JP4400360B2 - Free-cutting ceramics, manufacturing method thereof, and probe guide parts - Google Patents

Description

  The present invention relates to a free-cutting ceramic, particularly a high-strength free-cutting ceramic that exhibits a uniform color with little light reflectivity and has a coefficient of thermal expansion controlled within a range suitable for the intended use. The present invention also relates to a method for producing such a free-cutting ceramic and a machined part such as a probe guide part produced from such a ceramic by cutting such as cutting, grinding and / or drilling.

  In general, ceramic materials are attracting attention as component materials for semiconductor manufacturing equipment because they are excellent in mechanical properties and insulation properties, and also in high temperature properties. However, ceramics have a large shrinkage during sintering, and cutting such as grinding is required to obtain a desired shape and size with high accuracy. However, most ceramics are difficult to process.

  The workability of ceramics can be improved by dispersing another ceramic having a cleavage property, such as mica or boron nitride, in ceramics or, in the case of glass ceramics, in its glass matrix. This type of ceramic is generally called free-cutting ceramic. Since they have good machinability, they are often used in the manufacture of parts for semiconductor inspection devices that require high-precision fine workability and insulation.

  However, few ceramic materials have both high strength and excellent workability required for high-precision fine processing, and a thermal expansion coefficient close to that of silicon. In addition, the conventional free-cutting ceramics have a poor appearance because the hue is not uniform, and therefore the commercial value is lowered. Further, since this type of ceramic has a white light tint with high light reflectivity, it is difficult to accurately inspect and measure a processed part produced from the processed part by image processing.

  For example, the electrical characteristics of semiconductor elements such as IC and LSI are usually inspected using a probe card having a large number of electrode pads. The inspection is performed by bringing all probes of the probe card into contact with the electrode pads of the semiconductor element at the same time.

  FIG. 1A is a schematic longitudinal sectional view of a probe card provided with a measurement probe used for inspection of a semiconductor element. A probe card 1 formed of an insulating material such as ceramics has an opening 10 at substantially the same center as or larger than the semiconductor element to be inspected. As shown in the figure, the opening 10 is usually shaped like a morning glory that opens upward. On the upper surface of the probe card 1, the same number of measurement probes 2 as electrode pads formed on a semiconductor element are attached by, for example, an adhesive.

  The measuring probe 2 is usually made of a conductive metal material. The tip of the probe 2 is bent into a substantially L-shape and protrudes slightly from the lower surface of the probe card 1 through the opening 10 to form the same arrangement pattern as the electrode pads of the semiconductor element. Although not shown, the other end of the probe 2 is electrically connected to a conductive circuit formed on the upper surface of the probe card 1 with solder or the like. You may coat | cover the circumference | surroundings of each probe 2 except the front-end | tip with heat resistant resin so that each probe 2 may not contact mutually.

  The electrical characteristics of the semiconductor element (not shown) are inspected by placing the probe card 1 on the semiconductor element to be inspected and pressing it, and the tip of the measurement probe 2 protruding from the opening 10 is the electrode pad of the semiconductor element. This is done by making contact. In order to perform inspection accurately, it is indispensable that all of a large number of measurement probes simultaneously come into contact with the electrode pads of the semiconductor element located thereunder. However, the probe is usually a thin metal material and bends when the probe card 1 is pressed, and the position of the tip of the probe 2 tends to shift due to the bending. For this reason, it is difficult to reliably contact the probe 2 with the electrode pad.

  As shown in FIG. 1B, in order to facilitate precise positioning of the measurement probe 2, a probe guide component (probe guide) 3 formed from an insulating plate is used as an opening of the probe card 1. It is possible to fit into the opening 10 so as to block 10. The probe guide part 3 has a through hole 12, and the probe 2 passes through the through hole 12, and its tip protrudes from the bottom surface of the probe guide part 3. The through holes 12 are arranged in the same pattern as the electrode pads. The probe guide part 3 acts to limit the lateral movement of the probe 2 due to bending, allowing the probe 2 to make more reliable contact with the electrode pad.

  The through holes 12 having a slightly larger diameter than the measurement probe 2 are formed in the probe guide component 3 at the same pitch as the electrode pads. In recent LSIs, it is not uncommon for the pitch of electrode pads to become 100 μm or less due to the progress of higher density.

  For example, as shown in FIGS. 1 (C) and 1 (D) in a plan view and a cross-sectional view, when the electrode pad pitch is 70 μm and the diameter of the through hole 12 is 60 μm, the wall between adjacent through holes is The thickness (minimum distance between holes) is 10 μm, and the wall thickness is very thin. Thus, it is necessary to form such a fine and thin through hole with high accuracy in the probe guide component by, for example, drilling.

