provided on the surface of the plasma generating electrode, and the plasma distribution. The test results show that the plasma is uniformly distributed when the surface roughness Ra of the plasma generating electrode is in the range of 0.05 to 10 μm and the surface of the plasma generating electrode is provided with protrusions with a height of 100 to 200 μm. It became clear that This fact is a result of the fact that when the surface roughness Ra of the plasma generating electrode is in the range of 0.05 to 10 μm, ions in the plasma state are not affected at all by the lightning rod effect. In the case where protrusions with a height of 100 to 200 μm are provided on the surface of the metal, it is suggested that the result is that ions in the plasma state are caused by the effect of the lightning rod effect on the surface of the plasma generating member uniformly. It is.

  INDUSTRIAL APPLICABILITY The present invention is applicable to an electrode burying member for a plasma generator used for processing a silicon wafer or the like in a plasma generating atmosphere in the field of a semiconductor manufacturing apparatus or the like.

It is a fragmentary sectional view of the electrode embedding member for plasma generators of the present invention. It is a top view which shows typically an example of the electrode for plasma generation. It is sectional drawing which shows the example which embedded the electrode for plasma generation in the multilayer in the board | substrate. It is a top view which shows typically the other example of the electrode for plasma generation. (A)-(c) is sectional drawing which shows an example of the manufacturing method of the electrode embedding member for plasma generators of this invention. It is an expanded sectional view of an external terminal attachment part.

Explanation of symbols

10, 30, 40 Electrode-embedding members 11, 31, 41 Ceramic substrate 11a Heating surface 11b Bottom surface 11c Emboss 12, 32, 42 Heater electrodes 13, 53 Through hole 14 Bottomed hole 15 Through hole 17 Terminal protection cylinder 19 Bag hole 23 External Terminal 24 Conductive wire 26 Lead wire 110 Green sheet 120 Motor electrode pattern layer 130 Conductive paste filling layer 180 Side temperature element

Claims (5)

  In an electrode embedding member in which a plasma generating electrode is arranged in a ceramic substrate, the electrode has at least a surface on the wafer holding side having a surface roughness Ra specified in JIS B 0601 in a range of 0.05 to 10 μm. An electrode embedding member for a plasma generator, comprising:   The electrode embedding member for a plasma generator according to claim 1, wherein the electrode is made of conductive carbide ceramics or conductive nitride ceramics.   In an electrode embedding member in which a plasma generating electrode is disposed in a ceramic substrate, the electrode is provided with protrusions regularly arranged on at least a surface on a wafer holding side. Electrode buried member.   The electrode embedding member for a plasma generating apparatus according to claim 3, wherein the protrusion has a height of 100 μm to 200 μm. The electrode embedding member for a plasma generator according to any one of claims 3 and 4, wherein the electrode is made of conductive carbide ceramics or conductive nitride ceramics.

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