  Another type of probe guide component is shown in perspective view in FIG. In FIG. 2, a frame-shaped probe guide part 3a (which may be an integral insulating part or made by combining insulating long plates) has at least one side of the frame, usually Are provided with slits 14 in the vertical direction at the same pitch as the electrode pads of the semiconductor element to be inspected (not shown) on two or four sides. The probe guide component 3a can be fitted into the opening of the probe card by inserting it into the opening of the probe card (not shown) from below. In this way, each probe 2 of the probe card passes through the corresponding slit 14 and protrudes into the opening of the probe card. Also in this case, the lateral movement of the probe 2 is limited by passing through the slit 14 of the probe guide part 3a, and the probe can be brought into more accurate contact with the electrode pad.

  FIG. 3 is a schematic cross-sectional view of one side of the frame-shaped probe guide component 3a having the slit 14 as shown in FIG. As shown, the shape of the slit 14 is generally defined by the depth and width of each slit and the wall thickness, which is the distance between adjacent slits. This type of slit is usually deep and thin, with a thin wall thickness. For example, as shown in FIG. 3, the slit 14 may have dimensions of a depth of 300 μm, a width of 40 μm, and a wall thickness of 15 μm. Such a slit is generally formed by slit processing using a grinding wheel.

As a matter of course, the probe card is required to have insulation properties in order to prevent a short circuit between the measurement probes, and the volume specific resistance is required to be 1.0 × 10 ¹⁰ Ω · cm or more.
Conventional probe guide parts have been made of plastic or free-cutting crystallized glass-based ceramic material made of Al2O3, SiO2, K2O or the like. Recently, it has also been produced from free-cutting ceramics containing boron nitride.

Plastic probe guide parts cannot be used when there is a need to inspect at high temperatures, and sufficient dimensional accuracy of through holes or slits cannot be obtained.
Probe guide parts made of crystallized glass ceramic material can be used for high temperature inspection. However, the thermal expansion coefficient of crystallized glass ceramics is larger than that of a semiconductor element, and depending on the measurement temperature, there may be a displacement between the measurement probe and the electrode pad of the semiconductor element. Further, since the strength of crystallized glass ceramics is not so high, chipping and cracking are likely to occur during drilling and other cutting processes, and sufficient dimensional accuracy cannot be obtained. See Patent Document 1.

  Further, ordinary crystallized glass ceramic materials are white in color. For this reason, light is reflected from the surface of the probe guide part during dimensional inspection of minute through holes or slits formed in the probe guide part and image processing measurement for alignment when the probe guide part is mounted on the probe card. This makes it difficult to obtain an accurate image. In addition, in the case of a white color, stains are conspicuous in appearance, and the product value decreases due to the stains. See Patent Document 1.

  A composite material of aluminum nitride and boron nitride has a thermal expansion coefficient close to that of silicon. Therefore, when a probe guide component made from this material is used, there is little misalignment caused by thermal expansion. However, since this material has poor processability, it is not suitable for high-precision fine processing. There are also color irregularities that reduce the commercial value. See Patent Document 2.

  A high-strength free-cutting silicon nitride / boron nitride composite material has also been proposed, but has a smaller thermal expansion coefficient than silicon. Therefore, when it is used for a semiconductor inspection jig such as a probe guide component, a positional deviation occurs depending on the measurement temperature. See Patent Document 3.

JP 58-165056 A JP 60-195059 JP 2000-327402 A

  The object of the present invention is to provide a high-strength and excellent workability required for high-precision microfabrication, a thermal expansion coefficient close to that of silicon, and a uniform black hue that is suitable for image processing measurement and increases commercial value. And a method of manufacturing the ceramic, and a probe guide component manufactured therefrom.

  The present invention provides a high-strength free-cutting ceramic having a strength of 240 MPa or more. This ceramic exhibits good machinability with a tool flank wear width VB of 0.2 mm or less and a workpiece surface roughness Rmax of 5 μm or less in a 5-minute turning with a carbide K-10 type tool. Such high-strength and excellent machinability ceramics enables micron-level fine processing. Since this ceramic also has a uniform blackish hue and a thermal expansion coefficient close to that of silicon, it is useful, for example, as an insulating material for probe guide parts and the like.

In one embodiment of the present invention, the high-strength free-cutting ceramic includes a main component and a sintering aid, the main components being boron nitride: 30 to 59.95% by mass, zirconia: 40 to 69.95% by mass, and silicon nitride: It contains 0 to 20% by mass and has a blackish tint. Preferably, the ceramic has a coefficient of thermal expansion of 3 to 5 × 10 ⁻⁶ / ° C. at 25 ° C. to 600 ° C.

  The blackish hue of the ceramic can be imparted by mixing a coloring component into the main component of the ceramic. The coloring component is one or more elements selected from elements of C, Si, the fourth period IIIA to IVB group, the fifth period IVA to VB group, and the sixth period IVA to VIB group in the long period type periodic table. . The element can exist in either a single form, a compound form, or both. The total amount of the coloring component is 0.05 to 2.5% by mass in terms of a single element based on the main component of the ceramic.

  Here, the “main component” in the present invention means a solid particle component constituting the main body of the ceramic, and does not include a sintering aid. The main component of the ceramic according to the present invention is a combination of boron nitride, zirconia, coloring components, and optionally added silicon nitride.

  Further, the “sintering aid” is a material that generates a liquid phase during sintering and promotes sintering. After sintering, the sintering aid remains in an indefinite shape at the grain boundaries of the particulate main component aggregate or partially volatilizes during sintering.

  Zirconia has three crystal forms of monoclinic, tetragonal, and cubic in order from the low temperature side, and the normal form of zirconia at normal temperature is monoclinic. In order to avoid the occurrence of cracks due to expansion or contraction associated with the transition of crystal form, zirconia ceramics are usually used in the state of stabilized zirconia in which tetragonal crystals and / or cubic crystals are formed at room temperature. Such stabilized zirconia includes fully stabilized zirconia (FSZ, cubic), partially stabilized zirconia (PSZ, cubic + tetragonal), and tetragonal zirconia polycrystal (TZP, tetragonal). In general, PSZ and TZP are tougher than FSZ.

In the present invention, in order to achieve both high strength and free machinability (high toughness), it is desirable that FSZ having relatively better workability than PSZ or TZP is mainly precipitated.
A free-cutting ceramic according to the present invention comprises sintering a main component raw material powder containing boron nitride, zirconia and an optional component silicon nitride and at least one coloring component in an amount of 1 to 15% by mass of the main component raw material powder. It can be manufactured by a method including a step of obtaining a raw material powder by mixing an auxiliary agent and a step of sintering the mixed raw material powder under high temperature and pressure. A processed part such as a probe guide part can be manufactured from this ceramic by machining including grinding and grinding for forming slits and / or drilling for forming through holes.

  Since the free-cutting ceramic according to the present invention is colored in a uniform black color shade, it has a small light reflection, and after processing, it has a special reduction in processing dimensional accuracy such as metal or ceramic vapor deposition or resin coating. It is not necessary to perform a coloring process. For this reason, measurement such as image processing measurement and alignment can be performed accurately, and since the appearance is excellent, the commercial value is also high.

Furthermore, since the thermal expansion coefficient at 25 ° C. to 600 ° C. is controlled within the range of 3 to 5 × 10 ⁻⁶ / ° C., which is close to the thermal expansion coefficient of silicon 4 × 10 ⁻⁶ / ° C., Alternatively, when used in a probe guide component (probe guide) for a semiconductor inspection apparatus in which a hole is formed, there is no positional deviation from the semiconductor element to be inspected due to thermal expansion.

  According to the present invention, a deep slit or a through-hole having a small wall thickness and a small width or diameter can be formed with high accuracy, so that a probe provided at a high density can be held at a predetermined position, and a displacement due to a measurement temperature is small. As a result, it is possible to realize a semiconductor element inspection apparatus that can cope with higher density of LSI.

According to the present invention, the thermal expansion coefficient at 25 ° C. to 600 ° C. is 3 to 5 × 10 ⁻⁶ / ° C. and a thermal expansion coefficient close to that of silicon, and the following (1), ( New ceramic processed parts like 2) are provided.

  (1) A machined part made of a free-cutting ceramic sintered body having a plurality of slits formed by grinding, wherein the wall thickness between the slits is 5 μm or more and less than 20 μm, and the slit depth / wall thickness ratio 15 or more and the pitch accuracy between the slits is within ± 4 μm.

  (2) A machined part made of a free-cutting ceramic sintered body having a plurality of holes formed by drilling, wherein the hole diameter is 65 μm or less, the wall thickness between the holes is 5 μm or more and less than 20 μm, A ceramic processed part having a hole depth / wall thickness ratio of 15 or more and an accuracy of the hole diameter and hole pitch both within ± 4 μm.

Here, the wall thickness between the holes means the minimum distance between the holes.
These ceramic processed parts may be probe guide parts having a plurality of slits and / or holes through which the probe passes.

  A processed part according to the present invention comprises a raw material powder obtained by mixing an appropriate sintering aid with a main component composed of boron nitride, zirconia, optionally added silicon nitride and a coloring component under high temperature pressure, for example, hot pressing or It can be produced by a method including a step of obtaining a ceramic sintered body by sintering with HIP and a step of processing the ceramic sintered body with a grinding wheel or a drill.

  Here, it is preferable that the raw material powder of boron nitride and zirconia has an average particle diameter of less than 1 μm. By adding boron nitride, high thermal conductivity is imparted in addition to the original free machinability, both of which provide excellent workability. Zirconia has high strength, but its coefficient of thermal expansion is larger than that of silicon. Silicon nitride is not essential, but has a lower coefficient of thermal expansion than silicon and high strength.

  Therefore, the thermal expansion coefficient of the ceramic of the present invention can be adjusted by the ratio of zirconia, boron nitride and silicon nitride in the raw material powder. Further, the strength can be further increased by the addition of silicon nitride.

  In the present invention, the coloring component is one or more selected from elements of C, Si, and the fourth period IIIA to IVB group, the fifth period IVA to VB group, and the sixth period IVA to VIB group in the long period periodic table. An elemental element or a compound thereof. Suitable compounds include nitrides, carbides, borides, oxides, silicides, acid hydrates, nitrates, carbonates, acetates, sulfates and the like. However, the compound species contained in the main component is excluded. Even with boron nitride and zirconia alone, a uniform black hue with little light reflection cannot be produced.

  The coloring component raw material may undergo a reaction during heating before sintering or during sintering. That is, this raw material may be a precursor of a coloring component present in the sintered ceramic. For example, an organic resin may be used as the C precursor, and a metal salt may be used as the metal oxide precursor. In particular, in the latter case, the raw material powder may be preliminarily calcined in air or another oxidizing atmosphere in order to convert the metal salt or other precursor to a metal oxide before sintering. The calcination may be performed either before or after the sintering aid is added.

  C and Si can be added in the form of carbon or silicon alone or silicon carbide, respectively. Otherwise, when it is contained as a metal carbide or silicide, it is treated as a carbide or silicide of the metal element.

  The elements of the fourth period IIIA to IVB group of the long period type periodic table include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Ge. Examples of the elements of the fifth period IVA to VB group include Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, and Sb. The elements of the sixth period IVA to VIB group include Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, and Po.

  Among these elements, when a single element and / or oxide of a transition metal such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and W is added, a metal or Reduced blackening to low valence oxide occurs, resulting in a particularly uniform color, and these oxides are preferred because they have lower hardness and less influence on workability than nitrides, carbides and borides.

In particular, when a simple substance of Ti and / or an oxide is added, the color unevenness becomes more inconspicuous, and it is more suitable because it has a less influence on workability.
C (carbon) addition is also preferable because it has little influence on processability, but these may be added in the form of carbon powder or carbonized resin. In the case of a carbonized resin, the addition amount may be adjusted so that a desired C addition rate is obtained after carbonization.

The ceramic according to the present invention has a high strength of 240 MPa or more, exhibits free-cutting properties, and can perform fine processing with high accuracy. And when the thermal expansion coefficient at 25 ° C to 600 ° C is 3-5x10 ^-6 / ° C, which is close to silicon, it is used for probe guide parts (probe guides) used in semiconductor inspection equipment. Even if there is a temperature change, no positional deviation occurs between the semiconductor element to be inspected. In addition, since it is colored in a uniform blackish hue, it is possible to accurately perform measurement such as image processing after processing, and it is excellent in appearance and increases its commercial value.

  As a simple coloring method for ceramic processed parts, vapor deposition of metals and ceramics, and coating with a resin film can be considered. However, in these methods, the coating is easy to peel off, and the coating itself has a thickness of about 10 μm, and the film thickness tends to be non-uniform. It is desirable to color.

  Moreover, about the addition amount of a coloring component, when too small, the sintered compact which exhibited the uniform color with little light reflection cannot be obtained. On the other hand, if the amount is too large, the strength will decrease and the machinability will also deteriorate, affecting the fine workability, and also the insulation will be reduced, so when used for probe guide parts for semiconductor inspection equipment, Problems such as short circuit occur.

  In addition, the uniform blackish hue with less light reflection in the present invention includes black, gray, dark blue, dark purple, dark green, and the like. Specifically, for example, in terms of lightness in the Munsell color system (JIS Z8721: display method using three attributes of color), the range is 8.5 or less.

  According to the method for producing free-cutting ceramics of the present invention, the sintering aid component is a main component consisting of 30 to 59.95% by weight of boron nitride, 40 to 69.95% by weight of zirconia, 0 to 20% by weight of silicon nitride, and a coloring component. Are added and mixed to prepare a raw material powder. This mixing can be performed by, for example, a wet ball mill.

  Boron nitride may be hexagonal (h-BN). From the viewpoint of obtaining the high strength required for microfabrication, it is preferable that the main component raw material powder, particularly boron nitride powder, has an average particle size of less than 1 μm. Similarly, by using zirconia having an average particle size of less than 1 μm, more preferably less than 0.5 μm, a desired high-strength free-cutting ceramic can be reliably produced.

  The sintering aid used in the present invention can be selected from those conventionally used for sintering boron nitride and silicon nitride. Preferred sintering aids are one or more obtained from complex oxides such as aluminum oxide (alumina), magnesium oxide (magnesia), yttrium oxide (yttria), and lanthanoid metal oxides and spinels. More preferably, it is a mixture of alumina and yttria, or a mixture obtained by further adding magnesia thereto.

  The blending amount of the sintering aid component is desirably in the range of 1 to 15% by mass, particularly 3 to 10% by mass of the main component raw material powder. If the blending amount is too small, sintering becomes insufficient and the strength of the sintered body is lowered. When there are too many compounding quantities, a low-intensity grain boundary glass layer will increase, and the intensity | strength fall of a sintered compact will be caused.

  When the raw material powder is calcined after adding a sintering aid in order to convert the metal salt, which is a precursor of the coloring component, into a metal oxide, the agglomeration of the powder usually occurs during the calcining. It is preferable to wet-mill the powder again for deagglomeration.

  The raw material powder in which the main component raw material powder and the sintering aid component are mixed is sintered under high temperature and pressure. As a high-temperature pressure sintering method, there is a hot press, which may be performed in a nitrogen atmosphere or in pressurized nitrogen. The hot press temperature is preferably in the range of 1400-1800 ° C. If the temperature is too low, sintering becomes insufficient, and if it is too high, problems such as elution of the auxiliary component occur. The pressure is suitably in the range of 20-50 MPa. The duration of hot pressing is usually about 1 to 4 hours, although it depends on the temperature and dimensions.

High-temperature pressure sintering can also be performed by HIP (hot isostatic press). The sintering conditions in this case can also be set as appropriate by those skilled in the art.
The obtained sintered body is uniformly colored in a blackish hue. If the kind and amount of the sintering aid and the ratio of zirconia and silicon nitride (when used) are appropriately selected, 25 to 600 ° C. The coefficient of thermal expansion at 3 ° C. is 3 to 5 × 10 ⁻⁶ / ° C.

  Further, when the microstructure of the sintered body was observed with a scanning electron microscope (SEM), the average particle diameters of boron nitride, zirconia, silicon nitride and coloring components as main components were 5 μm or less.

  Since this sintered body has excellent machinability and high strength, fine slit processing or hole processing can be performed with high accuracy. In addition, since it exhibits a thermal expansion coefficient close to that of silicon, when used in a probe guide component (probe guide) used in a semiconductor inspection apparatus, even if there is a temperature change, a positional deviation occurs with respect to the semiconductor element to be inspected. Absent. Furthermore, because it is colored in a uniform black color shade with low light reflectivity, without special coloring treatment that causes deterioration of processing dimensional accuracy, such as vapor deposition of metal and ceramic after processing, coating treatment with resin coating, Measurement such as image processing measurement and alignment can be performed accurately. In addition, it has a good commercial value due to its excellent appearance.

  As shown in FIGS. 1B and 2, the ceramic processed part according to the present invention may generally have a plate shape or a frame shape, and a plurality of slits and / or drills formed by slit processing using a grinding wheel. It is possible to obtain a probe guide component having a plurality of through holes formed by. The outer shape may be determined so as to be fitted into the opening of the probe card to which the probe guide component is mounted.

  Since the wall thickness or the wall thickness between holes is as thin as 5 μm or more and less than 20 μm and can be processed with high accuracy, the probe guide component according to the present invention can hold the probe at a high density and The alignment accuracy is improved and the reliability of the inspection apparatus is increased.

  Therefore, the use of the high strength free-cutting ceramics thus produced with a uniform black hue and a thermal expansion coefficient close to that of silicon is not particularly limited, but is attached to a probe card used for inspection of semiconductor elements. It is useful as a probe guide component.

  The Example in this invention and the comparative example with respect to it are described, and a result is shown in Table 1. “%” In Examples and Comparative Examples is “% by mass” unless otherwise specified.

[Example 1]
Hexagonal boron nitride (h-BN) powder having an average particle size of 0.9 μm and a purity of 99%, zirconia powder having an average particle size of 0.1 μm, and carbon powder having an average particle size of 0.1 μm were mixed at a ratio shown in Table 1. To this mixed powder (main component raw material powder), 2% alumina and 6% yttria were added as sintering aids, and wet ball mill mixing was performed using ethyl alcohol as a solvent. At this time, a polyethylene pot and zirconia balls as media were used, and the resulting slurry was dried by a vacuum evaporator to obtain a raw material powder.

  This raw material powder is filled in a graphite die and hot press sintered at 1600 ° C for 2 hours while applying a pressure of 30 MPa in a nitrogen atmosphere to obtain a ceramic sintered body of 65 mm × 65 mm and 10 mm thickness. It was.

  A test piece was cut out from the sintered body, and the fracture strength was measured by a three-point bending test. In order to evaluate machinability, a turning test was conducted using a carbide K-lO type tool at a grinding speed of 18 m / min, a feed rate of 0.03 mm / rev, and a cutting depth of 0.1 mm. The surface roughness of the work material and the flank wear width of the tool (indicating the degree of tool wear) were measured. Furthermore, the thermal expansion coefficient of this sintered body was measured in the range of room temperature (25 ° C.) to 600 ° C. Further, the volume resistivity was measured at room temperature.

  Regarding the hue, after grinding and removing the surface layer of the 65 mm × 65 mm sintered body, it is visually evaluated. If there is no color unevenness in the “uniformity” column, ○, if color unevenness is seen X. Also check the color tone, and if the image processing measurement of the processing shape (hole diameter, hole processing position, etc.) can be performed smoothly in the “Coloring degree” column, the coloration degree ○, light reflection, etc. The case where it was not able to measure was made into coloring degree x. Furthermore, the brightness in the Munsell color system (JIS Z8721) was measured by comparing the standard color chart with the product ground surface color. These results are shown in Table 1.

  By slitting this sintered body using a grinding wheel (resin bond diamond wheel No. 200, thickness 40 μm, outer diameter 50 mm), a slit having the shape shown in FIG. 3 (width = 40 μm, wall thickness = 15 μm, depth) 100 = 300 μm). In the “Slit” column, x indicates that slitting is not possible, slitting is possible, but accuracy is insufficient (pitch accuracy exceeds ± 4 μm), or cracking and / or chipping (chipping) occurs. Δ, when slitting was possible with sufficient accuracy and no cracks or chipping occurred, it was evaluated as ○.

  Further, after cutting the obtained sintered body into a thin plate having a thickness of 300 μm, using a carbide drill material SKH 9) having a diameter of 50 μm, as shown in FIGS. 1 (C) and (D), the wall thickness Drilling was performed in 20 rows (total 200 pieces) at 10 μm. The diameter of the hole is 60 μm and the depth is 300 μm.

  Measure the hole diameter and hole pitch accuracy of the obtained through holes, and in the “Drilling” column, if this accuracy is within ± 4μm and there are no cracks or chips, drilling is possible. Was evaluated as “C” when the crack was insufficient or cracks or chips were generated, and “C” was evaluated when drilling was not possible. The results are shown in Table 1.

[Example 2]
Hexagonal boron nitride (h-BN) powder having an average particle size of 0.9 μm and purity of 99%, zirconia powder having an average particle size of 0.1 μm, silicon nitride powder having an average particle size of 0.1 μm, and carbon having an average particle size of 0.1 μm Powders were mixed at a ratio shown in Table 1 to prepare a main component raw material powder. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 3]
Hexagonal boron nitride (h-BN) powder having an average particle size of 0.9 μm and purity of 99%, zirconia powder having an average particle size of 0.1 μm, and phenol resin as a C source so as to have the ratio shown in Table 1 after carbonization. To prepare a main component raw material powder. The other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 4]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, and molybdic acid (H2MoO4) so as to have the ratio shown in Table 1 in terms of Mo. The main component raw material powder was prepared by mixing. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Examples 5 to 8]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, and optionally a silicon nitride powder with an average particle size of 0.1μm, and titanium oxide (TiO2) Were mixed so as to have the ratio shown in Table 1 in terms of Ti to prepare a main component raw material powder. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 9]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, and titanium carbide (TiC) so that the ratio shown in Table 1 is converted to Ti. The main component raw material powder was prepared by mixing. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 10]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9 μm and purity of 99%, zirconia powder with an average particle size of 0.1 μm, silicon nitride powder with an average particle size of 0.1 μm, and titanium nitride (TiN) The main component raw material powder was prepared by mixing so as to have the ratio shown in Table 1 in terms of conversion. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 11]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, and titanium boride (TiB2) to the ratio shown in Table 1 in terms of Ti To prepare a main component raw material powder. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 12]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, silicon nitride powder with an average particle size of 0.1μm, and tungsten carbide in terms of W The main component raw material powder was prepared by mixing so as to have the ratio shown in 1. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 13]
Hexagonal boron nitride (h-BN) powder having an average particle size of 0.9 μm and purity of 99%, zirconia powder having an average particle size of 0.1 μm, silicon nitride powder having an average particle size of 0.1 μm, and basic cobalt carbonate (II) In the same manner as in Example 1, a sintering aid was added to a main component raw material powder prepared by mixing so as to have a ratio shown in Table 1 in terms of Co, and wet ball mill mixed. The obtained raw material powder was calcined at 400 ° C. in the atmosphere to decompose cobalt carbonate into cobalt oxide, and this calcined powder was again wet-milled using ethyl alcohol and deagglomerated, and then the same as in Example 1. Thus, a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 14]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, silicon nitride powder with an average particle size of 0.1μm, average particle size of 0.1μm, purity Main component raw material powder was prepared by mixing 99.9% of nickel powder in the proportion shown in Table 1. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 15]
Hexagonal boron nitride (h-BN) powder having an average particle size of 0.9 μm and purity of 99%, zirconia powder having an average particle size of 0.1 μm, silicon nitride powder having an average particle size of 0.1 μm, and manganese (II) acetate 4 water In the same manner as in Example 1, a sintering aid was added to a main component raw material powder prepared by mixing a Japanese product so as to have a ratio shown in Table 1 in terms of Mn, and wet ball mill mixing was performed. The obtained raw material powder was calcined at 400 ° C. in the atmosphere to decompose manganese acetate into manganese oxide, and this calcined powder was again wet-milled using ethyl alcohol and deagglomerated, and then the same as in Example 1. Thus, a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 16]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9 μm and purity of 99%, zirconia powder with an average particle size of 0.1 μm, silicon nitride powder with an average particle size of 0.1 μm, and copper (II) nitrate 3 water In the same manner as in Example 1, a sintering aid was added to the main component raw material powder prepared by mixing the Japanese product so as to have a ratio shown in Table 1 in terms of Cu, and wet ball mill mixing was performed. The obtained raw material powder was calcined at 400 ° C. in the atmosphere to decompose copper nitrate into copper oxide, and this calcined powder was again wet-milled using ethyl alcohol and deagglomerated, and then the same as in Example 1. Thus, a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 17]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9 μm and purity of 99%, zirconia powder with an average particle size of 0.1 μm, silicon nitride powder with an average particle size of 0.1 μm, and silver (I) (Ag2O ) Were mixed so as to have the ratio shown in Table 1 in terms of Ag to prepare a main component raw material powder. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 18]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, silicon nitride powder with an average particle size of 0.1μm, and scandium oxide (Sc2O3) The main component raw material powder was prepared by mixing so as to have the ratio shown in Table 1 in terms of conversion. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 19]
Hexagonal boron nitride (h-BN) powder having an average particle size of 0.9 μm and purity of 99%, zirconia powder having an average particle size of 0.1 μm, silicon nitride powder having an average particle size of 0.1 μm, and vanadium oxide (V) (V2O5 ) Were mixed so as to have the ratio shown in Table 1 in terms of V to prepare a main component raw material powder. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 20]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, silicon nitride powder with an average particle size of 0.1μm, and zinc oxide (ZnO) in Zn The main component raw material powder was prepared by mixing so as to have the ratio shown in Table 1 in terms of conversion. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 21]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9 μm and purity of 99%, zirconia powder with an average particle size of 0.1 μm, silicon nitride powder with an average particle size of 0.1 μm, and gallium (III) oxide (Ga2O3 ) Were mixed so as to have the ratio shown in Table 1 in terms of Ga to prepare a main component raw material powder. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 22]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9 μm and purity of 99%, zirconia powder with an average particle size of 0.1 μm, silicon nitride powder with an average particle size of 0.1 μm, and iron (III) nitrate 9 water In the same manner as in Example 1, a sintering aid was added to a main component raw material powder prepared by mixing Japanese products so as to have a ratio shown in Table 1 in terms of Fe, and wet ball mill mixing was performed. The obtained raw material powder was calcined at 400 ° C. in the atmosphere to decompose iron nitrate into iron oxide, and this calcined powder was again wet-milled using ethyl alcohol and deagglomerated, and then the same as in Example 1. Thus, a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 23]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9μm and purity of 99%, zirconia powder with an average particle size of 0.1μm, silicon nitride powder with an average particle size of 0.1μm, and chromium oxide (Cr2O3) converted to Cr The main component raw material powder was prepared by mixing so as to have the ratio shown in Table 1. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Example 24]
Hexagonal boron nitride (h-BN) powder with an average particle size of 0.9 μm and purity of 99%, zirconia powder with an average particle size of 0.1 μm, silicon nitride powder with an average particle size of 0.1 μm, and tin (II) oxide (SnO ) Were mixed so as to have the ratio shown in Table 1 in terms of Sn to prepare main component raw material powder. Other conditions were the same as in Example 1, and a sintered body was produced and evaluated. The results are shown in Table 1.

[Comparative Examples 1-3]
For comparison, the same as in Example 4 except that the mass ratio of boron nitride, zirconia, and / or coloring additive was outside the scope of the present invention (provided that the main component raw material powder has an average particle size) A sintered body was prepared and evaluated. The results are shown in Table 1.

[Comparative Example 4]
For comparison, the conventional free-cutting crystallized glass-based ceramic material was subjected to slit processing and hole processing similar to those of the examples. However, the strength of the material was weak, and chipping (chipping) occurred when fine processing was performed. It was not possible to drill holes with good precision. Various characteristics and processing results of this ceramic material are also shown in Table 1.

[Comparative Example 5]
For comparison, when a conventional free-cutting ceramic material of aluminum nitride and boron nitride was subjected to slitting and drilling similar to the examples, the workability of the material was poor and it was not possible to drill accurately and cleanly. It was. Various characteristics and processing results of this ceramic material are also shown in Table 1.

  As can be seen from Table 1, when a ceramic material made of a sintered body produced under conditions within the range of the examples is used, high-precision fine processing can be performed without causing cracks or chips. In addition, it has a uniform blackish hue and can be smoothly measured for processing dimensions such as image measurement. Furthermore, it can be seen that the thermal expansion coefficient of this material is smaller than that of a conventional crystallized glass-based ceramic material, and shows a value close to that of silicon.

FIG. 1 (A) is a partially schematic explanatory view showing a cross section of a conventional probe card, FIG. 1 (B) is a schematic explanatory view showing a cross section of a probe card equipped with a probe guide component having a through hole, and FIG. C) is a schematic top view of the probe guide component showing the shape of the through hole, and FIG. 1 (D) is a schematic explanatory view of the probe guide component showing its cross section. It is a schematic explanatory drawing of the probe guide component provided with the slit. It is explanatory drawing of the slit shape formed in the Example.

Explanation of symbols

1: probe card, 2: probe, 3, 3a: probe guide component, 10: opening, 12: through hole, 14: slit

Claims (6)

As main components, boron nitride: 30 to 59.95% by mass, zirconia: 40 to 69.95% by mass, and C, Si, the fourth period IIIA to IVB group, the fifth period IVA to VB group and the sixth in the long period type periodic table A coloring component composed of a single element and / or a compound of one or more elements selected from the elements of the groups IVA to VIB having a period: 0.05 to 2.5% by mass (however, converted to a single element) , boron nitride, zirconia and the coloring component A free-cutting ceramic capable of micromachining characterized by having an average particle size of 5 μm or less, FSZ mainly precipitated by FSZ, and having a bending strength of 240 MPa or more and a uniform blackish hue. . As main components, boron nitride: 30 to 59.95% by mass, zirconia: 40 to 69.95% by mass, and 1 selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo and W A coloring component composed of a simple substance and / or an oxide of at least one kind of metal: 0.05 to 2.5% by mass (however, converted to a simple element) , boron nitride, zirconia and the average particle diameter of the coloring component are 5 μm or less, and zirconia Is a free-cutting ceramic capable of microfabrication , characterized in that FSZ is mainly precipitated and has a bending strength of 240 MPa or more and a uniform blackish hue . 3. The free-cutting ceramic according to claim 1 , comprising 20% by mass or less of silicon nitride as a main component instead of a part of the main component . The free-cutting ceramics according to any one of claims 1 to 3 , which has a thermal expansion coefficient of 3 to 5 x ^10-6 / ° C at 25 ° C to 600 ° C. A step of mixing raw material powder containing boron nitride, zirconia and coloring components and 1 to 15% by mass of a sintering aid of the main component raw material powder to obtain raw material powder, and heating the mixed raw material powder at high temperature The manufacturing method of the free-cutting ceramics in any one of Claims 1-4 including the process of sintering under pressure. A probe guide component comprising a plurality of slits and / or through-holes through which the probe passes, the probe guide component comprising the free-cutting ceramic according to claim 1 .

Images